Europäisches Patentamt (19) European Patent Office &  

Office européen des brevets (11) EP 0 954 558 B1

(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) Int Cl.: of the grant of the patent: C10L 1/14 (2006.01) C10L 1/10 (2006.01) 14.06.2006 Bulletin 2006/24 C10L 1/02 (2006.01)

(21) Application number: 97954909.4 (86) International application number: PCT/US1997/022046 (22) Date of filing: 08.12.1997 (87) International publication number: WO 1998/026028 (18.06.1998 Gazette 1998/24)

(54) FUEL COMPOSITIONS EXHIBITING IMPROVED FUEL STABILITY VERBESSERTE BRENNSTOFFESTABILITÄT AUFWEISENDE BRENNSTOFFEZUSAMMENSETZUNGEN COMPOSITIONS DE CARBURANT CARACTERISEES PAR UNE STABILITE AMELIOREE DUDIT CARBURANT

(84) Designated Contracting States: (56) References cited: DE FR GB IT NL WO-A-95/23836 WO-A-95/33022 WO-A-96/40844 DE-C- 508 917 (30) Priority: 09.12.1996 US 763696 US-A- 4 390 344 US-A- 4 397 655 US-A- 4 929 252 (43) Date of publication of application: 10.11.1999 Bulletin 1999/45 • DATABASE WPI Section Ch, Week 7626 Derwent Publications Ltd., London, GB; Class E11, AN (73) Proprietor: ORR, William C. 76-48473X XP002065173 & JP 51 052 403 A Denver, (ADACHI M) , 10 May 1976 Colorado 80210 (US) Remarks: (72) Inventor: ORR, William C. The file contains technical information submitted after Denver, the application was filed and not included in this Colorado 80210 (US) specification

(74) Representative: Weydert, Robert Dennemeyer & Associates Sàrl P.O. Box 1502 1015 Luxembourg (LU)

Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 0 954 558 B1

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Description Application # 91306278.2 Karas. Thus, it would be rea- sonable to expect fuels containing lower dialkyl carbon- Field of the Invention ates to store and perform optimally only when in moder- ately strong or strongly alkaline environments, i.e., pH’s [0001] The present invention relates to enhanced 5 exceeding 11 or more. Fuels having pH’s lower than 11, structured fuel compositions for use in jet, turbine, diesel, e.g. moderately alkaline, neutral and acidic would be ex- gasoline, and other combustion systems. More particu- pected to be problematic. larly, the present invention relates to fuel compositions [0005] In addition, conventional thinking and regulato- using viscous hydrocarbons, which are substantially neu- ry standards encourage the utilization of more refined tral pH, and which employ a silicon based combustion 10 less viscous base fuel hydrocarbons. The longer chain catalyst. or more complex hydrocarbons, e.g., heavy oils, heavy fuel oils, diesels, etc., are typically not preferred as fuels Background of the Invention due to handling, emission and combustion concerns. [0006] A primary object of the present invention is the [0002] International patent applications Nos. 15 development and utilization of fuels having enhanced PCT/US95/02691, PCT/US95/06758, and PCT/US96/ combustion structure which have increased stability. A 09653, disclose fuel compositions and combustion tech- further object of the present invention is the development niques for achieving vapor phase combustion based on of enhanced combustion structures in which the base an enhanced combustion structure ("ECS"). This en- fuel may be more viscous, or not as highly refined, as hanced combustion structure includes a combustible me- 20 now required to meet minimum fuel standards. A further tallic and free radical generating oxygenated compound. object is the employment of a co-metallic catalyst, which It has been found that such free radical generating oxy- further enhances the combustion structure of the DMC genates include C2 - C12 aldehydes, aldehydic acids, and metal/non-metals component, further improving C2 -C12 ethers, C1 - C 15 alcohols, C2 - C 12 oxides, thermal efficiency, fuel economy, power and emissions. C3 - C 15 ketones, ketonic acids, C3 - C15 esters, oth- 25 [0007] In accordance therewith, the substantially non- roesters, C3 - C12 diesters, C5 -C12 phenols, C5 - C20 alkaline fuel compositions of the present invention exhib- glycol ethers, C2 - C12 glycols, C3 - C20 alkyl carbon- its improved stability, with no apparent hydrolysis after ates, C3 - C20 dialkyl carbonates, C3 - C20 di-carbon- storage for six months or more. In addition, the presence ates, C1 to C20 organic and inorganic peroxides, hy- of lower dialkyl carbonates and metals in the fuel com- droperoxides, carboxylic acids, amines, nitrates, di-ni- 30 positions of the present invention allows for the use of trates, oxalates, phenols, acetic acids, boric acids, or- highly viscous base fuels. thoborates, hydroxyacids, orthoacids, anhydrides, ace- [0008] The improved fuels described herein contain a tates, acetyls, formic acids, nitrates, di-nitrates, nitro- base hydrocarbon fuel or propellant (including hydrogen) ethers, which can meet minimum burning velocity (BV) co-fuel, as provided in the PCT applications referenced and latent heats of vaporization (LHV) requirements of 35 above. Such co-fuels may be viscous, moderately vis- aforementioned PCT Applications. Specific compounds cous, or highly viscous (e.g. having viscosities outside can be found in detail in Organic Chemistry 6th Ed, industry standards). Said viscous fuels are combined T.W.G. Solomons, John Wiley & Sons, N.Y., (1995), with high energy non-lead metallic or non-metallics (pre- Physical Chemistry, 5th Ed, P.W. Atkins, Oxford Univer- sented below), together with symmetrical dialkyl carbon- sity Press, U.K. (1994), Physical Organic Chemistry, 2 40 ates, e.g., dimethyl or diethyl carbonate, and preferably Ed, N.S. Issacs, John Wiley & Sons, N.Y. (1995) and a silicon co-metallic combustion catalyst. When the fuel Lange’s Handbook of Chemistry, 14th Ed, J.A. Dean, Mc- compositions of the present invention are then construct- Graw-Hill, N.Y. (1992), and their minimum BV/LHV re- ed to a weakly alkaline (7.5 to 11.0 pH), substantially quirements in aforementioned PCT Applications, which neutral (6.5 to 7.5 pH), or acidic (4.5 to 6.5 pH), whether are herein by incorporated by reference. 45 or not water is present, they exhibit improved stability [0003] Said enhanced combustion structure oxygen- with no substantial hydrolytic propensity. ates, when in combination with a combustible non-lead metal or non-metal (as set forth below), exhibit high heats Detailed Description of the Present Invention of enthalpy capable, of improved combustion, thermal efficiency, fuel economy, and power. Of particularly in- 50 [0009] The improved fuel composition of the present terest to this invention are the enhanced combustion stru- invention includes an alkyl carbonate (dimethyl and/or ture oxygenates of symmetrical dialkyl carbonates, es- diethyl carbonate) a metal or non-metallic compound, pecially dimethyl and diethyl carbonates. more fully described below, and optionally a silicon cat- [0004] However, it has been reported symmetrical di- alyst, co-fuel(propellant), and/or oxidizer. So long as the alkyl carbonates, such as dimethyl carbonate can be 55 composition is not strongly alkaline, i.e., has a pH of from problematical fuel additives due to their potential insta- 3.0 to about 10.5, hydrolysis of the fuel composition is bility in fuel compositions, which can result in undesired avoided. A desirable pH range of the fuel composition of hydrolysis in acidic and aqueous environments. See EPO the present invention is from approximately 4.5 to ap-

2 3 EP 0 954 558 B1 4 proximately 10.5, with a more desirable pH range of from components, dialkyl carbonates, and metallic(s) to approximately 4.5 to approximately 9.5. An even more achieve requisite pH. However, individual circumstances desireable pH range is from approximately 4.5 to 9.0. will dictate proper approach and additive acids are con- Another highly preferred pH range is from approximately templated. 5.5. to 8.0. A preferred pH range is from approximately 5 [0016] Naturally, acidic metals of this invention may be 4.5 to approximately 6.5. The most preferred pH range used individually and/or in conjunction with one or more for the fuel composition of the present invention is from other metallics to reduce pH. Non-limiting examples of approximately 6.3 to approximately 6.8. such acidic metallics include binary, ternary and higher [0010] When the pH of the fuel composition of the metallic acid salts, hydroxy acids, etc. Other non-limiting present invention is less than 11.0, preferably 10.5 or 10 compounds are set forth below and include for example, below, 9.5 or below, and more preferably 8.5 or below, oxamic acid, lithium acetate acid, lithium salt acetic acid, the fuel, whether anhydrous or hydrous, may be stored propanoic acid lithium salt, cyclohexanebutyric acid lith- at ambient temperature for up to 6 six months without ium salt, aminobenzole acid lithium salt, borate ester, substantial apparent hydrolysis. dimethyl borate, di- n-butyl borate, dicyclohexyl borate, [0011] For example, Fuel A containing 5% by volume 15 didodecylborate, di-p-cresyl borates, boric acids, orthob- dimethyl carbonate, 95% by volume unleaded regular orates, henylboronic acid, diphenylboronic acid, o-tolyl- grade commercially available 87 octane (R+M)/2, 1/8 boronic acid, p-tolylboronic acid, m- tolylboronic acid, cy- gram Mn/gal of methylcyclopentadienyl manganese tri- lohexylboronic acid, cylohexenylboronic acid, cy- carbonyl, a pH of 7.0, and 5% by volume of water, was clopentylboronic acid, methylphenylboronic acid, meth- stored for six months, the fuel exhibited no apparent hy- 20 ylcylohexyl- boronic acid, methylcyclopentylboronic acid, drolysis. methylbenzylboronic acid, dimethylphenylboronic acid, [0012] When such fuel composition was titrated with dimethylcylohexylboronic acid, dimethylcyclopentylbo- acetic acid to a pH of 6.4, still containing 5% by volume ronic acid, dimethylbenzylboronic acid, diphenylboronic of water (Fuel B) and was then stored for six months, the acid, dibenzylboronic acid, dicylohexylboronic acid, di- fuel exhibited no apparent hydrolysis. 25 cylohexenylboronic acid, dicyclopentylboronic acid, [0013] However, when a fuel composition containing methyldiphenylboronic acid, bis[(methyl)cylohexyl]bo- dimethyl carbonate and cyclopentadienyl manganese tri- ronic acid, bis[(methyl)cyclopentyl]boronic acid, bis[(me- carbonyl was prepared with a pH of approximately 11, thyl)benzyl]boronic acid, bis[(dimethyl)phenyl]boronic contained 5% by volume of water and was stored for six acid, bis[(dimethyl)- cylohexyl]boronic acid, bis[(dime- months, the fuel showed slight evidence of hydrolysis. 30 thyl)cyclopentyl]boronic acid, or bis[(dimethyl)benzyl]bo- The same fuel at a pH of 12.5, however, showed stronger ronic acid. Many other acidic metallics are set forth below evidence of hydrolysis. and contemplated. [0014] It should be appreciated that although acetic [0017] If an additive acid is employed, it is preferred it acid was used to acidify the pH of the fuel in the present be compatible with the base fuel and have low toxicity, case, many other fuel soluble acids, including but not 35 low corrosivity, and be as envirnomentally friendly as limited to benzoic acid derivatives e.g. 2,4-dimethyl ben- possible. zoic acid, methyl red, p-tert- butylbenzoic acid, 2-(1- [0018] PCT/US95/02691 and PCT/US95/06758 dis- methylethyl) benzoic acid, benzoic acid anhydride, 4- close compositions and methods achieving vapor phase benzoyl benzoic acid, 2,4-dihdroxy benzoic acid, 2,4- combustion employing symmetrical dialkyl carbonates dimethyl-benzoic acid, 3-ethoxy benzoic acid, 2-hydroxy- 40 and certain non-leaded high energy metals and non-met- 4-methyl benzoic acid, 2-hydroxy benzontrile, 4-methoxy als (herein "metals"). It has been discovered in the con- benzotrile, acetic acid derivatives, e.g. anhydride acetic struction of a fuel composition, which employs one metal acid, chloroacetic acid, decyl ester acetic acid, dibro- or a mixture of metals, together with at least one C3 to moacetic acid, and the like, may be employed. See for C13 dialkyl symmetrical carbonate, as taught therein, im- example CRC Handbook of Chemistry and Physics, 75th 45 proved fuel stability can be obtained when the pH is kept Ed, Lide, CRC Press (1994-1995) "Dissociation Con- as close to neutral as possible, such that if alkaline, it is stants for Inorganic Acids and Bases," and "Dissociation only weakly alkaline (i.e., preferably equal or less than Constants for Organic Acids and Bases," incorporated 11.0, 10.5, 10.0, 9.5, 9.0, 8.5, 8.0 pH), but that it prefer- herein by reference. ably be either substantially neutral (i.e., 6.5 to 7.5) or [0015] Naturally, acidic fuel components, which are in- 50 slightly acidic (6.3 to 6.9 pH). digenous to the either the base fuel composition, e.g. [0019] Anhydrous fuels or substantially anhydrous fu- individual fuel components, metallic, DMC, or an addi- els are contemplated and particularly preferred when em- tional ECS component (e.g. aldehydic acids, ketonic ac- ploying water reactive group Ia, IIa, IIb, IIIA metals and ids, carboxylic acids, hydroxyacids, orthoacids, formic derivative compounds. Other circumstances will require acids, and the like) are desireable, and should be em- 55 anhydrous fuels as well, e.g. jet aviation applications, ployed/modified first to achieve minimum pH’s, prior to etc. Although anhydrous fuels are preferable, when the addition of an additive acid. Thus, the pH of the compo- fuel compositions of the present invention have a pH in sition may be tailored using normal hydrocarbon fuel the preferred range of from approximately 10.5 to 4.5,

3 5 EP 0 954 558 B1 6 there is no apparent hydrolysis, even when such fuels knock compound (e.g. hydrocarbyl ethers, alcohols, include an aqueous layer. When the pH of the fuel com- etc.), other additive, and additive set forth in incorporated position is in the preferred range, the composition may PCT Applications. Said known additive is incorporated contain water up to 10.0% by volume of the fuel with no herein by reference. apparent hydrolysis of the organic phase after six months 5 [0024] A preferred fuel of the present invention com- of storage. prises 1) dimethyl carbonate or dimethyl carbonate, rep- [0020] It should be appreciated in the practice of this resenting 0.1 % to 99.5% wt of composition; 2) at least invention and the examples set forth herein, it is required one metal as set forth below, representing 0.01% to that a hydrocarbon fuel containing a lower dialkyl car- 99.5% wt of composition; optionally a metal deactivator bonate have a pH of less than 10.5. The addition of metals 10 representing 0.00001% to 10.0% wt of composition, or or non-metals herein, co-metallics, viscous hydrocar- an antioxidant representing 0.00001% to 10.0% wt, or a bons are further embodiments, and not necessary ele- detergent/dispersant representing 0.00001% to 10.0% ments to this aspect of the invention. Thus, the claims wt, or an ignition promoter representing 0.000001% to below may reflect only a hydrocarbon fuel containing a 20.0% wt, or a demulsifier representing 0.00001% to lower dialkyl carbonate having a pH of less than 10.5, 15 10.0% wt, or a co-solvent or salt representing 0.000001% absent any additional limitation. As example, a compo- to 40.0% wt, or a hydrocarbon representing 0.1 % to sition of this invention includes a hydrocarbon base to- 99.0% volume of the composition, or a silicon based com- gether with dimethyl carbonate or diethyl carbonate, said bustion catalyst (described below) representing composition adjusted such that its maximum pH is 10.5 0.000001 % to 80.0% wt, or mixture. Said fuel is con- of less, a more preferred pH is 6.8 or less. 20 structed with a pH no greater than 11.0 or 10.5, and pre- [0021] Acidity level of fuels is sometimes measured in ferrably less than 9.5. More preferably, the pH is from terms of equivalents, e.g., equivalents of KOH required 6.3 to 6.8. When such fuel is a jet aviation turbine hydro- to neutralize the fuel composition. The fuels of the present carbon based-fuel, preferred acidity does not exceed invention show improved operation at acidity levels which equivalent of 0.1 mg KOH/g. are 100%, 150%, 200%, 300%, or more, above such 25 [0025] As described in the aforementioned PCT appli- standards. Acidity levels below such standards, including cations, the presence of a co-solvent is also preferred, those at least 50% less, are expressly contemplated. Al- so long as pH is maintained. Co-solvents that enhance so by way of example, when the fuel compositions of the mutual solubility of fuel components, fuel stability, water present invention are used in jet turbine engines, such tolerance are preferred (e.g. C1 to C12 alcohols, al- fuels typically must meet ASTM D 1655 specifications 30 kanolamines, etc.). These are known in the art and in- (incorporated herein by reference) or other international corporated herein by reference. Additionally, co-solvents specifications, including maximum acidity levels ASTM that increase flash point or reduce vapor pressure are D 3242 and IP 354 standards. However, it is believed contemplated. Non-limiting examples include, ethanetri- that the increased efficiency of the fuels of the present ols, propanetriols, butanetriols, 1,2,3 butanetriol, penta- invention are less destructive to engines during combus- 35 netriols, 1,2,3 pentanetriol, 2,3,4 pentanetriol, hexanetri- tion, and operation with lower pH’s than presently ac- ols, septanetriols, octanetriols, or tertraethylene glycol, ceptable. International, industry and government fuel triethylene glycol, 1-octene, high flash point ketone, standards, including ASTM, IP, GOST, DERD, MIL, AN, naphthalenes, triethylene glycol, trimethylene glycol, iso- U.S. Clean Air Act, California Air Resources Board, and propyl acetone, diisopropyl acetone, diisopropyl diace- Swedish/European EPEFET standards, etc., governing 40 tone, diethylene acetate, diethylene diacetate, ethylene hydrocarbon fuels containing applicant’s alkyl dicarbo- acetate compound, phenol, or other flash point temper- nates/metal are incorporated herein by reference. ature reducing co-solvent set forth in aforementioned [0022] When the fuel compositions of the present in- PCT Applications. Co-solvents should not be corrosive vention have a pH in the desired range of from approxi- or hazardous to fuel systems. mately 4.5 to 11.0, stability is maintained and hydrolysis 45 [0026] It is desirable the resultant fuel be constructed is substantially avoided so long as fuel storage temper- to have an average latent heat of vaporization (LHV) no ature is at or below 90°F. Preferably, the fuel composi- less than typical industry standards. Prefered LHV’s are tions of the present invention have pH’s less than 10.5 generally greater. For example, the latent heat of vapor- and are stored at or below 65°F. When Fuels A and B, ization or enthalpy of vaporization ( vapH(Tb)/kJ mol-1) described above, were stored at 65°F during the period 50 for commercial grade diesel, gas turbine, or fuel oils from 6 months after mixing to 9 months after mixing, fuel range from about 90 to 105 btu/Ib (at 60°F) or 18 to 21 stability was maintained without apparent hydrolysis. jK/mole or (at boiling temperatures). Likewise, commer- [0023] In addition to the preferred pH ranges described cial motor gasolines have a LHV ranging from 135 to 145 above, it is further contemplated that Applicant’s pH ad- btu/Ib or 27 to 29 jK/mole, aviation gasolines about 130 justed hydrocarbon based fuels will additionally contain 55 to 150 btu/Ib or 26 to 30 jk/mole, and aviation jet fuels known additive, including but not limited to antioxidants, about 105 to 115 btu/Ib or 21 to 23 jK/mole. co-solvents, metal deactivators, detergents, dispersants, [0027] Thus, it is preferred that the LHV for commercial corrosion inhibitors, mutual solvents, oxygenated anti- grade diesel, gas turbine, or fuel oils at 60°F exceed 105

4 7 EP 0 954 558 B1 8 btu/Ib or 21 jK/mole (at boiling temperatures), for com- 445 No. 1-GT fuels, and be adapted to meet the 2.4 stand- mercial motor gasolines LHV’s should exceed 145 btu/Ib ard, by addition of the components described herein. Al- or 29 jK/mole, for aviation gasolines LHV’s should exceed ternatively, base fuel kinetic viscosities of 4.15 to 6.0, or 150 btu/Ib or 30 jk/mole, and for aviation jet fuels LHV’s more, mm2/s for ASTM D 445 No. 2-GT fuels, may be should exceed 115 btu/Ib or 23 jK/mole. LHV’s at least 5 adapted to meet the 4.1 standard by addition of appli- 2%, 5%, 10%, 20%, 30% or greater than these amounts cantbs additives, as described herein. are however preferred. [0033] In an analogous manner, a diesel fuel oil base [0028] The burning velocities (as measured by laminar may have maximum kinetic viscosities at 40°C equal or Bunsen burner flame) for commercial grade diesel, gas exceeding 2.45 to 7.0, or greater, mm2/s for ASTM D turbine, and fuel oils range from about 35-37 cm/sec, 10 445 low sulfur or regular No. 1-D fuels, and be adapted kerosine about 36 cm/sec, automotive gasoline about to meet the 2.4 standard by addition of applicantps ad- 47-50 cm/sec, aviation gasoline about 45-47 cm/sec, avi- ditives. Alternatively, a diesel fuel oil base having maxi- ation jet fuels about 36-38 cm/sec. Methanol is reported mum kinetic viscosities of 4.15 to 9.0 or more, mm2/s for at 57.2 cm/sec. Thus, in Applicant’s fuels it is desireable ASTM D 445 low sulfur or regular No. 2-D fuels, and be that burning velocities for commercial grade diesel, gas 15 adapted to meet the 4.1 standard, by addition of appli- turbine, and fuel oils exceed 37 cm/sec, kerosine exceed cantbs additives. Similarly, fuels having a maximum ki- 36 cm/sec, automotive gasoline exceed 50 cm/sec, avi- netic viscosity of 24.5 to 60.0 ore more mm2/s for ASTM ation gasoline exceed 47 cm/sec, and aviation jet fuels D 445 No. 4-D fuels, and be adapted to meet 24.0 by exceed 38 cm/sec. However, BV’s at least 2%, 5%, 10%, addition of applicant‹s additives. Additionally, a low 20%, 30%, or greater than above speeds are preferred. 20 emission diesel base may have viscosities exceeding [0029] It is also desirable that the hydrocarbon based 2.45 to 5.5, or more, cSt at 40°C (where 1mm2/s = 1cSt), fuels have high possible allowable densities. High den- and be adapted to meet the 2.4 standard. sities of base fuels permit higher concentrations of me- [0034] Furthermore, a fuel oil base may have kinetic tallics and dialkyl carbonates. For example, aviation tur- viscosities equal or exceeding 2.15 10.0, or more, mm2/s bine densities equal or exceeding 841 kg/m3 @ 15°C 25 at 40°C ASTM D 445 for No. 1 fuels, and can be adapted are contemplated. More generally, the fuel compositions to the 2.1 standard by addition of applicant‹s additives. of the present invention allow for base fuel densities of A fuel base having kinetic viscosities of from 3.45 to 10,0, from 840 to 1200 kg/m3 @ 15°C, and even 900 to over or more, mm2/s at 40°C ASTM D 445 for No. 2 fuels can 1200 kg/ m3 @ 15°C. Moderate, low, to very low densities be similarly adapted to meet 3.4. A fuel base having ki- are also contemplated so long as the increased burning 30 netic viscosities of 5.55 to 25.0 or more, mm2/s at 40°C velocity object of above PCT Applications is accom- ASTM for D 445 No. 4 fuels (Light), may be similarly plished and a pH is not greater than 10.5, preferably be- adapted to meet 5.5. A fuel base having kinetic viscosities low 9.0, and most preferably from 6.3 to 6.8 is maintained. of from 24.5 to 40.0, or more, mm2/s at 40°C ASTM D [0030] Moreover, highly viscous hydrocarbon fuel bas- 445 for No. 4 fuels (regular), may be adapted to meet 24. es with viscosities above fuel specification, are unexpect- 35 A fuel base having kinetic viscosities of from 8.95 to 25.0, edly brought to within fuel viscosity limits by the addition or more, mm3/s at 100°C ASTM D 445 for No. 5 fuels of dialkyl carbonates and metal. For example, is has been (Light), may be adapted to meet 8.9. A fuel base having found that a diesel fuel oil having a viscosity of 2.6 mm2/S kinetic viscosities of from 15.0 to 30.0, or more, mm3/s at 40o C was acceptably combined with dimethyl carbon- at 100°C ASTM D 445 for No. 5 fuels (Heavy), may be ate representing 5% volume of the composition, and 2.0 40 adapted to meet 14.9. A fuel base having kinetic viscos- grs Mn/gal of methylcyclopentadienyl manganese tricar- ities of from 50.5 to 80.0, or more, mm3/s at 100°C ASTM bonyl (MMT). The resultant fuel composition had a lower D 445 for No. 6 fuel oils, and adapted to meet 50.0. viscosity of 2.4 mm2/S at 40°C. In this way, highly viscous [0035] Similarly, a heavy diesel, locomotive or marine fuels can be adapted by the addition of applicant’s ingre- engine base fuel, exceeding ISO DIS 8217, BS MA 100, dients, whereby non-conforming highly viscous fuels can 45 government and/or other industry viscosity specifica- be made less viscous and brought into compliance with tions, but adapted to meet such standards (incorporated ASTM or other specification (herein incorporated by ref- by reference), typically uncorrected viscosity exceeds ererence). such standards by 1.0, 2.0,10.0, 50.0, or more centis- [0031] Also by way of example, Jet A hydrocarbon bas- tokes at 50°C. Applicant has discovered by incorporating es having a viscosity of 8.1 to 15.0 or more, (ASTM 445) 50 his lower dialkyl carbonates and metals, fuels having ex- can be adapted to meet the current 8.0 mm2/sL at -20°C cessive viscosities can meet government, or other vis- standard by addition of the components described above. cosity standards. Alternatively, base fuel viscosity of from 13.5 to 23.0 Cs [0036] By way of further example, an enhanced com- at -30°F, or more, may be met by the addition of the com- bustion aviation turbine fuel composition of the present ponents described above. 55 invention includes a symmetrical alkyl dicarbonate, pref- [0032] Similarly, a gas oil turbine hydrocarbon base erably dimethyl carbonate, a metal, an aviation turbine may have maximum kinetic viscosities at 40°C equal or hydrocarbon base having a viscosity of from 8.1 to 9.0 exceeding 2.45 to 7.0, or greater, mm2/s for ASTM D MM2/S (ASTM 445); optionally one or more of the fol-

5 9 EP 0 954 558 B1 10 lowing: a salt, a co-solvent, antioxidant, freeze point ad- octane or performance number of from 87 to 130 (ASTM ditive, anti- icing additive, metal deactivator, corrosion 909). It is further characterized as having a distillation inhibitor, hydroscopic control additive, lubricity agent, lu- fraction wherein the sum of the T-10 plus T-50 fractions bricant or friction modifier, anti-wear additive, combus- are 307°F, the T-40 temperature is 167°F and the T-90 tion chamber or deposit control additive, any other rec- 5 temperature is less than 250°F, a maximum sulfur con- ognized additive, additive disclosed in aforementioned tent of 0.05 wt%, or sulfur free, a latent heat of vaporiza- PCT Applications, or mixture thereof. The resultant fuel tion preferably exceeding 120, more preferably exceed- is characterized as being slightly alkaline, substantially ing 150, most preferably exceeding 160 BTU/Ib, a lami- neutral or acidic, and having a maximum viscosity equal nar bunsen burning velocity preferably equal to or in ex- or less than 8.2 MM2/SI (ASTM 445). The fuel preferably 10 cess of 40, more preferably greater than 48, most pref- has a density of from 840.5 to 850, or greater, kg/m3 @ erably greater than 52 cm/sec, a heat of combustion (as 15°C, a flash point of at least 38°C, a maximum vapor measured by the sum of fuel ingredients) equal or less pressure of 21 kPa @ 38°C, minimum thermal stability than 43.0 kJ/kg, or equal or less than from 18,720 to meeting ASTM D 1655 standards, a heat of combustion 15,000, or less, BTU/Ib. or equivalent equal to or exceeding 42.8 MJ/kg (lower 15 [0039] A gasoline composition of the present invention heats of combustion are contemplated, including those includes an dialkyl carbonate, a metal and an unleaded less than or equal to 42.5, 42, 41, 40, 39, 38, 37, 36 base fuel composition. The resultant composition is char- MJ/kg, based upon additive heats of individual compo- acterized as having a pH less than 10.5, and optionally nents), and a maximum freezing temperature of from - being phosphorus free hydrocarbons, a maximum Reid 40 to - 50°C, optionally a LHV not less than 115 btu/lb or 20 Vapor Pressure of from 6.0 to 12.0 psi, 6.0 to 10 psi, 6.0 23 jK/mole, optionally a burning velocity exceeding 37 to 9.0 psi; a maximum of 12% to 5.0% by volume, or less cm/sec. of olefins, a maximum of 30% to 20% or less by volume [0037] A diesel fuel composition of the present inven- of aromatics (more preferably 15% to 10%, or less), a tion includes dimethyl carbonate representing 0.01% to maximum of 2.0% to 0.8% or less benzene, a maximum 40.0% oxygen by weight of the fuel; a compound or ele- 25 of 40 ppm sulfur, most preferably sulfur free, a total 02 ment containing a combustion improving amount of tran- concentration ranging of 0.5% to 10.0% wt of dimethyl sition metal, alkaline metal, alkaline earth, group IIIa, IVa, carbonate, a manganese tricarbonyl compound at 1/64 Va, VIa, VIIa element or derivative compound, or mixture, to 3/16 gr. Mn/gal (preferably 1/32 gr. Mn) or other me- optionally in an concentration of 0.001 to about 100.0 gr tallic in a combustion improving amount, a maximum T- element/gal, preferably 2.0 to 20.0 gr element/gal; and a 30 90 temperature of 330°F to 280°F, a T-50 temperature No. 1 (ASTM) diesel fuel base having a viscosity of from of approx. 170°F to 230°F., 175°F preferred, a minimum 2.45 to 3.0, MM2/S at 40°C, said fuel base optionally (R+M)/2 octane of 85, to 92, a bromine number of 20 or characterized as having one or more of the following: a less, an average latent heat of vaporization of 880 to 920, density ranging from 880 to 800 kg/m3 , a cetane index or more, BTU/gal at 60°F; a heating value greater than of 40 to 70, an aromatic content by vol. ranging from 35 106,000 btu/gal at 60°F (more preferably greater than approximately 0 to 35%,prefereably 0% to 10%, provided 108,000, 114,000 btu/gal), as measured by the sum of that 3-ring + aromatics not to exceed 0.16 volume %; a individual fuel substituents. T10 fraction temperature of about 190 to 230°C, a T 50 [0040] Another gasoline composition of the present in- fraction temperature of about 220 to 280°C, a T90 fraction vention includes an dialkyl carbonate, a metal and an of about 260 to 340°C, a cloud point temperature of °C 40 unleaded base fuel composition, characterized as having -10, - 28, -32 or 6°C above tenth percentile minimum a pH less than 10.5, and optionally characterized as hav- ambient temperature, a sulfur content preferably not ing one or more of the following: being phosphorus free greater than 250 ppm, more preferably not greater than hydrocarbons, with a maximum Reid Vapor Pressure of 50 ppm, most preferably not exceeding 5 ppm, a bunsen 12.0 psi, a maximum of 12% olefins, a maximum of 30% laminar burning velocity of at preferably greater than 37, 45 aromatics, a maximum of 2.0% benzene, a maximum of more preferably greater than 44, most preferably 50 ore 50 ppm sulfur or sulfur free, a total 02 concentration rang- more, cm/sec, a latent heat of vaporization of preferably ing from 0.5% to 10.0% wt of dialkyl carbonate, a com- at least 105, more preferably at least 120, most preferably bustible metal or non-metal selected from groups set 130 or more, BTU/Ib. The resultant fuel is characterized forth below including (but not limited to) those consisting as having a pH less than 10.5 and a viscosity equal to or 50 of the preferred manganese, silicon, potassium, and iron less than 2.4 MM2/S at 40°C, optionally a LHV at 60°F compounds, or mixture, a maximum T-90 temperature equal or in excess of 105 btu/Ib or 21, 22, 23, 25, 27 jK/ of 330°F to 280°F, a T-50 temperature of approx. 170°F mole (at boiling temperatures), optionally a minimum to 230°F., a minimum (R+M)/2 octane of 85, to 92, a laminar bunsen burner flame of 37, 39, 40, 41 cm/sec. bromine number of 20 or less, an average latent heat of [0038] An aviation gasoline fuel composition of the 55 vaporization of 880 to 920 BTU/gal at 60°F, a heating present invention includes a dialkyl carbonate, a metal value greater than 106,000 btu/gal at 60°F (as measured and an aviation gasoline base. The resultant fuel is char- by the sum of individual fuel substituents), a burning ve- acterized as having a pH less than 7.0 and a minimum locity exceeding 50 cm/sec, a latent heat of vaporization

