CA2024915A1 - Process for the preparation of methyl 2-formylbutyrate - Google Patents
Process for the preparation of methyl 2-formylbutyrateInfo
- Publication number
- CA2024915A1 CA2024915A1 CA002024915A CA2024915A CA2024915A1 CA 2024915 A1 CA2024915 A1 CA 2024915A1 CA 002024915 A CA002024915 A CA 002024915A CA 2024915 A CA2024915 A CA 2024915A CA 2024915 A1 CA2024915 A1 CA 2024915A1
- Authority
- CA
- Canada
- Prior art keywords
- methyl
- reaction
- rhodium
- ppm
- formylbutyrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 238000000034 method Methods 0.000 title claims abstract description 17
- PCMAGGCVCMXDTQ-UHFFFAOYSA-N methyl 2-formylbutanoate Chemical compound CCC(C=O)C(=O)OC PCMAGGCVCMXDTQ-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000010948 rhodium Substances 0.000 claims abstract description 23
- MCVVUJPXSBQTRZ-ONEGZZNKSA-N methyl (e)-but-2-enoate Chemical compound COC(=O)\C=C\C MCVVUJPXSBQTRZ-ONEGZZNKSA-N 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 17
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000007037 hydroformylation reaction Methods 0.000 claims abstract description 9
- 150000003003 phosphines Chemical class 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000011541 reaction mixture Substances 0.000 claims description 9
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 8
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 5
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 4
- 239000012429 reaction media Substances 0.000 claims description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 4
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 description 4
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 4
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- FKJHLNDJJGVDEE-UHFFFAOYSA-N 2-formylbutanoic acid Chemical class CCC(C=O)C(O)=O FKJHLNDJJGVDEE-UHFFFAOYSA-N 0.000 description 2
- NJUSKFMQOHRMIP-UHFFFAOYSA-N 3-methyl-4-oxobutanoic acid Chemical compound O=CC(C)CC(O)=O NJUSKFMQOHRMIP-UHFFFAOYSA-N 0.000 description 2
- VBKPPDYGFUZOAJ-UHFFFAOYSA-N 5-oxopentanoic acid Chemical class OC(=O)CCCC=O VBKPPDYGFUZOAJ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- ZFDIRQKJPRINOQ-HWKANZROSA-N Ethyl crotonate Chemical compound CCOC(=O)\C=C\C ZFDIRQKJPRINOQ-HWKANZROSA-N 0.000 description 2
- 244000309464 bull Species 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical class C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- ZFDIRQKJPRINOQ-UHFFFAOYSA-N transbutenic acid ethyl ester Natural products CCOC(=O)C=CC ZFDIRQKJPRINOQ-UHFFFAOYSA-N 0.000 description 2
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- HBICVCPHTYGKKD-UHFFFAOYSA-N 2-(azaniumylmethyl)butanoate Chemical class CCC(CN)C(O)=O HBICVCPHTYGKKD-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 229910019603 Rh2O3 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001656 butanoic acid esters Chemical class 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- -1 crotonic acid ester Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- CAPGOHOZIOVEOQ-UHFFFAOYSA-N ethyl 2-formylbutanoate Chemical compound CCOC(=O)C(CC)C=O CAPGOHOZIOVEOQ-UHFFFAOYSA-N 0.000 description 1
- PTVUASUIMPCWSD-UHFFFAOYSA-N ethyl 3-methyl-4-oxobutanoate Chemical compound CCOC(=O)CC(C)C=O PTVUASUIMPCWSD-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- ZFAVADMJZHASIM-UHFFFAOYSA-N hydroxymethyl butanoate Chemical compound CCCC(=O)OCO ZFAVADMJZHASIM-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- MPHWBQQPAIUPAC-UHFFFAOYSA-N methyl 3-methyl-4-oxobutanoate Chemical compound COC(=O)CC(C)C=O MPHWBQQPAIUPAC-UHFFFAOYSA-N 0.000 description 1
- YBTZROCKNUIONO-UHFFFAOYSA-N methyl 5-oxopentanoate Chemical group COC(=O)CCCC=O YBTZROCKNUIONO-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- WJIBZZVTNMAURL-UHFFFAOYSA-N phosphane;rhodium Chemical compound P.[Rh] WJIBZZVTNMAURL-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C67/347—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
Abstract of the disclosure The invention relates to a process for the preparation of methyl 2-formylbutyrate by hydroformylation of methyl crotonate in the presence of catalysts containing rhodium and organic phosphines.
