![United States Patent (19) [11] 3,832,391 Parshall (45) Aug](http://data.docslib.org/img/9243eba4954751db23f50551b08525ec-1.webp)
United States Patent (19) [11] 3,832,391 Parshall (45) Aug. 27, 1974
54 CATALYSS BY DISPERSIONS OF METAL 260/570.8 R, 260/5709, 260/593 R HALDES IN MOLTEN (51) int. Cl...... C07c51/14, C07c45/08 TRHALOSTANNATE (II) AND 58) Field of Search... 260/604 HF, 533 A, 533 AN, TRIHALOGERMANATE (II) SALTS 260/497 B, 497 V 75) Inventor: George W. Parshall, Wilmington, 56) References Cited Del. UNITED STATES PATENTS 73) Assignee: E. I. du Pont de Nemours and 3,700,706 10/1972 Butter...... 260/533 AX Company, Wilmington, Del. FOREIGN PATENTS ORAPPLICATIONS 22 Filed: Dec. 30, 1971 1,965,942 10/1970 Germany...... 200/533 A 21 Appl. No.: 214,376 Primary Examiner-Lorraine A. Weinberger Related U.S. Application Data Assistant Examiner-Richard D. Kelly 60) Division of Ser. No. 92,541, Nov. 24, 1970, Pat. No. 3,657,368, Continuation-in-part of Ser. No. 727,710, 57 ABSTRACT May 8, 1968, Pat. No. 3,565,823. Dispersions of transition and other metal halides in 52 U.S. CI...... 260/497 A, 260/410.5, 260/410.6, molten tetrahydrocarbylammonium or phosphonium 260/410.9 R, 260/413, 260/468 M, 260/469, trihalostannate (II) and trihalogermanate (II) salts are 260/476 R, 260/483, 260/485 R, 260/485 G, useful as catalysts for the hydrogenation, isomeri 260/491, 260/514 M, 260/515 R, 260/598, zation or carbonylation of olefins and the hydrogena 260/599, 260/601 R, 260/604 HF, 260/409, tion of nitriles. 260/497 R, 260/526 R, 260/563 R, 9 Claims, No Drawings 3,832,391 1 2 CATALYSS BY DESPERSIONS OF METAL catalyst for the hydrogenation of terminal olefins and HALIDES IN MOLTEN TRIHALOSTANNATE (I) for the hydrogenation and isomerization of dienes. AND TRHALOGERMANATE (II) SALTS 11. L. J. Kehoe et al., J. Org. Chem., 35, 2846 (1970). Solutions of chloroplatinic acid and SnCl2 in RELATED APPLICATION 5 ketones or ethers are used to catalyze the carbonyla This application is a division of my copending appli tion of terminal olefins to alkyl esters. cation Ser. No. 92,541, filed Nov. 24, 1970, and now U.S. Pat. No. 3,657,368, itself a division and continua SUMMARY OF THE INVENTION tion-in-part of my copending application Ser. No. This invention is directed to processes employing as 727,710 filed May 8, 1968, and now U.S. Pat. No. O catalysts the liquid dispersions of my above-identified 3,565,823. copending application. These dispersions, which in clude molecular dispersions, consist essentially of: (A) BACKGROUND OF THE INVENTION at least 0.05 weight percent of a chloride-, bromide- or A. Field of the Invention iodide-containing salt of a metal having an atomic num 5 ber of 26-28, 44-46 or 76-78, and (B) a molten salt This invention relates to the use of the dispersions of of a compound of the formula (R'R'R'R''QYXa metal halides in molten quaternary ammonium triha wherein R, R, R and R, independently, contain up lostannate(II) or trihalogermanate(II) salts of my to 18 carbons and are alkyl, cycloalkyl, aryl, alkaryl or above-mentioned application as catalysts in processes aralkyl; or R and R', conjointly, contain 4 to 6 carbons for hydrogenating, isomerizing and carbonylating ole and is alkylene; or R, R, R and Q conjointly is pyri fins and for hydrogenating nitriles. dinium or quinolinium; Q is nitrogen or phosphorus; Y B. Description of the Prior Art is tin or germanium; and X is chlorine or bromine. The dispersions can be made, for example, by mixing The following references are of interest in connec components A and B at a temperature above the melt tion with the invention of this application: 25 ing point of component B, as is fully disclosed in my co 1. R. D. Cramer et al., J. Am. Chem. Soc., 85, 1691 pending application. Dispersions formed and claimed (1963). Solutions of chloroplatinic acid and stannous in the copending application include the following: chloride are effective catalysts for the hydrogenation of N,N,N,N-tetraethylammonium trichlorostannate(II) olefins. - containing: PtCl2, PdCl2; RuCls hydrate; RhCl3 hydrate; 2. G. C. Bond et al., J. Catal.., 7, 217 (1967). Solu 30 IrCl34HO, OsCl ReCls, CoCl2, CoCl26H2O, tions of chloroplatinic acid and stannous chloride are HPtClinHO; FeCl; FeCls, MnOl. CrCl; CrCla; effective catalysts for the isomerization of 1-pentene to VC, TiCl, NiCl, NiBr. NiI6HO; IrBra; KPtCl; its equilibrium mixture with 2-pentenes. KPdCI, WCls, MoCla; (Etap):PtCl(Et is ethyl); 3. H. van Bekkum et al., J. Catal. 