6 11 EP 0 954 558 B1 12 exceeding 29 jK/mole (or equivalent). is expansive with elevated exhaust velocities, and result- [0041] In the practice of this invention it is contemplat- ant metallic oxide particles are formed in the submicron ed at least one combustible reactive non-lead transition range. Typically fuel economy, power output, exhaust metal, alkaline metal, alkaline earth, group llla, IVa (ex- emissions, combustion temperatures are materially im- cept carbon), Va, Vla (except oxygen), VIIa element, or 5 proved. derivative thereof, as set forth herein, or mixture (herein [0045] Thus, a very wide range of acceptable metals referred to as "metal" or "metallic") be together with at and derivative compounds are contemplated. Group IA least one C3 to C13 symmetrical dialkyl ester of carbonic (alkali metals), IIA (alkaline earths) elements, the transi- acid, and mixture, in a fuel stable composition; said com- tion elements/metals of group IIIb, IVb, Vb, Vlb, VIIb, VIIIb position optionally containing a combustion catalyst as 10 [8, 9, 10], the elements of group Ib, IIb, IIIa, IVa (absent set forth below, a hydrocarbon, and/or an oxidizer; re- carbon), and group Va, VIa, VIIa elements are contem- sultant composition as having a pH slightly alkaline, neu- plated. Non-limiting examples include aluminum, boron, tral or acidic. bromine, bismuth, beryllium, calcium, cesium, chromium, [0042] Non-limiting examples of suitable dialkyl car- cobalt, copper, francium, gallium, germanium, iodine, bonates include, dimethyl carbonate, diethyl carbonate, 15 iron, indium, lithium, magnesium, manganese, molybde- dipropyl carbonate, diisopropyl carbonate, dibutyl car- num, nickel, niobium, phosphorus, potassium, palladium, bonate, diisobutyl carbonate, ditertiary butyl carbonate, rubidium, sodium, tin, zinc, praseodymium, rhenium, sil- diisoamyl carbonate, methyl ethyl carbonate, diphenyl icon, vanadium, strontium, barium, radium, scandium, yt- carbonate, or mixture. C3 to C8 symmetrical dialkyl car- trium, lanthanum, actinium, cerium, thorium, titanium, zir- bonates are more desirable, with C3 to C5 being pre- 20 conium, hafium, praseodymium, protactinium, tantalum, ferred. It is contemplated that such carbonates will be neodyium, uranium, tungsten, promethium, neptunium, introduced into the composition in concentrations of 0.01 samarium, plutonium, ruthenium, osmium, europium, to 100.0 volume percent in an amount sufficient to im- americium, rhodium, iridium, gadolinium, curium, plati- prove combustion. The carbonates may be additionally num, terbium, berkelium, silver, gold, dysprosium, cali- combined with one or more oxygenated compounds, in- 25 fornium, cadmium, mercury, holmium, titanium, erbium, cluding but not limited to alkyl butyl ethers (e.g. MTBE, thulium, arsenic, antimony, ytterbium, selenium, telluri- ETBE, TAME, ETAME, etc.), alkyl alcohols, and/or um, polonium, lutetium, and astatine, including their or- known co- solvents. In the practice of this invention meth- ganic and inorganic derivative compounds, which are ca- ylal, ethylal, C1 to C6 aliphatic alcohols, may be substi- pable of vapor phase combustion, are contemplated in tuted for dialkyl carbonates, absent compromise of vapor 30 the claims hereto and incorporated herein by reference. phase combustion. Applicant’s metals, including derivative compound, may [0043] Non-limiting examples of optional fuel, which be organo-metallic or inorganic. Accordingly, the inor- may be additionally contained with the dialkyl carbonate ganic and organic compounds of CRC Handbook of and metal, include hydrogen or any hydrocarbon, includ- Chemistry and Physics, Lide, 75th (1994-1995) and ear- ing but not limited to carbonaceous liquid or solid fuels, 35 lier editions, Ann Arbor, CRC Press; Sigma-Aldrich alternative fuels, gaseous fuels (including natural gas, Chemical Directory, Aldrich Chemical Company (1997), methane, ethane, propane, butane, etc.), automotive Chemical Abstract Service (CAS), on line Registry File gasolines, diesel fuel oils, heavy diesel fuel oils, aviation [1], American Chemical Society, Chemical Abstract Serv- gasoline, gas oils, fuel oils, aviation jet turbine oils, coal, ice, Ohio State University, A Manual of Inorganic Chem- coal oils, coal liquids, and the like. Industry specifications, 40 istry, Thorpe, N.Y., Putnam & Son’s (1896), Inorganic including ASTM and all others known in the art, and Materials, 2 ed., Ducan, N.Y. J.Wiley & Son (1996), above PCT Applications, and Criteria for Quality of Pe- Handbook of Inorganic Compounds, Perry, Phillips, CRC troleum Products, J.P. Allison, 1973 (and subsequent Press, Boco Raton, (1995), Inorganic Chemistry, Phillips, editions), are incorporated herein by reference. Williams, N.Y. Oxford University Press (1965-1966), In- 45 organic Materials Chemistry, D. Seneeta, G.E. R & D METALS PRACTICE Center, N.Y., CRC Press (1997), Inorganometallic Chemistry, Fehlner, N.Y., Plenum (1992), Nontransition- [0044] In the practice of this invention contemplated Metal Compounds, Eisch, N.Y., Academic Press (1981), metallics include all non-lead metals, metalloids, and Metal & Metalloid Amides, Horwood, N.Y., Halsted Press non-metals (herein "metals" or "metallics"), and their de- 50 (1980), Kirk-Othmer Encyclopedia of Chemical Technol- rivative compounds, whose combustion product accom- ogy, 2nd and subsequent editions, John Wiley & Sons plishes primary object of vapor phase combustion, which (1963), Dictionary of Chemical Names & Synonyms, is evidenced by a brilliant luminous reaction zone extend- Howard, Neal, Lewis Publishers, Ann Arbor, (1992), Dic- ing some distance from the metal’s surface. Such com- tionary of Chemical Solubilities, Inorganic, Comey, Mac- bustion does not take place on the surface of the metal, 55 Millian Press (1921), Solubilities of Inorganic and Metal or on and/or within the molten layer of oxide covering the Organic Substances, Seidell, N.Y., Van Nostrand metal, typical of heretofore metallic combustion. Distin- (1940-1941), Solubility of Inorganic and Metal-Organic guishing vapor phase combustion is that its combustion Compounds, Like, Princeton N.J., Van Nostrand

7 13 EP 0 954 558 B1 14

(1958-1965), Organometallics (cite omitted), Organo ical Society (1983), which are capable of vapor phase Metallic Chemistry, F.G.A. Stone, Academic Press (1972 combustion, together with said publications (including and subsequent years), Organo Metallic Compounds, 2 subsequent editions, volumes, or supplements), are in- Ed, Michael Dub, Springer-Verlag, New York Inc. (1966 corporated herein by reference. Vol. 1 to 3, and subsequent volumes/supplments), Or- 5 [0047] Desireable metal containing cyclomatic com- gano-metallic Compounds, Coates, Edward, New York, pounds are those with cyclic rings having high burning Wiley (1960), Comprehensive Organometallic Chemistry velocities. The higher the burning the velocity, generally II (A Review of the Literature 1982-1994), Abel, Stone, the higher the preference. Generally larger rings have Wilkinson, El Sevier Science Ltd (1995), Handbook of higher burning velocities compared to smaller rings. Organometallic Compounds, Kaufman, D. Van Nostranl 10 Thus, a cyclooctane ring is preferred over cyclohexane, Company Inc. (1961), Handbook of Organometallic which is perferred over a cyclobutane ring. Saturated Compounds, Hagihara, Kumanda, Okawars, W.A. Ben- rings are normally more perferred over unsaturated rings. jamin Inc (1968), Organometallic Chemistry, Mehrotra, The more saturated the ring the more preferred. Thus, Singh, John Wiley and Sons, (1991), Organometallic cyclohexane is preferred over benzene. Ring systems Chemistry, Chemical Society (1971 and all subsequent 15 where the metal is in turn attached to one or more a hy- publications), London, Metal- Organic Compounds, droxyl, carbonyl, an alkyloxy radicals is preferred. American Chemical Society (1959 to present), Chemical [0048] Non-limiting examples of desireable ring sys- Abstracts, American Chemical Society, Chemical Ab- tems/complexes include: cyclohexane, cyclohexene, cy- stract Service, Ohio State University, (From 1907 to clopentane, cyclobutane, cyclopentadiene, phenyl, ben- present), Structure Reports 1913 to 1973 (Metals and 20 zene, and naphthalene. More desireable are cyclohex- Inorganic Compounds), International Union of Crystal- ane, cyclohexene, and cyclopentadienyl. It is contem- lography, Bohn, Scheltena & Hellema (volumes 1-40), plated each elemental metal of this invention can be em- The Merck Index, 12th Ed., Budavari, O’Neil, Merck Re- ployed in a cyclomatic compound. search Laboratories, N.J. (1996), which are capable of [0049] Transition metal ring systems are well known vapor phase combustion, together with said publications 25 in the art and highly desireable. See U.S. Patents Nos. (including all related/subsequent editions, volumes, sup- 2,818,416, 3,127,351, 2,818,417, 2,839,552, 2,680, ; plements, updates, or related publications) are incorpo- 2,804,468; 3,341,311, 3,272,606, 3,718,444), Canadian rated herein by reference. Patent #1073207, European Patent Application # [0046] Cyclomatic compounds are particularly desire- 93303488.6, pages 6-8 (1993), incorporated herein by able. Non-limiting examples of cyclomatic compounds 30 reference. include compounds with one or more rings systems, in- [0050] As contemplated herein, attachment may be di- cluding alicylic or aromatic ring systems. Ring systems rect or indirect. Attachment may be via molecular bond, which may be wholely organic, wholely inorganic, or het- ionic bond, coordination bond or other bond known in the erocyclic. Such ring systems may include cyclic borons art. Indirect attachment may be via one or more radical (borazoles), cyclic silanes (silacyclobutane, 2,4,6,8,10- 35 or element, or be via other bond as described below or pentamethylcyclopentasilazane, cyclohexasilanes, cy- known in the art. See The Chemistry of Organometallic clopropenyl silanes, etc.), cyclic nitrogens (pyrazoles, py- Compounds, Rochow, Hurd, Lewis, New York, John Wi- ridines, pyrroles, piperazines, imidazals, etc.), cyclic ox- ley & Sons, Inc. (latest edition), incorporated by refer- ygens (benzoyls, furans, pyrans, e.g. tetrahydropyran, ence. pyrones, dioxins, etc,), cyclic sulfurs (thiophens, dithiles, 40 [0051] One or more radicals (including cyclic radicals), etc.) or other cyclic inorganics. Cyclomatic organic ring side chains, saturated or unsaturated, may be attached systems include saturated rings (cyclopropyl, cyclobutyl, to one or more locations on the ring, and/or to one or cyclopentyl, cyclohexyl, cyclooctyl, etc.), unsaturated more locations of each metal. Thus, the metal may con- rings, rings with one or more multiple or double bonds tain between one to as many radicals as available va- (cyclohexadiene, cyclopentadiene, cyclotetraene, etc.), 45 lence electrons (oxidation states) permit. See Handbook aromatic rings/cycloalkyl radicals (phenyl, benzyl, styryl, of Data on Organic Compounds 2ed, Weast, Grasselli, etc.), fused rings, fused aromatic rings (naphthls, naph- CRC (185). thenates, etc.), fused ring with cyclopentadienyl moiety, [0052] Non-limiting examples of radicals, include or- rings containing oxygen or a hydroxyl (phenol, etc.). The ganic or inorganic, saturated or unsaturated, or combi- disclosed metallic cyclomatics contained in Heterocyclic 50 nations thereof, including: hydrogen (hydride), hydroxyl, Chemistry, Katritzy, Boulton, Academic Press (1966 to hydrocarbyl group radicals, including alkyl radicals (e.g. 1997 all volumes), Benzenoid-Metal Complexes, Zeiss, methyl, ethyl, propyl, issopropyl, butyl, isobutyl, sec- Wheatley, Winkler, The Ronald Press Co (1966), The butyl, tert-butyl, amyl, pentyl, hexyl, etc.), alkyloxy radi- Ring Index 2 Ed, Patterson, Capell, American Chemical cals, various positional isomers thereof (e.g. 1- methyl- Society, Reinhold Publishing Corp (1960 and subse- 55 butyl, 2-methyl-butyl, 3-methyl-butyl, 1,1-dimethyl-pro- quent editions), Ring Enlargement of Organic Chemistry, pyl, 1,2-dimethyl-propyl, etc.), corresponding straight Hesse, VCH Publishers (1991), Rings, Cluster, and Ply- and branched chain isomers (e.g. hexyl, hepyl, octyl, no- mers of Main Group Elements, Cowley, American Chem- nyl, decyl, etc.), alkenyl radicals (ethyl, /\1-propenyl, /\2-

8 15 EP 0 954 558 B1 16 propenyl, isopropenyl, etc.), corresponding branch chain bamyl, carbazoyl, chromyl, cinnamoyl, crotoxyl, cyanato, isomers thereof, other isomers thereof (e.g. heptenyl, oc- decanoly, disiloxanoxy, epoxy, formamido, formyl, furyl, tenyl, nonyl, decenyl, etc.), alkenyloxy radicals, aryl rad- furfuryl, furfurylidene, glutaryl, glycinamido, glycolyl, gly- icals (e.g. phenyl, a-napthyl, b-naphthyl, a- anthryl, b- cyl, glyocylyl, heptadecanoyl, heptanolyl, hydroperoxy, anthryl, etc.), aryloxy radicals, including monovalent rad- 5 hydroxamino, hydroxylamido, hydrazido/hydrazide, hy- icals of such aromatics (e.g. indene, isoindene, acenaph- droxy, iodoso, isoccyanato, isonitroso, keto, lactyl, meth- thene, flourene, phenanthrene, naphthacene, chrysene, acrylyl, malonyl, nitroamino, nitro, nitrosamino, nitrosimi- pyrene, triphenylene, etc.), aralkyl radicals (e.g. benzyl, no, nitrosyl/nitroso, nitrilo, oxamido, peroxy, phosphinyl, a-phenyl-ethyl, b-phenyl-ethyl, a-phenylpropyl, etc.), ar- phosphide/phosphido, phosphite/phosphito, phospho, alkyloxy radicals, various positional isomers thereof (e.g. 10 phosphono, phosphoryl, seleninyl, selenonyl, siloxy, suc- derivatives of 1-methyl- butyl, 2-methyl-butyl, 3-methyl- cinamyl, sulfamino, sulfamyl, sulfeno, thiocarboxy, toluyl, butyl, 1,1 dimethyl-propyl, etc.), corresponding alkyl de- ureido, valeryl radicals, etc., including derivatives, ho- rivatives of phenanthrene, flourene, acenapthene, etc., mologes, analoges, and isomers thereof. alkaryl radicals, (e.g. o-tolyl, m-tolyl, p-tolyl, o-ethylphe- [0055] Additional non-limiting examples of other radi- nyl, etc.), arylalkenyl, cycloalkyl radicals (benzyl, etc.), 15 cals, include: acetimido, amidino, amido, amino, aniline, cycloalkyloxy radicals, aliphatic radicals, mesityl. See anilino, arsino, azido, azino, azo, azoxy, benzylidine, generally Canadian Patent 1073207, pages 4-7, Euro- benzldyne, biphenylyl, butylene, iso-butylene, sec-buty- pean Patent Application # 93303488.6, pages 6-8, lene, tert-butylene, cyano, cyanamido, diazo, diazoami- 10/11/93), Handbook of Data on Organic Compounds 2 no, ethylene, disilanyl, glycidyl, guanidino, guanyl, hep- Ed, Weast, Grasselli, CRC 1985, CRC Handbook of 20 tanamido, hydrazino, hydrazo, hypophosphite (hypo- Chemistry and Physics, 75th and earlier editions, sec- phosphito), imido, isobutylidene, isopropylidene, silyl, si- tions re: "Nomenclature For Inorganic Ions and Radi- lylene, methylene, mercapto, methylene, ethylene, naph- cals," "Organic Radicals and Ring Systems," Nomencla- thal, napthobenzyl, naphthyl, naphthylidene, propylene, ture of Inorganic Chemistry (Recommendations), Black- propylidene, pryidyl, pyrryl, phenethyl, phenylene, pyrid- well Scientific Publications, Offord 1990; Richer, J.C., 25 ino, sulfinyl, sulfo, sulfonyl, tetramethylene, thenyl, Panico, R., and Powell, W.H. A Guide to IUPAC Nomen- thienyl, thiobenzyl; thiocarbamyl, thiocarbonyl, thiocy- clature of Organic Compounds, Blackwell Scientific Pub- anato, thionyl, thiuram, toluidino, tolyl, a-tolyl, tolylene, lications, Offord 1993, Weast, R.C., and Grasselli, J.C., a-tolylene, tosyl, triazano, ethenyl (vinyl), selenyl, trihy- Handbook of Data on Organic Compounds, 2nd Ed. CRC drocarbylamino, trihaloamino, trihydrocarbyl phosphite, Press, Boca Raton, FL, 1989; incorporated by reference. 30 trihalophosphine, trimethylene, trityl, vinylidene, xenyl, [0053] Hydroxyl, alkanol, alkanolamine, oxy and/or ox- xylidino, xylyl, xylylene, 1,3-diene, hydrocarbyl radicals, ygen containing radicals, including derivatives of thereof etc., including derivatives, homologes, analoges, and and derivative of above radical are also contemplated. isomers thereof. Thus, ring compounds or metals them- Non-limiting examples include hydroxy, methoxide, selves may directly or indirectly contain one or more ethoxide, propoxide, isopropoxide, butoxide, isobutox- 35 chelating radicals (e.g. carbonyl, cyano, etc.). ide, sec-butoxide, tert-butoxide, pentoxide, amyloxide, [0056] One or more of the above radicals may be at- phenyloxidesperhydroxy, methoxy, methylol, methylen- tached directly or indirectly to another. Indirect attach- edioxy, ethoxy, ethylol, ethylenedioxy, enanthyl, pro- ment may be via one or more intermediate atom, includ- poxy, proprylol, propylene- dioxy, isopropoxy, isopropy- ing but not limited to carbon, nitrogen, oxygen, phoso- lol, isopropylenedioxy, butoxy, butylenedioxy, butylol, 40 phorus, silicon, boron, sulfur, or another metal. iso-butoxy, iso-butylol, isobutylenedioxy, isobutyryl, sec- [0057] Metallic compounds may have one or more butoxy, sec-butylol, sec-butylenedioxy, tert- butoxy, tert- non-ring radicals attached. Desireable metals may for butylol, tert-butylenedioxy, butyryl, caproyl, capryl, example have one or more alkyl, alkylene or similar rad- caprylrl, pentoxy, pentylol, pentalenedioxy, amylol, ical attached to the metal, or one or more hydroxyl, car- amylenedioxy, phenoxy, phenylol, phenylenedioxy, phe- 45 bonyl, alkyloxy, alkanol radicals, or combination thereof. nylmethoxy, diphenylmethoxy, benzoyl, benzyloxy, ben- [0058] Other metallic compounds may have one or zoxy, iso-benzoyl, napthoxy, napthylol, hexylol, hexam- more ring systems attached directly or indirectly to a met- ethylol, amylenedioxy, hexadecanoyl, heptanedioyl, al, with or without an attached non- ring radical to the hexylenedioxy, carbomethoxy, carbethoxy, carboben- metal. zoxy, carbpropoxy, carbisopropoxy, carbutoxy, phena- 50 [0059] One or more cyclic rings maybe attached, fused cyl, phenacylidene, propionyl radicals, methylenedioxyl, or indirectly attached together or linked together via one carbonyldioxy, etc., including derivatives, homologes, or more radicals, one or more atoms, including but not analoges, and isomers thereof. limited to carbon, nitrogen, oxygen, phosophorus, silicon, [0054] Additional non-limiting oxygen containing radi- boron, sulfur, or a metal. cals include acetyl, acetamido, acetoacetyl, acetonyl, ac- 55 [0060] One or more metals may be attached to each etonylidene, acrylyl, alanyl, B-alanyl, allophanoyl, anisyl, other, for example hexamethyldisilane, which is a pre- benzamido, butryl, carbonyl, carboxy, carbazoyl, ferred metallic. Indirect attachment herein includes at- caproyl, capryl, caprylrl, carbamido, car- bamoyl, car- tachment via one or more radicals, and/or one or more

9 17 EP 0 954 558 B1 18 atoms, including but not limited to carbon, nitrogen, ox- or more ring systems, optionally with one or more non- ygen, phosophorus, silicon, boron, sulfur, or another met- ring radicals attached thereto. Said ring(s) then may be al. attached directly or indirectly to a metal, with said metal [0061] As contemplated herein said carbon, nitrogen, in turn optionally attached directly or indirectly to a radical, oxygen, phosophorus, silicon, boron, sulfur, or other met- 5 with said radical being optionally a non- ring radical se- al atom, may be attached to itself or to another herein, lected from one or more hydrogen, hydroxyl, alkyl, aryl, one or more times, with each atom optionally having one carbonyl, alkanol, alkanolamine, alkyloxy, oxy or oxygen or more hydrogen and/or radical(s). Said attachment may containing radical. Non-limiting examples include meth- be independent of attachment to any other radical or met- ylcyclopentadienyl manganese tricarbonyl, [2-(cyclohex- al, or may include an attachment to another radical or 10 enyl)ethyl]triethoxysilane, and cyclohexenyl dimeth- metal. oxymethylsilane. [0062] Likewise one or more cyclic rings may be at- [0070] A class of metallics, which are capable of vapor tached directly to the metal, or indirectly via one or more phase combustion include spiral compounds based for non-ring radicals, and/or via one or more intermediate example upon ferricyanhydric acid derivatives, namely atoms, including but not limited to carbon, nitrogen, ox- 15 ferricyanides. See Dictionary of Chemical Solubilties, su- ygen, phosophorus, silicon, boron, sulfur, or another met- pra, pages 334-342, which lists various ferrocyanides, al. incorporated herein by reference. Alkali metals and alkali [0063] Thus, one or more metals may be attached at earth metals are desireable ferricyanides. Potassium one, or up to every location possible on the ring system, hexacyanoferrate (II) and potassium hexacyanoferrate directly and/or indirectly. Likewise, one or more ring sys- 20 (III) are desireable. Non-limiting examples of substitutes tems may be attached at one, or up to every metal loca- include potassium hexacyanocobalt II- ferrate, potassi- tion possible, directly and/or indirectly. um Hexacyanocobalt III, potassium hexachloroosmate [0064] A non-ring radical may be independently at- (IV), potassium hexachloroplatinate (IV), potassium hex- tached directly or indirectly to the metal, absent its at- afluorosilicate, potassium hexafluoromanganate (IV), tachment of a ring system. In the practice of this invention 25 potassium Hexaflourozirconate. potassium hexathiocy- the attachment of one or more non-ring radical(s) to a anatoplatinate (IV), potassium sodium ferricyanide, po- metal, absent a ring system is expressly contemplated. tassium hexacyanoplatinate, potassium hexacyanoruth- [0065] Contemplated oxygenated metallic compounds inate (II)hydrate, potassium hexacyanoplatinate (IV), po- include metallic alkanols, ethers, ketones, hydroxides, tassium hexafluoroaluminate, potassium hexafluoroars- alkyloxy, including methoxy, dimethoxy, trimethoxy, 30 enate, potassium hexafluorophosphite, potassium hex- ethoxy, diethoxy, triethoxy, oxalate, carbonate, dicarbo- afluorophosphite, potassium hexafluorosilicate, potassi- nate, tricarbonate, and similar structured compounds, in- um hexahydroxyantimonate, potassium hexafluoro ti- cluding mixture thereof. For example trimethoxymethyl- tante, Potassium copper ferracyanide, potassium cya- silane (as set forth below) is desireable. Metallic carbon- nide, iron (III) ferrocyanide, sodium ferrocyanide ates, including dimetallic carbonates, dimetallic dicarbo- 35 decahydrate. Naturally other cyano-spiral, including hex- nates, and the like, are also contemplated. It is contem- acyano compounds are contemplated. Substitutions for plated these oxygenated metallic or organo-metallic potassium and/or iron are also contemplated. Examples compounds may be employed absent a dialkyl carbonate of such substitution include potassium hexacyanocobal- or other oxygenated ECS structure. tate (III), sodium hexacyanocobaltate (III), etc. Structur- [0066] Likewise one or more non-ring radicals may be 40 ally similar compounds, analogues, and homologues, independently attached directly or indirectly to the ring ect., are incorporated herein by reference. system, absent attachment of a metal. An independent [0071] It is contemplated these compounds will require attachment of a metal may be via intermediate radical, a solvent inorder to be adapted to Applicant’s invention. one or more intermediate atoms, including but not limited Non-limiting examples of solvents, include alkyl ketones to carbon, nitrogen, oxygen, phosophorus, silicon, boron, 45 (acetone, etc.), alkyl alcohols, alkyl ethers, glycerols, al- sulfur, or another metal. kanol amines (ethanolamine, etc.), and the like. Other [0067] A cyclic ring/radical/side chain may be indirectly contemplated solvents are known in the art and those attached to the metal through one of more atom, including which are both soluable with said hexacyanides and but not limited to carbon, nitrogen, oxygen, phosophorus, DMC are incorporated herein by reference. silicon, boron, sulfur, or a metal. Indirect attachment via 50 [0072] An example of this fuel composition would in- oxygen is contemplated but less desireable. clude those already provided herein, except the metal [0068] Cyclic rings may be attached to one or more component would be a hexacyanide, preferrably potas- non-ring radicals, atoms and/or ring systems prior to a sium hexacyanoferrate (II) or (III). direct or indirect attachment of the metal. For example, [0073] Other example, would be a fuel composition in- [2-(cyclohexenyl)ethyl]triethoxysilane contains a ethyl 55 cluding DMC and potassium hexacyanoferrate (II) with radical attached to the cyclohexenyl ring, which is then a mutual solvent, optionally containing trimethoxymeth- attached to silicon. This is a preferred metallic structure. ylsilane, a hydrocarbon/hydrogen, and/or an oxidizer, [0069] Thus, cyclomatic compounds may contain one formulated to acheive vapor phase combustion. Said

10 19 EP 0 954 558 B1 20 composition may also be constructed to have maximum decamethylruthenocene, decamethylzirconocene, silic- pH of 10.5. ocene, decamethylsilicocene, etc.). are also contemplat- [0074] Another class of desireable metallics include ed. Metallocenes that accomplish primary object of vapor metal hydrides or metallic hydryls. Examples of metallic phase combustion are contemplated in the claims below hydryls include sodium hydride, lithium hydride, alumi- 5 and incorporated herein by reference. See also Hawley’s num hydride, aluminum borohydride, boron hydride, bo- Condensed Chemical Dictionary 12th ed, Lewis, Van ron anhydride, beryllium borohydride, lithium borohy- Nostrand Reinhold Company, New York (1993), also in- dride,lithium aluminum hydride, lithium borohydride, so- corporated by reference. dium borohydride, transition-metal hydrides, transition- [0080] Carbonyl compounds are expressly contem- metal carbonyl hydrides, transition-metal cyclopentadi- 10 plated. A limited number of examples include decacarb- enyl hydrides, and mixture. Those hydrides known in the onyl dimanganese, (acetylacetonato)di- carbonylrho- art and those disclosed in Metal Hydrides, Bambakidis, dium. See for example Carbonylation: New York, Plenum Press (1981), Boron Hydride Chem- istry, Muetterties, New York, Academic Press (1975), Direct Synthesis of Carbonyl Compounds, H.M. which accomplish primary vapor phase combustion ob- 15 Colquhoun, Plenum Press (1991), incorporated ject of this invention, are contemplated in the claims be- herein by reference. low and incorporated herein by reference. [0075] Organometallic nitrosyls are also desireable. [0081] Alkyl metal and alkyl earth metal salts and de- See for example Metal Nitrosyls, Richter-Addo, Oxford rivative compound are expressly contemplated. For ex- University Press, U.K. (1992). 20 ample, potassium salts are contemplated including those [0076] Alkyl metal carbonates, multi-metal alkyl car- commercially marketed by Shell Chemical, known as bonates, or carbonates including those with a hydrogen "SparkAid or SparkAde." Other acceptable potassium (e.g. LiHCO3, Na2CO3, NaHCO3, MnCO3, MgCO3, salts include potassium alkanols, e.g. potassium meth- CaCO3, CaMg(CO3)2, etc.), alkali metal carbonates, oxide, potassium ethoxide, potassium propoxide, potas- and other metal carbonates (e.g. AgCO3, TI2CO3, etc.) 25 sium isopropoxide, potassium butoxide, potassium sec- are contemplated. Contemplated salts also include acid butoxide, potassium tert-butoxide, potassium pentoxide, salts containing replaceable hydrogen. Double oxides potassium tert-pentoxide, etc. Other non-limiting exam- and hydroxides are also contemplated. ples of potassium salts include potassium hydrogenph- [0077] Transition metals and their known cyclomatic thalate, potassium hydrogensulfate, monopotassium compounds, including carbonyl compounds are express- 30 acetylenedicarboxylic acid, potassium phenoxide, potas- ly contemplated. See Fundamental Transition Metal Or- sium pyrophosphate, potassium dihydrogenphosphate, ganometallic Chemistry, Lukehart, Monteray, Calif, potassium benzoate, potassium chloride, potassium Brooks/Cole (1985), Transition Metal Compounds, King, hexoate (potassium salt hexoic acid), potassium acetate, New York, Academic Press (1965), Transition-Metal Or- potassium diphenylphosphide, potassium trimethylsi- ganometallic Chemistry, King, New York, Academic 35 lonalate, potassium phthalic acid, P-aminobenzoic acid Press (1969), Fundamental Transition Metal Organome- potassium salt, monopotassium L-aspartic acid. Corre- tallic Chemistry, lukehart, Monterey, Ca., Brooks/Cole sponding sodium, Lithium, rubidium, sesium compounds (1985), incorporated herein by reference. A preferred cy- are contemplated. clomatic transition metallic is MMT. [0082] As noted above, non-limiting non-leaded simple [0078] As contemplated herein non-transition-metal 40 binary/ternary metallic compounds, including binary/ter- compounds known in the art. See Nontransition-Metal nary and higher metallic salts, acid salts, including those Compounds, Eisch, New York, Academic Press (1981). with replaceable hydrogen, etc., are contemplated. Hy- Non-transition metal compounds that accomplish prima- droxy acids, perchlorates, sulfates, nitrates, carbonates, ry object of vapor phase combustion are contemplated hydroxides, methylates, ethylates, propylates, and oth- in the claims below and incorporated herein by reference. 45 ers, are also contemplated. Non-limiting examples in- [0079] Likewise known metallocenes are contemplat- clude potassium nitrite, sodium nitrite, lithium nitrite, and ed. Non-limiting examples include alkylmetallocenes, hexamethylphosphoric triamide. arylmetallocenes, including dicyclopentadienyl-metal [0083] Silicon containing metallics are particularly pre- with the general formula (C5H5)2M, dicyclopentadienyl- ferred. Non-limiting examples preferred silicons include metal halides with the general formula (C5H5)2MX1-3, 50 [2-(cyclohexenyl)ethyl]triethoxysilane, cyclohexenyl monocyclopentadienyl-metal compounds with the gen- dimethoxymethylsilane, benzyltrimethylsilane, N-(3-(tri- eral formula C5H5MR1-3, where R is CO, NO, halide methoxysilyl)propyl)ethylenediamine, N-1-(3-(trimeth- group, alkyl group, etc. Non-limiting examples include oxysilyl)propyl)diethylenetriamine, N-(3-(trimethoxysilyl) napthacenes, ferrocene, methylferrocene, cobaltocene, propyl)ethylenediamine, 1- (trimethyl(silyl)pyrrolidine, nickelocene, titanocene dichloride, zirconocene dichlo- 55 triphenylsilanol, octamethyltrisiloxane, 2,2,4,4,6,6-hex- ride, uranocene, decamethylferrocene, decamethylsilic- amethylcyclotrisilazane, hexamethylcyctrisiloxane, hex- ocene, decamethylgermaniumocene, decamethylstan- amethyldisilane, 1,1,1,3,3,3- hexamethyl disilazane, nocene, decamethylphosocene, decamethylosmocene, hexamethyldisiloxane, hexamethyldisilthiane, allyltribu-