Description
Process_for the pre~aration of methyl 2-formylbutyrate The invention relat~s to a process for the preparation of methyl 2-formylbutyrate by reaction of methyl crotonate with hydrogen and carbon monoxide.
2-Formylbutyric acid esters are useful intermediate products in chemical syntheses. They can be converted by reduction into hydroxy compounds, which are used, for example, for the preparation of polyesters. Reaction with ammonia and hydrogen gives esters of aminomethylbutyric acids, and oxidation of the formylbutyric acid esters leads to half-esters of dicarboxylic acids.
The hydroformylation of crotonic acid esters always leads to product mixtures which essentially contain 2-, 3- and 4-formylbutyric acid esters and, by hydrogenation of the crotonic acid ester, also butyric acid esters. The reaction has been investigated repeatedly.
Adkins et al. in J.Am.Chem.Soc. 71 (1949~, page 3051 et seq. thus r~port on the reaction of ethyl cro~onate with watergas (C0 : H2 = 1: 1) at 120 to 125C under a total pressure of 200 to 300 atmospheres in the presence of cobalt as a catalyst and ben2ene as the reaction medi.um.
The reaction gives ethyl 3-formylbutyrate in a yield of 71%.
According to Piacenti et al., Ullmanns Encyklopadie der technischen Chemie (Ullmann's Encyclopedia of Industrial Chemistry) 62, Volume 13, page 65, ethyl 2-, 3- and 4-formylbutyrate are obtained in a ratio of 15 : 15 : 70 in 70% yield from ethyl crotonate, evidently in the presence of a CO catalyst.
Falbe et al. have publ.ished the results of the hydro-formyl~tion of ethyl crotonate in the presence of 1~ by weight of Rh2O3 in a two-stage reacti.on in Brennstoff ~ ~2~
Chemie 48 (1967), page 46 et seq. Thus, a reaction mixture which essentially consists of ~-methyl-~-butyrol-actone, ethyl butyrate, ~ -valerolactone and ethyl c~_ hydroxymethylbutyrate thus results at 135C under a pressure of 200 atmospheres in the first stage and at 200~C under a pressure of 300 atmospheres in the second stage.
Lai and Ucciani (Adv.Chem.Ser. 1974, (132), page 1 et seq.) hydroformylated methyl crotonate under various conditions and ~ound that the ~electivity of the reaction decreases if rhodium is used as the catalyst in compari-son with the cobalt-catalyzed reaction. The selectivity becomes e~en lower if rhodium is used together with triphenylphosphine. The main product of the reaction catalyzed by cobalt is methyl 4-formylbutyrate. Rhodium alone gives the 3-formyl compound as the main product, and rhodium with triphenylphosphine gives predominantly the 2-formyl compound, but the selectivity of the reac-tion is completely unsatisfactory when rhodium cat~lysts are used.
According to Tanaka et al., Bull.Chem.Soc.Jap. 50 ~1977~, 2351 et seq., the product distribution on hydrofonnyla-tion of methyl crotonate in the presence of rhodium depends very greatly on the nature of the ligands used.
If triphenylphosphine is used as the ligand, 3-formyl-butyric acid ester is formed as the main product in a moderate yield, and the 2-formyl compound is formed only in a minor amount. Using (H5C6)2P(CHz),,P(C~H5)z as the ligand, ethyl 2-formylbutyrate is preferably obtained.
Finally, Okano et al., Bull.Chem.Soc.Jap. 54 (1981), 3799 et seq. found that mainly butyric acid and in addition small amounts o methyl 2- and 3-formylbutyrate are formed in the reaction of methyl crotonate with water in the presence of rhodium-phosphine comple~ compaunds as catalysts on the basis of the watergas equilibrium which is established. This reaction route also does not offer the possibility of an economically satisfactory prepara-tion of methyl 2-formylbutyrate on an industrial scale.
There was therefore the object of developing a process which allows hydroformylation of methyl crotonate to give methyl 2-formylbutyrate in a high yield with a high selectivity using readily accessible catalysts.
This objec~ is achi.eved by a process for the preparation of methyl 2-formylbutyrate by hydroformylation of methyl crotonate in the presence of catalysts containing rhodium and organic phosphines. It comprises carrying out the reaction at temperatures of 80 to 120C, under pressures of 20 to 30 MPa, with a rhodium concentration of 10 to S00 ppm, based on the methyl crotonate employed, and in an organic solvent as the reaction medium.