7, 292 (1967). So (NO)RuOl3HO; AuCla; and lutions of chloroplatinic acid and stannous chloride 35 N.N.N,N-tetraethylammonium trichloroger catalyze the hydrogenation of cyclohexene and the se manate(II) containing: NiBréHO, CoCl2, PdCl2; lective hydrogenation of dienes to monoenes. RuCl3HO, RhCls HO, etc. 4. L. P. van't Hoffet al., J. Catal.., 7, 295 (1967). So In the present invention, all the above-mentioned dis lutions of chloroplatinic acid and stannous chloride are persions serve as catalysts in: used as catalysts for the hydrogenation of soybean oil. 40 A. A process for the hydrogenation of olefins and ni Methyl linoleate gives predominantly methyl oleate. triles and for the isomerization of olefins; and 5. E. L. Jenner et al., U.S. Pat. No. 2,876,254 (1959). The carboxymethylation of propylene gives a product B. A process for the carbonylation of olefins. mixture containing approximately equal amounts of A. HYDROGENATION AND ISOMERIZATION methylbutyrate and methyl isobutyrate. 45 The process for the hydrogenation of olefins or ni 6. F. N. Jones, J. Org. Chem., 32, 1667 (1967) and triles is conducted by heating a mixture of hydrogen U.S. Pat. No. 3,397,252 (1968). Inter alia, vinyl chlo and an olefin, including a cycloolefin, or a nitrile in the ride is reductively coupled to yield butadiene by Sn(II presence of a catalytically effective amount of at least in solutions containing catalytic amounts of PtCl2, ce one of the above-noted metal halide-trihalostannate(II) sium fluoride acting as cocatalyst. 50 or -trihalogermanate(II) dispersions at a temperature The following art may also be of interest: of at least the melting point temperature of said disper 7. Th. Kruck et al., Angew Chem. internat. Edit., 8, sion, 679 (1969). The reaction of trichlorostannate salts Any olefin can be hydrogenated according to the in with metal carbonyls is used to produce complexes vention, but the reaction may be expressed more par containing the SnCls ligand. Tetraethylammonium tri 55 ticularly by the equation which follows (A signifies that chlorostannate is used in one experiment although not the temperature is high enough to keep the catalyst above its melting point. molten): 8. Japanese Patent 7,005,255 (1970). Aliphatic poly olefins will hydrogenate to monoolefins with the cata 60 R5 R8 Rs. Rs N A lyst HPtSnCl(PR). C=C - H -- H-C-C-H 9. W. Wilkinson, U.S. Pat. No. 3,501,531 (1970). / cat. Complexes prepared from mixtures of rhodium chlo R7 R8 R7 R8 ride and stannous chloride are used as catalysts for the hydroformylation of olefins. 10. R. W. Adams et al., Inorg. Nucl. Chem. Letters, 65 wherein R, R, R and R, individually, are hydrogen, 4,455 (1968). A mixture of dichlorobis(triphenylphos alkyl of up to 12 carbons, alkenyl of up to 12 carbons, phine)-platinum and stannous chloride is effective as a aryl of up to 10 carbons, aralkyl of up to 10 carbons, 3,832,391 3 4 alkaryl of up to 10 carbons, aralkenyl of up to 10 car position of the group consisting of hydrogen, water and bons, alkoxycarbonylalkyl of up to 14 carbons, alkox alcohols. Except for the reactants, all three of these re ycarbonylalkenyl of up to 14 carbons, -COOR or actions employ essentially the conditions of the hydro -COR where R is lower alkyl; or R and R conjointly genations noted above. is alkylene or alkenylene of 4 to 6 carbons; or R and Hydroformylation