11 21 EP 0 954 558 B1 22 tylsilane, tetraalkylsilanes (e.g. tetraethylsilane, tetrabu- metallic structure includes M1-O(CO)O-M2, wherein M1 tylsilane, etc.), 3-aminopropyltriethoxysilane, benzytri- or M2 are the same or different metal or element. M1 methylsilane, benzytriethylsilane, N- benzyltrimethylsi- may be a double valence cation, wherein M2 is absent lylamine, diphenylsilanediol, dihexylsilanediol, (trimeth- from above structure, unless additional carbonate is in- ylsilyl)cyclopentadiene, including homologues, ana- 5 cluded. Preferred M valences are 1 or 2. M valences or logues and derivative thereof. multiple M1M2 combinations having combined valence [0084] An an example of a desirable fuel composition greater than two are acceptable. In which case, additional of this invention would then include a lower molecular carbonate structure would be added, e.g. CaMg(CO3)2. weight dialkyl carbonate (preferrably DMC or EMC), a [0090] In the immediate structure above, M1/M2 va- silane selected from preferred silicons immediately 10 lence’s may be greater than one, wherein excess valence above (or as set forth elsewhere in this specification), is occupied by same or additional metal (element), and/or and optionally trimethoxymethylsilane as a co- metallic, wherein M1 or M2 are substituted for a single or double a hydrogen or a hydrocarbon co-fuel, and/or an oxidizer. bond oxygen, and/or by one or more radicals. M1 or M2 [0085] Preferrable tin compounds include benzltriphe- also may be substituted for single bond oxygen, or nitro- nyltin and allyltributyltin. A preferrable phosphorus com- 15 gen, and/or by one or more radicals, including methyl, pound includes benzyldiethylphosphite. hydrogen, hydroxy, ethoxy, carbethoxy, carbomethoxy, [0086] It is also within the scope and practice of this carbonyl, carbonyldioxy, carboxy, methyoxy, isonitro, invention to employ oxygenated containing metallic com- isonitroso, or methylenedioxyl radical. Non-limiting ex- pounds, including oxygenated organo metallic com- amples include carbonates of lithium [Li2O2(CO)], am- pounds, which are metallic alcohols, alkanolamines, ke- 20 monium manganese, potassium [K2O2(CO)], sodium, tones, esters, ethers, carbonates, and the like, which are calcium, cesium, copper, rubidium, lithium hydrogen, so- themselves ECS compounds, in hydrocarbon fuels with dium hydrogen, potassium hydrogen, potassium sodium, additional dialkyl carbonate Thus, it is an express em- magnesium, and the like. bodiment to use metallic compounds added to DMC, op- [0091] It is contemplated that C2 to C8 metallic ethers, tionally a co-fuel, an oxidizer, catalyst, and/or a hydro- 25 C2 to C4/C5 metallic ethers being more desireable, will carbon. be used as metallic structure in this invention. For exam- [0087] The compositions of this invention contemplate ple, M’1-CH2-CH2-O-CH2-CH2- M’2 structure is con- usage of an oxidizer and other ingredients. See incorpo- templated wherein M’1 and M’2 may be same or different rated references, including aforementioned PCT appli- metallic or wherein one M’1 or M’2 may be hydrogen, or cations, for the definitions incorporated in the claims be- 30 other atom, or radical with one available valence. low. [0092] Other contemplated structure include metallic [0088] It is also within the practice of this invention to ketone, ester, alcohol, acid, and the like. Non-limiting ex- employ a metallic compound, including homologue, an- amples include M’1-C- OH3-R, wherein M’1 is one or alogue, isomer, or derivative thereof, having a structure more metallic comprising valence of 3 or greater, and R or structure similar to M-Rn, Rn-M-M-Rn, Rn-M-Q-M-Rn, 35 is radical, whereby resulting structure is ketone, ester, Rn-M-Q’-M-Rn, Rn-M-R’-M-Rn, wherein M is one or acid, alcohol, or ether. Other structure include M’1-C2O4, more non-leaded metal(s), metalloid(s), or non-metal el- wherein M’1 has a valence of 2. M1-C-C-O-C-C-M2 ement(s), and R is one or more hydrogen, cyclic ring structure is also contemplated wherein M1 and M2 may system/radical/side chain(s), and/or non-ring radical/ be same or different metallic or wherein M2 may be hy- side chain(s) as provided herein above, including but not 40 drogen or atom of one valence. Other structure includes limited to alkyl, aryl, alkyloxy, alkylanol (alkanol), hy- RO-M, where RO is an alkanol and M is a metal. Similar droxyl, aryloxy, polyalkyl, polyaryl, polyalkyloxy, poly- structure is contemplated for M have available valence alkylanol, polyaryloxy, polyhydroxyl radicals. R’ is one or greater than 1. more cyclic ring system/radical/side chain(s), and/or non- [0093] It is preferred when an oxygenated organo-me- ring radical/side chain(s) as provided herein. If R is great- 45 tallic compound is employed, it have ECS properties er than 1, then subsequent R’s may be same or different when ever possible, e.g. higher heats of vaporization, radical, etc. R also be a single radical or one radical at- high burning velocities, favorable decomposition charac- tached to one or more radicals. "n" is an interger ranging teristic (e.g. decomposition at post ignition pre-combus- from 1 to the number of valence electrons (or common tion temperatures into enhanced combustion or free rad- oxidation states) available of M. Q is an atom having a 50 icals structure), be thermally stable at normal handling minimum oxidation available of 2, including but not limited temperatures, etc.; and have high heat and energy re- to carbon, nitrogen, oxygen, phosophorus, silicon, boron, leasing characteristics of metals, etc.. Non limiting ex- sulfur, or a differing metal than M. Q’ is an atom with a amples of lithium derivative compounds of this invention, minimum available oxidation state of 2, including but not include: lithium bis(dimethylsilyl)amide, lithium bis(tri- limited to carbon, nitrogen, oxygen, phosophorus, silicon, 55 methylsilyl)amide, oxamic acid, P-aminosalicylic acid boron, sulfur, or a differing metal than M, also containing lithium salt, lithium salt 5-nitroorotic acid, lithium D-glu- one or more radicals. conate, lithium hexacyanoferrate(III) (Li3Fe(CN)6), lithi- [0089] Additional oxygenated-organo or oxygenated um diphenylphosphide, lithium acetate, lithium acetate

12 23 EP 0 954 558 B1 24 acid, lithium salt acetic acid, lithium acetamide, lithium lithium-p-chlorophenyl, lithium p-bromophenyl, lithium anilide, lithium azide, lithium benzamide, lithium antimo- lithium o- anisyl, lithium m-anisyl, lithium p-anisyl, lithium nide, lithium orthoarsenate, lithium orthoarsenite, lithium diethoxyphenyl, lithium dimethoxyphenol, lithium m- meta-arsenite, lithium diborane, lithium pentaborate, lith- cumyl, lithium p-ethoxyphenyl, lithium m-dimethylami- ium dihydroxy diborane, lithium borohydride, lithium ca- 5 nophenyl, lithium 9-flourene, lithium a-napthyl, lithium b- dium iodide, lithium chloride, lithium calcium chloride, lith- napthyl, lithium p-phenylphenyl, lithium 9-phenylanthryl, ium carbide, lithium carbonate, lithium hydrogen carbon- lithium 9-anthryl, lithium 9-methyl- phenanthryl, lithium ate, lithium carbonate, lithium carbonyl, lithium cobalt (II) pyridyl, lithium 2-pyridyl, lithium 3-pyridyl, lithium 6-bro- cyanide, lithium cobalt (III) cyanide, lithium cobaltinitrite, mo-2-pyridyl, lithium 5-bromo-2-pyridyl, lithium dibenzo- lithium cynomanganate (II), lithium cynomanganate (III), 10 furyl, lithium 3-quinoyl, lithium 2-lepidyl, lithium triphenyl- lithium citrate, lithium ferricyanide, lithium ferrocyanide, methyl, lithium 2,4,6-trimethylphenyl, lithium 2,4,6- triiso- lithium hydride, lithium hydroxide, lithium manganate, propylphenyl, lithium 2,3,5,6-tetraisopropylphenyl, lithi- lithium permanganate, lithium methionate, lithium napth- um tetrabutylphenyl, thiophenedilithium, toluenedilithi- enate, lithium nitride, lithium nitrate, lithium nitrite, lithium um, dipheny- lethylenedilithium, lithiumamylethynyl, lith- nitrobenzene (e.g. lithium-p-nitrobenzene), lithium nitro- 15 iumphenylethynyl, lithiummethoxybromophenyl, lithium phenoxide, lithium etherate, lithium chromate, lithium phenylisopropyl, lithium tetraphenylboron, lithium te- oleate, lithium oxalate, lithium oxalatoferrate (II), lithium tramethylboron, lithium a-thienyl, lithium m-trifluorometh- oxalatoferrate (III), lithium monoxide, lithium oxide, lithi- ylphenyl, phenylethynyllithium, 3-furyl- lithium, phenyl- um peroxide, lithium , lithium mono- orthophosphate, lith- isopropyllithium, dibenzofuranyllithium, lithium dimethyl- ium hypophosphite, lithium orthophosphite, lithium hy- 20 benzyl, lithium selenocyanate, lithium trimethylsi- droxoplumbate, lithium rhodium cyanide, lithium sele- lanolate, diphenylphosphide, lithium benzoate, lithium nide, lithium selenite, lithium selenocynate, lithium se- tert-butyl carbonate, lithium azide, di-lithiumcyanamide, lenocyanoplatinate, lithium disilicate, lithium metasili- lithium cyanide, lithium dicyanamide, cyclohexanebutyr- cate, lithium sodium carbonate, lithium sodium ferricya- ic acid lithium salt, cyclohexane acid lithium salt, cy- nide, lithium hydroxostannate, lithium disufide, lithium 25 clopentadientyllithium, lithium tri-tert-butoxy- aluminum hydrosulfide, lithium pentasulfide, lithium tetrasulfide, hydride, lithium triethylborohydride, lithium trimethyl- lithium trisulfide, lithium telluride, lithium thioarsenate, borohydride, lithium tripropylborohydride, lithium triiso- lithium thioarsenite, lithium trithiocarbonate, lithium thio- propyl- borohydride, lithium tributylborohydride, lithium cyanate, lithium amide, lithium salt (E,E)-2,4-hexadieno- triisobutyl- borohydride, lithium tri-sec-butylborohydride, ic acid, dilithium fluorophosphate, dilithium fluorophos- 30 lithium tri-tert- butylborohydride, lithium trisiamylborohy- phite, trilithium phosphate, trilithium phosphite, lithium dride, lithium chlorate, lithium tert-butoxide, lithium sec- perchlorate, propanoic acid lithium salt, lithium formate, butoxide, iso-butoxide, lithium antimonate, lithium diphe- lithium cyanate, lithium hexacyanocobaltate (III), lithium nylphosphide, lithium bis(trismethylsilyl) amide, trilithium hypophosphite, lithium hexaflurorsilicate, lithium nitro- phosphite, lithium selenocyanate, lithium tri- sec-butyl- prusside, lithium phenoxide, lithium phosphate (dibasic, 35 borohydride, lithium triethylsilanolate, lithiumthiocyan- monobasic, tribasic), lithium salicylate, lithium selenide, ate, lithium acetylide, lithium chlorate, lithium salicylate, lithium tetracyanonickelate (11), lithium tetrafluorobo- lithium di-lithium tetracarbonylferrate, lithium tetraphe- rate, lithium xanthogenate, lithium -p-aminobenzoate, nylborate, lithium triethylborohydride, lithium triacetoxy- lithium copper ferrocynanide, lithium cupric ferrocyanide, borohydride, lithium triphenylborane, lithium hydroxide, lithium hexafluorophosphate, lithium hexanitricobaltate 40 lithium diphenylphosphide, lithium methoxide, lithium III, lithium naphthenate, lithium -B-naphthoxide, lithium ethoxide, lithium tri-sec-butyl- borohydride, tri-tert-butyl- polysulfide, lithium - sodium phosphate, lithium stearate, borohydride, lithium triethylborohydride, lithium triphe- lithium sulfide, lithium sulfite, lithium sulfate, lithium thi- nylborohydride, lithium trisiamylboro- hydride, lithium ocyanate, lithium xanthate, lithium fluorosilicate, N-lithi- metavanadate, lithium cyclohexanebutyrate, lithium hex- umethylenediamine, oxalic acid dilithium salt, lithium be- 45 achloroplatinate, lithium thiocyanate, lithium selenocy- ta-hydropyruvic acid, lithium 1,1- dimethylurea, lithium anate, lithium cyanate, lithium floride, lithium hexafluor- 1,1-diethylurea, lithium 1,1-diepropylurea, lithium xant- oantimonate, lithium hexafluoroaluminate, lithiumalumi- hate, lithium ethylxanthate, lithium methylxanthate, lithi- nate, lithiumaluminum-tri- tert-butoxide, lithium hex- um salt thiophenol, lithium triphenylmethyllithium, me- afluoroarsenate, lithium hexafluorosili- cate, lithium hex- thyl- lithium, ethyllithium, lithiumethynyl(acetylide), pro- 50 acyanocobalt(II)ferrate(li), lithium ferrosilicon, dilithium- pyllithium, isopropyllithium, butyllithium, isobutyllithium, hexacyanocobalt(II)ferrate(li), lithium hexafluorotitan- secbutyllithium, tertbutyllithium, pentalithium, hexyllithi- ate, lithium hexafluorozirconate, lithium hexahydroxyan- um, heptalithium, amyllithium, isoamyllithium, benzyllith- timonate, lithium hexachlororuthenate, lithium hexachlo- ium, dimethylbenzyllithium, tolyllithium, dodecyllithium, ropalladate, lithium formate, lithium tetracyanonickelate, cyclopentadienyllithium, methyl- cyclopentadienyllithi- 55 lithium tetrafluoroaluminate, lithium tetrafluoroborate, um, cyclohexyllithium, lithiumheptyl, lithiumdodecyl, lith- lithium thioacetate, L-glutamic acid monolithium salt, fu- ium tetradecyl, lithium hexadecyl, lithium octadecyl, phe- maric acid lithium salt, oxamic acid lithium salt, lithium nyllithium, lithium o-tolyl, lithium m-tolyl, lithium p-tolyl, salt diphenyl-phospane, P-aminobenzoic lithium salt,

13 25 EP 0 954 558 B1 26 aminobenzole acid lithium salt, alpha-napthaleneacetic bisulfide, lithium metaperiodate, lithium methacrylate, acid lithium salt, dilithium salt 2,6-naphthalenedicarboxlic lithium nitrofer- ricyanide, oxybate, lithium pentamethyl- acid, lithium cyclcohexanetherate; lithium phthalimide, P- cyclopentadienide, lithium phenolate, polyphosphate, aminosalicylic acid lithium salt, lithium salt 3,5-dimethyl- lithium polyphosphite, lithium propion- ate, lithium pyro- cyclohexyl sulfate, indolebutyric acid lithium salt,indole- 5 phosphate, lithium selenate, lithium selenite, lithium tet- 3-butyric acid lithium salt, diphenylphosphide, lithium rachloroaluminate, lithium thiomethoxide, lithium thiosul- dimethylsilanolate, lithium triethyl- borohydride, lithium fate, lithium thiosulfide, lithium thiosulfite, lithium tri- ac- propoxide, lithium isopropoxide, lithium butoxide, lithium toxyborohydride, lithium lithium trimethylsilonate, lithium sec-butoxide, lithium pentoxide, lithium tert-pentoxide, triethylsilonate, lithium tris(1-pyrazoly)borohydride, in- lithium hydrogenphthalate, lithium oxalate, lithium hydro- 10 cluding analogues, homologue, isomers and derivatives gensulfate, monolithium acetylenedicarboxylic acid, lith- thereof. See Lithium Chemistry: A Theorical and Exper- ium pyrophosphate, lithium dihydrogenphosphate, lithi- imental Overview, Sapse, Schleyer, John Wiley & Sons, um hexoate (lithium salt hexoic acid), lithium diphenyl- N.Y. (1995), incorporated herein by reference. phosphide, lithium trimethylsilonalate, lithium phthalic [0094] Non limiting examples of the boron derivative acid, P-aminobenzoic acid lithium salt, monolithium L- 15 compounds of this invention include: alkyl boron com- aspartic acid, tetraphenyldilithium (C6H5)2CLi2C(C6H5) pounds, aryl boron compounds, 1,3,2-benzodioxabo- 2, lithiumethylphenyl (LiCH2C6H5), lithium bromate, lith- role, diisopropoxymethylborane, ethylborane, diethylbo- ium hydrogenphospate, monlithium salt D-shaccharic rane, diemthylborane, dicyclohexylborane, boric acid es- acid, DI-asparatic lithium salt, (R)-alpha-hyroxymethyl- ters (e.g. borate ester, dimethyl borate, di-n-butyl borate, aspartic acid lithium salt, lithium fluoride, lithium iodate, 20 dicyclohexyl borate, didodecylborate, di-p-cresyl bo- lithium salt ethyl malonate, lithium thioacetate, lithium rates), phenylboronic acid, 2-phenyl-1,3,2-dioxborinane, phenol, lithium salt aminobenzoic acid, lithium ami- pyrrolyboranes (e.g. 1-pyrrolyborane, 2-pyrrolyborane), nophenol salt, lithium cyclohexenol, lithium methylcy- tetrabutylammonium borohydride, tetramethylammoni- clohexenol, lithium cyclopropanol, lithium methylcyclo- um borohydride, tetraisoproplyam- monium borohydride, propanol, lithium cyclobutanol, lithium methylcyclobuta- 25 tetrapropylammonium borohydride, tetraethylam- mo- nol, lithium methylcyclopentanol, lithium cyclopentanol, nium borohydride, tetraisobutylammonium borohydride, lithium cyclohexenol, lithium methylcyclohexenol, lithium tetra-tert-butylammonium borohydride, tetra-sec-buty- dimethylcyclohexenols (e.g. lithium 3,5-dimethylcy- lammonium borohydride, tetrabutylammonium cy- clohexanol, lithium 2,3-dimethylcyclohexanol, lithium anoborohydride, tetramethylammonium cyanoborohy- 2,6-dimethylcyclohexanol, lithium 2,5-dimethylcyclohex- 30 dride, tetraisoproplyammonium cyanoborohydride, anol, 3,5-dimethylcyclohexanol), lithium o-ethylxanthic tetrapropylammonium cyanoborohydride, tetraethylam- acid, monolithium salt 2-ketoglutaric acid, dilithium salt, monium cyanoborohydride, tetraisobutylammonium cy- ketomalonic acid, lithium salt lactic acid, dilithium thio- anoborohydride, tetra-tert-butylammonium cyanoboro- sulfate, lithium antimony tartrate, lithium dichloroacetate, hydride, tetra-sec-butylammonium cyanoboro- hydride, lithium dimethylacetate, lithium diethylacetate, lithium 35 tetramethylammonium triacetoxyborohydride, thi- dipropyl- acetate, lithium metaborate, lithium tetraborate, opheneboric acid, 2-thiopheneboric acid, 3-thiophene- lithium tetra- chlorocuprate, lithium acetoacetate, lithium boric acid, tolylboronic acid (e.g. o-tolylboronic acid, p- diisopropylamide, lithium diethylamide, lithium dimethy- tolylboronic acid, m-tolylboronic acid), tributoxyborane, lamide, lithium bis(dimethyl- silyl)amide, dilithium tributylborane, tri-sec-butylborane, tri- tert-butylborane, phthalocyanine, dilithiumtetrabromocuprate, dilithium 40 tributylborate, tri-tert-butylborate, tri-methoxyboroxine, tetrabromonickelate, dilithiumtetrachloromanganate, di- trimethylamineboran, trimethylborate, trimethyl-borox- lithiumbutadiyne, lithium cyclopentadienide, lithium dicy- ine, trimethylborazine, trimethylene borate, triphenylbo- clo- hexylamide, lithium diethylamide, lithium dimethyla- rate, triphenylborane, tribenzyl borate, borate, trisiamyl- mide, lithium dipropylamide, lithium diisopropylamide, borane, tris(2-methoxyethyl)borate, boron hydride, lithi- lithium thexylborohydride, lithium tri-tert-butoxyalumino- 45 um borohydride, sodium borohydride, boron hydrate, bo- hydride, lithium trimethyl- silyl)acetylide, lithium triethyl- ron hydride, boron anhydride, triethylboron (C2H5)3, de- silyl)acetylide, lithium tris[(3-ethyl-3-pentyl)oxy]alumino- caborane, borazoles, aluminimum borohydride, berylli- hydride, (phenylethynyl)lithium, 2-thienyllithium, lithium um borohydride, lithium borohydride, hexamethyl-di- diethyldihydroaluminate, lithium dimethyl-dihydroalumi- amineborane (CH3)3NBH(CH3)3), (CH3)2BI, beryllium- nate, lithium aluminum hydride, lithium bifluoride, lithium 50 borohydride (Be(BH4)2), trimethoxytriborate (BO)3 biphenyl, lithium biselenite, lithium bis(2-methox- (OCH3)3, C4H9B(OH)2, AI(BH4)2, Be(BH4)2, LiBH4, B yethoxy)-aluminum hydride, lithium bismuthate, lithium (OC2H5)3, B(OCH3)3, trimethoxytriborane, 3- borate, lithium chlorite, lithium cobaltnitrite, lithium cy- bromophenylboronic acid, trimethoxy borate, triethoxy anoborohydride, lithium cyclopentadienide, lithium dicy- borate, triproxyborate, tributoxyborate, triisobutoxybo- anamide, lithium hexametaphosphate, lithium hexanitro- 55 rate, tri-tert- butoxyborate, tri-sec-butoxyborate, tri-phe- colbaltate, lithium hydrogenphosphite, lithium hydro- noxyborate, tri-phenoxyboroamine, tri-phenoxyborane, genselenite, lithium hydrogensulfite, lithium hydrosulfite, phenylboronic acid, benzylboronic acid, cylohexylboron- lithium hypochloride, lithium metaarsenite, lithium meta- ic acid, cylohexenylboronic acid, cyclopentylboronic ac-

14 27 EP 0 954 558 B1 28 id, methylphenylboronic acid, methylcylohexylboronic boroethoxide, methylcyclopentylboroethoxide, dimethyl- acid, methylcyclopentylboronic acid, methylbenzylbo- cyclopentylboroethoxide, methylbenzylboroethoxide, ronic acid, dimethylphenylboronic acid, dimethylcylohex- dimethylbenzylboroethoxide, diphenylboroethoxide, ylboronic acid, dimethylcyclopentylboronic acid, dimeth- dibenzylboroethoxide, dicylohexylboroethoxide, dicylo- ylbenzylboronic acid, diphenylboronic acid, dibenzylbo- 5 hexenylboroethoxide, dicyclopentylboroethoxide, di(me- ronic acid, dicylohexylboronic acid, dicylohexenylboronic thyl-phenyl)boroethoxide, di(methylcylohexyl) acid, dicyclopentylboronic acid, methyldiphenylboronic boroethoxide, di(methylcyclopentyl)boroethoxide, di acid, bis[(methyl)cylohexyl]boronic acid, bis[(methyl)cy- (methylbenzyl)boroethoxide, di(di-methylphenyl) clopentyl]boronic acid, bis[(methyl)benzyl]boronic acid, boroethoxide, di(dimethylcylohexyl)boroethoxide, di bis[(dimethyl)phenyl]boronic acid, bis[(dimethyl)- cylo- 10 (dimethylcyclopentyl)boroethoxide, di(dimethylbenzyl) hexyl]boronic acid, bis[(dimethyl)cyclopentyl]boronic ac- boro- ethoxide, phenylboric acid, benzylboric acid, cylo- id, bis[(dimethyl)benzyl]boronic acid, phenylboroncarb- hexylboric acid, cylohexenylboric acid, cyclopentylboric onyl, benzylboroncarbonyl, cylohexylboroncarbonyl, cy- acid, methylphenylboric acid, methylcylohexylboric acid, lohexenylboroncarbonyl, cyclopentylboroncarbonyl, methylcyclopentylboric acid, methylbenzylboric acid, methylphenylboroncarbonyl, methylcylohexylboroncar- 15 dimethylphenylboric acid, dimethylcylohexylboric acid, bonyl, methylcyclopentylboroncarbonyl, methylbenzyl- dimethylcyclopentylboric acid, dimethylbenzylboric acid, boroncarbonyl, phenylboronic acid carbonyl, benzylbo- dibenzylboric acid, dicylohexylboric acid, dicylohexenyl- ronic acid carbonyl, cylohexylboronic acid carbonyl, cy- boric acid, dicyclopentylboric acid, methyldiphenylboric lohexenylboronic acid carbonyl, cyclopentylboronic acid acid, bis(methylcylohexyl)boric acid, bis[methylcy- carbonyl, methylphenylboronic acid carbonyl, methylcy- 20 clopentyl]boric acid, bis[methylbenzyl]boric acid, bis lohexylboronic acid carbonyl, methylcyclopentylboronic [dimethylphenyl]boric acid, bis[dimethylcylohexyl]boric acid carbonyl, methylbenzylboroncarbonyl, dimethyl- acid, bis[dimethylcyclopentyl]boric acid, bis[dimethyl- phenylboroncarbonyl, dimethylcylohexylboroncarbonyl, benzyl]boric acid, aminophenylboronic acid,3-ami- dimethylcyclopentylboroncarbonyl, dimethylbenzylbo- nophenylboronic acid, diborane, tetramethoxydiborane, roncarbonyl, diphenylboroncarbonyl, dibenzylboroncar- 25 tetraethoxydiborane, boric acid, borazine, borocar- bonyl, dicylohexylboroncarbonyl, dicylohexenylbo- bonate, borane- tert-butylamine, tetraethylammonium roncarbonyl, dicyclopentylboroncarbonyl, methyldiphe- borohydride, tetraethyl- ammonium tetrafluoroborate, nylboroncarbonyl, di[(methyl)cylohexyl]boroncarbonyl, tetrapropylammonium tetrafluoroborate, naphthylboron- di[(methyl)cyclopentyl]boroncarbonyl, di[(methyl)ben- ic acids (e.g. 1-naphthylboronic acid, 2-naphthyl- boronic zyl]boroncarbonyl, di[(dimethyl)phenyl]boroncarbonyl, 30 acid, 3-naphthylboronic acid, 4-naphthylboronic acid), di[(dimethyl)cylohexyl]boroncarbonyl, di[(dimethyl)cy- methylnaphthlboronic acid, biphenylboronic acid, carbo- clopentyl]boroncarbonyl, di[(dimethyl)benzyl]boroncarb- rane, cyclohexylamine diborane, methylbenzeneboric onyl, phenylboromethoxide (pheny-lborodimethoxide acid, dimethylbenzeneboric acids (e.g. 3,5-dimethylben- C6H5B(OCH3)2), benzylboromethoxide, cylohexyl- zeneboric acid), hexadecaneboronic acid, tetreade- boromethoxide, cylohexenylboromethoxide, cy- 35 caneboronic acide, phenylethylboroamine, methylbora- clopentylboromethoxide, methylphenylboromethoxide, zine, dimethylborazine, trimethylborazine, ethylbora- methylcylohexylboromethoxide, methylcyclopentyl- zine, diethylborazine, triethylborazine, carboborazine, boromethoxide, methylbenzylboromethoxide, methyl- dicarboborazine, tricarboborazine, triisopropoxyborox- phenylboromethoxide, dimethylphenylboromethoxide, ine, tripropoxyboroxine, trimenthyl borate, trimenthyl methylcylohexylboromethoxide, dimethylcylohexyl- 40 borine, trimenthyl borane, trimethal- lyl borate, trimeth- boromethoxide, methylcyclopentylboromethoxide, allyl borine, tripentyl borate, tripentyl borine, tripentyl bo- dimethylcyclopentylboromethoxide, methylbenzyl- rane, trimethyl borate, trimethylborine, triethylborine, tri- boromethoxide, dimethylbenzylboromethoxide, diphe- ethylborane, triethylborate, tripropylborane, tripropyl- nylboromethoxide, dibenzylboromethoxide, dicylohexyl- borine, tripropylborate (tripropoxyborane), triisopropyl- boromethoxide, dicylohexenylboromethoxide, dicy- 45 borane, triisopropylborate, triisopropylborine, tri-iso- clopentyiboromethoxide, di(methylphenyl)boromethox- butyl- borane, tri-iso-butylborate, tri-sec-borane, tri-sec- ide, di(methylcylohexyl)boromethoxide, di(methylcy- borate, tri- sec-borine, tributyl borate, tributyl borine, trib- clopentyl)boromethoxide, di(methylbenzyl)boromethox- utyl borane, tri- tert-butyl borate, tri-tert-butyl borine, tri- ide, di(dimethylphenyl)boromethoxide, di(dimethylcylo- tert-butyl borane, triphenyl borate, triphenyl borane, tri- hexyl)boromethoxide, di(dimethylcyclopentyl)borometh- 50 cyclohexylborate, tri-cyclohexylborane, dimethyl boric oxide, di(dimethylbenzyl)boromethoxide, phenylboro- acid, diethylboric acid, dipropyl- boric acid, diisopropyl- ethoxide (phenylborodiethoxide C6H5B(OCH3)2), ben- boric acid, di-iso-butylboric acid, di-sec- boric acid, dib- zylboroethoxide, cylohexylboroethoxide, cylohexenyl- utylboratic acid, di-tert-butylboric acid, diphenyl- boric ac- boroethoxide, cyclopentylboroethoxide, methylphenyl- id, dicyclohexylboric acid, boron tribromide, sodium boroethoxide, methylcylohexylboroethoxide, methylcy- 55 tetrafluoroborane, sodium trimethylborohydride, triethyl- clopentylboroethoxide, methylbenzylboroethoxide, borohydride, sodium tripropylborohydride, sodium triiso- methylphenylboroethoxide, dimethylphenylboroethox- propyl- borohydride, sodium tributylborohydride, sodium ide, methylcylohexylboroethoxide, dimethylcylohexyl- triisobutyl- borohydride, sodium-tert-butylborohydride,

15 29 EP 0 954 558 B1 30 sodium-sec-butyl- borohydride, sodiumphenylborohy- isobutylboron, potassium hydroxide with tri-sec-butylbo- dride, potassium tetrafluoroborane, potassium trimethyl- ron, tri- tert-butylboron, potassium hydroxide with triphe- borohydride, triethylborohydride, potassium tripropyl- nylboron, vinyl- phenylboronic acid, 4-vinylphenylboron- borohydride, potassium triisopropylborohydride, potas- ic acid, boron phosphide, boron carbide, borinoamino- sium tributylborohydride, potassium triisobutylborohy- 5 borine, boroethane, pentaborane, hexaborane, decabo- dride, potassium- tert-butylborohydride, potassium-sec- rane, triselenideborane, hexasilicide borane, trisilicide butylborohydride, potassium phenylborohydride, butyl- borane, trichloroborine dimethyletherate, trichloro- boronic acid, sodiumborohydride, methyldichloroborane, borine trimethlyammine, trimethylborine trimethlyam- ethyldichloroborane, propyldichloroborane, isopropyl- mine, trimethyl- borine triethlyammine, triethylborine tri- dichloroborane, butyldichloroborane, isobutyldi- chlorob- 10 methlyammine, tricyclo- hexylborine, tri-n-hexyltriborine orane, tertbutytdichloroborane, secbutyldichloroborane, trioxane, triisoamylborate, triisoamylborine, tri-p-anisyl- phenyldichloroborane, methylboric acid, ethylboric acid, borine, trimethoxyboroxine, tri- methylamminoborine, tri- trichloro- borazine, boranetetrahydrofuran, tetrafluoro- ethylamminoborine, tripropylamminoborine, triisopropy- boric acid, boron trichloride, tre-sec-butylborane, boran- lamminoborine, triisobutylamminoborine, tributylam- mi- trimethylamine, borane- triethylamine, borane-N,N-di- 15 noborine, tri-sec-butylamminoborine, tri-tert-butylammi- ethylaniline, boran-pyridine, borane- tert-butylamine, bo- noborine, triphenylamminoborine, tribenzylammino- rane-morpholine, borane-dimethylamine, borane- di- borine, trimethylamminoboric acid, triethylamminoboric ethylamine, trisiamylborane, trisiamylborate, disiamylb- acid, tripropylamminoboric acid, triisopropylamminobo- orane, disiamylborate, trimesitylborane, sodium metab- ric acid, triisobutylamminoboric acid, tributylamminobo- orate, lithium metaborate, potassium metaborate, sodi- 20 ric acid, tri-sec-butylamminoboric acid, tri-tert- butylam- um metaborane, borane- tributylphosphine, lanthanum minoboric acid, triphenylamminoboric acid, tribenzylam- hexaboride, boran-triphenylphosphine, boran-tributyl- minoboric acid, trimethyldiborane, triethyldiborane, phosphine, cyclopentadienylboran, methylcyclopen- tripropyl- diborane, trimethyltriborinetriamine (B), tri- tadienylboran, boran-N,N-diisopropylborohydride, N,N’- ethyltriborinetriamine (B), trimethyltriborinetriamine (N), bis(mono- isoipinocampheylborane)-N,N,N’N’-tetrame- 25 triethyltriborinetriamine (N), trimethyltriborinetriamine thylethylenediamine, boron nitride, 4-(borane-dimethyl- (N-B-B’), triethyltriborinetriamine (N-B-B’), tri-B-naph- amine)benzene, 4-(borane-dimethylamine)- pyridyl, thylborate, tri-a-naphthaborate, tripehnyl- borineam- 3-(methylthio)proplyborane, tris(dimethylamino)borane, mine, tri-p-tolyborine, tri-p-xylxborine, including ana- butyldiisopropoxyborane, triphenyl borane sodium, sodi- logues, homologues, isomers and derivatives thereof. umtetraphenylborane, sodiumtetraphenylborane, sodi- 30 Corresponding compounds of aluminum, gallium, indi- um tetrakis(1-imidazolyl)borane, sodium tetrakis(1-imi- um, and thallium are contemplated. See Organo Boron dazolyl)borate, diisopropoxyphenylborate, diisopro- Chemistry, Volumes I & II (and subsequent volumes, edi- poxymethylborate, diisopropoxyethyl-borate, boron-am- tions, or supplements), Howard Steinberg, InterScience monia, borontrifluoride, diethyl(3-pyridyl)borane, dime- Publishers (1966), Boron-Nitrogen Compounds, Nieden- thyl(3-pyridyl)borane, lithium thexylborohydride, dichlo- 35 zu, Dawson, New york, Academic Press (1965), The Or- romethyldiisopropylborate, diethylmethoxyborane, ganic Compounds of Boron, Aluminum, Gallium, Indium, dipropylmethoxyborane, diisopropylmethoxyborane, di- and Thallium, Nesmeianov, Nikolaevich, Amterdam, ethylethoxyborane, dipropylethoxyborane, diisopropyl- North-Holland Pub. Co. (1967), Peroxides, Superperox- ethoxyborane, boran-piperidine, diphenylborinic anhy- ides, and azomides of Alkali and Alkali Earth Metals, dride, tris(trimethylsilyl)borate, tris(trimethylsilyl)borane, 40 Perekisi, N.Y., Plenum Press (19966), incorporated trimethylacetic acid with diethylboinic acid, (2-methylpro- herein by reference. pyl)borinic acid, boroglycine, boron alchols, boron ether- [0095] Non-limiting examples of sodium derivative ates, boron acetates (e.g. propylborodiacetate, phenyl- compounds of this invention include: sodium bis(dimeth- borodiacetate, boron tris(trifluoro)acetate), sodium tris ylsilyl)amide, sodium bis(trimethylsilyl)amide, oxamic (1- pyrazolyl)borohydride, sodium perborate, tolylboron- 45 acid, P-aminosalicylic acid sodium salt, sodium salt 5- ic acid, aluminum diboride, chlorodicyclohexylborane, nitroorotic acid, sodium D-gluconate, sodium hexacy- methyldicyclohexyl- borane, ethyldicyclohexylborane, anoferrate(lll) (Li3Fe(CN)6), sodium diphenylphosphide, propyldicyclohexylborane, isopropyldicyclohexylborane, sodium acetate, sodium acetate acid, sodium salt acetic dimethylcyclohexylborane, diethylcyclohexylborane, acid, sodium acetamide, sodium anilide, sodium azide, dipropylcyclohexylborane, diisopropylcyciohexyl-bo- 50 ammonium diisodium amminepentacyanoferrate, sodi- rane, lithium tetramethylboron, lithium tetraethylboron, um benzamide, sodium antimonide, sodium orthoarse- lithium tetrapropyllboron, lithium tetraisopropylboron, nate, sodium orthoarsenite, sodium meta-arsenite, sodi- tetrabutylboron, lithium tetraisobutylboron, lithium tetra- um diborane, sodium pentaborate, sodium dihydroxy di- sec-butylboron, tetra- tert-butylboron, lithium tetraphe- borane, sodium borohydride, sodium cadium iodide, so- nylboron, potassium hydroxide with trimethylboron, po- 55 dium chloride, sodium calcium chloride, sodium carbide, tassium hydroxide with triethylboron, potassium hydrox- sodium carbonate, sodium hydrogen carbonate, sodium ide with tripropyllboron, potassium hydroxide with tri- iso- carbonate, sodium carbonyl, sodium cobalt (II) cyanide, propylboron, tributylboron, potassium hydroxide with tri- sodium cobalt (III) cyanide, sodium cobaltinitrite, sodium

