A PROCESS FOR CONVERTING OLEFINS TO CARBOXYLIC ACIDS OR ESTERS USING SOLUBLE IRIDIUM COMPOUNDS

Abstract: A homogeneous process for converting olefins to carbo­ xylic acids and/or esters. The process comprises contacting an olefin and a formate ester or transesterification product thereof with a soluble iridium cytalyst and iodide promoter at temperatures of from 150 to 300 °C in a carboxylic acid solvent.

Description: This invention relates to a homogeneous process for converting olefins to carboxylic acids and/or esters. More particularly, olefins are contacted with a formate ester or trans-esterification product thereof in the presence b, a soluble iridium compound and iodide promoter in a carboxylic acid solvent. It is known that olefins can be converted to carboxylic acids or esters in the presence of a hydroxy compound, carbon monoxide or carbon dioxide and Group VIII catalyst. U.S. Patent 2,739,169 discloses the reaction of CO and steam with organic compounds such as olefins, alcohols, ethers and esters to produce carboxylic acids and/or anhydrides. Metal carbonyls are stated to be catalysts with Ni, Co, Fe, Cr, Mo, Ru, Pd, Pt, Re, Os and Ir being described as typical carbonylforming materials. If steam is replaced by carboxylic acid, an anhydride is produced in the place of a carboxylic acid. U.S. Patent 3,816,489 teaches a process for preparing carboxylic acids from olefins, CO and H20 using an iridium catalyst plus an iodide promoter wherein the iodine to iridium ratio is maintained between critical limits. U.S. Patent 4,000,170 describes a similar reaction with the iridium in the catalyst system being at least 50 wt.% in a highly catalytically active form as defined by a characteristic infrared spectrum. U.S. Patent 4,132,734 is directed to the addition of cobalt, iron or manganese to a catalyst system containing a rhodium or iridium compound and a halogen to produce carboxylic acids from olefins, CO and H20. I. S. Kolomnikov et al., in Kinetics and Catalysis, 13, 227 (1972) state that group VIII metals catalyse hydrogenation of olefins in the presence of formic acid, and if a triphenylpllosphine complex of said metals is used, the addition of formic acid to olefin to form a carboxylic acid may also occur. (Ph3P)3RhCl is stated to convert cyclohexene and HCOOH to cyclohexane carboxylic acid in 10% yield. Reaction conditions are not stated. T. Mizorogi, Shokubai (Catalysts), 19, 90-95 (1977) reviews thë > :synthesis of C2-containing oxygen compounds using CO. The author cites a reference 10 indicating that IrCl4.H20-CH3I catalyst shows isomerization activity. This reference, however, is to unpublished data. U.S. Patent No. 3,839,428 which was reissued as Re. 29,981 teaches a process for converting formic acid esters to the corresponding carboxylic acids which comprises contacting the ester with carbon monoxide (CO) at an elevated CO pressure. Although the reaction will occur in the absence of a catalyst, Group VIII metals such as iron, cobalt and nickel, Group IIb metals and halogens may be advantageously employed to increase the conversion rate. U.S. Patent 3,488,383 concerns the selective decomposition of formic acid in admixture with another aliphatic acid or ester of an aliphatic acid, e.g., methyl formate. The process comprises contacting the formic acid-containing mixture with a soluble complex compound of a Group VIII metal or rhenium. The complex compound is a compound of Pt, Os, Rh, or preferably Ru or Ir. Formate esters are unreactive and may be present as part of the solvent system. Example 1 indicates that at least part of the formic acid is decomposed to H2 and CO2. It has been discovered that olefins can