United States Patent 19 11) 4,081,445 Hermans 45) Mar. 28, 1978

54 CERTAIN BISPIPERAZIDO 58) Field of Search ...... 260/268 K, 959, 958, COMPOUNDS 260/268 MK 75) Inventor: Johny C. Hermans, Wespelaar, (56) References Cited Belgium U.S. PATENT DOCUMENTS 73. Assignee: s.a. Texaco Belgium in.v., Brussels, 3,298,937 1/1967 Strauss et al...... 260/959 Belgium 3,531,550 9/1970 Herber et al...... 260/959 Primary Examiner-R. Gallagher 21 Appl. No.: 628,288 Attorney, Agent, or Firm-Thomas H. Whaley; Carl G. 22 Filed: Nov. 3, 1975 Ries; Carl G. Seutter (30) Foreign Application Priority Data 57 ABSTRACT Compounds useful as lube oil additives are prepared by May 21, 1975 United Kingdom ...... 21796/75 reaction of phosphorus halides and piperazine deriva 51 int. C.?...... C07D 295/16; CO7D 295/22 tives. 52 U.S. Cl...... 260/268 K; 252/46.7; 252/49.9; 252/389 A; 544/121 5 Claims, No Drawings 4,081,445 1. 2 X represents an oxygen or sulphur atom or is absent, CERTAN BESPPERAZIDO PHOSPHORUS Y represents an (i) aliphatic, cycloalliphatic, or COMPOUNDS aromatic hydrocarbon group or a heterocyclic group; (ii) a group of the formula -NR in which FIELD OF THE INVENTION each group R represents a atom, an ali This invention concerns bis-piperazido phosphorus phatic, cycloaliphatic, or aromatic hydrocarbon and trispiperazido phosphorus compounds, and meth group or a heterocyclic group, or the two groups ods for the preparation of these compounds. R, together with the nitrogen atom to which they Various of the compounds obtained according to the are attached, represent a N-containing heterocyclic invention are of interest as components of petroleum 10 ring; (iii) a group of the formula -OR in which R compositions, as additives for plastics materials, as com has the meaning given above; or (iv) a group of the ponents of flameresistant or flame-retardant polymers, formula: as pharmaceuticals or as intermediates in the production of pharmaceuticals. 15 III BACKGROUND OF THE INVENTION a-N N-R It is known that halides of phosphorus are able to react with primary and secondary amines, thereby pro (R), ducing amides of the various acids or phosphorus. For instance, as long ago as 1898, Michaelis and Kaehner in 20 R represents a substituent on the piperazine ring; Ber, 31 (1898), pp 1040-1047 described the reaction of R’ represents a hydrogen atom or a substituted or piperidine and tetrahydroquinoline with phenyl phos unsubstituted aliphatic, cycloaliphatic or heterocy phorus dichloride to form the corresponding bispiperi clic radical or heterocyclic group, an acyl group, a dide and bis-tetrahydroquinolide. These compounds sulphonyl group a substituted phosphonyl group or could be converted into the corresponding amides of 25 phosphonic and phosphonothionic acid. a substituted carbamoyl group; and Subsequent work has described the reaction of phos in represents 0 or an integer, and salt of such com phorus halides or oxyhalides with a variety of amines, pounds in which at least one of the groups Rrepre and . Attention is to be directed in this con sents a hydrogen atom; nection, for instance, to U.S. Pat. No. 2906770; 3107231; 30 but with the proviso that Y does not represent di 3260702 and 3649594. Little attention, however, has methylamino when X represents oxygen and R' been paid to the use of piperazine or substituted pipera and Rboth represent hydrogen. zines as amine reactants. DESCRIPTION OF THE INVENTION A paper by Bello etal in Macromolecules, 3 (1970) pp 35 In the present invention the symbol X can represent 98-100 describes the reaction of dimethylphosphora an oxygen or sulphur atom, or it can be absent. The midic dichloride (CH3)-N-POCl, with an excess of compounds according to the invention are therefore piperazine to give phosphoric dimethylamidobispipera amides of phosphoric acid (when X represents oxygen), zide. thiophosphoric acid (when X represents sulphur), and phosphorous acid (when X is absent).