16 31 EP 0 954 558 B1 32 cynomanganate (II), sodium cynomanganate (III), sodi- thryl, sodium 9-anthryl, sodium 9- methylphenanthryl, so- um citrate, sodium ferrosilicon, sodium ferricyanide, so- dium pyridyl, sodium 2-pyridyl, sodium 3- pyridyl, sodium dium ferrocyanide, sodium nitroferricyanide, sodium am- 6-bromo-2-pyridyl, sodium 5-bromo-2-pyridyl, sodium minepentacyanide, sodium hydride, sodium hydroxide, dibenzofuryl, sodium 3-quinoyl, sodium 2-lepidyl, sodium sodium manganate, sodium permanganate, sodium me- 5 triphenyl- methyl, sodium 2,4,6-trimethylphenyl, sodium thionate, sodium napthenate, sodium nitride, sodium ni- 2,4,6-triisopropyl- phenyl, sodium 2,3,5,6-tetraisopropyl- trate, sodium nitrite, sodium nitrobenzene (e.g. sodium- phenyl, sodium tetrabutyl- phenyl, thiophenedisodium, p- nitrobenzene), sodium nitrophenoxide, sodium ether- toluenedisodium, diphenylethylenedi- sodium, sodiu- ate, sodium chromate, sodium oleate, sodium oxalate, mamylethynyl, sodiumphenylethynyl, sodium- methoxy- sodium oxalatoferrate (II), sodium oxalatoferrate (III), so- 10 bromophenyl, sodium phenylisopropyl, sodium tetraphe- dium monoxide, sodium oxide, sodium peroxide, sodium, nyl- boron, sodium tetramethyl boron, sodium a-thienyl, sodium mono-orthophosphate, sodium hypophosphite, sodium m- trifluoromethylphenyl, phenylethynylsodium, sodium orthophosphite, sodium hydroxoplumbate, sodi- 3-furylsodium, phenylisopropylsodium, dibenzofuranyl- um rhodium cyanide, sodium selenide, sodium selenite, sodium, sodium dimethylbenzyl, sodium selenocyanate, sodium selenocynate, sodium selenocyanoplatinate, so- 15 sodium trimethylsilanolate, diphenyl- phosphide, sodium dium disilicate, sodium metasilicate, lithium sodium car- benzoate, sodium tert-butyl carbonate, sodium azide, di- bonate, lithium sodium ferricyanide, sodium hydroxos- sodiumcyanamide, sodium cyanide, sodium dicyana- tannate, sodium disufide, sodium hydrosulfide, sodium mide, cyclohexanebutyric acid sodium salt, cyclohexane pentasulfide, sodium tetrasulfide, sodium trisulfide, so- acid sodium salt, cyclopentadientylsodium, sodium tri- dium telluride, sodium thioarsenate, sodium thioar- sen- 20 tert-butoxyaluminum hydride, sodiurnaluminum-tri-tert- ite, sodium trithiocarbonate, sodium thiocyanate, sodium butoxide, sodium triethylborohydride, sodium trimethyl- amide, sodium salt (E,E)-2,4-hexadienoic acid, disodium borohydride, sodium tripropylborohydride, sodium triiso- fluorophosphate, disodium fluorophosphite, trisodium propylborohydride, sodium tributylborohydride, sodium phosphate, trisodium phosphite, sodium perchlorate, triisobutylborohydride, sodium tri-sec-butylborohydride, propanoic acid sodium salt, sodium formate, sodium cy- 25 sodium tri-tert-butylborohydride, sodium trisiamylboro- anate, sodium hexacyanocobaltate (III), sodium hypo- hydride, sodium chlorate, sodium tert-butoxide, sodium phosphite, sodium hexaflurorsilicate, sodium nitroprus- sec-butoxide, iso-butoxide, sodium antimonate, sodium side, sodium phenoxide, sodium phosphate (dibasic, diphenylphosphide, sodium bis(trismethyl- silyl) amide, monobasic, tribasic), sodium salicylate, sodium selenide, trisodium phosphite, sodium selenocyanate, sodium tri- sodium tetracyanonickelate (II), sodium tetrafluorobo- 30 sec-butylborohydride, sodium triethylsilanolate, sodium rate, sodium xanthogenate, sodium -p-aminoben- zoate, thiocyanate, sodium acetylide, sodium chlorate, sodium sodium copper ferrocynanide, sodium cupric ferrocya- salicylate, sodium di-sodium tetracarbonylferrate, sodi- nide, sodium hexafluorophosphate, sodium hexanitrico- um tetraphenylborate, sodium triethylborohydride, sodi- baltate III, sodium naphthenate, sodium -B-naphthoxide, um triacetoxyborohydride, sodium triphenylborane, so- sodium polysulfide, lithium - sodium phosphate, sodium 35 dium hydroxide, sodium diphenylphosphide, sodium stearate, sodium sulfide, sodium sulfite, sodium sulfate, methoxide, sodium ethoxide, sodium tri-sec-butylboro- sodium thiocyanate, sodium xanthate, sodium fluorosil- hydride, tri- tert-butylborohydride, sodium triethylborohy- icate, N-sodiumethylenediamine, oxalic acid disodium dride, sodium tri-phenylborohydride, sodium trisiamyl- salt, sodium beta-hydropyruvic acid, sodium 1,1-dimeth- borohydride, sodium metavanadate, sodium cyclohex- ylurea, sodium 1,1-diethylurea, sodium 1,1-diepropylu- 40 anebutyrate, sodium hexachloroplatinate, sodium thio- rea, sodium xanthate, sodium ethylxanthate, sodium cyanate, sodium selenocyanate, sodium cyanate, sodi- methylxanthate, sodium salt thio- phenol, sodium triphe- um floride, sodium hexafluoroantimonate, sodium hex- nylmethylsodium, methylsodium, ethylsodium, sodi- afluoroaluminate, sodium hexafluoroarsenate, sodium umethynyl(acetylide), propylsodium, isopropylsodium, hexafluorosilicate, sodium hexacyanocobalt(II)ferrate butyl-sodium, isobutylsodium, secbutylsodium, tertbutyl- 45 (II), disodiumhexacyanocobalt(II)- ferrate(II), sodium sodium, pentasodium, hexylsodium, heptasodium, amyl- hexafluorotitanate, sodium hexafluorozirconate, sodium sodium, isoamylsodium, benzylsodium, dimethylbenzyl- hexahydroxyantimonate, sodium hexachlororuthenate, sodium, tolylsodium, dodecylsodium, cyclopentadienyl- sodium hexachloropalladate, sodium formate, sodium sodium, methylcyclopentadienylsodium, cyclohexyl-so- tetracyanonickelate, sodium tetrafluoroaluminate, sodi- dium, sodiumheptyl, sodiumdodecyl, sodium tetradecyl, 50 um tetrafluoroborate, sodium thioacetate, L-glutamic ac- sodium hexadecyl, sodium octadecyl, phenylsodium, so- id monosodium salt, fumaric acid sodium salt, oxamic dium o-tolyl, sodium m-tolyl, sodium p-tolyl, sodium-p- acid sodium salt, sodium salt diphenyl-phospane, P-ami- chlorophenyl, sodium p-bromo- phenyl, sodium sodium nobenzoic sodium salt, aminobenzole acid sodium salt, o- anisyl, sodium m-anisyl, sodium p-anisyl, sodium di- alpha-napthaleneacetic acid sodium salt, disodium salt ethoxyphenyl, sodium dimethoxyphenol, sodium m- 55 2,6-naphthalenedicarboxlic acid, sodium cyclcohexane- cumyl, sodium p-ethoxyphenyl, sodium m-dimethylami- therate, sodium phthalimide, P-aminosalicylic acid sodi- nophenyl, sodium 9- flourene, sodium a-napthyl, sodium um salt, sodium salt 3,5-dimethylcyclohexyl sulfate, in- b-napthyl, sodium p-phenyl- phenyl, sodium 9-phenylan- dolebutyric acid sodium salt,indole-3-butyric acid sodium

17 33 EP 0 954 558 B1 34 salt, diphenylphosphide, sodium dimethylsilanolate, so- ate, sodium pyrophosphate, sodium selenate, sodium dium triethylborohydride, sodium propoxide, sodium iso- selenite, sodium tetrachloroaluminate, sodium thiometh- propoxide, sodium butoxide, sodium sec-butoxide, sodi- oxide, sodium thiosulfate, sodium thiosulfide, sodium thi- um pentoxide, sodium tert-pentoxide, sodium hydrogen- osulfite, sodium tri- actoxyborohydride, sodium sodium phthalate, sodium oxalate, sodium hydrogensulfate, 5 trimethylsilonate, sodium triethylsilonate, sodium tris(1- monosodium acetylenedicarboxylic acid, sodium pyro- pyrazoly)borohydride, including analogues, homo- phosphate, sodium dihydrogenphosphate, sodium hex- logues, isomers and derivatives thereof. oate (sodium salt hexoic acid), sodium diphenylphos- [0096] The non limiting examples of aluminum deriv- phide, sodium trimethylsilonalate, sodium phthalic acid, ative compounds of this invention include: diisobutylalu- P-aminobenzoic acid sodium salt, monosodium L-aspar- 10 minum hydride, dimethylaluminum hydride, dimethylalu- tic acid, tetraphenyldisodium (C6H5)2-CLi2C(C6H5)2, minum hydride, dipropylaluminumhydride, diisopropyla- sodiumethylphenyl (LiCH2C6H5), sodium bromate, so- luminumhydride, dibutylaluminumhydride, di-tert-butyla- dium hydrogenphospate, monsodium salt D-shaccharic luminum hydride, di-sec-butylaluminum hydride, di-iso- acid, Dl-asparatic sodium salt, (R)-alpha-hyroxymethyl- butylaluminum chloride, ethylaluminum sesquichloride, aspartic acid sodium salt, sodium fluoride, sodium iodate, 15 lithium aluminum hydride, lithium tri-tert-butoxyalumi- sodium salt ethyl malonate, sodium thioacetate, sodium num hydride, lithiumaluminum alloy, aluminum triethox- phenol, sodium salt aminobenzoic acid, sodium ami- ide, aluminum trimethoxide, aluminum tripropoxide, alu- nophenol salt, sodium cyclohexenol, sodium methylcy- minum triisopropoxide, aluminum tri-tert-butoxide, alumi- clohexenol, sodium cyclopropanol, sodium methylcyclo- num tri-sec-butoxide (aluminum sec-butoxide), alumi- propanol, sodium cyclobutanol, sodium methylcyclobu- 20 num tri-isobutoxide, aluminum tributoxide, aluminum tanol, sodium methylcyclopentanol, sodium cyclopenta- pentoxide, diethylaluminum ethoxide, aluminum phos- nol, sodium cyclohexenol, sodium methylcyclohexenol, phate, diethylaluminum chloride, diethylaluminum cya- sodium dimethylcyclohexenols (e.g. sodium 3,5-dimeth- nide, diethylaluminum ethoxide, diethylaluminum meth- ylcyclohexanol, sodium 2,3-dimethylcyclohexanol, sodi- oxide, diisobutylaluminum hydride, diisobutylaluminum um 2,6-dimethylcyclohexanol, sodium 2,5-dimethylcy- 25 chloride, diisobutyalumnum fluoride, tetraisobutyl-dialu- clohexanol, 3,5-dimethylcyclohexanol), sodium o-ethyl- minoxane, triethylaluminum, trimethylaluminum, tributyl- xanthic acid, monosodium salt 2-ketoglutaric acid, diso- aluminum, triisobutylaluminum, tri-sec-butylaluminum, dium salt, ketomalonic acid, sodium salt lactic acid, dis- tri-tert- butylaluminum, tripentaluminum, triphenylalumi- odium thiosulfate, sodium antimony tartrate, sodium num, triamylaluminum, triisoamylaluminum, tripropylalu- dichloroacetate, sodium dimethylacetate, sodium diethy- 30 minum, triisopropylaluminum, triisobutylaluminum, tri- lacetate, sodium dipropylacetate, sodium metaborate, isobutyldialuminoxane, trioctylaluminum, sodium alumi- sodium tetraborate, sodium tetrachlorocuprate, sodium num hydride, bis(2-methoxyethoxy)aluminum hydride, acetoacetate, sodium diisopropylamide, sodium diethy- aluminum borohydride, aluminum hydride, dimethlylbe- lamide, sodium dimethylamide, sodium bis(dimethylsilyl) ryllium, potassium tri-tert-butoxyaluminum hydride, sodi- amide, disodium phthalocyanine, disodium- tetrabromo- 35 um tri-tert- butoxyaluminum hydride, lithium tri-tert-bu- cuprate, disodium tetrabromonickelate, disodium- tetra- toxyaluminum hydride, aluminum sec butoxide, alumi- chloromanganate, disodiumbutadiyne, sodium cy- num tert-butoxide, aluminum acetyl- acetone, aluminum clopentadienide, sodium dicyclohexylamide, sodium di- ethoxide, aluminum methoxide, aluminum propoxide, ethylamide, sodium dimethylamide, sodium dipropyla- aluminum isopropoxide, aluminum butoxide, aluminum mide, sodium diisopropylamide, sodium thexylborohy- 40 isobutoxide, aluminum pentoxide, aluminum metaphos- dride, sodium tri-tert-butoxyaluminohydride, sodium tri- phate, aluminum hydroxide, aluminum metaphosphite, methylsilyl)acetylide, sodium triethylsilyl)acetylide, sodi- aluminum monostearate, aluminum hydroxys- tearate, um tris[(3-ethyl-3-pentyl)oxy]aluminohydride, (phe- aluminum nitrate, aluminum fluoride, aluminum fluoride nylethynyl)sodium, 2-thienylsodium, sodium trihydrate, sodium diethyldihydroaluminate, sodium hex- diethyldihydroaluminate, sodium dimethyldihydroalumi- 45 afluoro- aluminate, aluminum hexafluorosilicate, lithium nate, sodium aluminum hydride, sodium bifluoride, sodi- aluminum hydride, lithium aluminum hydride bis(tetrahy- um biphenyl, sodium biselenite, sodium bis(2-methox- drofuran), lithium tris((3- thyl-3-pentyl)oxy)aluminohy- yethoxy)- aluminum hydride, sodium bismuthate, sodium dride, lithium tri-tert-aluminohydride, aluminum-nickel borate, sodium chlorite, sodium cobaltnitrite, sodium cy- catalyst, aluminum silicate, aluminum silicate hydroxide, anoborohydride, sodium cyclopentadienide, sodium di- 50 aluminum chloride hydrate, diethylaluminum chloride, cyanamide, sodium hexametaphosphate, sodium hex- sodium bis(2-methoxyethoxy)aluminum dihydride, alu- anitrocolbaltate, sodium hydrogenphosphite, sodium hy- minum carbide, aluminum phosphate, aluminum acetate drogenselenite, sodium hydrogensulfite, sodium hydro- (aluminum diacetate hydr- oxide), dihydroaluminum ac- sulfite, sodium hypochloride, sodium metaarsenite, so- etate, aluminum formoacetate, lithium aluminate, alumi- dium metabisulfide, sodium metaperiodate, sodium 55 num salt lactic acid, tetra methyllith iuma lumi num salt methacrylate, sodium nitro- ferricyanide, oxybate, sodi- (LiAI(CH3)4), tetaethyllithiumaluminum salt, tetrapropyl- um pentamethylcyclopentadienide, sodium phenolate, lithiumaluminum salt, tetraisopropyllithiumaluminum polyphosphate, sodium polyphosphite, sodium propion- salt, tetra- butyllithiumaluminum salt, tetraisobutyllithiu-

18 35 EP 0 954 558 B1 36 maluminum salt, tetra-sec-butyllithiumaluminum salt, tet- zane, [1,1’-biphenyl]-4-yltrichlorosilane, (bromomethyl) ra-tert-butyl- lithiumaluminum salt, tetraphenyllithium chlorodimethylsilane, bromomethyltrimethylsilane, (4- aluminum salt, aluminum tririconoleate, aluminum met- bromophenoxy)trimethylsilane, butylchlorodimethylsi- aphosphate, sodium aluminum hydride, aluminum do- lane, trichlorobutylsilane, trimethylbutylsilane, chloro decaboride, aluminum diboride, aluminum arsenide, alu- 5 (chloromethyl)dimethyl- silane, chloro(dichloromethyl) minum lactate, aluminum titanium chloride, tri(N-nitroso- dimethylsilane, chlorodimethylphenyl- silane, chlo- N-phenylhydroxylaminoato)aluminum, aluminum acety- rodimethyl-2-propenylsilane, chloroethenyldimethyl- si- lacetonate, methylaluminum dichloride, ethylaluminum lane, chloromethylsilane, (chloromethyl)dimethylphenyl- dichloride, propylaluminum dichloride, isopropylalumi- silane, chloromethyldiphenyfsilane, chloromethylphe- num dichloride, butylaluminum dichloride , sec-butylalu- 10 nylsilane, (chloromethyl)trimethylsilane, (4-chlorope- minum dichloride, tert-butylaluminum dichloride, isobuty- hoxy)trimethylsilane, phenyl-chlorosilane, (3-chlorophe- laluminum dichloride, phenylaluminum dichloride, ethyl- nyl)trimethylsilane, (3-chloropropyl)-trimethylsilane, aluminum sesquichloride, methylaluminum sesquichlo- chlorotriethoxysilane, chlorotriethylsilane, trimethylchlo- ride, methylaluminoxane, propylaluminum sesquichlo- rosilane, dichloro(chtoromethyl)methylsilane, dichloro ride, ethylaluminoxane, sodium bis(2-methoxyethoxy) 15 (dichloromethyl)methylsilane, dichlorodiethoxysilane, aluminum, aluminum magnesium silicate, aluminum hy- dichlorodiethylsilane, dichlorodimethylsilane, dichlo- droxychloride, aluminum phosphide, aluminum potassi- rodiphenyl- silane, dichloroethenylmethylsilane, methyl- um sulfide, aluminum stearate, aluminum octoate (alu- ethyldichlorosilane, dichloromethylsilane, dichlorome- minum ethylhexonate), aluminum diformate, aluminum thyl(1-methylethyl)silane, dichloromethyl(4-methylphe- triformate, aluminum chromate, aluminum napthenate, 20 nyl)silane, dichloromethylphenylsilane, dichloromethyl- aluminum oleate, aluminum palmite, aluminum pictrate, 2-propenylsilane,dichlorophenylsilane, diethenyldiphe- aluminum sodium silicate, aluminum sodium chloride, nylsilane, diethoxydimethylsilane, diphenyldiethoxysi- aluminum isopropylate, aluminum magnesium ethoxide, lane, diethoxymethylphenylsilane, diethyloxymethyl-2- trimethylaluminum etherate, triethylaluminum etherate, propenylsilane, diethylsilane, diethyldifluorosilane, dif- including analogues, homologues, isomers and deriva- 25 luorodiphenylsilane, dimethyoxydimethylsilane, dimeth- tives thereof. Corresponding compounds of gallium, in- oxydiphenylsilane, dimethylsilane, dimethyldiphenoxysi- dium, thallium are contemplated in the practice of this lane, dimethyldiphenylsilane, dimethyl-2-propenylsi- invention. lane, dimethylphenylsilane, dimethyl-diacetatesilane, [0097] The non-limiting examples of silicon derivative diphenylsilane, 1,2,-ethenediylbis[trimethyl-(E)]silane compounds of this invention include: dimethoxymethyl- 30 (C8H20Si2), ethenyldiethoxymethylsilane, ethe- silane, dimethoxyethylsilane, diethoxymethylsilane, nylethoxydimethylsilane, ethenyltriethoxysilane, ethe- dipropoxymethylsilane, diisopropoxymethylsilane, dibu- nyltrimethylsilane, ethenyltris(1-methyl- ethoxy)-silane, toxymethylsilane, diisobutoxymethylsilane, di-sec-bu- ethenyltris(2-propenyloxy)silane, ethoxytriethyl- silane, toxymethylsilane, di-sec-butoxymethylsilane, diethox- ethoxytrifluorosilane, ethoxytrimethylsilane, ethoxytri- yethylsilane, dipropoxyethylsilane, diisopropoxyethylsi- 35 phenylsilane, ethyltrifluorosilane, ethyltrimethoxysilane, lane, dibutoxyethylsilane, diisobutoxyethylsilane, di-sec- 1,2,- ethynediylbis[trimethyl]-silane, ethynylsilane, meth- butoxyethylsilane, di-sec-butoxyethylsilane, diethoxy- oxysilane, methylsilane, methyldiphenylsilane, methyl- dimethylsilane, dimethoxydi- methylsilane, dipropoxy- enebissilane, methylene- bis[trichloro]silane, (2-methyl- dimethylsilane, diisopropoxydimethylsilane, dibutoxy- phenoxy)triphenylsilane, methyl- phenylsilane, methylt- dimethylsilane, diisobutoxydimethylsilane, di-sec-butox- 40 riphenoxysilane, methyltriphenylsilane, methyltri-p-toly- ydimethylsilane, di-sec-butoxydimethylsilane, di- silane, phenylsilane, [1,3-phenylenebis(oxy)]bis- [trime- ethoxymethylethyl- silane, ethoxytrimethylsilane, ethox- thyl]silane, phenyltripropylsilane, tetra-ethenylsilane, ytriethylsilane, ethoxytri- propylsilane, ethoxytriispropyl- tetraethylsilane, tetraethoxysilane, tetramethylsilane, silane, methoxytrimethylsilane, propoxytrimethylsilane, tetra- methoxysilane, tetrapropylsilane, tetrapropoxysi- isopropoxytrimethylsilane, butoxytrimethyl- silane, iso- 45 lane, tetraisopropylsilane, tetraisopropoxysilane, butoxytrimethylsilane, sec-butoxytrimethylsilane, sec- tetrabutylsilane, tetra-butoxysilane, tetra-sec-butylsi- butoxytrimethylsilane, phenoxytrimethylsilane, ethoxydi- lane, tetra-sec-butoxysilane, tetra- tert-butylsilane, tetra- ethytsilane, isobutyldiethoxysilane, sec-butyldiethoxysi- tert-butoxysilane, tert-iso-butylsilane, tetra-iso-butoxysi- lane, butyldiethoxy- silane, tertbutyldiethoxysilane, lane, tetraphenylsilane, tetraphenoxysilane, triethylsi- pentyldiethoxysilane, isobutyl- dimethoxysilane, 50 lane, triethoxysilane, trimethylsilane, trimethoxysilane, secbutyldimethoxysilane, butyldimethoxysilane, tert- tripropylsilane, tripropoxysilane, triisopropylsilane, triiso- butyltrimethoxysilane, methyltrimethoxysifane, methyl- propoxysilane, tributylsilane, tributoxysilane, tri-sec- triethoxysilane, pentyldimethoxysilane, diethylsilandiol, butyl- silane, tri-sec-butoxysilane, tri-tert-butylsilane, tri- tripropylsilan- diol, triisopropylsilandiol, tertbutyldimeth- tert- butoxysilane, tert-iso-butylsilane, tri-iso-butoxysi- ylsilane, diethyl- silanediol (C2H5Si(OH)2), methyl- 55 lane, tripheny- Isilane, triphenoxysilane, triethylmethylsi- tripropoxysilane, methyltris(dimethylsiloxy)silane, 1,1- lane, triethoxymethyl- silane, trimethoxymethylsiiane, diphenylsilacyclohexane, pentamethylsilanime, 1,1,1- tripropylmethylsilane, tripro- poxymethylsilane, triisopro- trimethyl-N-phenyl-N-silanamine, hexamethyldisila- pylmethylsilane, triisoproxymethylsilane, tributylmethyl-

19 37 EP 0 954 558 B1 38 silane, tributoxymethylsilane, tri-sec- butylmethylsilane, zane, ethenylhep- tamethylcyctetrasiloxane, ethenyl- tri-sec-butoxymethylsilane, tri-tert-butyl- methylsilane, heptamethylcyctetrasilazane, heptamethylcyclotetrasi- tri-tert-butoxymethylsilane, tert-iso-butylmethyl- silane, foxane, heptamethylcyclotetrasilazane, octaphenylcy- tri-iso-butoxymethylsilane, triphenylmethylsilane, triphe- clotetrasiloxane, butylmethyl(cyclic tetramer)siloxane, noxymethylsilane, diethylsilane, diethoxysilane, dime- 5 2,4,6,8-tetraethenyl-2,4,6,8-tetramethylcyclotetrasi- thyl- silane, dimethoxysilane, dipropylsilane, dipropox- loxane (C12H2404Si4), 2,4,6,8-tetraethyl-2,4,6,8-cy- ysilane, di- isopropylsilane, diisopropoxysilane, dibutyl- clotetrasiloxane, 2,4,6,8-tetraethyl-2,4,6,8-cyclotet- silane, dibutoxysilane, di-sec-butylsilane, di-sec-butox- rasilazane, 2,4,6,8-tetraethyl- 2,4,6,8-cyclotetrasi- ysilane, di-tert-butylsilane, di- tert-butoxysilane, tert-iso- loxane, 2,4,6,8-tetramethylcyclotetrasiloxane, 2,4,6,8- butylsilane, di-iso-butoxysilane, diphenylsilane, diphe- 10 tetra methylcyclotetrasilazane, 2,4,6,8-tetramethyl- noxysilane, ethylsilane, ethoxysilane, methylsilane, 2,4,6,8-tetraphenylcyclotetrasiloxane, 2,2,4,4,6,6-hex- methoxysilane, propylsilane, propoxysilane, iso- propyl- amethyl- cyclotrisilazane, hexamethylcyclotrisiloxane, silane, isoproxysilane, butylsilane, butoxysilane, sec-bu- 2,4,6-triethyl-2,4,6-trimethylcyclotrisiloxane, 2,4,6-trie- tylsilane, sec-butoxysilane, tert-butylsilane, tert-butox- thyl-2,4,6-trimethyl- cyclotrisiloxane, 2,4,6-triethyl-2,4,6- ysilane, iso-butylsilane, iso-butoxysilane, phenylsilane, 15 triphenylcyclotrisiloxane, 2,4,6-trimethyl-2,4,6-tripehnyl- phenoxysilane, tribromomethylsilane, tributylsilane, trib- cyclotrisiloxane, decamethyl- cyclopentasiloxane, utylphenylsilane, trichloro(chloromethyl)silane, trichloro decamethylcyclopentasilazane, 2,4,6,8,10-pentameth- (4-chforophenyl)silane, trichloro(3-chloropropyl)silane, ylcyclopentasiloxane, 2,4,6,8,10-pentamethylcyclopen- trichloro(dichloromethyl)silane, trichlorododecylsilane, tasilazane, octademethylcyclononasiloxane, octa- trichloroethenylsilane, trichloroethoxy- silane, trichlo- 20 demethylcyclononasilazane, hexadecamethylcy- roethylsilane, trichlorohexylsilane, trichloromethy- Isi- clooctasiloxane, hexadecamethyl- cyclooctasilazane, lane, trichloro(1-methylethyl)silane, trichloro(2-methyl- dodecamethylcyclohexasiloxane, dodecamethyl- cy- phenyl)silane, trichloro(3-methylphenyl)silane, trichloro clohexasilazane, hexamethylcyclohexasiloxane, tetra- (2- methylpropyl)silane, trichlorootadectylsilane, trichlo- decamethyl- cycloheptasiloxane, tetradecamethylcy- rooctyl- silane, trichloropentylsilane, trichlorophenylsi- 25 cloheptasilazane, decamethyl- tetrasiloxane, lane, trichloro(2- phenylethyl)silane, trichloro-2-prope- 1,1,1,3,5,7,7,7-octamethyltetrasiloxane, aminotri- si- nylsilane, trichloropropylsilane, triethoxysilane, triethox- lane, benzyltriethoxysilane, butyltrifluorosilane, carbox- yethylsilane, triethoxyethylsilane, triethoxyphenylsilane, yethyl- dimethylsilane, chloromethylsilicane, chlorotriiso- triethoxypentylsilane, triethoxy-2-propenylsilane, tri- cyanatesilane, dichloromethylsilicane, diethoxydibutox- ethylsilane, triethylfluorosilane, triethylphenylsilane, trif- 30 ysilane, diethylaniline- fluorosilicate, diethyldichlorosi- luorophenylsilane, trimethoxymethylsilane, trimethox- lane, [2-(cyclohexenyl)ethyl]tri- ethoxysilane, [2-(cy- yethylsilane, trimethoxypropylsilane, trimethoxyisopro- clohexenyl)ethyl]methyldiethoxysilane, [2-(cyclohexe- pyfsilane, trimethoxybutylsilane, trimethoxyisobutylsi- nyl)ethyl]dimethylethoxysilane, [2-(cyclohexenyl)-ethyl] lane,trimethoxy-sec-butylsilane, trimethoxy-tert-butylsi- trimethylsilane, [2-(cyclohexenyl)ethyl]triethylsilane, cy- lane, trimethoxyphenylsiiane, trimethylsilane, trimethyl 35 clohexyldimethoxymethylsilane, cyclohexylmethoxy- (4-methylphenyl)-silane, trimethyl(2-methylpropyl)si- dimethylsilane, cyclohexyltrimethylsilane, cyclohexyltri- lane, trimethylphenoxysilane, trimethylphenylsilane, tri- ethylsilane, dicyclohexyldimethylsilane, cyclohexyld- methyl(phenylmethyl)silane, trimethyl(cyclohexylme- imethylsilane, cyclohex-1-enyl-trimethylsilane, benzyltri- thyl)silane, trimethyl-2-propenylsilane, trimethylpropylsi- methylsilane, (1-cyclohexen-1-ylethynyl)trimethylsilane, lane, trimethyl[4-[(trimethylsilyl)oxy]phenyl]silane, ethe- 40 1-cyclohexenyltrimethylsilane, cyclohexenyloxytrimeth- nyltriacetatesilanetriol, methyltriacetatesilantriol, tripro- ylsilane, cyclohexyltrichlorosilane, 1-cyclopropyl-1-(tri- pylsilane, ethyldimethylsilanol, methyldiphenylsilanol, methy-Isilyloxy)ethylene, phenyldimethylsilanol, phenyl- triethylsilanol, triphenylsilanol, tetrabutyl ester silicic acid silandiol, cyclohexylsilandiol, cyclohexylethylsilandiol, (C16H3604Si), tetraethyl ester silicic acid, tetrakis(2- tert-butylsilandiol, cyclohexyldimethylsilanol, cyclohexy- ethylbutyl) ester silicic acid, methylsilicate (C4H12SiO4), 45 ldiethylsilanol, benzyltrimethylsilane, N-benzyltrimethyl- tetraphenyl ester silicic acid, tetrapropyl ester silicic acid, silylamine, phenyl dimethylsilanol, phenyl diethylsilanol, triethyl phenyl ester silicic acid, 1,2-dichloro-1,1,2,2-te- cyclohexylethylenetrimethylsilane, N-cyclohexylethylen- tramethyldisilane, 1,2,-difluorotetramethyldisilane, hex- etrimethylsilylamine, cycloethylenetrimethyl- silane, ameth.yldisilane, 1,3-diethenyl-1,1,3,3-tetramethyldisi- diphenyldiethoxysilane, diphenyldimethoxysilane, loxane, 1,3-diethenyl-1,1,3,3-tetramethyldisilazane, 50 diphenyl- methylethoxysilane, diphenylmethylsilane, bis-(methoxydimethylsilyl)-oxide, 1,1,1,3,3,3-hexaethyl- diphenylmethylsilandiol, diphenylsilandiol, methyl-phe- disiloxane, 1,1,1,3,3, 3-hexaethyldisilazane, hexameth- nyl-diethoxysilane, methyl-phenyl-dimethoxysilane, me- yldisiloxane, hexamethyl- disilazane, 1,1,3,3-tetrameth- thyl-phenyl-dichlorosilane, octadecyltrimethoxysilane, yldisiloxane, 1,1,3,3-tetramethyl- disilazane, 1,1,3,3-te- octyltriethoxysilane, octyltrimethoxysilane, 1,3- bis(3- tramethyl-1,3-diphenyldisiloxane, 1,1,3,3- tetramethyl- 55 aminopropyl)-1,1,3,3-tetramethyldisiloxane, 1,3-bis(3- 1,3-diphenyldisilazane, 1,1,1-trimethyl-3,3,3-tri- phe- aminopropyl)-1,1,3,3-tetramethyldisiiazane, tertbutyld- nyldisiloxane, 1,1,1-trimethyl-3,3,3-triphenyldisilazxane, imethylsilan- diol, hydroxymethylenetrimethylsilane docosamethyldecasiloxane, docosamethyldecasila- (CH3)3CH2OH), hydroxyethylenetrimethylsilane, hy-