is conducted by heating a mixture R is alkylene or alkenylene of up to 10 carbons or the of carbon monoxide, hydrogen and any olefin in the divalent radical of the formula:- presence of a catalytically effective amount of at least one of the metal halide-trihalostannate(II) or -trihalo -(-CH2-)-CH CH-CH-)-CH A. CH-CH2-)-2, germanate(II) dispersions at a temperature of at least with the proviso that at least two of R, R, R and R' 10 the melting point temperature of said dispersion. The are hydrogen. Included within the definition of the ole process of hydroformylation may be particularly ex fin are 1,5-cyclooctadiene, 1,5-cyclododecadiene and pressed by the equation: l,5,9-cyclododecatriene. t In the hydrogenation of olefins, as in all the processes of the invention, an effective catalytic amount of the 15 dispersions of my above-mentioned application or mix tures thereof is used. In general, an effective catalytic amount will be dependent upon the conditions, the re Rs R6 actants, the particular process and metal halide disper Yc-c -- H -- CO A ( R7 R8 sion. Preferably, 0.005 to 10 weight percent of the 20 RF R8 cat, \ H R R' metal halide in the dispersion based on the olefin reac OscC-C-C-H tant is used. Most preferably, 0.5 to 5 weight percent k k. of the metal halide in the dispersion is used. The rates of reaction of the processes are dependent upon the temperature and the reactants used. In gen eral, the temperature of reaction will be as low as about wherein R, R, R and R are defined as above. 10°C. and up to 350°C. Carboxylation is conducted by heating a mixture of Pressure reactors may be necessary for the processes carbon monoxide, water and any olefin in the presence to effect reaction. In general, the pressure will be au of a catalytically effective amount of a catalyst as de togenous pressures to 1,500 atmospheres or higher. fined above for hydroformylation. This process may be The time of the reaction will vary from a very short particularly expressed by the equation: time of a few minutes or less to a few hours or longer. Shorter reaction times are preferred since they give more economical processes. Concomitant with the present hydrogenation of the olefins occurs an isomerization of starting material or H-C-C-C-OHf : 9 product. The isomerization may, in fact, occur at such k k. a low hydrogen concentration that no hydrogenation RS R6 takes place, but a small (catalytic) amount of hydrogen N A / / CsC -- H2O -- CO cat. Y is believed always to be present. Conditions are other R7 RS wise the same as for the hydrogenation. The isomeriza O R5 R8 tion of the olefins is of two types: (1) isomerization of HO-C-C-C-Hd a cis isomer to the trans isomer or vice versa; and (2) k' k. position isomerization such as isomerization of the ole fin to a different structure. An example of the latter 45 type of isomerization is the conversion of a cy-pinene to o-terpinene, dipentene or y-terpinene. wherein R, R, R', and Rare defined as above. The process of hydrogenation of nitriles, except for Alkoxycarbonylation is conducted by heating a mix the nitrile reactant, employs essentially the conditions ture of carbon monoxide, a mono- or dihydric aliphatic of the hydrogenation of olefins, and may be expressed 50 alcohol and any olefin in the presence of a catalytically by the equation: effective amount of a catalyst as defined above for hy droformylation. This process may be particularly ex H A pressed by the equation(s): R10-CEN -- H. - R1O-C-NH cat. H