Y N The symbol Y can represent a group of the formula: (CH)-N-PON NH N-1 2. I This compound was subsequently reacted with oxalyl 45 dichloride or piperazine - 1,4-dicarbonyl chloride to -la.N. N-R give polymers. Polymers with alternating piperazine and (CH),N-PO: groups were obtained by using an (R') excess of the phosphorus halide. The object of the present invention is the preparation 50 in which case, the compounds of the invention are tris of novel phosphorus compounds containing piperazine piperazides. When Y has one of its other meanings, the rings. Other objects of the invention are to produce compounds are bispiperazides. . novel phosphorus compounds useful as components of Y can for example represent a substituted or unsubsti petroleum compositions. Further objects will be appar-5s tuted hydrocarbon group, which can be of aliphatic, ent to those skilled in the art. cycloaliphatic or aromatic nature. Examples of suitable aliphatic groups are alkyl, such as methyl, ethyl, propyl, STATEMENT OF THE INVENTION butyl, octyl, dodecyl, or octadecyl; alkenyl, such as The present invention provides compounds of the allyl; or alkynyl, such as propargyl. formula: 60 Examples of suitable cycloaliphatic groups are cyclo alkyl, such as cyclohexyl, tetrahydronaphthyl or (R'), decahydronaphthyl; and cycloalkenyl, such as cyclo X hexenyl. / N 2 Examples of suitable aromatic hydrocarbon groups YeP N NaR 2 65 are aryl groups, such as phenyl, naphthyl, biphenyl, or N-1 phenanthryl; aralkyl, such as benzyl, or phenylethyl; and alkaryl, such as tolyl, dimethylphenyl, trimethyl and salts of such compounds, wherein phenyl, cumyl, or p-octylphenyl. 4,081,445 3 4. Y can alternatively represent a heterocyclic group, Rcan also represent a substituted phoshorus-contain linked to the phosphorus atom through a carbon atom, ing group, e.g. a group of the formula as in the tetrahydrofurfuryl or 2-pyridyl radicals. Y can also represent a group of the formula-NR2, in -PX R. which each R represents a hydrogen atom, or an ali- 5 phatic, cycloaliphatic, or aromatic hydrocarbon group in which X has the meaning given above, and or a heterocyclic group. Examples of these hydrocar R represents an aliphatic, cycloaliphatic or aromatic bon groups or heterocyclic groups are given above. group, or a group of the formula -OR, -SR or Specific examples of suitable amino radicals are dimeth NR, in which R has the meaning given above. An ylamino, diethylamino, dipropylamino, dibutyl amino, 10 example of such a group is dimethylaminophospho monomethyl amino, monoethylamino, monododecyl nyl. R can also represent a substituted carbamoyl amino, mono-(Co) alkylamino, monooctadecylamino, group -CO-NHR wherein R has the meaning given anilino, p-dodecylanilino, and N-butylanilino. above. An example of such a group is phenylcar Alternatively, both symbols R, and the nitrogen atom bamoyl. 5 The invention also provides lubricating compositions to which they are attached, can together represent a -- comprising a major amount of a lubricating oil, and a heterocyclic radical linked to the phosophorus atom minor amount (e.g. 0.1 to 10% by weight, preferably 0.5 through the nitrogen atom. Examples of such groups to 2.5% by weight) of a piperazidophosphorus com are morpholino, piperidino, tetrahydroquinolino, pyr pound as defined above. The invention further provides rolidino etc. The compounds in which Y represents a a concentrate suitable for incorporating in a lubricating further piperazino group are, of course, a special in oil comprising a piperazidophosphorus compound as stance of this. defined above and an inert diluent. The proportions of Y can also represent a group of the formula -OR in the diluent are not critical and the weight ratio of which R has the meaning given above. Examples of piperazidophosphorus compound to diluent may, for such groups are alkoxy, such as methoxy, ethoxy, 5 instance, range from 9:1 to 1:9 depending on miscibility. propoxy, butoxy, dodecyloxy and octadecyloxy; and Preferred lubricating compositions and concentrates aryloxy such as phenoxy, tolyloxy, or benzyloxy. comprise p-(p'-dodecylanilino) phenyl bispiperazido Any of the above radicals can if desired, be substi thiophosphate, and p-(p'-ethylanilino) phenyl bis-(N'-(3- tuted. The only limitation upon the nature of the substit carbethoxyethylpiperazido) thiophosphate. uents is that they should be inert under the conditions of 30 This invention also provides methods for the synthe the reaction employed in synthesizing the compound. sis of the compounds described above. According to a In the group of the formula: preferred method, a compound of the formula: I -N N-R 35 x= (Hal), N/ y (Y), wherein y is an interger 0-1 (When y is 0, the com pound has the formula iv.; when y is 1, the compound R represents a substituent on the piperazine ring. Here 40 has the formula v. again, the only limitation upon the nature of the substit uent is that it should be inert under the conditions of the XP(Hal) or IV reaction used to synthesize the compound. The substitu X tent can, for example, be one of the groups set out above for Y, provided that such a group is inert. When pres- 45 y--(Hal), ent, it can for example be an alkyl group, such as a methyl group. Alternatively, the substituent can have a in which X and Y have the meanings given above and meaning not set out above, insofar as it might not be an Hal represents chlorine and bromine) is reacted with an appropriate group for attachment to phosphorus; for excess of a piperazine derivative of the formula: example, an oxo group. Specific examples of substituted 50 piperazine groups are 2,5-dimethylpiperazino and 2,5- (R), dioxopiperazino groups, n is 0 or an integer, and is pref erably 0, 1 or 2: -- R2 can represent a hydrogn atom or a substituted or HeN N-R unsubstituted