20 39 EP 0 954 558 B1 40 droxymethyltriethylsilane, hydroxyethyltriethylsilane,di- lane, allyloxy-iso-butyldimethylsilane, allylchlorodiethyl- ethylsilanediol, dimethylsilanediol, dipropylsilanediol, di- silane, allylchloromethyldiethylsilane, allyldichloro- di- isopropylsilanediol, dibutylsilanediol, di- tert-butylsilane- ethylsilane, allyl(diisoproprylamino)diethylsilane, ally- diol, di-iso-butylsilanediol, di-sec-butyl- silanediol, diphe- loxy- tert-butyldiethylsilane, allyloxy-sec-butyldiethylsi- nylsilanediol, dicyclohexylsilanediol, cyclohexyl- methyl- 5 lane, allyloxy- iso-butyldiethylsilane, allyloxybutyldimeth- silanediol, cyclohexylethylsilanediol, dimethoxydichloro- ylsilane, allyloxy- trimethylsilane, allyloxytriethylsilane, silane, dimethyfanilineflourosilicate, dimethyldi(B-chlo- diallyloxydimethylsilane, triallyloxymethylsilane, dially- roethoxy)- silane, dimethylflourochlorosilane, dimethyl- loxydiethylsiiane, triallyloxyethyl- silane, diallyloxy- silicane, di-a-napthylamineflourosilicate, di-b-napthyl- dimethoxylsilane, triallyloxymethoxylsilane, diallyloxydi- amineflourosilicate, di-m-nitranilineflourosilicate, dini- 10 ethoxylsilane, triallyloxyethoxylsilane, allyltri- chlorosi- trosodiphenylamine, diphenylarsinophenylenetriethylsi- lane, allyltriethoxysilane, allyltriisopropylsilane, allyl- lane, diphenyldichlorophenoxysilane, di-o-toluidinefluor- tripropylsilane, allyltriisopropyloxysilane, allyl- tripropy- osilicate, di-m-toluidinefluorosilicate, di-p-toluidinefluor- loxysilane, allyltrimethoxysilane, allyltrimethylsilane, al- osilicate, docosamethyldecasiloxane, dodecamethylcy- lyltriethylsilane, allyltriphenylsilane, 3-aminopropyltri- clohexasifoxane, dodecamethylpentasiloxane, ei- 15 ethoxy- silane, 3-aminopropyltrimethoxysilane, 3-ami- cosamethylnonasiloxane, silanesilanesilanedocosa- noethyltriethoxysilane, 3-aminoethyltrimethoxysilane, 3- methyldecasilazane, dodecamethylcyclohexasilazane, aminomethyltriethoxysilane, 3- aminomethyltrimethox- dodecamethylpentasilazane, eicosamethylnonasila- ysilane, 3-aminotrimethoxysilane, 3-aminotri- ethoxysi- zane, ethyldiethoxyacetoxysilane, ethyldiethoxychloro- lane, 3-amino(cyclohexyl)propyltriethoxysilane, 3-ami- silane, ethylisocyanatesilane, ethyltriethoxysilane, ethyl- 20 no-(cyclohexyl)propyltrimethoxysilane, 3-amino(cy- tri- phenylsilicane, hexadacamethylcyclooctasiloxane, clohexyl)ethyltriethoxysilane, 3-amino(cyclohexyl)ethyl- hexadacamethyl- cyclooctasilazane, hexamethylsili- trimethoxysilane, 3-amino(cyclohexyl)methyltriethoxysi- cane (hexamethyldisilane), hexamethylmethylenedis- lane, 3-amino(cyclohexyl)-methyltrimethoxysilane, 3- lane, hydroxymethyltrimethylsilane, methyl- silicane, amino(cyclohexyl)trimethoxysilane, 3-amino(cytco- methyltriphenylsilicane, octadecamethylcotasiloxane, 25 hexyl)triethoxysilane, trimethoxypropylsilane, triethoxy- octamethylcyclotetrasiloxane, octamethyltrisiloxane, oc- propylsilane, trimethoxysilane, 3-aminopropyltrimethox- tadeca- methylcotasilazane, octamethylcyclotetrasila- ysilane, N-[3-(trimethoxysiiyl)propyl]aniline, N-[3-(tri- zane, octa- methyltrisilazane, tetraphenylenesilane, ethoxysilyl)propyl], aniline, N-[3-(triethoxysilyl)ethyl]ani- phenylenediamineflouro- silicate, phenylisocyanatesi- line, N’-[3-(trimethoxysilyl)propyl]diethylenetriamine, lane, phenyltrichlorosilicane, silicobenzoic acid, tetra-m- 30 N-[3-(trimethoxysilyl)propyl]-ethylenediamine, N-[3-(tri- aminophenylsilane, tetrabenzylsilicane, tetra-p-bipheny- ethoxysilyl)propyl]ethylenediamine, 3-(trimethoxysilyl) lytsilane, tetradecamethylcycloheptasiloxane, tetra- propyl methacrylate, 3-(triethoxysilyl)propyl methacr- decamethylcycloheptasilazane, tetradecamethylhexasi- ylate, aminotriphenylsilane, azidotrimethylsilane, azidot- loxane, tetradecamethylhexasilazane, tetraethylsilane, riethylsilane, azidotripropylsilane, azidotributylsilane, tetraethyl- thiosilane, tetrahexyloxysilane, tetraisopro- 35 azidotrimethoxysilane, azidotriethoxysilane, azidotripro- pylmercaptane silicon, tetramethoxysilane, tetramethyl- poxysilane, azidotributoxysilane, bis[3-(trimethoxysilyl) mercaptanesilicon, tetramethyl- silane, tetraphenoxysi- propyl]amine, N,O-bis(trimethylsilyl)acetamide, bis(tri- lane, tetraphenylsilane, tertapropoxysilane, tetratriethyl- methylsilyl)acetylene, bis(trimethylsilyl)cyclopentadi- siloxysilane, thioisocyanatotriethylsilane, tolidinefiuoro- ene, 1,4-bis(trimethylsilyl)benzene, N,O-bis(trimethylsi- silicate(o), tri-p-Biphenylylphenylsilane, trichloromethyl- 40 lyl)hydroxylamine, bis(trimethylsilyl)methane, 2,3-bis(tri- triethoxysilane, triethylbromosilane, triethylchlorosilane, methylsilyloxy)-1,3-butadiene, 1,2-bis(trimethylsilyloxy) triethylfluorosilane, triethylphenylsilane, trimethylchlo- cyclobutene, 1,2-bis(trirnethylsilyi)cyclobutene, 1,2,3- romethyl- silane, trimethylethoxysilane, triphenylacetox- bis(trimethylsilyl)cyclobutene, 1,2,3,4-bis(trimethylsilyl) ysilane, vinyltri- phenoxysilane, vinyltriethoxysilane, sili- cyclo- butene, bis(trimethylsilyl)cyclobutene, 1,2-bis(tri- cane cyanate, dibromo- silane, dibromodichlorosilane, 45 methylsilyl- oxy)ethane, 2,3-bis(trimethylsilyl)-1-pro- dichlorosilane, dichlorodifluoro- silane, hexaoxocyclosi- pene, 2,4-bis(trimethyl- silyloxy)pyrimidine, 1,3-bis(tri- lane, hexacyclosilazane, monooiodosilane, (tri-)nitrilosi- methylsilyl)urea, O,O’-bis(tri- methylsilyl)uracil, bis(tri- lane (silicylamine), trichlorosilane, tri-fluorosilane, sili- methylsilyl)trifluoroacetamide, (1- cyclohexenyl-1-ethy- cane diimide (Si(NH)2), silicane tetramide, silicane iso- nyl)trimethylsilane, 1-cyclohexenyloxytrimethyl- silane, cyanate, silicon tetracetate, tetrabromosilane, silicon hex 50 1-cyclohexyltrimethylsilane, cyclohexyldimethoxysilane, (di-)bromide, silcon carbide, tertachlorosilane, hexachlo- cyclohexyltrimethoxysilane, cyclohexyldiethoxysilane, rodi- silane, tetrafluorosilane, hexafluorodisilane, silicon cyclohexyltriethoxysilane, cyclohexyldimethoxymethyl- hydride (SiH4), disilane (Si2H6), trisilanepropane, tet- silane, cyclohexyltrimethoxysilane, cyclohexyldi- rasilane butane, silicon nitride, silicon thiocyanate, disil- ethoxymethylsilane, cyclohexyltriethoxysilane, cy- icic acid, silicon cyanate, allylchlorodimethylsilane, al- 55 clohexyldimethoxysilandiol, cyclohexyldiethoxysilandiol, lylchloromethyldimethylsilane, allyldichlorodimethylsi- cyclohexyldipropxymethylsilane, cyclohexyldipropxy- lane, allyl(diisoproprylamino)dimethylsilane, allyloxy- methylsilandiol, cyclohexyltrichlorosilane, [(1-cyclopro- tert-butyldimethylsilane, allyloxy-sec-butyldimethylsi- pyletheneyl)oxy]trimethylsilane, diallyldimethylsilane, di-

21 41 EP 0 954 558 B1 42 ethoxymethylphenylsilane, 3-(diethoxymethyfsilyl)pro- bis(chloromethyl)-1,1,3,3-tetramethyldisilazane, 1,3-bis pylamine, diethoxymethylsilane, dimethyloctadecyline, (chloromethyl)- 1,1,3,3-tetramethyldisiloxane, 1,2-bis ethyltriacetoxysilane, methyltriacetoxysilane, propyl- (chlorodimethylsilyl)ethane, 1,3-bis(3-cyanopropyl)te- triacetoxysilane, isopropyltriacetoxysilane, butyltriace- tramethyldisiloxane, 1,3-bis(3-cyanopropyl)tetramethyl- toxysilane, isobutyltriacetoxysilane, sec-butyltriacetox- 5 disilazane, bis(diethylamino)dimethylsilane, bis(dimeth- ysilane, tert-butyltriacetoxysilane, benzyltriacetoxysi- ylamino)dimethylsilane, bis(diethylamino)diethylsilane, lane, phenyltriacetoxysilane, cyclpentadienyltriacetox- bis(dimethylamino)diethylsilane, 1,2-bis[(dimethylami- ysilane, cyclohexyltriacetoxysilane, isopropoxytrimethyl- no)dimethylsilyl]ethane, 1,2-bis(dimethylsilyl)benzene, silane, isopropylaminotrimethylsilane, lithium bis(tri- 1,2-bis(dimethylsilyl)cyclohexene, 1,4-bis(dimethylsilyl) methylsilyl)amide, methoxydimethyloctylsilane, methyl- 10 benzene, 1,4-bis(dimethylsilyl)cyclohexene, 1,3-bis(4- bis(trimethylsilyloxy)vinyl- silane, octyltriethoxysilane, hydroxybutyl)-1,1,3,3-tetramethyldisiloxane, 1,3-bis(4- octyltrimethoxysilane, (phenylthiomethyl)trimethylsi- hydroxybutyl)-1,1,3,3-tetramethyldisilazane, bis(N- lane, phenyltriethoxysilane, phenyltrimethoxysilane, po- methylbenzamido)methylethoxysilane, 1,4-bis(trime- ly(dimethylsiloxane) silicon hexaboride, silicon nitride, thyl- silyl)butadiyne, N,O-bis(trimethylsilyl)acetimide, N, silicon tetracetate, silicon tetrachloride, silicon tetrafluo- 15 N-bis(tri- methylsilyl)methylamine, N,N-bis(trimethylsi- ride, sodium bis(trimethylsilyl)amide, tetrakis- (trimethyl- lyl)amine, N,N-bis(tri- ethylsilyl)amine, N,N’-bis(trimeth- silyl)silane, tetravinylsilane, trichloro-3-chloropropyl- si- ylsilyl)urea, bis(trimethyl- silyl)phosphite, N,O-bis(tri- lane, trichlorocyclopentysilane, cyclohexyltrichlorosi- methylsilyl)trifluoroacetimide, tert- butyldimethylsilane, lane, trichlorovinylsilane, 3-(triethoxysilyl)propionitrile, tert-butyldimethylsilanol, (tert-butyldimeth- silyl)acety- 3-(tri- methoxysilyl)propylamine, 3-(trimethoxysilyl)pro- 20 lene, tert-butyldimethylsilyl cyanide, N-(tert-butyl- pyl isocyanate, 3- (trimethoxysilyl)propyl thiocyanate, tri- dimethylsilyl)dimethylamine, butyldimethylchlorosilane, hexylsilane, triisopropyl- silane, (triisopropylsilyl)acety- tert- butyldimethylchlorosilane, O-(tertbutyldimethylsilyl) lene (chlorotriisopropylsilane), triisopropylsilylchloride, hydroxyl- amine, 1-(tert-butyldimethyfsilyl)imidazole, 1-(triisopropylsilyl)pyrrole, trimethylsilylacetate, (trimeth- tert-butyldiphenyl- silyl cyanide, tert-butyldicyclohexylsi- ylsilyl)acetic acid, (trimethylsilyl)- acetylene, trimethylsi- 25 lyl cyanide, N-tert- butyltrimethylsilylamine, tert-butyl-tri- lyl cyanide, (trimethylsilyl)diazomethane, 5-(trimethylsi- methylsilyl peroxide, tert-butyl-trimethylsilyl acetate, [2 - lyl)-1,3-cyclopentadiene, 1-(trimethylsilyl)imid- azole, (cyclohexenyl)ethyl]triethoxy- silane, N,N-diethyltrimeth- 1-(trimethylsilyl)pyrrolidine, triphenylsilane, 1,1,1- triphe- ylsilylamine, N,N-diethyftriethyl- silylamine, N,N-diethyl nylsilylamine, triphenylsilylchloride, tris(2-methox- (trimethylsilylmethyl)amine, diethyl trimethylsilyl phos- yethoxy)- vinylsilane, 2,5,5-tris(trimethylsilyl)-1,3-cylco- 30 phite, diphenylmethylsilane, dicyclohexylmethyl- silane, pentadiene, tris(trimethylsilyl)borate, tris(trimethylsilyl) diphenylethylsilane, dicyclohexylethylsilane, diphenylsi- amine, tris(tri- methylsilyl)germaniumhydride, tris(tri- lane, dicyclohexylsilane, dicyclohexylsiladiol, 1,3- diphe- methylsilyl)methane, tris(trimethylsilylmethyl)borane, nyl-1,1,3,3-tertamethyfdisilazane, 1,3-diphenyl-1,1,3,3- tris(trimethylsilyloxy)silane, vinyltrimethoxysilane, vinylt- tertamethyldisiloxane, 1,3-dicyclohexyl-1,1,3,3-tertame- rimethylsilane, trimethylsilyl N- (trimethylsilyl)-car- 35 thyl- disilazane, 1,3-dicyclohexyl-1,1,3,3-tertamethyldis- bamate, triphenylsilylamine, triethoxysilyl- amine, tribu- iloxane, 1,3- divinyl-1,1,3,3-tetramethyldisilazane, 1,3- toxysilyamine, tripropoxysilylamine, vinyltrichloro- si- divinyl-1,1,3,3-tetramethyldisiloxane, dodecyltriethox- lane, vinyltriethoxysilane, vinyl-triisopropoxsilane, vinyl- ysilane, 1,1,3,3,5,5-hexamethyltrisilazane, 1,1,3,3,5,5- tri- methoxysilane, vinyltriethoxysilane, dimethoxymeth- hexamethyltrisiloxane, methyltriethoxysilane, ethyltri- ylvinylsilane, diethoxymethylvinylsilane, dimethox- 40 ethoxysilane, propyltriethoxysilane, isopropyltriethoxysi- yethylvinylsilane, diethoxy- ethylvinyisilane, dimethyl- lane, butyltrimethoxysilane, butyltriethoxy- silane, iso- methoxyvinylsilane, dimethylethoxyvinyl- silane, dimeth- butyltriethoxysilane, sec-butyltriethoxysilane, tert-butyl- ylpropoxyvinylsilane, dimethylisopropoxyvinylsilane, triethoxysilane, hexyltriethoxysilane, (3-isocyanatropro- diethylmethoxyvinylsilane, diethylethoxyvinylsilane, di- pyl)-triethoxysilane, (isopropenyloxy)trimethylsilane, ethylpropoxyvinylsilane, diethylisopropoxyvinylsilane, 45 isopropyldimethylchlorosilane, lithium bis(trimethylsilyl) dimethylethoxy(methylvinyl)silane, dimethoxymethyl amide, potassium bis(trimethylsilyl)amide, (3-mercapto- (ethylvinyl)silane, diethoxymethyl(propylvinyl)silane, vi- propyl)methyldimethoxysilane, (3-mercaptopropyl)tri- nyltrimethylsilane, vinyltriethyl- silane, vinyltriphenylsi- ethoxysilane, (3-mercaptopropyl)trimethoxy- silane, lane, vinyltris(2-butylidenaminooxy)silane, vinyltris(2- (methoxymethyl)trimethylsilane, methoxytrimethylsi- methoxyethoxy)silane, vinyltris(2-methylethoxy)silane, 50 lane, ethoxytrimethylsilane, [3-(methylamino)propyl]tri- vinyltris(2-ethoxy)silane, vinyltris(trimethylsiloxy)silane, methoxysilane, methyldiethoxysilane, 2-methylbenzosi- 3-(2-aminoethylamino)propyltrimethoxysilane, 3-amino- lylazole, methyl-octadecyldichlorosilane, methyl-octyld- propyl-methyldiethoxysitane, 3-aminopropyltriethoxysi- imethoxysilane, methyl-octyldichlorosilane, methyl-phe- lane, 3-aminopropyltrimethoxysilane, 3-aminomethyltri- nyl-chlorosilane, methyl-phenyl-dichlorosilane, methyl- ethoxysilane, 3-aminoethyltriethoxy- silane, 3-aminopro- 55 phenyl-diethoxysilane, methyl-phenyl-dimethoxysilane, pyltrimethoxysilane, 3-aminomethyltrimethoxy- silane, (methylthio)trimethylsilane, methyltriactoxysilane, meth- 3-aminoethyltrimethoxysilane, (3-aminopropyl)tris[2-(2- yltrichlorosilane, ethyltrichlorosilane, methylethoxysi- methoxyethoxy)ethoxysilane, amyltriethoxysilane, 1,3- lane, ethylethoxysilane, methyltriethoxysi lane, ethyltri-

22 43 EP 0 954 558 B1 44 methoxysilane, ethyltriethoxysilane, N-methyl-N-trir- ylsilylamine, phenyldimethoxysilylamine, methylphe- nethylsilylacetamide, methylvinyldiethoxysilane, phenyl- nyldimethoxysilane, phenyldiethoxysilylamine, cy- triethoxysilane, cyclohexyltriethoxysilane, Phenyltri- clohexyl- dimethoxysilylamine, cyclohexyldiethoxysi- methoxysilane, cyclohexyltrimethoxysilane, Phenyl lylamine, dipheny- Imethoxysilylamine, diphenylethoxys- (methylene)trieth.oxysilane, cycfohexyl(methyfene)tri- 5 ilylamine, dicyclohexyl- methoxysilylamine, dicyclohexy- ethoxysilane, phenyl(methylene)trimethoxysilane, cy- lethoxysilylamine, cyclohexyl- silyltriamine, cyclohexyl clohexyl(methylene)trimethoxysilane, Phenyl(ethylene) (ethyl)silyltriamine, cyclohexyl(methyl)- silyltriamine, triethoxysiiane, cyclohexyl(ethylene)triethoxysilane, benzylsilyltriamine, benzyl(methyl)silyltriamine, diphe- phenyl(ethylene)trimethoxysilane, cyclohexyl(ethylene) nylsilyldiamine, phenylethoxysilyldiamine, cyclohexy- trimethoxysilane, phenyltrimethylsilane, phenyltriethylsi- 10 lethoxy- silyldiamine, cyclohexyldiethoxysilylamine, cy- lane, phenyltripropylsilane, phenyltriisopropylsilane, clohexylmethoxysilyl- diamine, cyclohexyl(ethyl)ethox- phenyltributyl- silane, phenyltri-sec-butylsilane, phenyl- ysilyldiamine, cyclohexyl(methyl)-ethoxysilyldiamine, tri-tert-butylsilane, phenyltriisobutylsilane, cyclohexyltri- benzylmethoxysilyldiamine, benzyl-dimethoxysi- methylsilane, cyclohexyltriethylsilane, cyclohexyltripro- lylamine, tris(trimethylsilyl)amine, tris(trimethoxylsilyl) pylsilane, cyclohexyltriisopropyl- silane, cyclohexyltribu- 15 amine, tris(triethoxylsilyl)amine, tris(trimethylsilyl)- bo- tylsilane, cyclohexyltri-sec-butylsifane, cyclohexyltri- rate, tris(trimethylsilyl)methane, tris(trimethylsilyl) tert-butylsilane, cyclohexyltriisobutylsilane, Phenyltri- ethane, tris(trimethylsilyl)phosphate, tris(trimethylsilyl) ethoxysilanediol, cyclohexyltriethoxysilanediol, Phenyl- phosphine, tris(trimethylsilyl)silane, vinyltriethoxysilane, trimethoxysilanediol, cyclohexyltrimethoxysilanediol, vinyltrichloro- silane, vinyltriisopropylsilane, vinyltrimeth- phenyltrimethylsilanediol, phenyltriethylsilanediol, phe- 20 ylsilane, vinyltri- phenylsilane, vintris(2-buytlidenami- nyltripro- pylsilanediol, phenyltriisopropylsilanediol, phe- nooxy)silane, vinyltris(2- methoxyethoxysilane), vinyltris nyltributyl- silanediol, phenyltri-sec-butylsilanediol, phe- (trimethylsiloxy)silane, allyldimethylsilane, allyldiethylsi- nyltri-tert-butyl- silanediol, phenyltriisobutylsilanediol, lane, diallyldimethylsilane, diallyldiethylsilane, allyoxytri- cyclohexyltrimethyl- silanediol, cyclohexyltriethylsilane- methylsilane, allyoxytriethyl- silane, allylphenylsilicon, diol, cyclohexyltripropyl- silanediol, cyclohexyltriisopro- 25 tripropylsilane, tris(trimethylsilyl)- silane, pentamethylcy- pylsilanediol, cyclohexyltributyl- silanediol, cyclohexyltri- clopentasiloxane, 2,4,6,8,10-pentamethyl- cyclopentasi- sec-butylsilanediol, cyclohexyltri-tert- butylsilanediol, cy- loxane, pentamethyldisiloxane, amyltriethoxysilane, vi- clohexyltriisobutylsilanediol, propyltrimethoxy- silane, te- nyltricholorsilane, vinyltriethylsilane, vinyltrimethylsi- tramethylsilane, 2,4,6,8-tetramethylcyclotetrasilazane, lane, vinyltriphenylsilane, vinyltriethoxysilane, vinyl- 1,1,3,3-tetramethyldisilazane, 1,1,3,3-tetramethyldisi- 30 tripropyoxysilane, vinyltrisopropyoxysilane, vinyltrimeth- loxane, tetramethyltetrasilylfulvalene, trimethylethoxysi- oxylsilane, vinyltriphenoxy- silane, vinyltributoxysilane, lane, N-(trimethylsilyl)acetamide, trimethylphenoxylsi- vinyltriisobutoxysilane, vinyltrisec- butoxysilane, vinyltri- lane, 1-(trimethy-Isiloxy)cyclopentene, 1-(trimethylsi- tert-butoxysilane, vinyltris(2-butylidenaminooxy)silane, loxy)cyclohexene. trimethoxylphenylsilane, 1-(trimeth- vinyltris(2-methoxyethoxy)silane, vinyltris-(trimethoxysi- oxylsilyl)cyclopentene, 1-(trimethoxylsilyl)cyclohexene, 35 loxy)silane, N,N-dimethyltrimethylsilyamine, N,N-di- triethoxylphenylsilane, 1-(triethoxylsilyl)cyclopentene, ethyltrimethylsilyamine, 3,3-dimethyl-1-trimethylsily-1- 1-(triethoxylsilyl)cyclohexene, trimethoxylcyclohexylsi- butyne, 3,3-diethyl-1-trimethylsily-1-butyne, dimethyltri- lane, (trimethoxylsilyl)cyclopentane, (trimethoxylsilyl)cy- methylsilylmethylphosphonate, dimethyltrimethylsilyl- clohexane, triethoxylcyclohexylsilane, (triethoxylsilyl)cy- phosphite, dimethyltritylbromosilane, dimethyl-vinyl- clopentane, (triethoxylsilyl)cyclohexane, trimethylsilyl 40 ethoxysilane, dimethylvinylchlorosilane, diphenylmeth- azide, triethylsilyl azide, tripropylsilyl azide, triisopropyls- ylchlorosilane, diphenylethylchlorosilane, phenyldimeth- ilyl azide, tributyl azide, triisobutyl azide, tri- tert-butyl ylchlorosilane, phenyldiethylchlorosilane, diphenyldi(M- azide, tri-sec-butyl azide, triphenyl azide, trimethoxylsilyl tolyl)silane, 1,2-dimethylsilane, 1,2-diethylsilane, azide, triethoxylsilyl azide, tripropoxylsilyl azide, triiso- 2,2,4,4,6,6-hexamethylcyclotrisilazane, N-benzyltri- propoxylsilyl azide, tributoxyl azide, triisobutoxyl azide, 45 methylsilylamine, chlorodimethyloctylsilane, trimethyl- tri-tert-butoxyl azide, tri-sec-butoxyl azide, (trimethylsilyl) octylsilane, disiloxane, silicon nitride, disilane, dimethyl- cyclopentadiene, trimethylsilyl cyanide, (trimethylsilyl) silanediol, trichlorocyclopen- tysilane, tris(isopropylthio) acetontrile, trans-3-(trimethylsilyl)allyl alcohol, 2-(tri- silane, chlorotrimethylsilane, chlorodimethylsilane, bis methylsilyl)methanol, 2-(triethylsilyl)ethanol, (trimethyls- (chloromethyl)dimethylsitane, propyltri- chlorosilane, tri- ilyl)methanol, (triethylsilyl)ethanol, triisobutylsilane, 50 methyl(pentafluorophenyl)silane, trichloro(1 H, 1H,- 2H, 2-(trimethylsilyl)methanol, 2-(trimethylsilyl)ethanol, 2H-perfluorooctyl)silane, silicon tetraboride, silicon O-(trimethylsilyl)hdroxylamine, 1-(trimethylsilyl)imida- hexa- boride, trimethyl-2-thienylsiiane, (4-bromophenyl) zole, trimethylsilylisocyanate, (trimethylsilyl)methyl ace- trimethylsilane, 4-(trimethylsilyl)phenol, 5-(trimethylsi- tate, trimethylsilyl methacrylate, (trimethylsilyl)methyl- lyl)-1,3-cyclopentadiene, trimethylsilylmethylmagnesi- amine, N-(trimethylsily- Imethyl)urea, 4-(trimethylsilyl) 55 umchloride, N,N-diisopropyltrimethylsilylamine, dicy- morpholine, 4-(triethoxysilyl)- butyronitrile, 1-(trimethyls- clohexyl-methyl-silane, tetracyclohexysilane, ilyl)pryrrolide, 1-trimethylsilyl- 1,2,4-triazoie, triphenylsi- 1,1,2,2,3,3,4,4,5,5-decaphenyl-6,6-dimethylcyclohex- lane, triphenylsilandiol, triphenyl- silylamine, tricyclohex- asilane, trimethylsilylpolyphosphate, trimethylsityl-