R3 R8 R. R. o. wherein R' may be saturated alkyl, saturated cycloal (-d -- Rai-OH -- CO - a H-C-C-E-O-Rt. -- kyl, aryl, alkaryl, aralkyl and aralkaryl, each of up to 18 60 k k cat. k k carbons, and nitrile mono-substituted derivatives of O R5 R6 these. Ril-O-(-)-(–H B. CARBONYLATION R7 RS The process for the carbonylation of an olefin in cludes hydroformylation, carboxylation and alkoxycar 65 bonylation and consists in reacting the olefin with car bon monoxide and an active-hydrogen-containing con or, with a dihydric alcohol, 3,832,391 6 as plasticizers for polymers such as polyvinyl chloride, ( " ' polymethyl methacrylate and polystyrene. R5 R6 O c---HR7 R8 A / EMBODIMENTS OF THE INVENTION C=C -- R11 (OH)2 CO --> Rii -- l. cat. N The following examples, in which parts and percent R7 RS o, ages are by weight, illustrate the catalytic activity of the c---H dispersions of the metal salts in tetraalkylammonium Ri R8 trihalostannate(II) and trihalogermanate(II) salts in the processes of the invention. R. R. R. " O The preparation of the catalyst dispersions or solu tions is in general obvious and described above. Exam H---k k O H---cyR. RS O N ples 1 to 8 involve a procedure sometimes preferred for Rli -- Rli convenience. In this procedure, component A was first / Rs R6 O O o, R R dissolved or dispersed in molten component B. The melt was then filtered to remove any undissolved or un H-b-c-3 c-g-g-H dispersed component A and the product allowed to so k k R7 R8 lidify by cooling. It was then crushed so that the indi cated amount of catalyst could be weighed out. In each example, the temperature specified for carrying out the R' being an alkyl or alkylene group of 6 or fewer car reaction was high enough to insure that the previously bons and the other R's being as before. prepared catalyst was molten during the process. C. PRODUCTS A. HYDROGENATION AND SOMERIZATION The hydrogenated, isomerized or carbonylated prod Example 1 ucts are, in general, known chemicals. They can be iso 25 lated by known methods, e.g., by distillation of the re Hydrogenation of Methyl Linoleate action mixture. Alternatively, the crude reaction mix A misture of 5.0 ml of methyl linoleate and 50 g of ture can be isolated by first washing with water fol a 1 percent solution of platinum dichloride prepared in lowed by separating of the hydrocarbon layer from the molten tetraethylammonium trichlorostannate(II) was water layer. Pure product is then obtained by distilla 30 agitated at 150°C for 6 hours in a 80-ml stainless steel tion. tube under a hydrogen pressure of 100 atmospheres. The compounds produced by the hydrogenation and The solid residue from the reaction vessel was distilled for isomerization of olefins are useful as solvents and as directly at 200°C at 0.2 mm to give 3 ml of a cloudy liq chemical intermediates, such as precursors of fiber uid. The liquid was redistilled to give 2.0 g of a clear, forming polyamides. For example, 15,9- colorless liquid, n° 1.4522. (The refractive index is cyclododecatriene can be hydrogenated to cyclododec that expected for methyl oleate or one of its positional ene which can be oxidized with dilute potassium per isomers.) The gas chromatogram of the product manganate to dodecanedioic acid. Dodecanedioic acid showed 62.8 area percent of a peak assignable to reacts with diamines such as hexamethylenediamine to methyl oleate and 15.4 area percent of a peak assign form a salt which can be heated under vacuum at a 40 able to an isomeric monoolefin. temperature of about 200°C. to form a fiber-forming When the unsaturated compounds shown in Table I polyamide. Fibers can be prepared from the polyamide are substituted for methyl linoleate in the hydrogena by melt spinning. tion procedures of Example 1, the compounds shown The amines produced by the hydrogenation of ni as hydrogenation products are the principal products triles are useful in the preparation of dyestuffs and as 45 obtained. It may be noted that with the unsaturated dispersing agents as shown for ethylamine; Turner, compounds of Example 1 and Table II, the formula be “The Condensed Chemical Dictionary," Reinhold Pub COeS lications, New York, 1950, p. 27 l. The amines ob tained are all primary amines and are also useful as acid R5 R0 scavengers. 