aliphatic, cycloaliphatic or aromatic 55 hydrocarbon group or a heterocyclic group. Ex amples of suitable groups are set out above. Specifi in which R, R and n have the meanings given above. cally preferred groups Compounds of the formula X=P(Hal), and R2 include alkyl, such as methyl, ethyl, phenyl, and X substituted groups such as 3-cyanoethyl and 3-car- 60 Y-P(Hal), bethoxy Rican also represent an acyl group, e.g. of an aliphtic, cycloaliphatic, aromatic or heterocy are well known in the art. Some of them will be com clic carboxylic acid, such as acetic, propionic, bu mercially available, and others may be prepared by the tyric or stearic acid, cyclohexane carboxylic acid, methods described in, for example Houben-Weyl , toluic acid, nicotinic acid or a me- 65 "Methoden der Organischen Chemie' Vol XII/2, or by thylnicotinic acid. Alternatively R' can represent a Olah and Oswald in Ann. 625 (1959) 92-94. sulphonyl group, for example a methane sulphonyl, Similarly, the piperazine derivatives will be well benzene sulphonyl or toluene sulphonyl group. known in the art, and the preferred compound, pipera 4,081,445 5 6 Zine itself, is commercially available. It is of course CH=CH-Z VIII possible to employ a mixture of piperazine derivatives, thereby giving compounds in which the groups Rand wherein Z represents a cyano, carboalkoxy, sulphone /or Ron different piperazine rings are themselves dif (SOR) or phosphonyl (PXR) group, e.g. with acrylo ferent. nitrile or an ester of acrylic acid. The products have the According to one preferred embodiment, the reac formula II in which R’represents a group of the formula tion according to the invention can be carried out by -CH-CH-Z. adding the phosphorus halide, as such or dissolved in an Yet another reaction which can be undergone by inert solvent, to a large excess of the piperazine, gener compounds of the formula VII is reaction with an isocy ally in a molar ratio of at least 1:4, either as such or 10 anate of the formula R-NCO wherein R has the mean dissolved in an inert solvent. Suitable solvents include, ing given above. The products of this reaction are sub benzene, other hydrocarbons, ether or chloroform. The stituted ureas of the formula II in which R2 represents a piperazine will act as both a catalyst and a halogen group of the formula: acid-acceptor. The reaction is exothermic and can be moderated by 15 CO-NH-R IX controlling the rate at which the phosphorus halide is Examples of suitable isocyanates are methylisocyanate added. The reaction can generally be carried out at and phenyl isocyanate. room temperature, but it is possible to carry it out at The compounds according to the invention have a elevated temperature, e.g. at a temperature of 60 to 80 variety of uses. They constitute multifunctional lubri C. in benzene, toluene or xylene or at the reflux temper cating oil additives, exhibiting an anti-corrosionoxida ature of the-solvent employed. Most conveniently the tion action and an anti-wear action, and are mild ex reaction is carried out at atmospheric pressure, but su treme pressure agents. Since the compounds in which peratmospheric pressures can be employed if desired. R’ represents hydrogen are difunctional and trifunc The piperazine hydrohalide that forms is insoluble in tional secondary amines, they are able to participate in many solvents, e.g. ether, benzene, and other hydrocar 25 polymer-forming and cross-linking by polyaddition and bons, and can be separated by filtration. It can also be removed by washing with water or an aqueous solution polycondensation reactions. The compounds in which of sodium carbonate. Subsequently, any solvent and any R’ for example represents a g-carboalkoxyethyl group excess of the piperazine can be distilled off, and the constitute flame-retardant plasticizers. Other actual and resulting crude product can be purified by recrystalliza 30 potential uses will be apparent to those skilled in the art. tion, low-pressure distillation or a chromatographic DESCRIPTION OF SPECIFIC EMBODIMENTS technique. Alternatively, the reaction can be carried out in the Practice of this invention will be apparent to those presence of a tertiary amine as catalyst and hydrogen skilled in the art from inspection of the following illus halideacceptor. Examples of a suitable tertiary amines 35 trative examples. are triethylamine, pyridine, dimethylaniline and luti EXAMPLE dine. The tertiary amine can be present in either or both 0.20 mole of phenyldichlorophosphate dissolved in 50 of the phosphorus halide and the piperazine. It is most ml of benzene was added dropwise to a mixture of 4.0 convenient however to use piperazine as catalyst and mole of piperazine and 0.50 mole of triethylamine dis hydrogen halide-acceptor as the reaction course is more solved in 800 ml of benzene at 50-80 C. The mixture easily followed. was mechanically stirred. When all the acid chloride At least stoichiometric amounts of piperazine, corre was added, the mixture was refluxed for one to two sponding to the phosphorus halide, are required in this hours and the precipitated triethylamine hydrochloride embodiment of the invention, and advantageously an 5 was filtered off. The filtrate was cooled, and more pre excess of the piperazine is employed. The molar ratio of cipitated hydrochloride was filtered off. The solvent phosphorus halide: piperazine: tertiary amine, can be, or and the excess of piperazine were distilled off at normal example 1:2:2. pressure. 