23 45 EP 0 954 558 B1 46 polyphosphite, including analogues, homologues, iso- clohexyl-secbutoxyphospine, dicyclohexyl-tert-butoxy- mers and derivatives thereof. Additional examples of ac- phospine, dicyclohexyl-iso-butoxyphospine, dicy- ceptable silicon derivatives can be found in Silicon Com- clopentylethoxyphospine, dicyclopentylmethoxyphos- pounds, Register and Review, Petrarch Systems, Inc. pine, dicyclopentylpropoxyphospine, dicyclopentyliso- (1984), Frontiers of Organosilicon Chemistry, Bassin- 5 propoxyphospine, dicyclopentylbutoxyphospine, dicy- dale, Gaspar, The Royal Society of Chemistry, (1991), clopentyl-sec-butoxyphospine, dicyclopentyl-tert- incorporated herein by reference. Corresponding com- butoxyphospine, dicyclopentyl-iso-butoxyphospine, di- pounds of germanium, tin, titanium, zirconium, selenium, cyclohexyl(ethyl)ethoxy- phospine, dicyclohexyl(ethyl) tellurium, are contemplated in the practice of this inven- methoxyphospine, dicyclohexyl(ethyl)-propoxyphos- tion. 10 pine, dicyclohexyl(ethyl)isopropoxyphospine, dicy- [0098] Other non-limiting germanium derivative com- clohexyl(ethyl)butoxyphospine, dicyclohexyl(ethyl)- pounds include: decamethylgerrnaniumocene (bis(pen- secbutoxyphospine, dicyclohexyl(ethyl)-tert-butoxy- tamethylcyclopentadienyl)germanium), tertbutylgerma- phospine, dicyclohexyl(ethyl)-iso-butoxyphospine, phe- nium, tetramethylgermanium, tetraethylgermanium, nyldiethoxyphospine (diethylphenylphosphonite), phe- tetrapropylgermanium, tetraisopropylgermanium, 15 nyldimethoxyphospine, phenyldipropoxyphospine, phe- tetrabutylgermanium, tetraisobutylgermanium, tetra- nyldiisopropoxyphospine, phenyldibutoxyphospine, tert-butylgermanium, tetra-sec-butylgermanium, tetra- phenyldisec-butoxyphospine, phenyldi-tert-butoxyphos- phenylgermanium, phenylgermanium, methylphenylger- pine, phenyldiisobutoxyphospine, cyclohexyldiethoxy- manium, methylphenolgermanium, including analogues, phospine, cyclohexyldimethoxyphospine, cyclohexyld- homologues, isomers and derivatives thereof. 20 ipropoxyphospine, cyclohexyldiisopropoxyphospine, cy- [0099] Other non-limiting derivative tin compounds in- clohexyldibutoxyphospine, cyclohexyldi-secbutoxy- clude: decamethylstannocene (bis(pentamethylcy- phospine, cyclohexyldi-tert-butoxyphospine, cyclohexy- clopentadienyl)tin), dibutyltin bis(2-ethylhexanoate), dib- ldi-iso-butoxyphospine, cyclopentyldiethoxyphospine, utyltin diacetate, dibutyloxo- tin (dibutyltin oxide), dimeth- cyclopentyldimethoxyphospine, cyclopentyldipropoxy- yltin, diethyltin, dipropyltin, diisopropyltin, dibutyltin, di- 25 phospine, cyclopentyldiisopropoxyphospine, cy- isobutyltin, di-tert-butyltin, di- sec-butyltin, di-phenyltin, clopentyldibutoxyphospine, cyclopentyldi-sec-butoxy- tetramethyltin, tetraethyltin, tetrapropyltin, tetraisopro- phospine, cyclopentyldi-tert-butoxyphospine, cy- pyltin, tetrabutyltin, tetraisobutyltin, tetra-tert-butyltin, tet- clopentyldiisobutoxyphospine, cyclohexyl(ethyl)diethox- ra-sec-butyltin, tetraphenyltin, tetrameth- oxytin, tetrae- yphospine, cyclohexyl-(ethyl)dimethoxyphospine, cy- thoxytin, tetrapropoxytin, tetraisopropoxytin, tetrabutox- 30 clohexyl(ethyl)dipropoxyphospine, cyclohexyl(ethyl)di- ytin, tetraisobutoxytin, tetra-tert-butoxytin, tetra-sec- bu- isopropoxyphospine, cyclohexyl(ethyl)dibutoxyphos- toxytin, tetraphenoxytin, trimethoxymethyltin, tri- pine, cyclohexyl(ethyl)di-sec-butoxyphospine, cy- ethoxymethyl- tin, tripropoxymethyltin, triisopro- clohexyl-(ethyl)ditert-butoxyphospine, cyclohexyl(ethyl) poxymethyltin, tributoxymethyl- tin, triisobutoxymethyl- diiso-butoxyphos- pine, dimethylmethylphosphate, di- tin, tri-tert-butoxymethyltin, tri-sec- butoxymethyltin, 35 ethylmethylphosphate, diethylethylphosphate, dimethyl- triphenoxymethyltin, dibutyltin dichloride, dibutyltin dilau- ethylphosphate, ethylenebis(diphenylphosphine), meth- rate, dibutyltin dimethoxide, dibutyltin dieth- oxide, dib- yldichlorophosphite, methyldichlorophosphate, methyl- utyltin methoxide, dibutyltin ethoxide, tetrabutyltin, te- dichlorophosphine, methyldiphenylphosphine, propyl- tramethyltin, tetraethyltin, tetrapropyltin, tetra-tert-butyl- phosphonic anhydride, dimethylphosphine, diethylphos- tin, allyldibutyltin, allyldiphenyltin, allyldiphenylstannane, 40 phine, dimethylphosphine, dipropylphosphine, diisopro- dichlorodiphenyltin, diphenyltin acetate, tributyltineace- pylphosphine, dibutylphosphine, diisobutylphosphine, tate, tributyltinechloride, tributyltincyanide, tributyltin disecbutylphosphine, di-t-butylphosphine, diphenyl- ethoxide, tributyltin methoxide, tributyltinhydride, tributyl- phosphine, diphenylphosphate, diphenylphosphineox- vinyltin, triphenyltinchloride, triphenyltinhydroxide, ide, diphenylphosphine oxide, diphenylphosphinesele- triphenyltinhydride, tributyltin ethoxide, including ana- 45 nide, dis(diethylamino)phosphine, dis(dimethylamino) logue, homologue, isomer, and derivative thereof. The phospine, dis(2-ethylhexyl)phosphate, dis(dimethylsilyl) non-limiting examples of phosphorus derivative com- phosphate, dis(dimethylsilyl)phosphite, di(toly)phos- pounds of this invention include: tetrabutylphosphonium phine, di(o-toly)phosphine, di(m-toly)phosphine, di(p- hydroxide, allyldiphenylphospine, diphenylphosphine, toly)phosphine, di(toly)phosphite, di(o-toly)phosphite, di phenylphosphine, diphenyl phosphate, diphenylphos- 50 (m-toly)phosphite, di(p-toly)phosphite, di(toly)-phos- phine, diphenylphosphinic acid, diphenylethoxyphos- phate, di(toly)hydrophosphate, di(toly)phosphonic acid pine, diphenylmethoxyphospine, diphenylpropoxy- [(CH3C6H4)2P(OH)], mono(toly)phosphonic acid phospine, diphenylisopropoxyphospine, diphenylbutox- [(CH3C6H4)P(OH)2], diethylphenylphosphine, diethyl- yphospine, diphenyl-secbutoxyphospine, diphenyl-tert- phenylphosphite, dipropylphosphite, diisopropylphos- butoxyphospine, diphenyl-iso-butoxyphospine, dicy- 55 phite, dibutylphosophite, diisobutylphosophite, di- clohexylethoxyphospine, dicyclohexylmethoxyphos- secbutylphosophite, di-tert-butytphosophite, diphenyl- pine, dicyclohexylpropoxyphospine, dicyclohexylisopro- phosphite, allydiphenylphosphonium, allydiphenylphos- poxyphospine, dicyclohexylbutoxyphospine, dicy- phonium hydride, allydiphenylphosphonium hydroxide,

24 47 EP 0 954 558 B1 48 allydiphenylphosphonium chloride, dimethylphospho- tris(trimethylsilyl)phosphate, tris(trimethylsilyf)phos- ramidous dichloride, hexamethylphosphoramide, hex- phite, tri(toly)phosphines (e.g. tri(o-toly)phosphine, tri(m- amethylphosphorus diamide, hexamethylphosphorus tri- toly)phosphine, tri(p-toly)phosphine), tri(toly)phosphite amide, hexamethylphospophorimidic triamide, trimethyl- (e.g. tri(o-toly)phosphite, tri(m-toly)phosphite, tri(p-toly) phosphine, trimethylphospate, trimethylphosphite, tri- 5 phosphite), tri(toly)phosphate, tri(toly)hydrophosphate, ethylylphosphite, tripropyl- phosphite, triisopropylphos- tri(toly)phosphonic acid [(CH3C6H4)3P(OH)2], bis(2- phite, tri-butyl-phosphite, tri-iso- butylphosphite, tri-sec- ethylhexel) phosphite, diallyphenyl- phosphine, diben- butylphosphite, tri-tert-butylphosphite, triphenylphos- zylphosphite, dibenzylphosphate, dibutyl phosphite, phite, dimethylphosphite, diethylphosphite, dipropyl- dimethyl methylphosphonate, dimethyl methylphos- phosphite, diisopropylphosphite, dibutylphosphite, di- 10 phine, dimethyl methylphosphonite, dimethylphenyl- isobutyl- phosphite, di-sec-butylphosphite, di-tert-butyl- phosphine, dimethylphenylphosphonite, dimethylphe- phosphite, diphenyl- phosphite, dimethylethylphosphine, nylphosphite, dimethylphosphinic acid, dimethyl(trimeth- dimethylethylphosphate, dimethylethylphosphite, di- ylsilylmethyl)phosphonate, dimethyl trimethylsilyl phos- ethylmethylphosphite, dipropylmethylphosphite, diiso- phite, dimethyl trimethylsilyl phosphonate, ethyldiphenyl- propylmethylphosphite, di-butyl-methylphosphite, di-iso- 15 phosphonite, diphenyl(2-methoxyphenyl)phosphine, butylmethylphosphite, di-sec-butylmethylphosphite, di- manganese (II) hydrogen phosphite, disodium fluoro- tert-butylmethylphosphite, diphenylmethyl phosphite, phosphate, disodium fluorophosphite, disodiumhydro- dimethylphosphonate, diethylphosphonate, dipropyl- genphosphite, trisodium phosphate, trisodium phos- phosphonate, diisopropylphosphonate, di-butyl-phos- phite, dipotassiium fluorophosphate, dipotassium fluor- phonate, di-iso-butylphosphonate, di-sec-butylphospho- 20 ophosphite, tripotassium phosphate, tripotassium phos- nate, di-tert-butylphosphonate, diphenylphosphonate, phite, ethyldiphenylphosphine, ethyldiphenylphosphi- dimethylmethylphosphonate, dimethylethylphospho- nite, ethyldiphenylphosphonate, methyldiphenylphos- nate, diethylmethylphosphonate, dipropylmethylphos- phine, methyldiphenylphosphinite, methyldiphenylphos- phonate, diisopropylmethylphosphonate, di-butyl-meth- phonate, phenylphosphine, phenylphosphonic acid, ylphosphonate, di-iso-butylmethylphosphonate, di-sec- 25 phenylphospate phosphorus acid, phosphoric acid, butylmethylphosphonate, di-tert-butylmethylphospho- phosphorus trichloride, phosurea, phosphorus trisulfide, nate, diphenylmethyl phosphonate, diethylethylphos- tributyl phosphate, tributylphosphine, tri-tert-butylphos- phonate, dipropylethylphosphonate, diisopropylethyl- phine, tributylphosphine oxide, tributylphosphite, tris phosphonate, di-butylethylphosphonate, di-iso- (2,4-di-tert-butylphenyl)phosphite, tris(nonlphenyl)phos- butylethylphosphonate, di-sec-butylethylphosphonate, 30 phite, phosphorous acid triphenylester with propane 1,3- di-tert-butylethylphosphonate, diphenylethyl phospho- diol, tris(2,2,2-tri- fluoroethyl)phosphite, tris(2-chforoe- nate, dimethylcarbophosphonate, diethylcarbophospho- thyl)phosphite, tris(1- chloroethyl)phosphite, trichioro- nate, dipropylcarbophosphonate, diisopropylcarbophos- phosphite, tris(tridecyl)phosphite, isooctyldiphenylphos- phonate, di-butyl-phosphonate, di-iso-butylcarbophos- phite, diisodecylphenylphosphite, triethyl 4- phospho- phonate, di-sec-butylcarbophosphonate, di-tert-butyl- 35 nocrotonate, trimethyl 4-phosphonocrotonate, triethyl- carbophosphonate, diphenylcarbophosphonate, dime- phosphonoacetate, trimethylphosphonoacetate, trime- thylmethylcarbophosphonate, dimethylethylcarbophos- thyl 2-phosphono- butyrate, triethyl 2-phosphonobu- phonate, diethylmethylcarbophosphonate, dipropyl- tyrate, trimethylphosphonoformate, triethylphosphono- methylcarbophosphonate, diisopropylmethylcarbophos- formate, trimethylphosponopropionate, trimethylphos- phonate, di-butyl-methylcarbophosphonate, di-iso-butyl- 40 ponopropionate, tricyclohexylphosphite, tricyclohexyl- methylcarbophosphonate, di-sec-butylmethylcarbo- phophine, triethylphosphine, triethylphosphite, trimethyl- phosphonate, di-tert-butylmethylcarbophosphonate, phosphine, triethylphosphate, trimethylphosphate, diphenylmethyl phosphonate, diethylethylcarbophos- tripropylphosphate, triisopropylphosphate, tributylphos- phonate, dipropylethylcarbophosphonate, diisopropyl- phate, triisobutylphosphate, tri-sec-butylphosphate, tri- ethylcarbophosphonate, di-butyl-ethylcarbophospho- 45 tert-butylphosphate, triphenylphosphate, dimethylphos- nate, di-iso-butylethylcarbophosphonate, di-sec- phate, diethylphosphate, dipropylphosphate, diisopro- butylethylcar- bophosphonate, di-tert-butylethylcarbo- pylphosphate, dibutylphosphate, diisobutylphosphate, phosphonate, diphenylethyl phosphonate, dimethyl- di-sec-butylphosphate, di-tert-butylphosphate, diphenyl- phospite, dimethylphosphite, trimethyl phosphonoace- methylphosphate, diphenylethylphosphate, diphenyl- tate, trimethyl 2-phosphonoacrylate, trimethyl 50 propylphosphate, diphenylisopropylphosphate, dimeth- phosphonoformate, trioctylphosphine oxide, triphenyl ylethylphosphate, diethylmethylphosphate, dipropyl- phospate, triphenylphosphine, triphenylphosphine ox- methylphosphate, diisopropylmethylphosphate, di-butyl- ide, triphenyl- phosphine-copper hydride, triphenylphos- methylphosphate, di-iso-butylmethylphosphate, di-sec- phine hydrobromide, triphenylphosphine dibromide, butylmethylphosphate, di-tert-butyimethylphosphate, triphenylphosphine oxide, triphenyl- phosphine selenide, 55 diphenylmethyl phosphate, triethylphosphoramide, tri- triphenylphosphine sulfide, tripiperidinophosphine oxide, methylphosphoramide, tripropylphosphoramide, triiso- tris(2-ethylhexyl)phosphate, tris(dimethylamino)phos- propylphosphoramide, tributylphosphoramide, tri-iso- phine, tris(hydroxymethyl)aminomethane phosphate, butylphosphoramide, tri-sec-butylphosphoramide, tri-

25 49 EP 0 954 558 B1 50 tert-butylphosphoramide, triphenylphosphoramide, nate, diethyl 4-aminoben- zylphosphite, diethylbenzyl- dimethoxyphosphorusamide (CH3O)2PNH2), diethoxy- phosphonate, diethylbenzylphosphite, tetraethylbenzyl- phosphorusamide, dipropoxyphosphorus- amide, diiso- phosphonate, diethyl (pyrrolidinomethyl)phos- phonate, propoxyphosphorusamide, dibutoxyphosphorusamide, diethyloxyphosphinyl isocyanate, 6-amino-1-hexylphos- diisobutoxyphosphorusamide, di-sec-butoxyphospho- 5 phate, diethyloxyphinyl isocyanate, diethylcyanomethyl- rusamide, di-tert- butoxyphosphorusamide, diphenoxy- phosphonate, diethylveinylphosphonate, dioctylphenyl- phosphorusamide, dimethylphosphor- amide (CH30) phosphonate, ethylphenylphosphinate, ethylphenyl- 2PONH2), diethylphosphoramide, dipropylphospho- phosphonic acid, methylphosphonic acid, ethylphos- ramide, diisopropylphosphoramide, dibutylphospho- phonic acid, propylphosphonic acid, isopropylphosphon- ramide, diisobutylphosphoramide, di-sec-butylphospho- 10 ic acid, butylphosphonic acid, sec-butylphosphonic acid, ramide, di-tert-butylphosphoramide, diphenylphospho- tert-butylphosphonic acid, isobutylphosphonic acid, phe- ramide, dimethylethylphosphoramide, diethylmethyl- nylphosphonic acid, phenylphosphoric acid, phenyl- phosphoramide, dipropylmethylphosphoramide, diiso- phosphinic acid, methylphenylphosphinate, methylphe- propylmethylphosphoramide, di-butyl-methylphospho- nylphosphine, aminomethylphosphonic acid, vinylphos- ramide, di-iso-butylmethylphosphoramide, di-sec-butyl- 15 phonic acid, hypophosphorus acid, sodium hypophos- methylphosphoramide, di-tert-butylmethylphospho- phate, sodium dihydrogenphosphate, fluorophosphoric ramide, diphenylmethyl phosphoramide, triethyl- acid, ammonium hydrogenphosphate, ammonium hy- carbophosphate, trimethylcarbophosphate, tripropylcar- drogenphosphite, ammonium hydrogen- phosphine, lith- bophosphate, triisopropylcarbophosphate, tri-butyl- iumdihydrogen phosphate, triphenylphosphineselenide, phosphate, tri-iso-butylcarbophosphate, tri-sec-butyl- 20 phosphoric acid, phosphorus oxychloride, phosphorus carbophosphate, tri-tert-butylcarbophosphate, triphenyl- pentasulfide, metaphosphoric acid, phenylphosphate carbophosphate, dimethylcarbophosphate, diethylcar- disodium salt, nitrilotris(methylene)triphosphonic acid, bophosphate, dipropylcarbophosphate, diisopropylcar- ethylenephosphite, ammonium salt benzylphosphite, po- bophosphate, dibutylcarbophosphate, diisobutylcarbo- tassiumhexafluorophosphate, diethyltrimethylsilylphos- phosphate, di-sec-butylcarbophosphate, di-tert-butyl- 25 phite, diethyl(trichloroethyl)phosponate, dimethyl(tri- carbophosphate, diphenylcarbophosphate, dimethyl- methylsilyl)phosphite, tris(trimethylsilyl)phosponate, 2- ethylcarbophosphate, diethylmethylcarbophosphate, chloro-1,3,2-dioxaphospolane, 2-chloro-1,3,2-dioxa- dipropylmethylcarbophosphate, diisopropylmethylcar- phospholane-2- oxide, dimethylmethylphosphonate, di- bophosphate, di-butyl-methylcarbophosphate, di-iso- ethylmethylphosphonate, dimethylethylphosphonate, di- butylmethylcarbophosphate, di-sec-butylmethylcarbo- 30 ethylethylphosphonate, ethylmethyl- phosphonate, 2- phosphate, di-tert-butylmethylcarbophosphate, diphe- carboxyehtylphosphonic acid, 2,2,2-trichloro-1,1- nylmethyl phosphate, dimethylvinylphosphate, diethylvi- dimethylethyldichlorophosphite, bis(2-chloroethyl)phos- nylphosphate, dipropylvinylphosphate, diisopropylvinyl- phoramidic dichloride, butyldichlorophosphite, butyl- phosphate, dibutylvinylphosphate, diisobutylvinylphos- phosphonic dichloride, tert-butylphosphonic dichloride, phate, di-sec-butylvinylphosphate, di-tert-butylvinyl- 35 tert-butyldichlorophosphine, trimethylphosphonofor- phosphate, diphenylvinylphosphate, triisobutylphos- mate, trimethylpropionamide, trimethylpropionanilide, di- phine, triisodecylphosphite, triisopropylphosphite, diben- ethylchlorophosphate, diethylchlorophosphite, chlorodi- zyldiethylphosphoramidite, dibenzyldiisopropylphos- ethylphosphine, diethylphosphoramidous dichloride, di- phoramidite, dibenzylphosphite, dibenzylphosphate, tris ethylthiophosphate, sodium salt diethylthiophosphate, (tridecyl)phosphite, tritolylphosphate, tritolyphophine, tri- 40 diethylphosphoramidate, dimethylphosphoramidate, te- tolyphos- phite, tricyclohexylphosphine, aliminum phos- tramethylphosophorodiamidic chloride, tetramethyl- phate, 1,2-bis(diphenylphosphino)propane, trioctylphos- phosphonium chloride, diethylcyanophosphate, diethyl- phine oxide, trioctyl- phosphine, dichloromethylphos- cyanophosphonate, diethylcyanomethylphosphonate, phine, dichlorophosphineoxide (Cl2PO), ethyldichloro- diethoxyphosphinyl isocyanate, O,O’-diethylmethyl- phosphite, tetraethylpyrophosphite, benzyldiethylphos- 45 phosphonothioate, diethylmethylphosphonate, diethyl phite, benzyldiethoxyphosphorus, cyclohexyldiethoxy- (hydroxymethyl)-phosphonate, dimethyltrimethylsilyl- phosphorus, dibenzyldiisopropylphosphoramite (disso- phosphite, 1-ethyl-3-methyl-1 H-imidzolium hexafluro- propyl-phosphoraramidous acid dibenyl ester), di-tert- phosphite, diethylcyanmethylphosphonate, phosphorus butyl diisopropylphosphoramidite, tert-butyl tetraisopro- napthenate, methylphenylphospholene, methylphenyl- pylphosphorodiamidite, (+/-)-1-amino-cis-3-phosphono- 50 phosolenedichloride, (aminobenzyl)phosphonic acid cyclopentanecarboxlic acid, diallyl diisopropylphospho- (e.g. (4-aminobenzyl)phosphonic acid), cyclophospha- ramide, tert-butyl tetraisopropylphosphorodiamite, (1- mide, pinacolylmethylphosphonate, diethyl(ethylthiome- aminobutyl)-phosponic acid, 6-amino-1-hexyl phos- thyl)phosphonate, 2-furyl tetra-methylphosphorodia- phate, 1-aminoethylphosponic acid, 2-aminoethyl dihy- midite, diisopropylcyanomethylphosphate, 1,3,5-tris(2- drogenphosphate, 2-aminoethylphosponic acid, methyl 55 hydroxyethyl)cyanuric acid, tris(2,4,-di-tert-butylphenyl) N,N,N’-tetraisopropylphosphordiamidite, hexamethyl- phosphite, tris(tridecyl)phosphite, tris(nonylphenyl) phosphoramide [(CH3)2N]3PO, hexamethylphosphortri- phos- phite, phosphorus anyhydride, phospham, phos- amidite [(CH3)2N]3P, diethyl 4-aminobenzylphospho- phonium chloride, phosphoniumsulfide, phosphonium-

26 51 EP 0 954 558 B1 52 sulfate, phosphoramide, phorphoramidite, metaphos- of this invention include: potassium bis(dimethylsilyl) phoramide, phosphorus chloride(di)nitride, phosphorus amide, potassium acetamide, potassium bis(trimethyls- cyanide, phosphorus trifluoride, phosphorus pentafluo- ilyl)amide, oxamic acid, P-aminosalicylic acid potassium ride, phosphorus oxybromide, phosphorus pentasele- salt, potassium salt 5-nitroorotic acid, potassium D-glu- nide, phosphorus trioxide, phosphorus sesquioxide, 5 conate, potassium hexacyanoferrate(III) (K3Fe(CN)6), phosphorus tri(tetra)selenide, phosphorus thiochloride, potassium diphenylphosphide, potassiumetherate, po- phosphorus thiocyanate, hypophosphorus acid, meta- tassium acetate, potassium acetate acid, potassium salt phosphorus acid, orthophosphorus acid, pyrophospho- acetic acid, potassiumbenzamide, potassium azide, po- rus acid, phosphine, phosphorus nitride, phosphorus tassium antimonide, potassium orthoarsenate, potassi- sesquisulfide, including analogues, homologues, iso- 10 um orthoarsenite, potassium meta-arsenite, potassium mers and derivatives thereof. The corresponding com- diborane, potassium pentaborate, potassium dihydroxy pounds of arsenic, antimony and bismuth are contem- diborane, potassium borohydride, potassium anilide, po- plated. tassium cadium iodide, potassium chloride, potassium [0100] Other non-limiting antimony derivative com- calcium chloride, potassium carbide, potassium carbon- pounds include: alkyl antimony compounds, trialkyl com- 15 ate, potassium hydrogen carbonate, potassium carbon- pounds, cyclomatic/ring system compounds, including, ate, potassium carbonyl, potassium cobalt (II) cyanide, trimethylantimony, triethylantimony, tripropylantimony, potassium cobalt (III) cyanide, potassium cobaltinitrite, triisopropylantimony, tributylantimony, triisobutylantimo- potassium cynomanganate (II), potassium cynomanga- ny, tri-tert-butylantimony, tri-sec-butylantimony, triphe- nate (III), potassium citrate, potassium ferricyanide, po- nylantimony, phenylantimony, tri(methylphenyl)antimo- 20 tassium ferrocyanide, potassium hydride, potassium hy- ny, triphenylantimony oxide, tri(methylphenol)antimony, droxide, potassium manganate, potassium permanga- antimony ethoxide, pentamethylantimony, phenyld- nate, potassium methionate, potassium napthenate, po- imethylantimony, phenyl- stibinic acid, tetramethyldistib- tassium nitride, potassium nitrate, potassium nitrite, po- yl, tributylstibene, triethylan- timony, triethylantimony tassium nitrophenoxide, potassium nitrobenzene (e.g. chloride, trimethylantimony, triphenylan- timony, triphe- 25 potassium-p- nitrobenzene)potassium oleate, potassium nylantimony dichloride, triphenylantimony sulfide, includ- oxalate, potassium oxalatoferrate (II), potassium ing analogue, homologue, isomers and derivative there- oxalatoferrate (III), potassium monoxide, potassium ox- of. ide, potassium peroxide, potassium mono- orthophos- [0101] Non-limiting arsenic derivative compounds in- phate, potassium hypophosphite, potassium orthophos- clude: alkyl arsenic compounds, dialkyl compounds, cy- 30 phite, potassium hydroxoplumbate, potassium rhodium clomatic/ring system compounds including, trimethylars- cyanide, potassium selenide, potassium selenite, potas- ine, triethylarsine, tripropylar- sine, triisopropylarsine, sium selenocynate, potassium selenocyanoplatinate, tributylarsine, triisobutylarsine, tri- tert-butylarsine, tri- potassium disilicate, potassium metasilicate, potassium sec-butylarsine, tri-phenylarsine, phenylar- sine, tri sodium carbonate, potassium sodium ferricyanide, po- (methylphenyl)arsine, triphenylarsine oxide, tri(methyl- 35 tassium hydroxostannate, potassium disufide, potassi- phenol)arsine, phenylarsenic acid, phenylcyclotetrame- um hydrosulfide, potassium pentasulfide, potassium tet- thylenearsine, arsenobenzene, cacodyl oxide, cacodyl rasulfide, potassium trisulfide, potassium telluride, po- amide, dimethylarsine, dimethylchlorarsine, dimethylcy- tassium thioarsenate, potassium thioarsenite, potassium anoarsine, diphenylarsinic acid, diphenylchloroarsine, trithiocarbonate, potassium thiocyanate, potassium ethylarsonic acid, methylarsine, methyl- dichloroarsine, 40 amide, potassium salt (E,E)-2,4-hexadienoic acid, dipo- phenylarsine, phenyldimethylarsine, tetraethyldiar- sine, tassium fluorophosphate, dipotassium fluorophosphite, tetramethylbiarsine, tribenzylarsine, trimethylarsine, tri- tripotassium phosphate, tripotassium phosphite, potas- ethylarsine, tributyl arsine, tri-isobutyl arsine, triphenyl sium perchlorate, propanoic acid potassium salt, potas- arsine, including analogue, homologue, isomers and de- sium formate, potassium cyanate, potassium hexacy- rivative thereof. See Organo Arsenial Compounds, Raiz- 45 anocobaltate (III), potassium hypophosphite, potassium iss, Gavron, American Chemical Society (1923) and re- hexaflurorsilicate, potassium nitroprusside, potassium lated/subsequent editions, volumes or supplements, in- phenoxide, potassium phosphate (dibasic, monobasic, corporated by reference. Corresponding compounds of tribasic), potassium salicylate, potassium selenide, po- phosporus, antimony, bismuth are also contemplated tassium tetracyanonickelate (II), potassium tetrafluorob- herein and incorporated by reference. 50 orate, potassium xanthogenate, potassium -p-ami- [0102] Non-limiting bismuth derivative compounds in- nobenzoate, potassium copper ferrocynanide, potassi- clude: alkyl bismuth compounds, dialkyl compounds, cy- um cupric ferrocyanide, potassium hexafluorophos- clomatic/ring system compounds including, triphenylbis- phate, potassium hexanitricobaltate III, potassium naph- muth, triphenylbismuth carbonate, diphenylbismuthine, thenate, potassium-B-naphthoxide,potassium polysul- methylbismuthine, triethylbismthine, trimethylbismthine, 55 fide, potassium -sodium phosphate, potassium stearate, triphenylbismuthine, tri-n-propylbismuth, including ana- potassium sulfide, potassium suffite, potassium sulfate, logue, homologue, isomers and derivative thereof. potassium thiocyanate, potassium xanthate, potassium [0103] Non-limiting potassium derivative compounds fluorosilicate, N-potassiumethylene- diamine, oxalic acid

27 53 EP 0 954 558 B1 54 dipotassium salt, potassium beta-hydropyruvic acid, po- um thiocyanate, potassium acetylide, potassium chlo- tassium 1,1-dimethylurea, potassium 1,1-diethylurea, rate, potassium salicylate, potassium di-potassium tet- potassium 1,1-diepropylurea, potassium xanthate, po- racarbonylferrate, potassium tetraphenylborate, potassi- tassium ethylxanthate, potassium methylxanthate, po- um triethylborohydride, potassium triacetoxyborohy- tassium salt thiophenol, potassiumaluminum-tri-tert-bu- 5 dride, potassium triphenylborane, potassium hydroxide, toxide, potassium ferrosilicon, triphenylmethylpotassi- potassium diphenylphosphide, potassium methoxide, um, methylpotassium, ethylpotassium, potassiumethy- potassium ethoxide, potassium tri-sec-butylborohydride, nyl(acetylide), propylpotassium, isopropylpotassium, tri-tert-butylborohydride, potassium triethylborohydride, butylpotassium, isobutylpotassium, secbutylpotassium, potassium triphenylborohydride, potassium trisiamyl- tertbutylpotassium, pentapotassium, hexylpotassium, 10 borohydride, potassium metavanadate, potassium cy- heptapotassium, amylpotassium, isoamylpotassium, clohexanebutyrate, potassium hexachloroplatinate, po- benzylpotassium, dimethylbenzylpotassium, tolylpotas- tassium thiocyanate, potassium selenocyanate, potassi- sium, dodecylpotassium, cyclopentadienylpotassium, um cyanate, potassium floride, potassium hexafluoroan- methylcyclopentadienylpotassium, cyclohexylpotassi- timonate, potassium hexafluoroaluminate, potassium um, potassiumheptyl, potassiumdodecyl, potassium tet- 15 hexafluoroar- senate, potassium hexafluorosilicate, po- radecyl, potassium hexadecyl, potassium octadecyl, tassium hexacyanocobalt(II)ferrate(II), dipotassiumhex- phenylpotassium, potassium o-tolyl, potassium m-tolyl, acyanocobalt(II)ferrate(II), potassium hexafluorotitan- potassium p-tolyl, potassium-p-chlorophenyl, potassium ate, potassium hexafluorozirconate, potassium hexahy- p-bromophenyl, potassium potassium o- anisyl, potassi- droxyantimonate, potassium hexachlororuthenate, po- um m-anisyl, potassium p-anisyl, potassium diethoxy- 20 tassium hexachloropalladate, potassium formate, potas- phenyl, potassium dimethoxyphenol, potassium m- sium tetracyanonickelate, potassium tetrafluoroalumi- cumyl, potassium p-ethoxyphenyl, potassium m-dimeth- nate, potassium tetrafluoroborate, potassium thioace- ylaminophenyl, potassium 9-flourene, potassium a-nap- tate, L-glutamic acid monopotassium salt, fumaric acid thyl, potassium b-napthyl, potassium p-phenylphenyl, potassium salt, oxamic acid potassium salt, potassium potassium 9-phenylanthryl, potassium 9-anthryl, potas- 25 salt diphenyl-phospane, P-aminobenzoic potassium salt, sium 9-methylphen- anthryl, potassium pyridyl, potassi- aminobenzole acid potassium salt, alpha-napthalene- um 2-pyridyl, potassium 3- pyridyl, potassium 6-bromo- acetic acid potassium salt, dipotassium salt 2,6-naphtha- 2-pyridyl, potassium 5-bromo-2-pyridyl, potassium lenedicarboxlic acid, potassium cyclcohexanetherate, dibenzofuryl, potassium 3-quinoyl, potassium 2-lepidyl, potassium phthalimide, P-aminosalicylic acid potassium potassium triphenylmethyl, potassium 2,4,6-trimethyl- 30 salt, potassium salt 3,5-dimethylcyclo- hexyl sulfate, in- phenyl, potassium 2,4,6-triisopropylphenyl, potassium dolebutyric acid potassium salt,indole-3-butyric acid po- 2,3,5,6-tetraiso- propylphenyl, potassium tetrabutylphe- tassium salt, potassium diphenylphosphide, potassium nyl, thiophenedipotassium, toluenedipotassium, diphe- dimethylsilanolate, potassium triethylborohydride, po- nylethylenedipotassium, potassium- amylethynyl, potas- tassium propoxide, potassium isopropoxide, potassium siumphenylethynyl, potassiummethoxybromophenyl, 35 butoxide, potassium sec-butoxide, potassium pentoxide, potassium phenylisopropyl, potassium tetraphenylbo- potassium tert-pentoxide, potassium hydrogenphtha- ron, potassium tetramethylboron, potassium a-thienyl, late, potassium oxalate, potassium hydrogen- sulfate, potassium m-trifluoromethylphenyl, phenylethynylpotas- monopotassium acetylenedicarboxylic acid, potassium sium, 3-furylpotassium, phenylisopropylpotassium, pyrophosphate, potassium dihydrogenphosphate, po- dibenzofuranylpotassium, potassium dimethylbenzyl, 40 tassium hexoate (potassium salt hexoic acid), potassium potassium selenocyanate, potassium trimethylsi- diphenylphosphide, potassium trimethylsilonalate, po- lanolate, diphenylphosphide, potassium benzoate, po- tassium phthalic acid, P-aminoben- zoic acid potassium tassium tert-butyl carbonate, potassium azide, di-potas- salt, monopotassium L-aspartic acid, tetraphenyldipo- siumcyanamide, potassium cyanide, potassium dicyan- tassium (C6H5)2CK2C(C6H5)2, potassiumethylphenyl amide, cyclohexanebutyric acid potassium salt, cy- 45 (KCH2C6H5), potassium bromate, potassium chromate, clohexane acid potassium salt, cyciopentadientylpotas- potassium hydrogenphospate, monpotassium salt D- sium, potassium tri-tert-butoxyaluminum hydride, potas- shaccharic acid, DI-asparatic potassium salt, (R)-alpha- sium triethylborohydride, potassium trimethylborohy- hyroxymethylaspartic acid potassium salt, potassium flu- dride, potassium tripropylborohydride, potassium triiso- oride, potassium iodate, potassium salt ethyl malonate, propylborohydride, potassium tributylborohydride, 50 potassium thioacetate, potassium phenol, potassium salt potassium triisobutylborohydride, potassium tri-sec- aminobenzoic acid, potassium aminophenol salt, potas- butylborohydride, potassium tri-tert-butylborohydride, sium cyclo- hexenol, potassium methylcyclohexenol, po- potassium trisiamylborohydride, potassium chlorate, po- tassium cyclopropanol, potassium methylcyclopropanol, tassium tert-butoxide, potassium sec-butoxide, iso-bu- potassium cyclobutanol, potassium methylcyclobutanol, toxide, potassium antimonate, potassium diphenylphos- 55 potassium methylcyclopentanol, potassium cyclopenta- phide, potassium bis(trismethylsilyl) amide, tripotassium nol, potassium cyclohexenol, potassium methylcy- phosphite, potassium selenocyanate, potassium tri-sec- clohexenol, potassium dimethylcyclohexenols (e.g. po- butylborohydride, potassium triethylsilanolate, potassi- tassium 3,5-dimethylcyclohexanol, potassium 2,3-