be converted to carboxylic acids or carboxylic acid esters without the presence of carbon monoxide or hydroxyl containing compound. The present homogeneous process for preparing a carboxylic acid ester comprises contacting an olefin and a formate ester with a catalytically effective amount of a soluble iridium salt or compound and an iodide promoter in the presence of a carboxylic acid at a temperature from 150 to 3000C. In another embodiment a homogeneous process for preparing a carboxylic acid comprises contacting an olefin and formic acid with a catalytically effective amount of a soluble iridium salt or compound and an iodide promoter at a temperature of from 150 to 3000C. As noted above, the process of the invention does not require CO or a hydroxy containing compound such as water or alcohol. Moreover, no special high pressure apparatus is required since autogenous pressures may be employed. Carboxylic acids and esters thereof are produced as illustrated by the following overall reactions employing a terminal olefin as reactant: EMI3.1 By suitable adjustments of reaction components either carboxylic acids or esters may be selectively obtained as the final product. As illustrated above, a mixture of acids and/or esters is typically produced. Formate esters may have the formula HCOOR1 where R1 is aliphatic, cycloaliphatic, araliphatic or aryl, preferably C1-C20 aliphatic, C3-C12 cycloaliphatic, C7-C16 araliphatic or C6-C12 aryl, more preferably C1-Cg aliphatic, C4-Cg cycloaliphatic, C7-C12 araliphatic and most preferably C1-C6 alkyl, C5-C6 cycloalkyl, C7 C10 aralkyl and especially methyl, ethyl, propyl or butyl. The R1 radical may also bear unreactive substituents such as halo, cyano and the like. Examples of suitable formate esters include methyl formate, ethyl formate, propyl formate, butyl formate, isobutyl formate, cyclohexyl formate, phenyl formate, benzyl formate, phenethyl fprmate, octyl formate and dodecyl formate. The olefin reactants may be linear, branched or cyclic monoolefins,dio-1efins or polyolefins, and preferably have the formula R2R3C=CR4R5 where R2, R3, R4 and R5 are independently hydrogen, C1-C12 aliphatic, C3-C10 cycloaliphatic, C7-C14 araliphatic or C6-C12 aryl, preferably C1-Cg aliphatic, Cs-Cg cycloaliphatic, C7-C12 araliphatic or C6-C10 aryl, with provisos that at least two of R2 to R5 are hydrogen and any two of R2 to R5 may be joined together to form a C3 to C10 ring. Highly branched olefins generally exhibit very low reactivities or are unreactive and are therefore not desirable as reactants. The aliphatic radicals may be saturated hydrocarbyl radicals giving rise to monolefin reactants, or may be ethylenically unsaturated hydrocarbyl radicals giving diolefins or polyolefins as reactants. In homogeneous catalytic reactions of the type set forth in the present processes, the olefin typically reacts with metal to form a metal-olefin intermediate complex. Thus any olefin capable of complexing with the catalyst may be employed. Examples of olefin reactants are ethylene, propylene, butene-l, butene-2, butadiene, isoprene, pentene-l, 1,4-pentadigne, 4,4-dimethylpentene-1, 2,3-dimethylhexene-l, 3-ethylhexene-1, hexene-2, cyclohexene, styrene, allyl benzene, stilbene, dicyclopentadiene, vinyl cyclohexene, octene-l, 1,7-octadiene, octene-4, dodecene-l, octadecene-l, fulvene, indene, eicosene-l, bicyclo[2.2.l]hepta-2,5-diene, 1,4-cyclooctadiene and limonene. Linear and cyclic monoolefins and diolefins are preferred with terminal monoolefins and diolefins being especially preferred. The processes of the invention are homogeneous and are carried out using carboxylic acid solvents or mixtures thereof with inert