Methyl crotonate is employed as the starting compound for the preparation of methyl 2-formylbutyrate. It can be used in the pure form, i.e. in the distilled form.
However, it has been found that crude products which also contain other constituents in addition to methyl croton-ate can also be employed without a disadvantage to theyield and selectivity. Thus, for ex~nple, mixtures which are obtained on esterification of crotonic acid with methyl alcohol and contain 40 to 60% by weight of methyl crotonate, 30 to 40% by weight of methanol and 5 to 15%
by weight of water are successfully used directly as the starting suhstances.
. .
Carbon monoxide and hydrogen are in general employed in ~ha form of synthesis gas, which is obtained by partial oxidation of carbonaceous material in the presence of water. It contains carbon monoxide and water in a ratio of about 1:1. However, mixtures in which one of the components is present in excess can also successfully be used as reaction partners. In practice, CO/H2 mixtures which contain 0.8 to 1.2 mol of CO per mol of H2 have proved to be suitable. It goes without saying that 2~2~91~
i~purities which may lead to poisoning of the catalyst must b~ removed from the gas. Thus, for e~ample, sulfur can be tolera~ed only up to a maximum concentration of about 2 ppm.
The starting substances are reacted in the presence of a catalyst system comprising rhodium and an organic phos-phine. The concentrati.on of the rhodium, based on the methyl crotonate originally employed, is 10 to 500 ppm, preferably 50 to 200 ppm and in particular 80 to 120 ppm.
The rhodium is employed as the metal, advantageously in finely divided form, or as a compound. In practice, Rh 2-ethylhexanoate has proved to be a particularly suitable starting substance for the catalyst. The second constitu-ent of the catalyst system is an organic phosphine. These are understood as being alkyl- and arylphosphines. Tri-n-butylphosphine and triphenylphosphine have proved to be particularly suitahle. 1 to 50, in particular 2 to 20 mol of phosphine are used per g-atom of rhodium. The catalyst system can be added to the reaction mixture in finished form. In this case it is obtained in its own process step independent of the actual reaction. However, the catalyst can also be prepared in situ, i.e. in the reaction mixture under hydroformylation conditions, with an equally good result.
It is an essential feature of the invention that certain pressure and temperature ranges are observed during the hydroformylation, i.e. 80 to 120C and 20 to 30 MPa. It is advantageous to use temperatures of 90 to 110C, and in particular 90 to 100C, and pressures of 200 to 300 bar. Temperatures higher than those mentioned above lead to increased hydrogenation, and lower temperatures lead to a reduction in the conversion.
Finally, the novel process comprises the use of organic solvents as the reaction medi~m. Aliphati.c hydrocarbons have proved to be particularly suitable, and cyclohexane is preferably employed. The proportion of the reaction medium in the reaction mixture can vary within wide ranges and can be from 20 to 80~ by weight. About 50~ by weight are preferred.
The process according to the invention can be carried out discontinuously or continuously. In the case of a discon-tinuous procedure, the ester, the reaction mediurn and the catalyst, which is formed beforehand or employed in the forJn of its components, are introduced into the reactor and the desired pressure is established by forcin~ in carbon monoxide and hydrogen, while heating at the same time. It is advisable to stir the reaction mixture if adequate mixing is not already achieved by the introduc-tion of carbon monoxide and hydxogen. Synthesis gas is fed to the reactor at the rate at which it is consumed by the reaction. The reaction has ended as soon as no further uptake of gas occurs.
The reaction is preferably carried out continuouslyO In this case, synthesis gas, methyl crotonate and reaction medium are introduced continuously into the reactox containing the catalyst system. The reaction product and some of the reac~ion medium are removed continuously. A
stationary state is maint~ined in the reactor by approp-riate adjustment of the feed rate of the reaction part-ners and the removal rate of the products. Interruption of the reaction only becomes necessary when the catalyst stability has decreased significantly. This point in time can be delayed by replacing some of the spent catalyst by fresh catalyst from time to time.
The methyl 2-formylbutyrate prepared by the process claimed is purified in a kno~l manner by distillation.
The yields are more than 85%. In addition to methyl 2-formylbutyrate, the crude product of the hydroformylation contains about 2 to 5~ of methyl 3-formylbutyrate and 5 to 10% of methylbutyrate.