28 55 EP 0 954 558 B1 56 dimethylcyclohexanol, potassium 2,6-dimethylcyclohex- dianion, bromomagnesium isopropylcyclohexylamide, anol, potassium 2,5-dimethylcyclohexanol, 3,5-dimeth- methylmagnesium bromide, methylmagnesium chloride, ylcyclohexanol), potassium o-ethylxanthic acid, mono- ethylmagnesium chloride, magnesium floride, magnesi- potassium salt 2-ketoglutaric acid, dipotassium salt, ke- um chloride, butylmagnesium chloride, isopropylmag- tomalonic acid, potassium salt lactic acid, dipotassium 5 nesium chloride, cyclopentylmagnesiumhydride, cy- thiosulfate, potassium antimony tartrate, potassium clopentylmagnesium- hydroxide, cyclopentylmagnesi- dichloroacetate, potassium dimethyl- acetate, potassium umchloride, cyclopentylmagnesium- methyl, cy- diethylacetate, potassium dipropylacetate, potassium clopentylmagnesiumethyl, cyclopentylmagnesiummeth- metaborate, potassium tetraborate, potassium tetrachlo- ylol, cyclopentylmagnesiumethylol, cyclopentylmagnesi- ro- cuprate, potassium acetoacetate, potassium diiso- 10 ummethoxy, cyclopen- tylmagnesiumethoxy,cyclohexy- propylamide, potassium diethylamide, potassium lmagnesiumhydride, cyclohexylmagnesiumhydroxide, dimethylamide, potassium bis(dimethylsilyl)amide, dipo- cyclohexylmagnesiumchloride, cyclohexylmagnesium- tassium phthalocyanine, dipotassium- tetrabromocu- methyl, cyclohexylmagnesiurnethyl, cyclohexylmagne- prate, dipotassium tetrabromonickelate, dipotassium- siummethylol, cyclohexylmagnesiumethylol, cyclohexy- tetrachloromanganate, dipotassiumbutadiyne, potassi- 15 lmagnesiummethoxy, cyclohexylmagnesiumethoxy, um cyclopen- tadienide, potassium dicyclohexylamide, tert-butylmagnesium chloride, isobutylmagnesium chlo- potassium diethylamide, potassium dimethylamide, po- ride, allymag- nesium chloride, benzylmagnesium chlo- tassium dipropylamide, potassium diisopropylamide, po- ride, benzylmagnesium hydride, benzylmagnesium tassium thexylborohydride, potassium tri-tert- butoxya- ethylate, benzylmagnesium methylate, benzylmagnesi- luminohydride, potassium trimethylsilyl)acetylide, potas- 20 um ethoxy, benzylmagnesium methoxy, magnesium ac- sium triethylsilyl)acetylide, potassium tris[(3-ethyl-3- etate, magnesium methyl carbonate, trimethylsilylmethyl pentyl)oxy]- aluminohydride, (phenylethynyl)potassium, magnesium chloride, magnesium acetate tetrahydrate, 2-thienylpotassium, potassium diethyldihydroaluminate, methylmagnesium isopropylcyclohexylamide, magnesi- potassium dimethyldihydroalumin- ate, potassium alumi- um pyrophosphate, phenylethynylmagnesium bromide, num hydride, potassium bifluoride, potassium biphenyl, 25 methylphenylmagnesiumchloride, methylmagnesium, potassium biselenite, potassium bis(2-methoxyethoxy)- ethylmagnesium, propylmagnesium, isopropylmagnesi- aluminum hydride, potassium bismuthate, potassium bo- um, butylmagnesium, isobutylmagnesium, tert-butyl- rate, potassium chlorite, potassium cobaltnitrite, potas- magnesium, sec-butylmagnesium, phenylmagnesium, sium cyanoborohydride, potassium cyclopentadienide, magnesium acetate, magnesium hydrogenphosphate, potassium dicyanamide, potassium hexametaphos- 30 cyclopentylmagnesium, cyclopentylmagnesium- hy- phate, potassium hexanitrocolbaltate, potassium hydro- droxide, cyclopentylmethylmagnesium, methylcy- genphosphite, potassium hydrogenselenite, potassium clopentylmethylmag- nesium, allylmagnesium, benzyl- hydrogen- sulfite, potassium hydrosulfite, potassium hy- magnesium, pentylmagnesium, 1,1-dimethylpropylmag- pochloride, potassium metaarsenite, potassium metabi- nesiumhydroxide, 1,1-dimethylpropylmethylmagnesi- sulfide, potassium metaperiodate, potassium methacr- 35 um, phenylmagnesium, phenolmagnesium, magnesium ylate, potassium nitroferricyanide, oxybate, potassium hydroxide, magnesiumcarbonate, magnesiumsilicide, pentamethylcyclopentadienide, potassium phenolate, magnesium phosphate, magnesium phosphite, magne- polyphosphate, potassium polyphosphite, potassium sium bisulfite, L-aspartic acid magnesium, DL-aspartic propionate, potassium pyrophosphate, potassium se- acid magnesium, including analogue, homologue, iso- lenate, potassium selenite, potassium tetrachloroalumi- 40 mer, and derivative thereof. Corresponding beryllium, nate, potassium thiomethoxide, potassium thiosulfate, calcium, strontium, barium, radium and zinc compounds potassium thiosulfide, potassium thiosulfite, potassium are contemplated in the practice of this invention. See triactoxyborohydride, potassium trimethylsilonate, po- The Organic Compounds of Magnesium, Beryllium, Cal- tassium triethylsilonate, potassium tris(1-pyrazoly)boro- cium, Strontium, and Barium, loffe, Nesmeyanov, Am- hydride, including analogues, homologues, isomers and 45 sterdam (1967), Organomagnesium Methods in Organic derivatives thereof. Corresponding compounds of rubid- Synthesis, Wakefield, Academic Press, FL (1995), incor- ium, caesium (cesium), francium are contemplated in the porated by reference. The mixture of dialkyl magnesium practice of this invention. compounds with pyrophoric metallics is specifically con- [0104] Non-limiting derivative magnesium compounds templated. contemplated by this invention include: alkyl manganese 50 [0105] Non-limiting selenium derivative compounds compounds, dialkyl magnesium compounds, magnesi- include: alkyl and dialkyl selenium compounds, dimeth- um ethylate (ethoxide), magnesium methoxide, dimeth- ylselenium, dimethyl selenide, diethylselenium, dipro- ylmagnesium, diethylmagnesium, dipropylmagnesium, pylselenium, diaisopropylselenium, diabutylselenium, di- diisopropylmagnesium, dibutylmagnesium, ditertbutyl- aisobutylselenium, dia-tert-butylselenium, dia-sec-bu- magnesium, di-iso-butylmagnesium, di-sec-butylmag- 55 tylselenium, di-phenylselenium, tetramethylselenium, nesium, diphenylmagnesium, methylmagnesium chlo- tetraethylselenium, tetrapropylselenium, tetraisopro- ride, methylmagnesium iodide, magnesium methylcar- pylselenium, tetrabutylselenium, tetraisobutylselenium, bonate, magnesium hydroxide, magnesium anthracene tetra-tert-butylselenium, tetra-sec-butylselenium, tetra-

29 57 EP 0 954 558 B1 58 phenylselenium, phenylselenium, methylphenylseleni- clopentadienyl)iron, bis(trimethyl- cyclopentadienyl)iron, um, methylphenylselenide, methylphenolselenium, zinc cyclopentadienyl tert-butylcyclopentadienyl iron, bis selenite, di-n-butylphosphane selenide, selenanthrene, (pentamethylcyclopentadienyl)iron, methylcyclopentadi- selenourea, selenophene, allylphenylselenide, 1,3-dihy- enyl ethylcyclopentadienyl iron, bis(hexylcyclopentadi- dro-benzoimid, 2,3- dihydro-3-methyl, 1,1-dimethyl-2- 5 enyl)iron, bisindenyl iron, butadiene iron tricarbonyl, di- selenourea, diphenyl diselenide, phenylselenyl chloride, cyclopentadienyl iron, cyclopentadienyl iron (di carbonyl) benzeneseleninic acid, sodium selenite, benzeneseninic (iodide), cyclopen- tadienyl iron (carbonyl) (iodide) anhydride, potassium selenocyanate, selenourea, sodi- (methyltetrahydrofuran), iron (III) ferrocyanide, ammoni- um hydrogenselenite, 4-chlorobenzeneseleninide, um hexacyanoferrate (II) hydrate, cyclopentadienyliron 4-(methylseleno)butyrate, benzyl selenide, alkyl seleni- 10 dicarbonyl dimer, cyclopentadienyliron dicarbonyl io- um, including dimethylselenide, diethylselenide, dipro- dide, iron pentacarbonyl, diiron nonacarbonyl, ferroce- pylselenide, etc., ally phenyl selenide, benzeneselenol, neacetic acid, ferroceneacetonitrile, ferrocenemethanol, benzyl selenide, (phenylselenomethyl)trimethylsilane, acetylferrocene, including analogue, homologue, iso- potassium selenate, potassium selenite, selenic acid, mer, and derivative thereof. Other examples are set forth dibenzyl diselenide, p-tolyl selenide, triphenylphosphine 15 U.S. Patents 2,680,; 2,804,468; 3,341,311, The Organic selenium, seleno-DL-methionine, P-tolyl selenide, in- Chemistry of Iron, Koerner, New York, Academic Press cluding analogue, homologue, isomer, and derivative (1978), incorporated herein by reference. thereof. See Organoselenium Chemistry, Liotta, John [0108] Non-limiting nickel derivative compounds in- Wiley & Sons, N.Y. (1987), incorporated herein by refer- clude: alkyl, aryl, alkyloxy, alkylanol, aryloxy, di/trialkyl, ence. 20 di/triaryl, di/trialkyloxy, di/trialkylanol, di/triaryloxy, and/or [0106] Non-limiting telluride derivative compounds in- cyclomatic complexes, including, biscyclopentadienyl clude: di-n-butylphosphane selenide, selenanthrene, se- nickel, cyclopentadienyl methylcyclopentadienyl nickel, lenourea, selenophene, allylphenylselenide, dimethyltel- bis(methylcyclopentadienyl) nickel, bis(triphenylphos- luride, diethyltelluride, dipropyltelluride, diisopropyltellu- phine)dicarbonyl nickel, bis(isopropylcyclopentadienyl) ride, dibutyltelluride, diaisobutyltel- luride, dia-tert- 25 nickel, bisindenyl nickel, cyclopentadienyl nickel nitrosyl, butyltelluride, dia-sec-butyltelluride, di- phenyltelluride, methylcyclopentadienyl nickel nitrosyl, including ana- tetramethyltelluride, tetraethyltelluride, tetrapropyltellu- logue, homologue, isomer, and derivative thereof. ride, tetraisopropyltelluride, tetrabutyltelluride, tetrai- [0109] Non-limiting cobalt derivative compounds in- sobutyltelluride, tetra-tert-butyltelluride, tetra-sec- clude: biscyclopentadienyl cobalt, bis(methylcyclopenta- butyltelluride, tetra-phenyltelluride, phenyltelluride, me- 30 dienyl) cobalt, bis(dimethylcyclopentadienyl) cobalt, cy- thyl-phenyltelluride, methylphenoltelluride, zinc selenite, clopentadienyl cobalt, dicarbonyl, cobalt(ous) hexame- di-n-butylphosphane telluride, diphenyl ditelluride, thylenetetramine, cobalt(ous) hydroxyquinone, cy- dimethyltelluride, diethyltelluride, dipropyltelluride, diiso- clopentadienylcobalt dicarbonyl, including analogue, propyltelluride, dibutyltelluride, diisobutyltelluride, di-tert- homologue, isomer, and derivative thereof. butyltelluride, di- sec-butyltelluride, di-phenyltelluride, 35 [0110] Non-limiting zinc derivative compounds in- dimethylditefluride, diethylditelluride, dipropylditelluride, clude: alkyl zinc, aryl zinc, alkyloxy zinc, aryloxy zinc, diisopropylditelluride, dibutylditelluride, diisobutylditellu- dialkyl zinc, diaryl zinc, dialkyloxy zinc, diaryloxy zinc, ride, di-tert-butylditelluride, di-sec-butylditelluride, di- cyclomatic zinc complexes, including, dimethylzinc, di- phenylditel- luride, including analogue, homologue, iso- ethylzinc, dipropylzinc, diisopropyl- zinc, dibutylzinc, di- mer, and derivative thereof. 40 isobutylzinc, di-tert-butylzinc, di-sec- butylzinc, di-phe- [0107] Non-limiting iron derivative compounds in- nylzinc, zinc acetate, zinc ethoxide, zinc arsenide, zinc clude: [cyclopentadienyl] methylcyclopentadienyl iron, hydroxide, zinc selenide, zinc selenite, zinc flouride, zinc ferrocene, methylferrocene, and butadiene iron tricarb- chloride, zinc cyanide, zinc floride, zinc chloride, zinc un- onyl, [butadiene iron tricarbonyl,] dicyclopentadienyl iron decylenate, zinc nitrate, zinc acrylate, zinc methacrylate, and dicyclopentadienyl iron compounds;ferrocene, 45 methyl zinc chloride, isobutylzinc chloride, zinc stearate, methylferrocenes, decamethylferrocene (bis(pentame- zinc dimethyldiethiocarbamate, di-n-propylzinc, di-o- thylcyclopentadienyl)iron), 1,1’-diacetylferrocene, fer- tolyzinc, isobutyl- zinc chloride, methylzinc chloride, zinc rocenecarboxylic acid, 1,1’-ferrocenecarboxylic acid, fer- methacrlate, zinc acrylate, zinc hexaflourosilicate, zinc roceneacetic acid, ferroceneacetronitrile, 1,1’-ferrocene- nitrate, zinc hydroxide, zinc undecylenate, zinc selenite, bis(diphenylphosphine), ferrocenecarbonxaldehyde, 50 zinc stearate, zinc cyanide, isobutylzinc chloride, methyl ferrocenecarboxylic acid, 1,1’ferrocenedicarboxylic acid, zinc chloride, L(+)lactic acid hemizinc, including ana- 1,1-’ferrocenedimethanol, ferrocenedimethanol, diiron logues, homologues, isomers and derivatives thereof. nonacarbonyl, di-irondodecacarbonyl, di-ironnonacarb- Corresponding magnesium compounds are contemplat- onyl, ironpentacarbonyl, triiron dodecacarbonyl, vinylfer- ed. See Zinc, The Science and Technology of the Metal, rocene, biscyclopentadienyl iron (ferrocene), cyclopen- 55 Its Alloys & Compounds, Mattewson, N.Y., Reinhold tadienyl methylcyclopentadienyl iron, bis(methylcy- (1959), incorporated by reference. clopentadienyl)iron, cyclopentadienyl ethylcyclopentadi- [0111] Non-limiting examples of transition metal deriv- enyl iron, bis(ethylcyclopentadienyl)iron, bis(dimethylcy- ative compounds, e.g. metals of scandium, titanium, va-

30 59 EP 0 954 558 B1 60 nadium, chromium, manganese, iron, cobalt, nickel, and logues, homologues, isomers and derivatives thereof. their respective chemical groups, include transition metal [0114] Non-limiting titanium derivative compounds in- alkyl, aryl, alkyloxy, aryloxy, and/or ring system type com- clude: titanium diisopropoxide bis(2,4-pentanedionate), pounds. Multiple alkyl, alkyloxy radicals per metal are titanium methoxide, titanium ethoxide, titanium (IV) 2- contemplate. Cyclomatic transition metal compounds are 5 ethylexoxide, titanium isopro- poxide, tetraethylorthoti- expressly contemplated. See Organometallic Chemistry tanate, including analogues, homologues, isomers and of Transition Metals, 2 Ed, Crabtree, John Wiley & Sons, derivatives thereof. N.Y. (1994), incorporated herein by reference. [0115] Non-limiting zirconium derivative compounds [0112] Non-limiting examples of manganese com- include: zirconium carbide, zirconium propoxide, zirco- pounds include benzyleyelopentadienyl manganese tri- 10 nium ethoxide, decamethylzirconocene, decamethylzir- carbonyl; 1.2-dipropyl 3-cyclohexylcyclopentadienyl conocene dichloride, bis-cyclopentadienyl zirconium, in- manganese tricarbonyl; 1.2-diphenylcyclopentadienyl cluding analogues, homologues, isomers and derivatives manganese tricarbonyl; 3-propenylienyl manganese tri- thereof. carbonyl; 2-tolyindenyl manganese tricarbonyl; fluorenyl [0116] Non-limiting molybdenum derivative com- manganese tricarbonyl; 2.3.4.7 - propyflourentyl manga- 15 pounds include: molybdenumcarbonyl, molybdenum nese tricarbonyl; 3-naphthylfluorenyl manganese tricar- hexacarbonyl, tripyridine tricarbonylmolybdenum, mo- bonyl; 4.5.6.7-tetrahydroindenyl manganese tricarbonyl; lybdenumoxytetrachloride, cyclopentadienyl molybde- 3-3ethenyl-4, 7-dihydroindenyl manganese tricarbonyl; num carbonyls, including but not limited to benzenemo- 2-ethyl 3 (a-phenylethenyl) 4,5,6,7 tetrahydroindenyl lybdenumtricar- bonyl, bicycloheptadienemolybdenum manganese tricarbonyl; 3 - (a-cyclohexylenthenyl) -4.7 - 20 tetracarbonyl, cycloheptatrien- molybdenum tricarbonyl, dihydroindenyl manganese tricarbonyl; 1,2,3,4,5,6,7,8 - bis-cyclopentadienylbimolybdenum pentacar- bonyl, octahydrofluorenyl manganese tricarbonyl and the like. mesitylenemolybdenum tricarbonyl, tropeniummolybde- A preferred cyclomatic manganese tricarbonyl is cy- num tricarbonyl fluoroborate, cyclopentadienylmolybde- clopentadienyl manganese tricarbonyl. A more preferred num tricarbonyl dimer, methylcyclopentadienylmolybde- cyclomatic manganese tricarbonyl is methyl cyclopenta- 25 num tricarbonyl dimer, anisole molybdenum tricarbonyl, dienyl manganese (MMT). Non-limiting examples of ac- mesitylene molybdenum tricarbonyl, including analogue, ceptable substitutes include the alkyl, aralkyl, aralkenyl, homologue, isomers and derivative thereof. See U.S. cycloalkyl, cycloalkenyl, aryl and alkenyl groups. The Patents 3,272,606, and 3,718,444, incorporated by ref- above compounds can be generally prepared by meth- erence. Corresponding chromium and tungsten com- ods that are known in the art. Corresponding compounds 30 pounds are contemplated in the practice of this invention. of technetium and rhenium (see Canadian Patent [0117] Non-limiting copper derivative compounds in- #1073207) are contemplated. clude: alkyl copper compounds, bis(ethylenediamine) [0113] Non-limiting nitrogen derivative compounds in- copper(II) hydroxide, copper carbonate, cyclopentadi- clude: 2-methoxybenzylamine, 2-methoxybenzylamine, enyltriethylphosphine copper, diazoaminobenzene 2-(4-methoxybenzylamino)pyridine, nitroanline, 1-ni- 35 (ous), copper acetate, copper acetylacetonate, copper troanline, 2-nitroanline, 3-nitroanline, 4-nitroanline, ni- aminoacetate, copper ethylacetate, copper ferrocyanide, troanisole, 1-nitroanisole, 2- nitroanisole, 3-nitroanisole, copper potassium ferrocyanide, copper nathenate, cop- 4-nitroanisole, aniline, 2-anilino- ethanol, anisamide, an- per nitrate, copper phosphide, copper phthalate, includ- isonitrile, acetonitrile, nitromethane, nitroethane, pico- ing analogue, homologue, isomers and derivative there- line, 1-picoline, 2-picoline, 3-picoline, 4- picoline, tetram- 40 of. See Copper, The Science and Technology of the Met- ethylammoniumhydroxide, tetraethylammoniumhydrox- al, Its Alloys & Compounds, Butts, N.Y., Reinhold (1954), ide, N,N,N’,N’-tetramethylethylenediamine, toluic hy- incorporated by reference. dazide, toluidine, m-toluidine, o-toluidine, p-toluidine, tol- [0118] Other contemplated organometallic com- unitrile, o-tolunitrile, p-tolunitrile, triazacyclononane, tri- pounds are metallocenes, non-limiting example com- azole, 1,2,4-triazole, triazine, 1,3,5-triazine, trib- 45 pounds include, ferrocene, cobaltocene, nickelocene, ti- utylamine, triethanolamine, trimethanolamine, tripropa- tanocene dichloride, zirconocene dichloride, uranocene, nolamine, trimethoxypyrimidine, 2,4,6-trimethoxypy- decamethylferrocene, decamethylsilicocene, decame- rimidine, tetramethylammonium, trimethylpyrazine, thyl-germaniumocene, decamethylstannocene, decam- urea, urazole, guanidine nitrate, guandine acetatic acid, ethylphosocene, decamethylosmocene, decamethylru- thiophenol, sodium salt thio- phenol, thiourea, cumidine, 50 thenocene, decamethylzirconocene, including ana- diphenylamine, m-xylidine, monmel- thylanine, toluidine, logue, homologue, isomers and derivative thereof. amylaminobenzene, ethylaminobenzene, aminophenyl, [0119] It is to be noted the above list is not exhaustive. methyl-o-toluidine, n-butylaminobenzene, n-propylami- The metals and their derivative compounds of this inven- nobenzene, monoethylaniline, mon-n-propylaniline, tion include every metal, metalloid, and/or non-metal ethyldiphenylamine, mono-n-butylaniline, diethylamine, 55 (herein "metal" or "metallic") capable of achieving vapor di-n-propylaniline, mono-isoamylaniline, diethylaniline, phase combustion, in combination with DMC. dimethylaniline, ethylamine, triethylamine, triphe- [0120] Applicant’s invention contemplates wide varia- nylamine, isopropylnitrite, ammonia, including ana- tion in metal substitution and mixing practice. Thus, it is

31 61 EP 0 954 558 B1 62 expressly contemplated the non-lead organo-metallics, tion system, efficiencies, fuel economy and power de- non-lead inorganic metallics, and/or their related high sired, as well as legal and/or environmental considera- heat releasing compounds, including those set forth tions. above may be mixed in varying proportions, and/or sub- [0125] It is expressly contemplated that Applicant’s stituted and/or replaced by any non-lead metallic or non- 5 metallics be incorporated into liquid fuel systems by metallic (organic or inorganic [atom, molecule or com- means of mutual solvents, mutual dispersents/solvents, pound, including those containing nitrogen, sulfur, chlo- colloidal media, suspension media, or other known rine, fluorine, helium, neon, argon, krpton, xenon, or ra- means, or being separately injected. Metallic’s, which are don atoms]) accomplishing the object of this invention. solid at ambiant temperatures may be introduced into the [0121] Derivative compounds and combinations may 10 combustor/combustion chamber by liquidification or gas- be entirely or may contain in part or whole non-metal ification means. atoms, e.g. nitrogen, sulfur, chlorine, fluorine, helium, ne- [0126] It is preferred the metallics of this invention be on, argon, krpton, xenon, or radon, etc., so long as pri- relatively inexpensive to manufacture on a mass produc- mary object of vapor phase combustion is accomplished. tion basis. It is contemplated said non-metals will employed in var- 15 [0127] The metal and concentration amounts are to be ying proportions within the compound or combination optimized, such that vapor phase combustion results. compounds to achieve synergistic improvements in heat Thus, the metal and its optimum concentration amount, releases, burning velocity, thermal efficiency, emissions, is an amount that results in vapor phase combustion, power generation, and the like. For example, hexameth- which is evidenced by improved fuel economy, emis- ylphosphoric triamide, N,N,N’,N’- hexamethylsilanedi- 20 sions, power, etc. In the practice of this invention, the amine, bis(diethylamono)-dimethylsilane may be added ratio of dialkyl carbonates (DMC) by weight to elemental as a co-metallic in minor amounts to the composition to metal weight concentration is equal to or less than further improve vapor phase combustion (e.g further en- 10,000:1 (by parts) to 1:1, including from 1, 000,000:1, hancing fuel ecomony or power, etc.). 100,000:1, 50, 000:1, 25,000:1, 15,000:1, 10,000:1, 5, [0122] Ranges vary depending upon the specific me- 25 000:1, 1, 000:1, 500:1, 300:1, 200:1, 150:1, 100:1, 90:1, tallic, fuels, fuel weight, regulations, advance applica- 80:1, 75:1, 70:1, 60:1, 50:1, 40:1, 30:1, 20:1, 10:1, 5:1 tions, thermodynamics, and the extent combustion sys- to 3:1, or interval ratio contained therein (e.g. 50:1 to 30: tems are modified to enhance the accelerated low tem- 1) and also 1:1 to 1:20, or other ratio that maximizes perature high energy nature of Applicant’s invention. vapor phase combustion. Thus, metallic concentrations that maximize combustion 30 [0128] Metallic salts may be employed in fuels at 0.01 velocity and/or the vapor phase combustion object of this to 4000.0 parts metallic per million fuel, 1.0 to 150 ppm invention are expressly contemplated. metallic being contemplated, with concentrations equal [0123] Thus, it is contemplated Applicant’s metals are or less than 50.0, 40.0, 30.0, 20.0, 16.0, 10.0, 5.0 ppm substitutents in the fuel, itself, which may also contain metallic also contemplated. Other salt concentrations will certain non-metals and their derivative compounds, in- 35 vary from 0.10 to 75.0 ppm metal per million, from 30.0 cluding but not limited to nitrogen, sulfur, fluorine, chlo- to 2000.0 per million, from 25 to 750 parts metallic or salt rine, helium, neon, argon, krpton, xenon, or radon, in per million fuel. In the application of Applicant’s invention combination with dialkyl carbonates. These non-metals, elemental metal concentrations from 3.0 to 500.0 ppm and their derivative compound, may be employed with metal are expressly contemplated and desirable. Con- or without any other contemplated metals. It is further 40 centrations outside these ranges are contemplated. contemplated to substitute or mix these non-metallics [0129] It has been found that higher oxygen weight with non-metallics, with metallics, or to mix metallics with concentrations in fuel compositions, particularly with metallics, etc., to achieve synergistic improvements in higher concentrations of enhanced combustion proper- heat releases, burning velocity, thermal efficiency, emis- ties, permit higher acceptable metallic concentrations. sion reductions, power generation, and the like. This is 45 Higher average fuel densities are also associated with set forth below in the practice of trimethoxymethylsilane. higher acceptable metallic concentrations and higher ex- However, it is contemplated that Applicant’s fuel also be haust velocities, and are preferred. Engine combustion absent any metal or non-metal. That is, Applicant’s in- thermal dynamics and stoichiometry dictate upper me- vention, by accelerating burning velocity and/or increas- tallic limits. ing latent heat of vaporization, adn/or reducing combus- 50 [0130] As noted above, elemental metallic concentra- tion temperatures by fuel substituent tailoring, chemical tions will vary substantially. Non-limiting examples in- and/or mechanical means, as set forth herein or in my clude elemental metallic concentrations equal to or great- co-pending Applications, said fuel can be employed ab- er than 1/64 grams/gal, preferably 1.0 or more grams/gal, sent a metallic or non-metallic. more preferably 10 or more grams/gal, even up to 90 [0124] In accordance with this invention, Applicant’s 55 grams/gal. Indeed, in advance aviation, rocket and/or fuels will contain that amount of at least non-lead metallic, propellant applications, elemental metal concentrations which constitutes a combustion improving amount con- can be on the order of 100 to 1000 or more grams/gal, sistent with the fuel composition, stoichiometry, combus- especially in hypergolic conditions. Concentrations

32 63 EP 0 954 558 B1 64 above these ranges are also contemplated. All combus- high energy combustible compounds of these metals are tion improving or stoichiometric amounts of elemental beleive to be environmentally friendly. metal are contemplated, which maximize combustion so [0136] Applicant’s metals also include a full range of long as the resultant fuel’s burning velocity increases combustion catalysts including ferrous picrate, potassi- compared to fuel absent metallic. 5 um salts, Li and LH promoters. As presented below tri- [0131] Thus, metallic concentrations that maximize methoxymethylsilane has immediate application in in- combustion velocity and/or other objects of this invention stant invention and is preferred. are expressly contemplated. Ranges will vary depending [0137] As noted, Applicant’s invention, by accelerating upon the specific metallic, its concentration, concentra- burning velocity and/or reducing combustion tempera- tion and type of dialkyl carbonate, concentration and na- 10 tures by fuel substituent tailoring, chemical and/or me- ture of hydrocarbon fuel composition, including its den- chanical means as set forth in above PCT Applications, sity, the intended application, relevant thermodynamics, can be employed absent a metallic. extent combustion systems are modified to enhance the [0138] Any example or disclosure of Mn may be sub- accelerated low temperature high energy nature of Ap- stituted for any metal or derivative compound set forth in plicant’s invention, environmental regulation, and the 15 herein, under proviso said metallic causes vapor phase like. Metallics used in the fuel compositions of the present combustion. Likewise, wide latitude in metal substitution invention should be fuel soluble generally having melting is contemplated. Thus, any metal, metalloid, or non-met- and boiling ranges compatible with liquid hydrocarbons, al, may be substituted with any other in a particular me- or be incorporated into liquid fuel systems by means of tallic compound. That is not to say substitution is blind, mutual solvents, dispersants, or other means, as re- 20 but rather if the element is likely to be advantageously quired. Alternatively, the metallics may be introduced into impacted, it may be substituted. Thus, non-leaded ele- the combustor/combustion chamber of liquide or gase- ments and their compounds, may be freely substituted ous fuels (e.g. natural gas) by separate means, including for one another, herein. separate injection, liquidification or gasification, colloidal [0139] It is preferred that metals in the fuel composition media, suspension media. Metallics may be introduced 25 of the present invention, including oxygenated metallic into the combustor in an atomized, vaporized, or gasified compounds, contribute to the fuel’s heat of vaporization, form, separately and/or in combination with the other in- its burning velocity, post ignition and pre-combustion gredients of the invention. temperatures which enhance generation and combus- [0132] In solid fuel applications, the metallic may be tion of free radicals, thermal stability at ambient temper- introduced as a solid. In hybrid applications, it may be 30 ature, and have high heat and energy releasing charac- introduced as either as solid, liquid or gas, together with teristics, etc. the balance of the invention’s ingredients. Most prefera- bly, the metallic is employed as a propellant or co-pro- METALLIC CATALYST PRACTICE pellant, or jointly together with a propellant. Hydrogen content of the metallic and/or metallic containing fuel 35 [0140] In the practice of this invention, it has been should be maximized, to the extent possible. found that combustion activity employing Applicant’s di- [0133] It is preferred practice that metals herein have alkyl carbonates and metallics, which together yield va- oxides whose heats of formation are negative, and por phase combustion, can be improved by the addition should be equal or exceed (e.g. be more negative) about of trimethoxymethylsilane or substitute. As contemplated -10,000 to -75,000 calories/mole. More preferred are 40 herein any reference to trimethoxymethylsilane those equal or exceeding -100,000 to -400,000 gr calo- ("TMMS") or metallic catalyst in the specification or ex- ries/mole, and greater (more negative). Acceptable sim- amples herein contemplates TMMS substitution, as set ple oxides containing one or two oxygens may have heats forth below. of formation equal or exceeding -50,000 to -200,000, or [0141] Applicant has discovered TMMS to be a cata- greater, calories/mole. 45 lyst, when in combination with a large population of me- [0134] It is also desirable the element metal employed tallics disclosed herein, and acts to benefically improve in this invention be of a low relative molecular weight. the overall results of this invention. Acceptable metals have molecular weights of 100 or less, [0142] TMMS is a desireable co-metallic of this inven- preferably 79 or less, more preferably 40 or less, and tion. Its use is contemplated with a majority of the metal- most preferably 30 or less. 50 lics, which may be utilized in the practice of this invention, [0135] Applicant’s fuel may include gaseous and solid including cyclomatic metallics, alkali metal alkanols, in- metals and/or their related compounds. It is preferred the organic metallics such as the metallic hexacyanides, etc. combustion products of the metals be environmentally Thus, it is an embodiment herein that disclose to any friendly, e.g. low or no toxicity. Potassium, sodium, mag- metallic also includes TMMS as a co-metallic. nesium, lithium, born, silicon, sodium, iron, copper, cal- 55 [0143] Non-limiting examples of TMMS substitutes in- cium, aluminum, and phosphorus are acceptable. Potas- clude those compounds, including metallic and non-me- sium, sodium, magnesium, lithium, born, silicon, sodium, tallic organics, whose structure is similar to TMMS’s, thus iron, and phosphorus are also acceptable. The related including derivative, analogue, homologue and isomers