250 g. of piperazine were recovered. The When R in the piperazine reactant is hydrogen, for remaining piperazine was removed under vacuum at instance in piperazine itself, the product of the synthetic 50 60°-90° C and a crude product was obtained, which reaction will have the structure: could be crystallized from benzene from acetone or from a mixture of both, yielding colourless white crys (R), VI tals of phenylbispiperazidophosphate mp, II4.5 - II5 C. The crude product can also be purified by vacuum 55 distillation b.p. 235/0.4mm. The total yield was more than 60% of the theoretical amount. A standard procedure used for the synthesis of bis piperazido compounds is as follows: and will itself be capable of undergoing further reac To l mole of anhydrous piperazine dissolved in 600 tions. For instance, the N-H group can be subjected to ml of dry benzene at 50-80' C is slowly added 0.10 a substitution reaction with a compound of the formula mole of the phosphorus acid dichloride (Y-PXCl; R’- Hal, for instance an acyl, phosphonyl or sulphonyl X-O, S or absent) dissolved in 50 to 100 ml of benzene, halide such as acetyl chloride, benzoyl chloride, phenyl while the mixture is gently stirred. The mixture is then dimethylaminophosphonyl chloride, benzene sulphonyl refluxed for 15 to 30 minutes and the precipitated piper chloride or toluene sulphonyl chloride. 65 azine hydrochloride is filtered off. Benzene and the Alternatively the compound of formula VII can be excess of piperazine are distilled off at reduced pressure reacted with an acrylic compound of the formula: (up to 80-100° C at 1 mm). This process easily occurs on a thin film rotating evaporator. The residue is redis 4,081,445 7 8 solved in benzene (400 ml) and the remaining piperazine TABLE 1-continued hydrochloride is filtered off. Benzene and the remaining Bispiperazidophosphoryl Compounds piperazine are then distilled off under vacuum (up to 100° C at 0.5-1 mm) which yields the crude piperazido - N / N phosphorus compound. 5 HNN-1 N-P-N N-1NH Sometimes toluene or xylene was used as a solvent to Yield provide a higher reaction temperature, needed to com Compound Y = % (C) plete the reaction (e.g. for bispiperazidophosphoric -NHCCH)-CH, 95 46-47 triamides), which also had the advantage that it pre -NH. (C-C) 82.7 oil vented blocking of the condensor by sublimed pipera 10 -N(CH), 100 oil zine when it was distilled off. Purification of the crude /-N 82 125 products was sometimes possible by recrystallization or amN O by distillation, but most compounds decomposed upon N / distillation; several were viscous oils which sometimes -NH-CH 56 155-157 solidified on standing. 15 -NH-CHCH 88.8 glassy solid For this preparation usually piperazine itself was used as HCl-acceptor because the use of other bases e.g. EXAMPLE3 triethylamine gave no advantages. In contrast, using triethylamine, it was not possible to determine the ex Ethyl bispiperazidothiophosphate: tent of conversion on the basis of the amount of salt 20 S formed, because a mixture of triethylamine hydrochlo / N ride and piperazine hydrochloride precipitated during CHO-P-e-N NH), the reaction. A variant of the work-up method consists in washing out the piperazine hydrochloride and piperazine from 25 (a) 0.1 mole (17.9 g) of ethyl thiophosphoryl dichlo the reaction mixture with water or dilute sodium car ride (C2H5O-PSC1) was reacted with 1 mole (86 g) of bonate solution, directly after the reaction or preferably piperazine dissolved in 600 ml of benzene at 70° C. after the removal of the main part of piperazine and/or Standard work up (with a maximum temperature of 70' its salt. This procedure is not suitable for piperazido C) yielded a crude yellow oil (27.45 g; 98.5%, mp phosphorus compounds which have good solubility in 30 84-95 C) which solidified on standing and which was water, and hence it is recommended to extract such recrystallized from ether: acetone (4:1) yielding yellow phosphorus compounds from the wash waters, for ex white crystals with mp 96-101° C. ample with chloroform, to avoid extensive losses of the (b) 0.0625 mole (11.2 g) of ethyl thiophosphoryl di reaction product. chloride was reacted at 40' C with 0.45 mole (39.4 g) of Typical examples of compounds prepared by the 35 piperazine dissolved in benzene. After removal of the standard procedure are: salt, benzene solution was extracted four times with water. The benzene solution was dried and concen EXAMPLE 2 trated (T < 40° C) yielding an oil F(2.2 g; 12.6%). The Phenyl bispiperazidophosphate collected wash water was extracted three times with chloroform which yielded, after evaporation of the solvent, an oil F (13.7 g; 78.7%; mp 78.5'-81.5° C) which crystallized out on standing. Overall yield: 15.9 g CH-O-P-e-N NH): (91.4%), Elemental analysis of F, was correct. Other 45 compounds, indicated in Table 2 below, were prepared 0.5 mole (105.5 g) of CH-O-POCl was reacted by similar methods. with 5 mole (430 g) of piperazine dissolved in 3 l of TABLE 2 benzene. The standard work up procedure, including Bispiperazidothiophosphoryl Compounds filtration of the hydrochloride, and distillation of the S solvent and excess piperazine, yielded 143 g (92%) of a 50 / N Il M N crude product which was first recrystallized from ben HN N-P-N NH zene (yield: 115.5 g; 74.3%) and then from benzene: Appearance acetone (1:1) which yielded 92.2 g (59.9%) with mp Yield Melting 117-118° C. From the remaining viscous oil another Compound Y= % range d) -o-CH-CH, 91.4 Yellow oil fraction of pure compound could be isolated by vacuum 55 (78.5-81.5) distillation (bp 235 C/0.4 mm). Other compounds, -O-CH 96 Yellow oil indicated in Table 1 below, were prepared by similar (56-63) methods. -o-CH-NH-CH-CH-6-Ci-Ni-Ci-Ei 94585 BrownRed Oil Oil TABLE 1. 60 -N(CH-CH-CH-CH), 53.7 Yao's85-92) -N(CH)(CH) 88.6 Brown oil Bispiperatidophaghoryl Compounds -6S-8iCHo) 93.2 Waxy solid / N / N (45-50) HN N-P-N NH . No good elemental analysis was obtained of this compound N-1 N-1 'Melting range of the solidified oil Yield Melting Point 65 Compound Y= 9% (C) . -O-CH 100 oil EXAMPLE 4 -6-di-CH, 86.4 66.5-68.5 -O-CH 74.3 17-18 Phosphorous Di-n-butylamidobispiperazide 4,081,445 10