50 / The aldehydes produced in the carbonylation process Yo-c , wherein are useful as solvents and as commercially important R7 R8 intermediates. For example, propionaldehyde is used in the production of polyvinyl acetals which are useful as at least two and not more than three of R, R, R and adhesives and for the production of rubber chemicals. 55 Rare hydrogen, with the proviso that when two are hy Turner, The Condensed Chemical Dictionary, Rein drogen, one may be alkyl of up to 12 carbons, and the hold Publications, New York, 1950, p. 547. other one or two of R, R, R and Rare alkoxycar The acids produced by the carbonylation of olefins in bonylalkyl or alkoxycarbonylalkenyl of up to 14 car the presence of water are all useful for preparing the bons, or -COOR or -COR', where R is lower alkyl. corresponding esters by reaction with alcohols. Esters, whether obtained from acids or by carbonylation of TABLE I olefins in the presence of an alcohol, are useful as sol vents and as plasticizers. Lower molecular weight es tem Olefin Hydrogenation Product(s) ters, particularly those containing up to 10 carbon 65 1 Ethyl 5-octenoate Ethyl octoate atoms, are useful as solvents and diluents in paints and 2 Amyl undecylenate Amyl undecanoate 3 Methyl sorbate Methyl 2-hexenoate and varnishes. Higher molecular weight esters, particularly methylhexanoate those containing 8 carbon atoms and more, are useful 4 Propyllinoleate Propyl oleate and propyl 3,832,391 7 8 oxide and was agitated at 90°C. for 6 hours. The vola TABLE I-Continued tile products were fractionated by vacuum distillation. The product retained by a trap cooled to -1 19C was ten Olefin Hydrogenation Product(s) propionaldehyde. Treatment with 2,4-dinitrophenylhy octadecanoate 5 Methyl acrylate Methyl propionate drazine gave a yellow-orange product. Recrystalli 6 Ethyl-2-nonenoate Ethylnonanoate zation from ethanol gave orange needles of the 7 Ethyl vinyl ketone Diethyl ketone 2,4-dinitrophenylhydrazone of propionaldehyde, melt 8 sopropenyl methyl ketone Isopropyl methyl ketone ing point 154-156°C. A mixture melting point with an authentic sample was not depressed. Vacuum distilla O tion of the residual liquid clinging to the frozen salt in Example 2 the pressure vessel gave 2.8 g. of clear colorless liquid. Hydrogenation of a Nitrile Gas chromatographic analysis showed the presence of propionaldehyde and 2-methyl-2-pentenal. A mixture of 5.0 ml of acetonitrile and a solution of 0.5 g of platinum dichloride prepared in molten tetra 15 Example 6 ethylammonium trichlorostannate(II) was agitated at A dispersion of 0.5 g. of NasRhCls prepared in 39.3 50C. for 8 hours in an 80-ml stainless steel tube g of molten tetraethylammonium trichlorostannate(II) under a hydrogen pressure of 100 atmospheres. The was heated in a glass-lined pressure vessel at 90°C for crude reaction product was extracted with benzene. 6 hours under a pressure of 1,000 atm. of a 1:2:10 mix Gas chromatographic analysis of the extract showed 20 ture of hydrogen, ethylene, and carbon monoxide. Vac the presence of ethylamine in addition to unchanged uum distillation of the volatile products showed the acetonitrile. presence of propionaldehyde which was identified by The following Examples were carried out as de its infrared spectrum and gas chromatography. scribed in Example 2: When the olefins shown in Table III are substituted 25 for ethylene in the procedures of Examples 5 and 6, the Example Metal Halide Temp/Pres. Result compounds shown as aldehyde products are among the principal products obtained. 3. rCl3HO 15C1160 atm. CHNH formed RhCl3HO 150°C/16() atm. . CHNH formed TABLE III