organic solvents. In the case of reaction (II) above, the solvent may be either formic acid, another carboxylic acid or mixtures -with inert organic solvent. Mixtures of carboxylic acids as solvents may also be used in either reactions (I) or (II) above, e.g., a mixture of formic and acetic acids. Suitable carboxylic acids are of the formula RCOOH where R is aliphatic, cycloaliphatic, araliphatic or aromatic. Preferred carboxylic acids are those wherein R is C1-C20 aliphatic, more preferably C1-C10 alkyl and most preferably C1-C6 alkyl. Formic, acetic, propionic and butyric acids are especially preferred. Other inert organic solvents such as ethers, ketones, amides, sulfoxides and hydrocarbons may be present provided that the carboxylic acid comprises at least about 50 wt. % of the solvent mixture. Lower amounts of carboxylic acid in the solvent system may lead to decreased reactivity. A small amount of water, i.e., less than about 10 wt. %, may be present. Larger amounts of water lead to decreased yields. It is preferred to have less than about 5 wt. % of water present in the solvent system. While not wishing to be bound to any particular theory or reaction mechanism, the presence of carboxylic acid is essential in the formation of esters according to reaction (l) above. One explanation for this requirement is summarised by the following reactions: EMI6.1 Reactions (A) and (C) are transesterification reactions which consume and regenerate RCOOH, respectively. Reaction (B) corresponds to reaction (II) above and provides an explanation for this particular embodiment. If carboxylic acids are desired as products of olefin reaction, i.e., reaction (II) above, then formic acid may be both reactant and solvent. Other carboxylic acids may, however, be present as solvent. Suitable catalysts or catalyst precursors for the conversion of olefins to carboxylic acid and/ or esters are iridium salts or compounds which are soluble in the reaction medium chosen. Iridium salts or compounds are simple salts or compounds such as halides or oxides, and complexes containing halides, phosphines, amines including heterocyclic amines, arsines, cyanides, sulfides, esters, betadiketonates, carboxylates, hydrido, sulfites, nitro and the like as ligands. The complexes may also be organometallic iridium complexes containing both a and # bonded organic ligands, e.g., carbonyl, alkyl, alkenes and alkynes. Examples of iridium salts and complexes are [Ir(cyclooctadiene)Cl]2, Na2IrCl6.xH2O, H2IrCl6.xH2O, HIrCO[P(C6H5)3]3, ClIrCO(PEt3)2, IrCl3.xH2O, IrI3.xH2O, Na3Ir(NO2)6.xH2O, K3Ir(CN)6, [(C5H5)2Ir]NO3, Ir4(CO)12, IrH3[P(C6H5)3]3, 1,2,3-PY3IrCl3, trans-[IrPY4Cl]Cl and (C8H12)2IrSnCl3. Preferred salts are [Ir(cyclooctadiene) C1]2, IrC13.xH2O, IrBr3.xH2O and IrI3.xH2O. [Ir(cyclooctadiene)Cl]2, IrC13.xH20 and IrI3.xH2O are especially preferred. The symbol x indicates differing degrees of hydration and varies from 0 to 12. Iodizes generally are promoters or co-catalysts for the conversion of olefins to carboxylic acids and/or esters. Examples of suitable promoters include iodine, HI, organic iodides, and ammonium or phosphonium iodides of the formulae N(R6)4I and P(R6)4I where each R6 is independently hydrogen or C1-C6 alkyl. Preferred iodides are alkyl iodides of the formula R7I where R7 is C1-C10 alkyl. Catalyst concentrations may range from about 0.001 to 15 wt. % of iridium calculated as metal, based on the reaction mixture, preferably from 0.01 to 10 wt. %, especially 0.01 to 2 wt. %. The amount of iodide promoter is not critical, but high iodide:Ir ratios may retard the reaction. Amounts in excess of about 0.01 wt. %, based on the reaction mixture may be