-N /-N (CH),N-P-e-N NH), (CH-NH-C-N N / N)-P-NBu To 0.93 mole (80.10 g) of piperazine dissolved in 1.51 of To 0.005 mole (1.647 g) of phosphorousdibutylamido benzene at 45 C was added slowly 0.07 mole (16.1 g) of bispiperazide in 30 ml of benzene at 20 C was slowly - BuNPCl, in 100 ml of benzene. Then the mixture was added 0.010 mole (1.19 g) of phenyl isocyanate in 20 ml warmed up till reflux, filtered, and benzene and the 10 of benzene. Immediately a white precipitate was formed excess of piperazine were removed under reduced pres which could be partly recrystallized from boiling etha sure (T: 100° C). The crude product obtained was nol. Yield of the title compound: 1.8 g; 63.5%, mp320 redissolved in benzene, filtered again and the mixture C. was concentrated, which yielded 19.4 g (84.12%) of the bispiperazidophosphorous compound. 15 EXAMPLE 8 Table 3 below indicates this compound, and the cor Phosphoric trispiperazide responding phenoxy compound, prepared in similar To 1 mole (86 g) of anhydrous piperazine dissolved in ac. 600 ml of dry benzene at 50°-60° C was added dropwise TABLE 3 with gentle stirring 0.05 mole (7.66 g) of POCl dis Bispiperazidophosphorus (P") Compounds 20 solved in 50 ml of dry benzene. The mixture was re fluxed for 2 hrs at 80' C and then filtered hot to remove HN N-P-N NH precipitated piperazine hydrochloride. Benzene and the excess of piperazine were distilled off at reduced pres Compound Yield sure (up to 80-100° C at 1 mm). The residue was redis Y= % Appearance 25 solved in dry benzene, filtered to remove remaining salt, CHO- 82.3 viscous oil and again benzene and piperazine were distilled off ?i).N- 84.1 viscous oil under reduced pressure. A crude product was obtained in a yield of 13.7 g (90.7%), melting point 130 C. Once it had absorbed EXAMPLE 5 30 water, the compound could not be redissolved and Phenyl bis (N'-3-cyanoethylpiperazido) phosphate recrystallized from benzene and it became very sticky. Pure product could be obtained again from it, by dis solving it in (ethanol) and distilling off all the solvents under vacuum (80-100' C/1 mm). A pale CH-O-P(O)-(N N-CH-CH-CN). 35 yellowish oil was obtained which crystallized out upon cooling and standing, and which gave a good elemental analysis. Yield 9 g (59.6%). 0.025 mole (7.75 g) of phenyl bispiperazidophosphate was refluxed with 0.075 mole of (5 ml) acrylonitrile in EXAMPLE 9 50 ml of toluene (6-7 hrs). After stripping off the sol 40 Thiophosphoric trispiperazide vent and the excess acrylonitrile, a crude oil was ob To l mole (86 g) of anhydrous piperazine dissolved in tained (10.2 g; 97.8%). Purification by vacuum distilla 200 ml of toluene at 100° C was added dropwise with tion resulted in decomposition of the product (250 gentle stirring 0.05 mole (8.47 g) of PSCls in 30 ml of C/0.6 mm), which however can be purified by column toluene. The mixture was refluxed for 21 hrs and the chromatography on silica gel (eluting with methanol) 45 precipitated piperazine hydrochloride was filtered off. yielding a yellow-red viscous oil. Toluene and the excess of piperazine were distilled off at reduced pressure (100 C/1 mm). EXAMPLE 6 15g of a crude solid were obtained and recrystallized p-(p'-ethylanilino)phenyl -bis(N'carbethoxyethyl from toluene/benzene yielding pale yellow crystals 13.1 piperazido) thiophosphate. g (86.7%) mp 129.5-130.5° C and which gave a good