tem Olefin Aldehyde(s) When the nitriles shown in Table II are substituted 1 2-Buteme 2-Methylbutyraldehyde for acetonitrile in the procedures of Examples 2-4, the 2 -Octene Nonanal and 2-methyloctanal indicated amines are the principal products obtained. 3 -Tctriccenc Pentadecanal and 2-methyltetradecanal 35 4 15-Hexadiene 6-Heptenal and TABLE 2-methyl-5-hexenal 5 1,1-Dodecadiene 12-Tridecenal and 2-methyl-11-dodecenal tem Nitrile Amine 6 3-Tetradiccadiene 4-Pentadecenal and 2-methyl-13-tetradecenal Acetonitrile Ethylamine 7 Styrene 2-Phenylpropionaldehyde and 2 Propianitrile Propylamine. 40 3-phenylpropionaldehyde 3 isobutyronitrile Isobutylamine 8 Stilbene 2,3-Diphenylpropionaldehyde 4 Laurynitrile Laurylamine 9 a-Vinylnaphthalene 2-(o-Naphthyl)propionaldehyde 5 Stearinitrile Stearylamine and 6 Cyclopropanecarbonitrile (Cyclopropylmethyl)amine 3-(o-naphthyl)propionaldehyde 7 Cyclopentanecarbonitrile (Cyclopentylmethyl)amine 10 4-Phenyl-l-butene 5-Phenylpentanal and 8 Cyclohexanecarbonitrile (Cyclohexylmethyl)amine 2-methyl-4-phenylbutanal 9 Dicyclopentylacetonitrile (2,2-Dicyclopenty lethyl) I 3-Phenylcyclobutylethylene 3-3-Phenylcyclobutyl)propional . and s . - - annine 2-(3-phenylcyclobutyl)-propional O Benzonitrile Benzylamine 12 2,3,5,6-Tetramethylstyrene 2-Durylpropional and ll p-Toiunitrile p-Methylbenzylamine 3-duryl-propional 2 -Phenylcyclopropanecar- (1-Phenylcyclopropyl 13 4,4'-Dimethylstilbene 2,3-Di(p-tolyl)propional htnitrile methyl)amine i4 5-Phenylpiperylene 6-Phenyl-3-hexenal and 13 a-Naphthonitrile a-Naphthylmethylamine 4-phenyl-2-vinylbutanal 4 -Phenantiremecurhynitril -Phenanthrylmethylamine 50 5 5-p-Tolylpiperylene 6-(p-Tolyl)-3-hexenal and 15 g.g.f3-Triphenylpropio- 3,3,3-Triphenylpropyl 4-(p-tolyl)-2-vinylbutanal nitrile amine . 6 Ethyl 6-octenoate Ethyl 7-formyloctanoate and 16 Maion nitrile 1,3-Propylenediamine ethyl 6-formyloctanoate 7 Sticcinonitrile 1,4-Butylencliamine 17 Amyl undecylenate Amy 1-formylundecanoate and 18 Adiponitrile Hexamethylenediamine amyl 10-formylundecanoate 9. Phthalonitrite c-Xylylene-oat'-diamine 18 Methyl sorbate Mcthy 5-formyl-2-hexenoate and 20 Sebalconitrite Decamethyleneciamine 55 methyl 3-formyl-4-hexenoate 21 Biphenyl-4.4'-dicarbo- 4.4'-Bibenzylamine 19 Propyl linoleate Propyl 13-formyloieate and nitrile propyl 2-formyloleate 20 Methyl acrylate Methyl 3-formylpropionate 21 Ethyl 2-nonenoate Ethyl 3-formylnonanoate B. CARBONYLATION 22 Ethyl vinyl ketone 4-Oxohexania 60 23 sopropenyl methyl 3-Methyl-4-oxopentanal Example 5 ketone Hydroformylation of Ethylene A dispersion of 0.6 g of platinum dichloride prepared Example 7 in 51 g of molten tetraethylammonium trichlorostan nate(II) was placed in a glass-lined 400 ml pressure ves 65 Carboxylation of 1-Hexene sel. The vessel was pressured to 1,000 atm. with a A mixture of 5.0 g of 1-hexene, 1.4 m of water and 1:2:10 mixture of hydrogen, ethylene, and carbon mon 25g of a 1 percent of platinum dichloride in tetraethyl 3,832,391 9 10 ammonium trichlorostannate(II) was shaken at 90°C ate and methyl 2-methylhexanoate. The ratio of linear for 6 hours under 400 atmospheres carbon monoxide isomer to branched isomer was 4:1. pressure in a 80-ml stainless steel tube. The gases were When the alcohols and olefins shown in Table V are vented. The residual solid was crushed and extracted substituted respectively for methanol and 1-hexene in with ether. Evaporation of the ether extract gave ca. 2 5 the procedure of Example 8, the indicated ester prod ml of a mixture of heptanoic acid and 2- ucts are among the principal products obtained. methylhexanoic acid in a ratio of about 3:1 as deter mined by esterification and gas chromatographic analy- TABLE V sis. When the olefins shown in Table IV are substituted 10 item Alcohol Olefin Ester(s) for 1-hexene in the procedure ofExample 7, the indi- 1 Methanol Cyclohexene Methyl cated acid products are the principal products ob- cyclohexanecarboxylate tained. 