33 65 EP 0 954 558 B1 66 of TMMS. Other subsitutes are also contemplated. Spe- trium, lanthanum, actinium, cerium, thorium, titanium, zir- cific non-limiting examples include, ethoxytrimethylsi- conium, hafium, praseodymium, protactinium, tantalum, lane, isobutyltriethoxysilane, tetramethylsilane, dimeth- neodyium, uranium, tungsten, promethium, neptunium, oxy-methyl-vinyl- silane, methyltriethoxysilane, 3-amino- samarium, plutonium, ruthenium, osmium, europium, propyltriethoxysilane, 3- aminopropyl-trimethoxysilane, 5 americium, rhodium, iridium, gadolinium, curium, plati- vinyltrimethoxysilane, diethoxydimethylsilane, dimeth- num, terbium, berkelium, silver, gold, dysprosium, cali- oxydimethylsilane, vinyltris(2-butyldenaminooxy)silane, fornium, cadmium, mercury, holmium, titanium, erbium, tetraalkyloxysilanes (e.g. tetramethoxysilane, tetrae- thulium, arsenic, antimony, ytterbium, selenium, telluri- thoxysilane, tetrapropyloxysilane, tetraisopropylsilane, um, polonium, lutetium, astatine, mixture thereof, includ- tetraisobutylsilane, etc.), dialkylphosphites (e.g. dimeth- 10 ing organic and inorganic derivatives (as set forth above). ylphosphite, dipropylphosphite, diethylphosphite, dib- Said fuel optionally containing hydrogen or a viscous hy- utylphosphite, di-tert-butylphosphite, etc.), trialkylphos- drocarbon base fuel, an oxidizer, or a co-metallic catalyst phites (e.g. trimethylphosphite, triethylphosphite, triiso- (as set forth above). Said fuel further characterized as propylphosphite, tributylphosphite), dimethylmethyl- having a pH of 10.5 or less. When this fuel composition phosphonate, diethylmethylphosphonate, potassium 15 contains a hydrocarbon base, said base may have a vis- pryophosphite, trimethylorthoacetate, triethylorthoace- cosity outside normal industry standards (as set forth tate, trimethylorthobutyrate, triethylorthobutyrate, tri- above). However, resultant fuel’s viscosity is to be within methylorthovalerate, trimethylorthoformate, including industry standards. Said result fuel is characterized as homolgues, analogues, isomers, and derivatives thereof. being a vapor phase composition wherein a luminous [0144] The examples of aforementioned PCT Applica- 20 reaction zone extends from surface of said element, typ- tions are incorporated herein and are optionally modified ically evidenced by increased fuel economy, range, for pH limitation, non-manganese metallics, and addition thrust, emissions, or power, as compared to the hydro- of a co-metallic catalyst. They are also optionally modifed carbon base alone. for the viscosity, burning velocity, and enthalpy of vapor- [0147] By further example, a method is contemplated ization limitations contained either therein or herein. 25 for minimizing hydrolysis of a fuel compositions compris- [0145] A vapor phase method of the present invention ing the steps of: providing or introducing a symmetrical for combusting a metallic includes the steps of introduc- lower dialkyl carbonate to a combustion improving ing kinetic free radicals into a combustor from a dialkyl amount of at one least metal or non-metal as set forth carbonate (dimethyl carbonate); igniting and combusting above (combustible compound) containing at least one a flammable metallic or metal compound in presence of 30 element selected from the group consisting of aluminum, said free radicals at temperature below said metal’s oxide boron, bromine, bismuth, beryllium, calcium, cesium, boiling point and preferably above said metal or metallic chromium, cobalt, copper, francium, gallium, germani- compound’s boiling point; combusting said metal; where- um, iodine, iron, indium, lithium, magnesium, manga- by accelerated burning occurs, evidenced by a brilliant nese, molybdenum, nickel, niobium, phosphorus, potas- luminous reaction zone extending some distance from 35 sium, palladium, rubidium, sodium, tin, zinc, praseodym- the metal’s surface; and wherein metallic oxide particles ium, rhenium, silicon, vanadium, strontium, barium, ra- resulting from combustion range in low to submicron dium, scandium, yttrium, lanthanum, actinium, cerium, range and/or remain in a gaseous state. Contemplated thorium, titanium, zirconium, hafium, praseodymium, metallics include all non-lead metals and their related protactinium, tantalum, neodyium, uranium, tungsten, compounds whose combustion product has negative 40 promethium, neptunium, samarium, plutonium, ruthe- high heat of formation. As provided herein metals also nium, osmium, europium, americium, rhodium, iridium, refer to non-metals. Contemplated compounds of said gadolinium, curium, platinum, terbium, berkelium, silver, elemental metals are those with have high heats of com- gold, dysprosium, californium, cadmium, mercury, hol- bustion. Metallics may be organo-metallics or inorganic mium, titanium, erbium, thulium, arsenic, antimony, yt- compounds. 45 terbium, selenium, tellurium, polonium, lutetium, asta- [0146] By way of further example, a fuel composition tine, mixture thereof, including their organic and inorganic of the present invention may include a combustion im- derivative compounds, then adding a hydrocarbon, in- proving amount of a lower dialkyl carbonate; a combus- cluding those whose viscosity is greater than acceptable tion improving amount of at least one high heating (ex- industry standards; mixing said carbonate, said combus- ceeding 2,000 to 8,000 to 12,000, or more, Kcal/kg) com- 50 tible compound, and said hydrocarbon so as to produce bustible compound containing at least one element se- a fuel composition having a pH of less than 11 (more lected from the group consisting of aluminum, boron, bro- preferrable ranges set forth above), which has accepta- mine, bismuth, beryllium, calcium, cesium, chromium, ble viscosities, can be stored at average temperatures cobalt, copper, francium, gallium, germanium, iodine, of 95°F or 65°F for up to 6 or 9 months, absent hydrolysis, iron, indium, lithium, magnesium, manganese, molybde- 55 and which is a vapor phase composition having upon num, nickel, niobium, phosphorus, potassium, palladium, combustion a luminous reaction zone that extends from rubidium, sodium, tin, zinc, praseodymium, rhenium, sil- surface of said combustible compound/element. icon, vanadium, strontium, barium, radium, scandium, yt-

34 67 EP 0 954 558 B1 68

Claims 8. The fuel composition of claim 1 or 2, wherein said combustible compound is a cyclopentadienyl man- 1. A fuel composition exhibiting minimum hydrolysis ganese tricarbonyl compound. comprising: 5 9. The composition of claim 1, wherein said composi- a symmetrical dialkyl carbonate; tion is a diesel fuel oil, said fuel being characterized a combustible compound containing at least one as having a viscosity equal to or less than 2.4 mm2/s element selected from the group consisting of at 40°C. aluminum, boron, bromine, bismuth, beryllium, calcium, cesium, chromium, cobalt, copper, 10 10. A fuel composition of claim 2, wherein said jet avia- francium, gallium, germanium, iodine, iron, indi- tion turbine fuel is characterized as having a vis- um, lithium, magnesium, manganese, molybde- cosity ranging from 8.1 to 15.0 mm2/sL at -20°C num, nickel, niobium, nitrogen, phosphorus, po- (ASTM 445); and a pH ranging from 4.5 to 10.5. tassium, palladium, rubidium, sodium, tin, zinc, praseodymium, rhenium, silicon, vanadium, or 15 11. The fuel composition of claim 1 or 2, wherein said a mixture thereof; dialkyl carbonate is dimethyl or diethyl carbonate. a hydrocarbon base fuel selected from the group consisting of alternative fuels, gaseous fuels, 12. The fuel composition of any preceding claim, where- automotive gasolines, aviation gasolines, diesel in said combustible compound is selected from the fuel oils, heavy diesels, locomotive diesels, ma- 20 group consisting of cyclopentadienyl manganese tri- rine diesels, gas oils, fuel oils, heavy fuel oils, carbonyl, [2-(cyclohexenyl)-ethyl]triethoxy-silane, gas turbine fuel oils, heavy gas turbine fuel oils, cyclohexenyl dimethoxymethylsilane, benzyltri- coal, coal oils, coal liquids, and heavy oils, methylsilane, N-(3-(trimethoxysilyl)propyl)ethylene- wherein the fuel composition has a pH of from diamine, N-1-(3-(trimethoxysilyl)propyl)diethylene- 3.0 to 11.0. 25 triamine, N-(3-(trimethoxysilyl)propyl)ethylenedi- amine, 1-(trimethylsilyl)pyrrolidine, triphenylsilanol, 2. An hydrocarbon base aviation turbine composition octamethyltrisiloxane,2,2,4,4,6,6-hexamethylcyclo- exhibiting minimum hydrolysis comprising: trisilazane, hexamethylcyclotrisiloxane, hexameth- yldisilane, 1,1,1,3,3,3-hexamethyl disilazane, hex- a symmetrical dialkyl carbonate; 30 amethyldisiloxane, hexamethyldisilthiane, allyltribu- a combustible compound containing at least one tylsilane, tetraalkylsilanes, 3-aminopropyl-triethox- element selected from the group consisting of ysilane, benzyltrimethylsilane, benzyltriethylsilane, aluminum, boron, bromine, bismuth, beryllium, N-benzyltrimethylsilyl-amine, diphenylsilanediol, di- calcium, cesium, chromium, cobalt, copper, hexylsilanediol, (trimethylsilyl)cyclopentadiene, po- francium, gallium, germanium, iodine, iron, indi- 35 tassium hexacyanoferrate (II), potassium hexacy- um, lithium, magnesium, manganese, molybde- anoferrate (III), potassium hexacyanocobalt (II) fer- num, nickel, niobium, nitrogen, phosphorus, po- rate, potassium hexacyanocobalt, potassium sodi- tassium, palladium, rubidium, sodium, tin, zinc, um ferricyanide, potassium ethoxide, a nitrogen praseodymium, rhenium, silicon, vanadium, or based compound, or a mixture thereof. a mixture thereof; 40 wherein the fuel composition has a pH of from 13. The fuel composition of claim 1, 2 or 8, additionally 3.0 to 10.5. containing a co-catalyst selected from group consist- ing of trimethoxymethylsilane, ethoxytrimethylsi- 3. The fuel composition of claim 1 or 2, wherein the pH lane, isobutyltriethoxysilane, tetramethylsilane, is from 4.5 to 10.5. 45 dimethoxy-methyl-vinyl-silane, methyltriethoxysi- lane, 3-aminopropyltriethoxysilane, 3-aminopropyl- 4. The fuel composition of claim 1 or 2, wherein the pH trimethoxysilane, vinyltrimethoxysilane, diethoxy- is from 4.5 to 9.5. dimethylsilane, dimethoxy-dimethylsilane, vinyltris (2-butylidenaminooxy)silane, tetramethoxysilane, 5. The fuel composition of claim 1 or 2, wherein the pH 50 tetraethoxysilane, tetrapropyloxysilane, tetraisopro- is from 4.5 to 8.5. pylsilane, tetraisobutylsilane, dimethylphosphite, dipropylphosphite, diethylphosphite, dibutylphos- 6. The fuel composition of claim 1 or 2, wherein the pH phite, di-tert-butyl-phosphite, trialkylphosphites, tri- is from 5.5 to 8.0. methylphosphite, triethylphosphite, triisopropyl- 55 phosphite, tributylphosphite, dimethylmethylphos- 7. The composition of claim 1 or 2, wherein the pH rang- phonate, diethylmethylphosphonate, potassium py- es from 6.3 to 6.8. rophosphite, trimethylorthoacetate, triethylorthoac- etate, trimethylorthobutyrate, triethylorthobutyrate,

35 69 EP 0 954 558 B1 70

trimethylorthovalerate, trimethylorthoformate, and amido, amino, aniline, anilino, azido, azino, azo, mixtures thereof. azoxy, benzylidine, anisyl, benzamido, toluyl, naph- thal, naphthobenzyl, naphthyl, naphthylidene, pro- 14. The composition of claim 2, wherein said dialkyl car- pylene, tolyl, α-tolyl, tolylene, or α-tolylene radical. 5 bonate is a C3 to C7 dialkyl dicarbonate.

15. A diesel fuel oil composition of claim 1, character- Patentansprüche ized as having a viscosity equal to or less than 2.4 mm2/s at 40°C. 1. Brennstoffzusammensetzung, die minimale Hydro- 10 lyse zeigt und Folgendes umfasst: 16. A automotive gasoline of claim 1, characterized as having a T-90 temperature ranging from 330°F to - ein symmetrisches Dialkylcarbonat, 280°F, a T-50 temperature ranging from 170°F to - eine brennbare Verbindung, die mindestens 230°F, and an average latent heat of vaporization of ein Element enthält, das aus der Gruppe aus- 880 to 920 BTU/gal at 60°F. 15 gewählt ist, die aus Aluminium, Bor, Brom, Wis- mut, Beryllium, Kalzium, Zäsium, Chrom, Ko- 17. The fuel composition of claims 1 or 2, additionally balt, Kupfer, Franzium, Gallium, Germanium, comprising a salt or co-solvent. Jod, Eisen, Indium, Lithium, Magnesium, Man- gan, Molybdän, Nickel, Niob, Stickstoff, Phos- 18. A method of minimizing hydrolysis of a hydrocarbon 20 phor, Kalium, Palladium, Rubidium, Natrium, fuel composition containing a dialkyl carbonate, said Zinn, Zink, Praseodym, Rhenium, Silikon, Va- method comprising: nadin oder einer Mischung aus diesen besteht, - einen Brennstoff auf Kohlenwasserstoffbasis, mixing a symmetrical lower dialkyl carbonate der aus der Gruppe ausgewählt ist, die aus al- with: 25 ternativen Brennstoffen, gasförmigen Brenn- stoffen, Automobilbenzinen, Flugbenzinen, Die- at least one combustible compound con- selheizölen, Schwerdieseln, Lokomotivdieseln, taining at least one element selected from Schiffsdieseln, Gasölen, Heizölen, schweren the group consisting of aluminum, boron, Heizölen, Heizölen für Gasturbinen, schweren bromine, bismuth, beryllium, calcium, cesi- 30 Heizölen für Gasturbinen, Kohle, Kohleölen, um, chromium, cobalt, copper, francium, Flüssigkohlestoffen und Schwerölen besteht, gallium, germanium, iodine, iron, indium, lithium, magnesium, manganese, molybde- wobei die Brennstoffzusammensetzung einen pH- num, nickel, niobium, nitrogen, phospho- Wert von 3,0 bis 11,0 aufweist. rus, potassium, palladium, rubidium, sodi- 35 um, tin, zinc, praseodymium, rhenium, sili- 2. Zusammensetzung für Flugzeugturbinen auf Koh- con, vanadium, or mixture; lenwasserstoffbasis, die minimale Hydrolyse zeigt and a hydrocarbon; und Folgendes umfasst:

whereby resultant composition has a pH ranging 40 - ein symmetrisches Dialkylcarbonat, from 4.5 to 10.5; - eine brennbare Verbindung, die mindestens storing said composition at a temperature of less ein Element enthält, das aus der Gruppe aus- than 32.2°C (90°F) . gewählt ist, die aus Aluminium, Bor, Brom, Wis- mut, Beryllium, Kalzium, Zäsium, Chrom, Ko- 19. The method of claim 18, wherein said storing in- 45 balt, Kupfer, Franzium, Gallium, Germanium, cludes the addition of an aqueous layer with said Jod, Eisen, Indium, Lithium, Magnesium, Man- hydrocarbon composition. gan, Molybdän, Nickel, Niob, Stickstoff, Phos- phor, Kalium, Palladium, Rubidium, Natrium, 20. The method of claim 18 or 19, wherein said storage Zinn, Zink, Praseodym, Rhenium, Silikon, Va- is for a period of 6 months. 50 nadin oder einer Mischung aus diesen besteht,

21. The claims of 1, 2, 12 or 18, wherein said combustible wobei die Brennstoffzusammensetzung einen pH- compound is a combustible compound containing Wert von 3,0 bis 10,5 aufweist. nitrogen in he form of an organic compound selected from a nitrate, dinitrate, a cyclic compound, a ring or 55 3. Brennstoffzusammensetzung nach Anspruch 1 oder cyclomatic system, an alkanolamine, compounds or 2, wobei der pH-Wert zwischen 4,5 und 10,5 liegt. a compound containing a nitroamino, nitro, nitro- samino, nitrosimino, nitrosyl/nitroso, nitrilo, amidino, 4. Brennstoffzusammensetzung nach Anspruch 1 oder

36 71 EP 0 954 558 B1 72

2, wobei der pH-Wert zwischen 4,5 und 9,5 liegt. tyltriethoxysilan, Tetramethylsilan, Dimethoxyme- thylvinylsilan, Methyltriethoxysilan, 3-Aminopro- 5. Brennstoffzusammensetzung nach Anspruch 1 oder pyltriethoxysilan, 3-Aminopropyltrimethoxysilan, 2, wobei der pH-Wert zwischen 4,5 und 8,5 liegt. Vinyltrimethoxysilan, Diethoxydimethylsilan, Dime- 5 thoxydimethylsilan, Vinyltris(2-butylidenaminooxy) 6. Brennstoffzusammensetzung nach Anspruch 1 oder silan, Tetramethoxysilan, Tetraethoxysilan, Tetra- 2, wobei der pH-Wert zwischen 5,5 und 8,0 liegt. propyloxysilan, Tetraisopropylsilan, Tetraisobutyl- silan, Dimethylphosphit, Dipropylphosphit, Diethylp- 7. Zusammensetzung nach Anspruch 1 oder 2, wobei hosphit, Dibutylphosphit, Ditertbutylphosphit, Trial- der pH-Wert im Bereich zwischen 6,3 und 6,8 liegt. 10 kylphosphite, Trimethylphosphit, Triethylphosphit, Triisopropylphosphit, Tributylphosphit, Dimethylme- 8. Brennstoffzusammensetzung nach Anspruch 1 oder thylphosphonat, Diethylmethylphosphonat, Kalium- 2, wobei es sich bei der brennbaren Verbindung um pyrophosphit, Trimethylorthoacetat, Triethylorthoa- eine Cyclopentadienylmangantricarbonyl-Verbin- cetat, Trimethylorthobutyrat, Triethylorthobutyrat, dung handelt. 15 Trimethylorthovalerat, Trimethylorthoformat und Mi- schungen aus diesen besteht. 9. Zusammensetzung nach Anspruch 1, wobei es sich bei der Zusammensetzung um ein Dieselheizöl han- 14. Zusammensetzung nach Anspruch 2, wobei es sich delt und der Brennstoff durch eine Viskosität von bei dem Dialkylcarbonat um ein C3- bis C7-Dialkyl- gleich oder weniger als 2,4 mm2/s bei 40 °C gekenn- 20 carbonat handelt. zeichnet ist. 15. Dieselheizölzusammensetzung nach Anspruch 1, 10. Brennstoffzusammensetzung nach Anspruch 2, wo- die durch eine Viskosität von gleich oder weniger als bei der Düsenturbinentreibstoff für Flugzeuge durch 2,4 mm2/s bei 40 °C gekennzeichnet ist. eine Viskosität im Bereich von 8,1 bis 15,0 mm2/sL 25 bei - 20 °C (ASTM 445) und einen pH-Wert im Be- 16. Automobilbenzin nach Anspruch 1, das durch eine reich von 4,5 bis 10,5 gekennzeichnet ist. T-90-Temperatur im Bereich von 330 °F bis 280 °F, eine T-50-Temperatur im Bereich von 170 °F bis 230 11. Brennstoffzusammensetzung nach Anspruch 1 oder °F und eine durchschnittliche latente Verdampfungs- 2, wobei es sich bei dem Dialkylcarbonat um Dime- 30 wärme von 880 bis 920 BTU/gal bei 60 °F gekenn- thyl- oder Diethylcarbonat handelt. zeichnet ist.

12. Brennstoffzusammensetzung nach einem der vor- 17. Brennstoffzusammensetzung nach Anspruch 1 oder hergehenden Ansprüche, wobei die brennbare Ver- 2, die außerdem ein Salz oder Co-Lösemittel enthält. bindung aus der Gruppe ausgewählt ist, die aus Cy- 35 clopentadienylmangantricarbonyl, [2-(Cyclohexe- 18. Verfahren zum Minimieren der Hydrolyse einer Koh- nyl)-ethyl]triethoxysilan, Cyclohexenyldimethoxy- lenwasserstoff-Brennstoffzusammensetzung, die methylsilan, Benzyltrimethylsilan, N-(3-(trimethoxy- ein Dialkylcarbonat enthält, wobei das Verfahren fol- silyl)propyl)ethylendiamin, N-1-(3-(trimethoxysilyl) gende Schritte umfasst: propyl)diethylentriamin, 1-(Trimethylsilyl)pyrrolidin, 40 Triphenylsilanol, Octamethyltrisiloxan, 2,2,4,4,6,6- - das Mischen eines kurzkettigen Dialkylcarbo- Hexamethylcyclotrisilazan, Hexamethylcyclotrisilo- nats mit: xan, Hexamethyldisilan, 1,1,1,3,3,3-Hexamethyldi- silazan, Hexamethyldisiloxan, Hexamethyldisilthi- mindestens einer brennbaren Verbindung, an, Allyltributylsilan, Tetraalkylsilane, 3-Aminopro- 45 die mindestens ein Element enthält, das pyltriethoxysilan, Benzyltrimethylsilan, Ben- aus der Gruppe ausgewählt ist, die aus Alu- zyltriethylsilan, N-Benzyltrimethylsilylamin, Diphe- minium, Bor, Brom, Wismut, Beryllium, Kal- nylsilandiol, Dihexylsilandiol, Trimethylsilylcyclo- zium, Zäsium, Chrom, Kobalt, Kupfer, Fran- pentadien, Kaliumhexacyanoferrat (II), Kaliumhexa- zium, Gallium, Germanium, Jod, Eisen, In- cyanoferrat (III), Kaliumhexacyanokobaltat-II-ferrat- 50 dium, Lithium, Magnesium, Mangan, Mo- II, Kaliumhexacyanokobaltat, Kaliumnatriumferro- lybdän, Nickel, Niob, Stickstoff, Phosphor, cyanid, Kaliumethoxid, eine Verbindung auf Stick- Kalium, Palladium, Rubidium, Natrium, stoffbasis oder einer Mischung aus diesen besteht. Zinn, Zink, Praseodym, Rhenium, Silikon, Vanadin oder einer Mischung aus diesen 13. Brennstoffzusammensetzung nach Anspruch 1, 2 55 besteht, oder 8, die außerdem einen Co-Katalysator enthält, und einem Kohlenwasserstoff, der aus der Gruppe ausgewählt ist, die aus Trime- thoxymethylsilan, Ethoxytrimethylsilan, Isobu- wobei die daraus resultierende Zusammensetzung

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einen pH-Wert im Bereich von 4,5 bis 10,5 aufweist, bure présentant une hydrolyse minimale comprenant : - das Lagern der Zusammensetzung bei einer Temperatur von weniger als 32,2 °C (90 °F). un dialkyl carbonate symétrique ; 5 un composé combustible contenant au moins 19. Verfahren nach Anspruch 18, wobei die Lagerung un élément choisi dans le groupe constitué par das Hinzufügen einer wässrigen Schicht mit der Koh- l’aluminium, le bore, le brome, le bismuth, le bé- lenwasserstoff-Zusammensetzung umfasst. ryllium, le calcium, le césium, le chrome, le co- balt, le cuivre, le francium, le gallium, le germa- 20. Verfahren nach Anspruch 18 oder 19, wobei die La- 10 nium, l’iode, le fer, l’indium, le lithium, le magné- gerung über einen Zeitraum von 6 Monaten erfolgt. sium, le manganèse, le molybdène, le nickel, le niobium, l’azote, le phosphore, le potassium, le 21. Anspruch 1, 2, 12 oder 18, wobei es sich bei der palladium, le rubidium, le sodium, l’étain, le zinc, brennbaren Verbindung um eine brennbare Verbin- le praséodymium, le rhénium, le silicium, le va- dung handelt, die Stickstoff in Form einer organi- 15 nadium, ou un mélange de ceux-ci ; schen Verbindung enthält, die aus einem Nitrat, Di- dans laquelle la composition a un pH de 3,0 à nitrat, einer Ringverbindung, einem Ring- oder zy- 10,5. klomatischen System, einem Alkanolamin, Verbin- dungen oder einer Verbindung, die ein Nitroamino-, 3. Composition de carburant selon la revendication 1 Nitro-, Nitrosamino-, Nitrosyl-/Nitroso-, Nitrilo-, Ami- 20 ou 2, dans laquelle le pH est de 4,5 à 10,5. dino-, Amido-, Anilin-, Anilino-, Azido-, Azino-, Azo-, Azoxy-, Benzylidin-, Anisyl-, Benzamido-, Toluyl-, 4. Composition de carburant selon la revendication 1 Naphthal-, Naphthobenzyl-, Naphthyl-, Naphthyli- ou 2, dans laquelle le pH est de 4,5 à 9,5. den-, Propylen-, Tolyl-, α-Tolyl-, Tolylen- oder α-To- lyl-Radikal enthält/enthalten, ausgewählt ist. 25 5. Composition de carburant selon la revendication 1 ou 2, dans laquelle le pH est de 4,5 à 8,5.

Revendications 6. Composition de carburant selon la revendication 1 ou 2, dans laquelle le pH est de 5,5 à 8,0. 1. Composition de carburant présentant une hydrolyse 30 minimale, comprenant : 7. Composition de carburant selon la revendication 1 ou 2, dans laquelle le pH se trouve dans la plage de un dialkyl carbonate symétrique ; 6,3 à 6, 8. un composé combustible contenant au moins un élément choisi dans le groupe constitué par 35 8. Composition de carburant selon la revendication 1 l’aluminium, le bore, le brome, le bismuth, le bé- ou 2, dans laquelle ledit composé combustible est ryllium, le calcium, le césium, le chrome, le co- un composé cyclopentadiényl tricarbonyle de man- balt, le cuivre, le francium, le gallium, le germa- ganèse. nium, l’iode, le fer, l’indium, le lithium, le magné- sium, le manganèse, le molybdène, le nickel, le 40 9. Composition selon la revendication 1, dans laquelle niobium, l’azote, le phosphore, le potassium, le ladite composition est un carburant diesel, ledit car- palladium, le rubidium, le sodium, l’étain, le zinc, burant étant caractérisé en ce qu’il a une viscosité le praséodymium, le rhénium, le silicium, le va- inférieure ou égale à 2,4 mm2/s à 40°C. nadium, ou un mélange de ceux-ci ; un carburant à base d’hydrocarbure choisi dans 45 10. Composition de carburant selon la revendication 2, le groupe constitué par les carburants de rem- dans laquelle ledit carburant pour turbine d’avion à placement, les carburants gazeux, les essences réaction est caractérisé en ce qu’il a une viscosité automobiles, les essences avions, les carbu- dans la plage de 8,1 à 15,0 mm/sL à -20°C (ASTM rants diesels, les diesels lourds, les diesels lo- 445) ; et un pH dans la plage de 4,5 à 10,5. comotives, les diesels marins, les gasoils, les 50 mazouts, les mazouts lourds, les mazouts à tur- 11. Composition de carburant selon la revendication 1 bine à gaz, les mazouts lourds à turbine à gaz, ou 2, dans laquelle ledit dialkyl carbonate est le di- le charbon, les kérosènes, les liquides dérivés méthyl ou diéthyl carbonate. du charbon, et les huiles lourdes, dans laquelle la composition de carburant a un 55 12. Composition de carburant selon l’une quelconque pH de 3,0 à 11,0. des revendications précédentes, dans laquelle ledit composé combustible est choisi dans le groupe 2. Composition pour turbine d’avion à base d’hydrocar- constitué par le cyclopentadiényl tricarbonyle de

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manganèse, le [2-(cyclohexenyl)éthyl]triéthoxysila- 17. Composition de carburant selon les revendications ne, le cyclohexenyl diméthoxyméthylsilane, le ben- 1 ou 2, comprenant en outre un sel ou un cosolvant. zyltriméthylsilane, la N-(3-(triméthoxysilyl)propyl) éthylènediamine, la N-1-(3-(triméthoxysilyl)propyl) 18. Procédé destiné à minimiser l’hydrolyse d’une com- diéthylènetriamine, la N-(3-(triméthoxysilyl)propyl) 5 position de carburant à base d’hydrocarbure conte- éthylènediamine, la 1-(triméthyl(silyl)pyrrolidine, le nant un dialkyl carbonate, ledit procédé triphénylsilanol, l’octaméthyltrisiloxane, le comprenant : 2,2,4,4,6,6-hexaméthylcyclotrisilazane, l’hexamé- thylcyclotrisiloxane, l’hexaméthyldisilane, le le mélange d’un dialkyl carbonate inférieur sy- 1,1,1,3,3,3-hexaméthyldisilazane, l’hexaméthyldisi- 10 métrique avec : loxane, l’hexaméthyldisilthiane, l’allyltributylsilane, les tétraalkylsilanes, le 3-aminopropyltriéthoxysila- au moins un composé combustible conte- ne, le benzyltriméthylsilane, le benzyltriéthylsilane, nant au moins un élément choisi dans le la N-benzyltriméthylsilylamine, le diphénylsilanediol, groupe constitué par l’aluminium, le bore, le dihexylsilanediol, le (triméthylsilyl) cyclopentadiè- 15 le brome, le bismuth, le béryllium, le cal- ne, l’hexacyanoferrate(II) de potassium, l’hexacya- cium, le césium, le chrome, le cobalt, le cui- noferrate(III) de potassium, le ferrate hexacyanoco- vre, le francium, le gallium, le germanium, balt(II) de potassium, l’hexacyanocobalt de potas- l’iode, le fer, l’indium, le lithium, le magné- sium, le ferricyanure de potassium et de sodium, sium, le manganèse, le molybdène, le nic- l’éthoxyde de potassium, un composé à base d’azo- 20 kel, le niobium, l’azote, le phosphore, le po- te, ou un mélange de ceux-ci. tassium, le palladium, le rubidium, le so- dium, l’étain, le zinc, le praséodymium, le 13. Composition de carburant selon la revendication 1, rhénium, le silicium, le vanadium, ou un mé- 2 ou 8, contenant en outre un cocatalyseur choisi lange de ceux-ci ; dans le groupe constitué par le triméthoxyméthylsi- 25 et un hydrocarbure ; lane, l’éthoxytriméthylsilane, l’isobutyltriéthoxysila- moyennant quoi la composition résultante ne, le tétraméthylsilane, le diméthoxy-méthyl-vinyl- a un pH dans la plage de 4,5 à 10,5 ; silane, le méthyltriéthoxysilane, le 3-aminopropyl- le stockage de ladite composition à une triéthoxysilane, le 3-aminopropyltriméthoxysilane, le température inférieure à 32,2°C (90°F). vinyltriméthoxysilane, le diéthoxydiméthylsilane, le 30 diméthoxydiméthylsilane, le vinyltris(2-butyldénami- 19. Procédé selon la revendication 18, dans lequel ledit noxy)silane, le tétraméthoxysilane, le tétraéthoxysi- stockage comprend l’addition d’une couche aqueu- lane, le tétrapropyloxysilane, le tétraisopropylsilane, se à ladite composition à base d’hydrocarbure. le tétraisobutylsilane, le diméthylphosphite, le dipro- pylphosphite, le diéthylphosphite, le dibutylphosphi- 35 20. Procédé selon la revendication 18 ou 19, dans lequel te, le di-tert-butyl-phosphite, les trialkylphosphites, ledit stockage est pour une période de 6 mois. le triméthylphosphite, le triéthylphosphite, le triiso- propylphosphite, le tributylphosphite, le diméthylmé- 21. Procédé selon les revendications 1, 2, 12 ou 18, dans thylphosphonate, le diéthylméthylphosphonate, le lequel ledit composé combustible est un composé pyrophosphite de potassium, le triméthylorthoacéta- 40 combustible contenant de l’azote sous la forme d’un te, le triéthylorthoacétate, le triméthylorthobutyrate, composé organique choisi parmi un nitrate, un dini- le triéthylorthobutyrate, le triméthylorthovalérate, le trate, un composé cyclique, un système cyclique ou triméthylorthoformate, et des mélanges de ceux-ci. cyclomatique, une alcanolamine, des composés ou un composé contenant un radical nitroamino, nitro, 14. Composition selon la revendication 2, dans laquelle 45 nitrosamino, nitrosimino, nitrosyl/nitroso, nitrilo, ami- ledit dialkyl carbonate est un dialkyl carbonate en C3 dino, amido, amino, aniline, anilino, azido, azino, à C7. azo, azoxy, benzylidine, anisyle, benzamido, toluyle, naphtal, naphtobenzyle, naphtyle, naphtylidène, 15. Composition de carburant diesel selon la revendica- propylène, tolyle, α-tolyle, tolylène, ou α-tolylène. tion 1, caractérisée en ce qu’elle a une viscosité 50 inférieure ou égale à 2,4 mm2/s à 40°C.

16. Essence automobile selon la revendication 1, ca- ractérisée en ce qu’elle a une température T-90 dans la plage de 330°F à 280°F, une température 55 T-50 dans la plage de 170°F à 230°F, et une chaleur latente moyenne de vaporisation de 880 à 920 BTU/gal à 60°F.

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