CH-CH-NH-CH-O-P(S)-(N NCH-CH-COOCH), analysis. This compound was fairly hygroscopic, and had good solubility in water and alcohol, but it was not A solution of 6.7 g (0.015 mole) of p-(p'-ethylanilino) soluble in base oils. phenyl-bis-piperazido thiophosphate and 5 g (0.05 mole) EXAMPLE 10 of ethyl acrylate in 100 ml of toluene was refluxed for 60 4-6 hrs. Then toluene and the excess ethyl acrylate Thiophosphoric tris-(N'-(3cyanoethylpiperazide) were stripped off under vacuum (temp. max. 100° C) A solution of 0.02 mole (6.37 g) of phosphorothioic which yielded the title compound, a viscous brown oil, trispiperazide and 0.09 mole (4.77 g) of acrylonitrile in in 96% yield (9.3 g). 110 ml benzene was refluxed for 6 hrs. Stripping off the 65 solvent and excess acrylonitrile (temp max 100 C/10 EXAMPLE 7 mm) yielded a crude yellow oil 9.5 g (99%) which was Phosphorous dibutylamidobis-(N'-carbanilidopipera purified by column chromatography over silica gel zide) using methanol as eluent. Pure white crystals of thio 4,081,445 11 12 phosphoric tris-(N'-3-cyanoethylpiperazide) were ob pounds in which X-S and Y-O-alkyl groups and with tained (7.83 g; 82%; mp 122 C). The solubility in base compounds in which X=S and in which R-carboxy oils of this compound was very low. lic ester (-CH-CH-COOR). All these compounds show mild extreme pressure activity and the EXAMPLE 11 5 diarylaminophosphorus compounds (Y=-O-CH Thiophosphoric tris-(N'-(3-carbethoxyethylpipera -NH-CH-R) are excellent oxidation inhibitors, zide) superior to ZDT. Bench test results of the trivalent (a) A mixture of 0.010 mole (3.18 g) phosphorothioic phosphorus compound, phenyl bispiperazidophosphite trispiperazide and 0.030 mole (3.0 g) of ethyl acrylate showed moderate anti-wear and anti-oxidation action was heated under reflux for 5 hrs at 140 C. After the 10 and mild extreme pressure properties. excess of ethyl acrylate was distilled off, a brown oil According to the test results the most promising com was obtained in 99.5% yield (6.15g) which gave a good pounds prepared are p-(p'-dodecylanilino)phenyl bis analysis. piperazidothiophosphate (b) A mixture of 0.0104 mole (3.30 g) of phosphoro thioic trispiperazide and 0.20 mole (20g) of ethyl acry 15 CH-CH-NH-CH-O-P(S)-N NH), late in 100 ml toluene was refluxed for 4 hrs. The soi vent and excess ethyl acrylate was stripped off which yielded the compound in 96.6% (6.2 g) yield. and derivatives of the arylaminophenylbispiperazidothi ophosphates 20