2 Ethano 1-Octene Ethylnonanoate and ethyl 2-methyloctanoate TABLE IV 5 3 Propanol Propylene Propylbutyrate and propyl isobutyrate 4. Butanol Isobutylene Butyl isovalerate and Itern Olefin Acid(s) butyl pivalate 5 Isobutanol Isobutylene lsobutyl isovalerate and 1 Cyclohexene Cyclohexanecarboxylic acid isobutyl pivalate 2 l-Octene Nonlinoic acid and 6 tert-butanol -Butene tert-Butyl valerate and 2-methyloctanoic acid tert-butyl 3 Propylene Butyric acid and isobutyric acid 2O 2-methylbutyrate 4 Isobutylene lsovaleric acid and pivalic acid 7 Pentanol Propylene Pentyl butyrate and 5 Ethylene Propionic acid pentyl isobutyrate 6 l-Tetradecene Pentadecanoic acid and 8 Hexanol l-Hexene Hexylheptanoate and 2-methyltetradecanoic acid hexyl 7 l. 3-Tetradccadiene 14-Pentadecenoic acid and 2-methylhexanoate 3Elyticcid 25 9 Ethylene glycol Ethylene Ethylene propionate 8 Styrene EEE S 10 1.2-Propylene Propylene Methylethylene butyrate 9 Stilbene 2,3-Diphenylpropionic acid glycol E.stylethylene 1() a-Vinylnaphthalenc AfSEE . it l 1,4-Butanediol Ethylene 1,4-Butylene propionate acid pntnyi)prop 12 15-Pentanediol l-Butene 1,5-Pentamethylene 11 4-Phenyl-1-butene 5-Phenylvaleric2-methyl-4-phenylbutyric acid and acid 30 valerate,l,5-pentamethylene 12 3-Phenylcyclobutylethylene 3-(3-Phenylcyclobutyl)pro- ES and pionic acid and ,5-pentamethylene 2-(3-phenylcyclobutyl)- 2-methylbutyrate propionic acid valerate 13 2,3,5,6-Tetramethylstyrene 2-Durylpropionic acid and 13 1.3-Hexanediol Propylene 3-Propyltrimethylene 3-durylpropionic acid butyrate, 4 4.4'-Dimethylstilhene 2,3-Dicp-tolyl)propionic acid 35 3-propyltrimethylene 15 5-Phenylpiperylene 6-Phenyl-4-hexenoic acid and isobutyrate and 4-phenyl-2-vinylbutyric acid 3-propyltrimethylene 16 5-p-Tolylpiperylene 6-(p-Tolyl)-4-hexenoic acid butyrate isobutyrate NG 4-(p-tolyl)-2-vinylbutyric 14 6-Hexanedic Ethylene 1,6-Hexamethylene - acid propionate 17 Ethyl 6-octenoate 2-Methyloctanedioic acid, 4C) 15 Ethanol Ethyl acrylate Dicthyl succinate monoethyl ester; and 16 Methanol Methyl Dimethyl monoethylitstretfoie es acid, undecylenate dodecanedioatedi thvi and 18 Amy undecylenate Dodecanedioic acid, monoamyl 3Matsundecanedioate Sindecanedioic acid 7 Methanol i-Tetradecenc My Estadecanoate monoamyl ester. Wi and methy 9 Methvi schrhite 5-Methyl-2-hexenedioic acid, 45 2-methyltetradecanoate monomethyl ester; and 8 Methanol 1,3- Methyl 2-propenylsuccinic acid, Tetradecadiene Radecenoate and monomethyl ester methy 20 Propyl linoleate 2-Pentyl-5-tetradecencedioic 2-methyl-3- acict, monopropyl estcr; and tetradccenoate 2-hexyl-4-tridecenedioic acid, 9 Ethnic Styrene Ethyl monopropyl ester 5() 2-phenylpropionate and 2 Methyl acrylate Succinic acid, monomethyl cthy st 3-phenylpropionate 22 Ethyl 2-nonenoate 2-Hexylsuccinic acid, 20 Ethanol Stilbenic Ethyl monoethyl ester 2,3-diphenylpropionate 23 Ethyl vinylketone 4-Oxchxanoic acid 2 Mcthanol o-Vinylnaphtha - Methyl 2-4 isopropenyl methyl ketone 3-Methyl-4-oxovaleric acid lenc 2-(o-naphthyl)propion 55 atc. and methyl 3-(a-naphthyl)- propionate 22 Methanol 4-Phenyl-1- Methyl 5-phenylvalerate Example 8 butcne and methyl Alkoxycarbonylation of 1-Hexene islate A mixture of 8.4 g of 1-hexene, 4.8g of methanol, 6) 23 Methanol henylcy. Shenylcyclobuyi). and 45g of a 1 percent solution of platinum dichloride clobutylethylene propionate and methyl prepared in molten tetraethylammonium trichlorostan- phylcyclobutyl)- nate(II) was agitated at 90°Ce for 6 hours in a 400-ml 24 Ethanol 2,3,5,6-tet- proponateEthyl 2-durylpropionate glass-lined shaker tube under a carbon monoxide pres- 65 ramethylstyrene and ethyl sure of 450 atmospheres. Gas chromatographic analy- 25 Methanol 4.4". is propionate sis of the undistilled liquid product showed an approxi- Dimethylstil. 