The novel process is described in more detail in the examples which follow.
~:xamPle 1 500 g of methyl crotonate, 500 g of cyclohexane, 0.6 g of triphenylphosphine and 100 ppm of Rh (as Rh 2-ethyl-hexanoate) are initially introduced into a 2 l autoclavewith a piston stirrer. The mixture is allowed to react at 90C under a CO/H2 pressllre of 27 MPa for about 8 hours, the con~ents of the autoclave are then cooled and the reaction mixture is analyzed by gas chromatography.
It has the following composition (in % by weight, without taking into account cyclohexane):
methyl butyrate 4.23 methyl crotonate 0.59 methyl 2-formylbutyrate91.67 methyl 3-formylbutyrate2.05 other substances 1.46 xample 2 250 g of methyl crotonate, 250 g of cyclohexane, 0.83 g of triphenylphosphine and 100 ppm of Rh (as Rh 2-ethyl-hexanoate) are initially introduced into a 1 l autoclavewith a piston stirrer. The mixture is allowed to react at 909C under a CO/H2 pressure of 27 MPa for about 7 hours, the contents of the autoclave are then cooled and the reaction mixture is analyæed by gas chromatography.
It has the following composition (in ~ by weight, without taking into account the cyclohexane):
methyl butyrate 5.23 methyl crotonate 0.11 methyl 2-formylbutyrate88.82 methyl 3-formylbutyrate4.21 other substances 1.63 2~2~
Example 3 250 g of methyl crotonate, 250 g of cyclohexane, 0.83 g of triphenylphosphine and 100 ppm of ~h (as Rh 2-ethyl-hexanoate) are initially introduced into a 1 1 autoclave with a piston stirrer. The mixture is allowed to react at 100C under a CO/H2 pressure of 28 MPa for about 7 hours, the contents of the autoclave are then cooled and the reaction mixture is analyzed by gas chromatography.
It has the following composition (in % by weight, without taking into account the cyclohexane):
methyl butyrate 7.11 methyl crotonate 0.08 methyl 2-formylbutyrate87.55 methyl 3-formylbutyrate4.01 other substances 1.25
The hydroformylation of crotonic acid esters always leads to product mixtures which essentially contain 2-, 3- and 4-formylbutyric acid esters and, by hydrogenation of the crotonic acid ester, also butyric acid esters. The reaction has been investigated repeatedly.
Adkins et al. in J.Am.Chem.Soc. 71 (1949~, page 3051 et seq. thus r~port on the reaction of ethyl cro~onate with watergas (C0 : H2 = 1: 1) at 120 to 125C under a total pressure of 200 to 300 atmospheres in the presence of cobalt as a catalyst and ben2ene as the reaction medi.um.
The reaction gives ethyl 3-formylbutyrate in a yield of 71%.
According to Piacenti et al., Ullmanns Encyklopadie der technischen Chemie (Ullmann's Encyclopedia of Industrial Chemistry) 62, Volume 13, page 65, ethyl 2-, 3- and 4-formylbutyrate are obtained in a ratio of 15 : 15 : 70 in 70% yield from ethyl crotonate, evidently in the presence of a CO catalyst.
Falbe et al. have publ.ished the results of the hydro-formyl~tion of ethyl crotonate in the presence of 1~ by weight of Rh2O3 in a two-stage reacti.on in Brennstoff ~ ~2~
Chemie 48 (1967), page 46 et seq. Thus, a reaction mixture which essentially consists of ~-methyl-~-butyrol-actone, ethyl butyrate, ~ -valerolactone and ethyl c~_ hydroxymethylbutyrate thus results at 135C under a pressure of 200 atmospheres in the first stage and at 200~C under a pressure of 300 atmospheres in the second stage.
Lai and Ucciani (Adv.Chem.Ser. 1974, (132), page 1 et seq.) hydroformylated methyl crotonate under various conditions and ~ound that the ~electivity of the reaction decreases if rhodium is used as the catalyst in compari-son with the cobalt-catalyzed reaction. The selectivity becomes e~en lower if rhodium is used together with triphenylphosphine. The main product of the reaction catalyzed by cobalt is methyl 4-formylbutyrate. Rhodium alone gives the 3-formyl compound as the main product, and rhodium with triphenylphosphine gives predominantly the 2-formyl compound, but the selectivity of the reac-tion is completely unsatisfactory when rhodium cat~lysts are used.