/ N CH-CH-NH-CH-O-p(S) (-N N-CH-CH-COOCH),

EXAMPLE 12 Only the piperazidophosphorus compounds and de which give a very good wear protection, an excellent rivatives which had a solubility in base oils (SNO-20; oxidation inhibition and mild extreme pressure activity. 145-PPT) of at least 0.5% wt were evaluated as lube oil 30 The hydrocarbon base oils designated SNO-20 and additives. The results are listed in Tables 4, 5, 6 and 7 below, and indicate that the bispiperazidophosphoryl 145-PPT have the following properties: compounds show a moderate wear protection and mild extreme pressure properties compared to ZDT, (a zinc SNO-20 145-PPT dialkyl dithiophosphate), and cause no copper corro-35 Gr {{F Osgift 0.860.876 ight to moderate rusting. ravity -31 30-33 sign e generalgy performanceO f off theEi thiophosphoryl hosphoryl com- Vis, SUS at 210100 F 325-35053-55 140-150- pounds was better than of the phosphoryl compounds. ... . 90 min. 95 min. Compared to ZDT, their wear protecting action is good "in 'F 10 10 to excellent, the best results being obtained with com-40 TABLE 4 Evaluation of Bispiperazidophosphoryl Compounds 4 Ball Mean Hertz Weld Rotary Bomb Blend Cu-Strip Navy Wear Load' Point' Oxidation Compound wt % in corrosion Rust micr?min kg kg min O 1.0 1A slight 4.6 53.3 158 20 / N M N SNO-20 DTA HN N-P-N NH N-/ N-1 (CH) O 0.75 1A moderate 4.1 53.9 58 40 / N II M N SNO-20 DTA HN N-1N--N NH N-/NH (Co-C) ZDT 0.5 m 48 224 m SNO-20 DTA 1.0 1A moderate 0.3 54.9 200 65 SNO-20 DTA SNO-20 DTA - 1A severe 7.3 24 126 40 ASTM-D130, 3 hr, 212"OF ASTM-D665A, 60' C, 24 hr ASTM-D 2266-64, 1800 rpm, 28 kg, room temp. ASTM-D2596, 1500 rpm, room temp. ASTM-2272, 100 rpm, 90 psi, 150' C 4,081,445 13 14 TABLE 5 Evaluation of Piperazidothiophosphoryl Compounds Compound S m

Y--N NH)2 wtBlend % in Cu-strip 4.Navy-Wear Bal MeanLoad Hertz Weld,Point OxidationRotary Bomb N-/ Base oil corrosion Rust micr/min kg kg min = -O-CH . 1.0 1A pass 1.9 54.6 158 20 mO(CH)m(CH)-CH No.200. DA 1A slight 0.5 43.2 158 35 17" WK 3 SNO-20 DTA -O-CH 1.0 iA pass 2.4 53.2 158 40 SNO-20 DTA 2.0 1B pass 2.6 43.2 158 30 145-PPT -N(CH) (CH) 1.0 1A pass 1.4 54.2 158 108 Sp-20 DTA -O-CH-NH-CH-CH64 s's Sopra47 1B slightvery 1. 29.1 158 508 Compound i Y-P(N N-(CH2)COOCH),

-O-CH-NH-CH-CH 0.5 1A O 0.3 29 158 220 6 4. . H-CHs SNO-20 DTA rust, deposit / N 0.6SNO-20-DTA 1A severe 0.5 43.3 158 30 -N N-(CH),-COOCH,