employed, preferably from about 0.05 to 2 wt. %. It is most preferred to maintain the I:Ir ratio at about 10:1. In addition to making carboxylic acid esters, the catalyst system of the invention may also be employ ed to convert olefins to carboxylic acids. In this embodiment, an olefin as defined above is contacted with formic acid in the presence of catalyst to produce a carboxylic acid. An example of this reaction is the conversion of propylene to butyric acid, i.e., EMI8.1 <tb> <SEP> catalyst <tb> CH3-CH <SEP> = <SEP> CH2 <SEP> + <SEP> HCOOH <SEP> < <SEP> > <SEP> CH3CH2CH2COOH <SEP> + <tb> <SEP> I <tb> <SEP> COOH <tb> As shown above, a mixture of primary and secondary carboxylic acids is obtained. Typically, primary acids are formed over secondary acids in a ratio of about 2:1. Commercially available formic acid is suitable. Water content, however, should be less than about 10 wt. % since excess water may lead to decreased yields. The present process may be conducted at temperatures of from 150 to 3000C, preferably from 170 to 2300C and especially from 190 to 210oC. Lower temperatures typically require longer reaction times and higher temperatures may result in catalyst instability. Carbon monoxide, nitrogen, Group 0 noble gases, carbon dioxide, hydrogen, C1-C6 hydrocarbons and the like may optionally be present as inert gases. Oxygen should be maintained at low levels ( < 50 ppm) if present. The pressure is autogenous, i.e., that generated by the reactants and any inert gases present at the desired - reaction temperature. Such pressures are typically in the range of from 0.1 to 20 MPa (1 MPa= 10 atm) . The pressure is not critical and greater pressures can be generated by added gas. There is generally, however, no advantage to operating at high pressures. Reaction times may vary from 0.1 to 24 hours or more depending on the reaction parameters chosen. Reaction times of from 1 to 10 hours are suitable when operating in preferred temperature ranges. The process m*dy be operated in either a batchwise or continuous mòde with continuous operation being preferred. If carboxylic acid is the desired product, it is preferred to use product carboxylic acid as solvent. This is advantageous since it permits recycle of a portion of the product stream without any expensive separations step. If esters are the desired product, they may be readily separated by conventional techniques such as distillation. By practising the process of the invention, formate esters can be converted to longer chain esters by reaction with olefin. Similarly, formic acid can be converted to a longer chain carboxylic acid, which can then be further reacted to form an ester, if desired. Neither reaction requires the presence of CO or hydroxyl containing compound. Moreover, no special high pressure equipment is needed. These processes are further exemplified by the following examples. EXAMPLE 1 A one-liter, Hastelloy-C, stirred autoclave was charged with the following reactants, solvent and catalyst: 0.5 gm. cyclooctadiene iridium (I) chloride 75 gms. 95-97% formic acid 10 ml. methyl iodide 300 g. glacial acetic acid The autoclave was flushed with nitrogen, sealed, charged with ethylene until the pressure reached 3 MPa at room temperature, and heated with stirring, to 2000C. At this temperature the pressure developed was 6.0 MPa (1 MPa = 10 atm.) . During the next 1.5 hours the pressure dropped to ,2.4 MPa. After four hours, further pressure drop was slight and the heating was discontinued. Upon cooling to ambient temperature and venting excess gases, the liquid contents were removed. The product weighed 425 gms. Analysis by gas liquid chromatography (thermal conductivity