According to Tanaka et al., Bull.Chem.Soc.Jap. 50 ~1977~, 2351 et seq., the product distribution on hydrofonnyla-tion of methyl crotonate in the presence of rhodium depends very greatly on the nature of the ligands used.
If triphenylphosphine is used as the ligand, 3-formyl-butyric acid ester is formed as the main product in a moderate yield, and the 2-formyl compound is formed only in a minor amount. Using (H5C6)2P(CHz),,P(C~H5)z as the ligand, ethyl 2-formylbutyrate is preferably obtained.
Finally, Okano et al., Bull.Chem.Soc.Jap. 54 (1981), 3799 et seq. found that mainly butyric acid and in addition small amounts o methyl 2- and 3-formylbutyrate are formed in the reaction of methyl crotonate with water in the presence of rhodium-phosphine comple~ compaunds as catalysts on the basis of the watergas equilibrium which is established. This reaction route also does not offer the possibility of an economically satisfactory prepara-tion of methyl 2-formylbutyrate on an industrial scale.
There was therefore the object of developing a process which allows hydroformylation of methyl crotonate to give methyl 2-formylbutyrate in a high yield with a high selectivity using readily accessible catalysts.
This objec~ is achi.eved by a process for the preparation of methyl 2-formylbutyrate by hydroformylation of methyl crotonate in the presence of catalysts containing rhodium and organic phosphines. It comprises carrying out the reaction at temperatures of 80 to 120C, under pressures of 20 to 30 MPa, with a rhodium concentration of 10 to S00 ppm, based on the methyl crotonate employed, and in an organic solvent as the reaction medium.
Methyl crotonate is employed as the starting compound for the preparation of methyl 2-formylbutyrate. It can be used in the pure form, i.e. in the distilled form.
However, it has been found that crude products which also contain other constituents in addition to methyl croton-ate can also be employed without a disadvantage to theyield and selectivity. Thus, for ex~nple, mixtures which are obtained on esterification of crotonic acid with methyl alcohol and contain 40 to 60% by weight of methyl crotonate, 30 to 40% by weight of methanol and 5 to 15%
by weight of water are successfully used directly as the starting suhstances.
. .
Carbon monoxide and hydrogen are in general employed in ~ha form of synthesis gas, which is obtained by partial oxidation of carbonaceous material in the presence of water. It contains carbon monoxide and water in a ratio of about 1:1. However, mixtures in which one of the components is present in excess can also successfully be used as reaction partners. In practice, CO/H2 mixtures which contain 0.8 to 1.2 mol of CO per mol of H2 have proved to be suitable. It goes without saying that 2~2~91~
i~purities which may lead to poisoning of the catalyst must b~ removed from the gas. Thus, for e~ample, sulfur can be tolera~ed only up to a maximum concentration of about 2 ppm.
The starting substances are reacted in the presence of a catalyst system comprising rhodium and an organic phos-phine. The concentrati.on of the rhodium, based on the methyl crotonate originally employed, is 10 to 500 ppm, preferably 50 to 200 ppm and in particular 80 to 120 ppm.
The rhodium is employed as the metal, advantageously in finely divided form, or as a compound. In practice, Rh 2-ethylhexanoate has proved to be a particularly suitable starting substance for the catalyst. The second constitu-ent of the catalyst system is an organic phosphine. These are understood as being alkyl- and arylphosphines. Tri-n-butylphosphine and triphenylphosphine have proved to be particularly suitahle. 1 to 50, in particular 2 to 20 mol of phosphine are used per g-atom of rhodium. The catalyst system can be added to the reaction mixture in finished form. In this case it is obtained in its own process step independent of the actual reaction. However, the catalyst can also be prepared in situ, i.e. in the reaction mixture under hydroformylation conditions, with an equally good result.
It is an essential feature of the invention that certain pressure and temperature ranges are observed during the hydroformylation, i.e. 80 to 120C and 20 to 30 MPa. It is advantageous to use temperatures of 90 to 110C, and in particular 90 to 100C, and pressures of 200 to 300 bar. Temperatures higher than those mentioned above lead to increased hydrogenation, and lower temperatures lead to a reduction in the conversion.