References ZDT 0.5 48 224 SNO-20-DTA .0 1A mod- 0.3 54.9 200 65 SNO-20-DTA erate 2.0 1A severe 2.6 67.4 200 210 145 PPT SNO-20-DTA - 1A severe 7.3 24 126 40 145 PPT - 6.6 23 126 20 ASTM-D130, 3 hr, 212" F. ASTM-D665A, 60' C. 24hr. ASTM-D2266-64, 1800 rpm 28 kg, room temp. ASTM-D2596, 1500 rpm, room temp. ASTM-2272, 100 rpm, 90 psi 150' C. The reaction product of CHOPSC, and piperazine, but with uncertain structure

TABLE 6 Evaluation of Phenyl Bispiperazidophosphite Blend 4 Bal Mean Hertz Rotary Bomb % wtin Cu-strip Navy Wear Load' Weld Point' Oxidation Compound Base oil Corrosion Rust micrymin kg kg min 2.0 1A pass 1.8 54.7 158 70 / N SNO-20 CH-O-P(N NH),

ZDT 2.0 ------0.2 62 251 120 SNO-20 SNO-20 - 1A Sevee 7.3 24 126 40 ASTM-D130, 3 hr, 212 F ASTM-D665A, 60' C, 24hr. ASTM-D2266-64, 1800 rpm, 28 kg, room temp. ASTM-D2596, 1500 rpm room temp. ASTM-2272, 100 rpm.90 psi, 150 C. The solubility in base oils at room temperature of phos- 55 The compound has good antiwear properties and phorothioic tris-(N'-(3-carbethoxyethylpiperazide) is mild extreme pressure activity, compared to ZDT a 0.6% wt in SNO-20 and 0.3% wt in 145-PPT, allowing zinc dialkyl dithiophosphate. an evaluation as lube oil additive. Test data are given in Table 7 below: TABLE 7 Phosphorothioic tris-(N'-3-carbethoxy ZDT in SNO-20 Bench Test ethylpiperazide) SNO-20 0.5 wt.% 1 wt.% Cu strip corrosion ASTM-D130; 3 hr; 1A 1A -- 1A 212°F Rust ASTM-D665A 60 C, 24 hr Sewere severe - moderate 4 ball Navy Wear ASTM-D2266-64 1800 rpm 0.5 micry 7.3 - 0.3 micry 28 kg, room temp min micramin min 4,081,445 15 16 TABLE 7-continued Phosphorothioic tris-(N-3-carbethoxy ZDT in SNO-20 Bench Test ethylpiperazide) SNO-20 0.5 wt % 1 wt.% Mean Hertz. Load ASTM-D2596 1500 rpm, room temp 43.3 kg 24 kg 48 kg 54.9 kg Weld Point ASTM-O2596 1500 rpm, room temp 158 kg 126 kg 224 kg 200 kg Rotary bomb oxi dation 30 min 40 min 65 min ASTM 2272, 100 rpm, 90 psi, 150 C

is X represents an oxygen or atom or is absent; Although this invention has been illustrated by refer- and ence to specific embodiments, it will be apparent to R represents a hydrogen atom, a C-C alkyl group, those skilled in the art that various changes and modifi- or a phenyl group. cations may be made which clearly fall within the scope 2. A compound selected from the group consisting of of this invention. Ethyl bispiperazidophosphate; What we claim is: n-Octadecyl bispiperazidophosphate; 1. Phenyl bispiperazidophosphate; Ethyl bispiperazidothiophosphate Phenyl bispiperazidothiophoshate; X Octadecyl bispiperazidothiophosphate; 1 N and RO-Pee-N NH Ethyl bispiperazidophophite. 3. Phenyl bispiperazidophosphate. 4. Ethyl bispiperazidophosphate. 5. Octadecyl bispiperazidophosphate. wherein s

35

45

50

55

65

UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. : 4 081, 445 DATED : March 28, 1978 INVENTOR(S) : Johny C. Hermans It is Certified that error appears in the above-identified patent and that said Letters Patent are hereby Corrected as shown below:

Col. 16, line 27, correct the spelling of -- bispiperazidophosphite --. signed and Sealed this Twenty-third O 2 y O f October 1979 SEAL Attest:

RUTH C. MASON L UTRELLEL F. PARKER Attesting Officer Acting Commissioner of Patents and Trademarks UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. : 4 081, 445 DATED March 28, 1978 INVENTOR(S) : Johny C. Hermans It is Certified that error appears in the above-identified patent and that said Letters Patent are hereby Corrected as shown below:

Col. 16, line 27, correct the spelling of -- bispiperazidophosphite --. eigned and sealed this Twenty-third Day of October 1979 SEAL Attest:

LUTRELLE F. PARKER RUTH C. MASON Attesting Officer Acting Commissioner of Patents and Trademarks