2,3-dicp-tolyl)- mate 15 percent yield of a mixture of methylheptano- bene propionate 3,832,391 11 12 TABLE V-Continued -(-CH2-)-CH=CH-CH-)-CH=CH-CH-)-2, with the proviso that at least two of R, R, R and Rare Item Alcohol Olefin Ester(s) hydrogen, 26 Ethanol 5- Ethyl which comprises Phenylpipery- 6-phenyl-4-hexenoate 5 reacting the olefin with carbon monoxide and an lene and ethyl 4-phenyl-2- active-hydrogen-containing member of the group vinylbutanoate consisting of hydrogen, water and mono- and dihy 27 Ethanol 5-p- Ethyl Tolylpiperylene 6-(p-tolyl)-4-hexenoate dric alcohols of up to 6 carbons, and ethyl in the presence of a catalytic amount of a dispersion 4-(p-tolyl)-2- O vinylbutanoate at a temperature between about 10 and 350°C. 28 Ethano Ethyl Diethyl and above its melting point, said dispersion consist 6-octenoate 2-methyloctanedioate and diethyl ing essentially of 2-ethylheptanedioate (A) at least 0.05 weight percent of a chloride-, bro 29 Amyl alcohol Amyl Diamyl dodecancedioate undecylenate and diamyl 15 mide- or iodide-containing salt of a metal having an 2-methylundecanedioate atomic number of 26-28, 44-46, or 76-78; and 30 Methanol Methyl sorbate Dimethyl 5-methyl-2- (B) a molten salt of the formula RRRROYX, hexencodioate and wherein R, R, R and R, independently, contain dimethyl 2-propenylsuccinate up to 18 carbons and are alkyl, cycloalkyl, aryl, al 3 Propanol Propyl linoleate Dipropyl 20 karyl or aralkyl; or 2-pentyl-5-tetradecene R' and R, conjointly, contains 4 to 6 carbons and is dioate and dipropyl 2-hexyl-4-tridecentedio alkylene; or altic R', R', R' and Q conjointly is pyridinium or quinolin 32 Methanol Mcthyl acrylate Dimethyl succinate 33 Ethanol Ethyl Dicthyl 2-hexylsuccinate 1unn, 2-nonenoate 25 O is nitrogen or phosphorus; 34 Methanol Ethyl vinyl Methyl 4-oxohexanoate ketone Y is tin or germanium; and 35 Miethin isopropenyi Methyl X is chlorine or bromine. methyl ketone 3-methyl-4-oxovalerate 2. The process of claim 1 wherein the olefin is re acted with hydrogen and carbon monoxide in the pres 30 ence of platinum dichloride dispersed in tetraethyl Since obvious modifications and equivalents will be ammonium trichlorostannate(II). evident to those skilled in the chemical arts, I propose 3. The process of claim 2 wherein the olefin is ethyl to be bound solely by the appended claims. CC. The embodiments of the invention in which an exclu 4. The process of claim 1 wherein the olefin is re sive property or privilege is claimed are defined as fol- 35 acted with hydrogen and carbon monoxide in the pres lows: ence of NagRhCls dispersed in tetraethylammonium tri 1. A process for the carbonylation of an olefin of the chlorostannate(II). formula 5. The process of claim 4 wherein the olefin is ethyl ene. RS RO 4() 6. The process of claim 1 wherein the olefin is re N ==C. , wherein acted with carbon monoxide and water in the presence R^ RS of platinum dichloride dispersed in tetraethyl ammonium trichlorostannate(II). R, R, R and R, individually, are hydrogen, alkyl of 7. The process of claim 6 wherein the olefin is 1 up to 12 carbons, alkenyl of up to 12 carbons, aryl of 45 hexene. up to 10 carbons, aralkyl of up to 10 carbons, alkaryl 8. The process of claim 1 wherein the olefin is re of up to 10 carbons, aralkenyl of up to 10 carbons, alk acted with carbon monoxide and a mono- or dihydric oxycarbonylalkyl of up to 14 carbons, alkoxycar aliphatic alcohol of up to 6 carbons in the presence of bonylalkenyl of up to 14 carbons, -COOR or -COR' platinum dichloride dispersed in tetraethylammonium where R is lower alkyl; or RandR conjointly is alkyl 50 trichlorostannate(II). ene or alkenylene of 4 to 6 carbons; or R and R is al 9. The process of claim 8 wherein the olefin is 1 kylene or alkenylene of up to 10 carbons or the diva hexene and the alcohol is methanol. lent radical of the formula: sk k k -k sk
5 5 PO-1050 UNITED STATES PATENT OFFICE (5/69) CERTIFICATE OF CORRECTION Patent No. 3,822:29 Dated August 27, 1974 Inventor(s) George W. Parshall It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below: - - Column l, line 48, "Sn(II" should read "Sn(II)". Column 6, line 27, "misture" should read "mixture". Column 6 line 7, "II" should read "I". Column 6 line 50, "R" should read nR6 it. Column ill, line 40, "R" should read IR6 it.
3isned and sealed this list day of April 1975.
(SEAI.) Attest : e re C ARSHAL DANE RUTH C. ASON Corninissioner of Patents Attesting Officer and Trademarks