Finally, the novel process comprises the use of organic solvents as the reaction medi~m. Aliphati.c hydrocarbons have proved to be particularly suitable, and cyclohexane is preferably employed. The proportion of the reaction medium in the reaction mixture can vary within wide ranges and can be from 20 to 80~ by weight. About 50~ by weight are preferred.
The process according to the invention can be carried out discontinuously or continuously. In the case of a discon-tinuous procedure, the ester, the reaction mediurn and the catalyst, which is formed beforehand or employed in the forJn of its components, are introduced into the reactor and the desired pressure is established by forcin~ in carbon monoxide and hydrogen, while heating at the same time. It is advisable to stir the reaction mixture if adequate mixing is not already achieved by the introduc-tion of carbon monoxide and hydxogen. Synthesis gas is fed to the reactor at the rate at which it is consumed by the reaction. The reaction has ended as soon as no further uptake of gas occurs.
The reaction is preferably carried out continuouslyO In this case, synthesis gas, methyl crotonate and reaction medium are introduced continuously into the reactox containing the catalyst system. The reaction product and some of the reac~ion medium are removed continuously. A
stationary state is maint~ined in the reactor by approp-riate adjustment of the feed rate of the reaction part-ners and the removal rate of the products. Interruption of the reaction only becomes necessary when the catalyst stability has decreased significantly. This point in time can be delayed by replacing some of the spent catalyst by fresh catalyst from time to time.
The methyl 2-formylbutyrate prepared by the process claimed is purified in a kno~l manner by distillation.
The yields are more than 85%. In addition to methyl 2-formylbutyrate, the crude product of the hydroformylation contains about 2 to 5~ of methyl 3-formylbutyrate and 5 to 10% of methylbutyrate.
The novel process is described in more detail in the examples which follow.
~:xamPle 1 500 g of methyl crotonate, 500 g of cyclohexane, 0.6 g of triphenylphosphine and 100 ppm of Rh (as Rh 2-ethyl-hexanoate) are initially introduced into a 2 l autoclavewith a piston stirrer. The mixture is allowed to react at 90C under a CO/H2 pressllre of 27 MPa for about 8 hours, the con~ents of the autoclave are then cooled and the reaction mixture is analyzed by gas chromatography.
It has the following composition (in % by weight, without taking into account cyclohexane):
methyl butyrate 4.23 methyl crotonate 0.59 methyl 2-formylbutyrate91.67 methyl 3-formylbutyrate2.05 other substances 1.46 xample 2 250 g of methyl crotonate, 250 g of cyclohexane, 0.83 g of triphenylphosphine and 100 ppm of Rh (as Rh 2-ethyl-hexanoate) are initially introduced into a 1 l autoclavewith a piston stirrer. The mixture is allowed to react at 909C under a CO/H2 pressure of 27 MPa for about 7 hours, the contents of the autoclave are then cooled and the reaction mixture is analyæed by gas chromatography.
It has the following composition (in ~ by weight, without taking into account the cyclohexane):
methyl butyrate 5.23 methyl crotonate 0.11 methyl 2-formylbutyrate88.82 methyl 3-formylbutyrate4.21 other substances 1.63 2~2~
Example 3 250 g of methyl crotonate, 250 g of cyclohexane, 0.83 g of triphenylphosphine and 100 ppm of ~h (as Rh 2-ethyl-hexanoate) are initially introduced into a 1 1 autoclave with a piston stirrer. The mixture is allowed to react at 100C under a CO/H2 pressure of 28 MPa for about 7 hours, the contents of the autoclave are then cooled and the reaction mixture is analyzed by gas chromatography.
It has the following composition (in % by weight, without taking into account the cyclohexane):
methyl butyrate 7.11 methyl crotonate 0.08 methyl 2-formylbutyrate87.55 methyl 3-formylbutyrate4.01 other substances 1.25
Claims (6)
1.) A process for the preparation of methyl 2 formyl-butyrate by hydroformylation of methyl crotonate in the presence of catalysts containing rhodium and organic phosphines, which comprises carrying out the reaction at temperatures of 80 to 120°C, under pressures of 20 to 30 MPa, with a rhodium concentration of 10 to 500 ppm, based on the methyl crotonate employed, and in an organic solvent as the reaction medium.
2.) The process as claimed in claim 1, wherein the concentration of the rhodium, based on the methyl crotonate originally employed, is 10 to 500 ppm, preferably 50 to 290 ppm and in particular 80 to 120 ppm.