dector, Poropak T column), with dimethyl formamide as internal standard, indicated the presence of 100.6 gms. of propionic acid (90% yield) . No significant quantities of by-products were indicated. EXAMPLE 2 A one-liter, Hastelloy C, stirred autoclave was charged with the following reactants, solvent and catalyst: 0.5 gm. cyclooctadiene iridium (I) chloride 75 gms. 95-97% formic acid 15 ml. methyl iodide 250 gm. propionic acid The autoclave was flushed with nitrogen and sealed. Propylene (66 gms.) was added as a liquid from another pressure vessel. Stirring was begun and the vessel and contents were heated to 2000C and held at this temperature for four hours. At this temperature, the pressure dropped from an initial 3.3 MPa. very quickly to 1.8 MPa, and then rose slowly to a final value of 3.1 MPa. The vessel was cooled to ambient temperature, the gases were vented and a sample was taken for analysis by a mass spectrograph. The gas was 67 mole % carbon monoxide, 12 mole % carbon dioxide, 3.9 mole % propylene, 4.3 mole % propane and 1.0 mole % hydrogen. The liquid contents weighed 400 grams. Analysis by gas liquid chromatography (glc.5; indicated the presence of 51 gms. of n-butyric acid, and 25 gms. of isobutyric acid. Further confirmation of the presence and identity of these acid products were obtained through analysis by gc-mass spectrograph combination. Other compounds present in lesser quantities were isopropyl iodide, isopropyl propionates and isopropyl iso- and n-butyrate. EXAMPLES 3-15 In each of the following examples, the solution of cyclooctadiene iridium (I) chloride dimer (0.50 g) , propionic acid (300 g) , 95-97% formic acid and a variable amount of methyl iodide was charged to a one-liter Hastelloy-C, stirred autoclave. The autoclave was flushed with nitrogen, sealed and then charged with butene-l as a liquid from another pressure vessel. Stirring was begun and the vessel and contents were heated to reaction temperature and held at that temperature for four hours. Samples were taken after 1/2, one and two hours at temperature. These were each analyzed by glc with a Poropak-T column programmed from 1700C to 1950C and a thermal conductivity detector. The vessel and contents were cooled to room temperature. Residual gases were vented. The liquid contents were removed and analyzed by glc. The results are given in Table I. 1 Table I 2 Example HCOOH CH3I Olefin Temp. Time Iso-acid n-acid 3 No. g g g C Hr g g 4 3a 144 18.2 64 195 0.5 7.7 18.2 5 1.0 9.7 22.1 6 2.0 16.7 29.5 7 4.0 27.6 34.6 8 4 72 9.1 62 195 0.5 11.1 29.5 9 1.0 16.2 40.9 10 2.0 19.3 50.2 11 4.0 21.3 53.6 12 5 72 4.5 63 195 0.5 16.5 38.1 13 1.0 20.8 52.6 14 2.0 23.2 61.8 15 4.0 24.8 67.0 16 6b 72 18.1 122 195 0.5 22.5 63.7 17 1.0 30.4 83.8 18 2.0 33.0 90.4 19 4.0 31.6 83.4 20 7 72 18.1 124 195 0.5 26.5 47.3 21 1.0 34.9 70.9 22 2.0 38.2 84.4 23 4.0 38.2 85.1 24 8 72 45.4 57 180 0.5 3.7 8.9 25 1.0 4.4 8.6 26 2.0 5.5 12.1 1 Table I (Continued) 2 Example HCOOH CH3I Olefin Temp. Time Iso-acid n-acid 3 No. g g g C Hr g g 4 9 72 4.5 66 180 0.5 4.8 10.7 5 1.0 9.2 21.1 6 2.0 15.8 39.2 7 4.0 22.9 56.3 8 10 72 18.1 53 180 0.5 6.4 13.2 9 1.0 8.0 18.2 10 2.0 10.6 21.7 11 4.0 11.6 25.6 12 11 72 2.3 66 195 0.5 15.7 39.3 13 1.0 20.6 53.4 14 2.0 25.1 66.5 15 4.0 27.0 75.5 16 12 72 1.0 66 195 0.5 10.4 25.1 17 1.0 21.2 52.0 18 2.0 32.7 73.3 19 4.0 34.5 77.5 20 13 72 0.5 66 195 0.5 6.7 26.6 21 1.0 13.6 48.6 22 2.0 21.7 70.3 23 4.0 24.2 82.2 24 14 72 0.4 72 195 0.5 2.7 13.4 25 1.0 7.8 36.7 26 2.0 20.7 73.8 27 4.0 25.7 89.4 28 15c 43 0 43 195 0.5 0 0 Table I (Continued) (a) Solvent: 225 g propionic acid in this example. (b) Propionic anhydride, 25 g, was added to dehydrate the