3.) The process as claimed in claim l or 2, wherein 1 to 50, in particular 2 to 20 mol of phosphine are used per g-atom of rhodium.
4.) The process as claimed in one ore more of claims 1 to 3, wherein the hydroformylation is carried out at temperatures of 90 to 110°C, in particular 90 to 100°C.
5.) The process as claimed in one ore more of claims 1 to 4, wherein the organic solvent is an aliphatic hydro-carbon, in particular cyclohexane.
6.) The process as claimed in one or more of claims 1 to 5, wherein the proportion of organic solvent in the reaction mixture is 20 to 80% by weight.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3930886.3 | 1989-09-15 | ||
| DE3930886A DE3930886A1 (en) | 1989-09-15 | 1989-09-15 | PROCESS FOR PREPARING 2-FORMYBUTTERIC ACID METHYL ETERS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2024915A1 true CA2024915A1 (en) | 1991-03-16 |
Family
ID=6389531
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002024915A Abandoned CA2024915A1 (en) | 1989-09-15 | 1990-09-07 | Process for the preparation of methyl 2-formylbutyrate |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0417597B1 (en) |
| JP (1) | JP2505633B2 (en) |
| KR (1) | KR920009042B1 (en) |
| AT (1) | ATE120727T1 (en) |
| AU (1) | AU629978B2 (en) |
| BR (1) | BR9004552A (en) |
| CA (1) | CA2024915A1 (en) |
| DE (2) | DE3930886A1 (en) |
| ES (1) | ES2072949T3 (en) |
| HU (1) | HU207981B (en) |
| MX (1) | MX174354B (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5273822A (en) * | 1975-12-16 | 1977-06-21 | Agency Of Ind Science & Technol | Production of alpha-formylcarboxylic acid esters |
| DE2643205A1 (en) * | 1976-09-25 | 1978-03-30 | Basf Ag | PROCESS FOR THE PRODUCTION OF ALPHA-FORMYLPROPIONIC ACID ALKYLESTERS |
| GB8720510D0 (en) * | 1987-09-01 | 1987-10-07 | Shell Int Research | Hydroformulation of alkyl acrylates |
-
1989
- 1989-09-15 DE DE3930886A patent/DE3930886A1/en not_active Withdrawn
-
1990
- 1990-08-24 KR KR1019900013150A patent/KR920009042B1/en not_active Expired
- 1990-09-04 DE DE59008835T patent/DE59008835D1/en not_active Expired - Fee Related
- 1990-09-04 EP EP90116918A patent/EP0417597B1/en not_active Expired - Lifetime
- 1990-09-04 ES ES90116918T patent/ES2072949T3/en not_active Expired - Lifetime
- 1990-09-04 AT AT90116918T patent/ATE120727T1/en not_active IP Right Cessation
- 1990-09-05 HU HU905793A patent/HU207981B/en not_active IP Right Cessation
- 1990-09-07 MX MX022265A patent/MX174354B/en unknown
- 1990-09-07 CA CA002024915A patent/CA2024915A1/en not_active Abandoned
- 1990-09-07 JP JP2235947A patent/JP2505633B2/en not_active Expired - Lifetime
- 1990-09-12 BR BR909004552A patent/BR9004552A/en not_active Application Discontinuation
- 1990-09-14 AU AU62526/90A patent/AU629978B2/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| AU629978B2 (en) | 1992-10-15 |
| KR920009042B1 (en) | 1992-10-13 |
| BR9004552A (en) | 1991-09-10 |
| JPH03112942A (en) | 1991-05-14 |
| DE3930886A1 (en) | 1991-03-28 |
| MX174354B (en) | 1994-05-10 |
| DE59008835D1 (en) | 1995-05-11 |
| EP0417597A3 (en) | 1992-03-04 |
| ATE120727T1 (en) | 1995-04-15 |
| HU905793D0 (en) | 1991-03-28 |
| AU6252690A (en) | 1991-03-21 |
| JP2505633B2 (en) | 1996-06-12 |
| ES2072949T3 (en) | 1995-08-01 |
| EP0417597A2 (en) | 1991-03-20 |
| HU207981B (en) | 1993-07-28 |
| KR910006207A (en) | 1991-04-27 |
| EP0417597B1 (en) | 1995-04-05 |
| HUT54968A (en) | 1991-04-29 |
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| EEER | Examination request | ||
| FZDE | Discontinued |