commercial 95-97% formic acid. (c) This reaction was conducted with the use of a glass liner in the autoclave. The catalyst was 0.8 g (Ph3P)2Ir(CO)I used as purchased from Stream Chemical Co. The iodide is equivalent to 0.13 g CH3I or 1 iodide per iridium atom. The solvent was 180 g of propionic acid. Examples 4, 5, 8, 9, 11, 12 and 13 illustrate the effect of varying the amount of methyl iodide. Examples 8 and 10 show that very high concentrations of methyl iodide (100-200 I/Ir) retard both rate and ultimate yield. Examples 4 and 5 show that I/Ir ranges of 20-40 give good initialtrates but not optimal yields. Examples 11, 12, 13 and 14 demonstrate that an I/Ir range of 2-10 gives the best results. Example 15 demonstrates the inferiority of an I/Ir ratio of unity. Examples 8, 9 and 10 show that the reaction operates well at a lower temperature. EXAMPLE 16 The procedure of examples 4-15 was followed, except that the reacting charge consisted of [Ir(COD)Cl]2 0.50 g 95-97% formic acid 72 g butene-2 64 g propionic acid 300 g methyl iodide 4.5 g The reaction was conducted at 1950C for four hours, with sampling and glc analyses after 1/2, one and two hours. The final sample was also analyzed after cooling and removed from the autoclave. The results obtained are given in Table II. A comparison of these results with those of Example 5, Table II Time (hrs) g iso-acid g n-acid 0.5 14.2 32.1 1.0 19.3 55.7 2.0 24.9 58.5 4.0 25.2 68.8 Table I shows that the productivities and isomer distributions are nearly identical. Thus it is proved that internal olefins are operable in the process. EXAMPLE 17 The process of Example 5 was repeated, except that the iridium catalyst utilized was hexachloroiridic acid, H2IrC16, 0.5 g (1.2 mmol), and the solvent was 300 g of acetic acid. The amount of butene-l was 67 g. The product distribution is shown in Table III. These data prove that different complexes of soluble iridium are operable in the process. It is also shown that acetic acid is a satisfactory solvent. Table III Time (hrs) g iso-acid g n-acid 0.5 9.5 25.2 1.0 14.2 40.1 2.0 17.3 47.6 4.0 18.3 50.2 EXAMPLE 18 The process of Example 5 was repeated, except that the solvent was 300 g of valeric acid, CH3CH2CH2CH2COOH, and the olefin was propylene (64 g). After the four-hour reaction period, the final solution contained 40.6 g of isobutyric acid and 84.8 g of butyric acid (94% total yield). This example shows that valeric acid is suitable as a solvent and that propylene is a suitable olefin. EXAMPLE 19 In this example, the catalyst, reactants and solvent charged to the autoclave were 65 g of propylene, 72 g of 95-97% formic acid, 0.50 g of bis(triphenylphosphine)iridium(I)carbonyl chloride and 150 g of propionic acid. A glass liner was; utilized in the autoclave. After only one-half hour at this temperature the pressure had risen to 13.55 MPa. The reaction was stopped by cooling the reactor and contents to room temperature. The product (125 g) consisted of a colorless liquid and black solid. This example proves the necessity of iodide promoter. EXAMPLE 20 A solution of 120 g of methyl formate, 36 g of 95% formic acid, 0.50 g of cyclooctadiene iridium (I) chloride dimer, 4.5 g of methyl iodide, 58 g of propylene in 250 g of propionic acid was charged to the one-liter Hastelloy-C, stirred autoclave. After flushing with nitrogen, stirring was applied and the autoclave and contents were heated to 1950C. Samples were taken after 1/2, one and two hours of reaction time. After four hours the pressure had dropped from 3.7 MPa to 2.2 MPa. The vessel and contents were cooled to ambient temperature and the excess gases were vented. The product solution was removed (wt. 456 g) . The product and the samples were analyzed by glc. The results are summarized in Table IV. Table IV g iso Time g methyl g methyl butyric g butyric g acetic (hrs) isobutyrate butyrate acid acid acid 0.5 0.2 1.5 3.6 7.8 3.4 1.0 0.7 3.2 7.3 16.0 6.1 2.0 1.8 8.3 ' 15.4 34.3 19.2 4.0 3.1 10.5 20.6 47.4 65.5 These results prove that the isomerization of methyl formate to acetic acid and the addition of methyl formate and formic acid to olefins can be effected in a single operation and that methyl formate as well as formic acid can be added to propylene. EXAMPLE 21 The procedure of Example 5 was followed except that the olefin was octene-l (112 g) and the reaction temperature was 2000C. Analysis of the final solution indicated the presence of 70 g of linear nonanoic acid and 47 g of branched-chain nonanoic acids. This experiment demonstrates the applicability of higher carbonchain olefins. EXAMPLE 22 A solution was prepared containing 250 ml. of acetic acid as solvent, 100 ml. of methyl formate, 15 ml. of methyl iodide and 0.30 gms. of bis [cyclooctadiene iridium (I) chloride]. This solution was placed in a one-liter, Hastelloy-C-lined autoclave and the atmosphere flushed with nitrogen. It was heated to 2000C at which temperature the pressure was 2.0' MPa. Ethylene was added to a total pressxure of 5.2 MPa. The heating was continued for eight hours and the pressure was maintained between 4.6-5.2 MPa by periodic addition of ethylene. The vessel and contents were cooled to room temperature and the excess gas vented. The residual amber solution weighed 40.5 g and a gc analysis showed that about 10% of the contents was methyl propionate.

Claims: CLAIMS: 1. A homogeneous process for preparing a carboxylic acid ester which comprises contacting an olefin and a formate ester with a catalytically effective amount of a soluble iridium salt or compound and an iodide promoter in the presence of a carboxylic acid at a 'temperature of from 150 to 3000C. 2. A homogeneous process for preparing a carboxylic acid which comprises contacting an olefin and formic acid with a catalytically effective amount of a soluble iridium salt or compound and an iodide promoter at temperatures of from 150 to 3000C. 3. A process according to claim 1 wherein the formate ester has the formula HCOOR1 where R1 is C1-C20 aliphatic, C3-C12 cycloaliphatic, C7-C16 araliphatic or C6-C12 aryl. 4. A process according to any one of the preceding claims wherein the olefin has the formula n2R3cCR4R5 where R2 R3 R4 and R5 are independently hydrogen, C1-C12 aliphatic, C3-C10 cycloaliphatic, C7-C14 araliphatic or C6-C10 aryl with the proviso that at least two of R2 to R5 are hydrogen and with the further proviso that any two of R2 to R5 may be joined together to form a C3 to C10 ring. 5. A process according to claim 1 wherein the carboxylic acid has the formula RCOOH where R is C1-C20 aliphatic. 6. A process according to any one of the preceding claims wherein the iodide promoter is iodine HI, organic iodide, ammonium iodide or ptosphonium iodide. 7. A process according to any one of the preceding claims wherein the iridium salt or compound is a complex containing halide, phosphine, amine, arsine, cyanide, sulfide, ester, betadiketonate, carboxylate, hydride, sulfite, nitro, carbonyl, alkyl, alkene or alkyne as ligands. 8. A process according to claim 7 wherein the salt or compound is [Ir(cyclooctadiene)Cl]2, IrC13.xH20, Irflr3.xH20 or IrI3.xH20 where x is from 0 to 12.

Inventors: BURK, PATRICK LEE, PRUETT, ROY LAVELLE
Applicants: EXXON RESEARCH AND ENGINEERING COMPANY
Application year: 1983
Main classification: C07C51
IPC codes: C07B61, B01J27, B01J23, C07C51, C07C67, B01J31