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WO2000037411A1 - Procede de preparation d'esters insatures beta-gamma - Google Patents

Procede de preparation d'esters insatures beta-gamma Download PDF

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Publication number
WO2000037411A1
WO2000037411A1 PCT/US1999/028247 US9928247W WO0037411A1 WO 2000037411 A1 WO2000037411 A1 WO 2000037411A1 US 9928247 W US9928247 W US 9928247W WO 0037411 A1 WO0037411 A1 WO 0037411A1
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WO
WIPO (PCT)
Prior art keywords
rhodium
methyl
beta
butadiene
carbonylation
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.)
Ceased
Application number
PCT/US1999/028247
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English (en)
Inventor
Patrick Michael Burke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Koninklijke DSM NV
EIDP Inc
Original Assignee
DSM NV
EI Du Pont de Nemours and Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by DSM NV, EI Du Pont de Nemours and Co filed Critical DSM NV
Priority to CA002347451A priority Critical patent/CA2347451A1/fr
Priority to EP99962928A priority patent/EP1140770A1/fr
Priority to KR1020017007611A priority patent/KR20010101275A/ko
Priority to JP2000589483A priority patent/JP2002533308A/ja
Publication of WO2000037411A1 publication Critical patent/WO2000037411A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
    • C07C67/37—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by reaction of ethers with carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
    • C07C67/38—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by addition to an unsaturated carbon-to-carbon bond

Definitions

  • the present invention relates to a process for the preparation of beta-gamma unsaturated carboxylic acid esters by catalytic carbonylation starting with either an allylic butentyl ether or mixture of butadiene and an alcohol. More specifically but not by way of limitation, the invention relates to the use of a rhodium-containing catalyst in combination with an iodide promoter for the carbonylation of methyl crotyl ether, 3-methoxybutene-l and mixtures thereof to produce methyl-3-pentenoate.
  • No. 4,603,020 claims a process for the carbonylation of O-acetyl compounds, such as acetic anhydride, at 130 to 250 °C using a rhodium catalyst and an aluminum accelerator.
  • U.S. Pat. No. 4,625,058 teaches a similar process but uses boron, bismuth or tertiary amide compounds as accelerators.
  • 4,563,309 claims a process for the production of carboxylic acid anhydride of the formula RC(0)0(0)CCH 3 by reaction of a methyl carboxylate ester of formula RC(0)OCH 3 with carbon monoxide in the presence of a rhodium catalyst and a phosphorous-containing ligand.
  • European patent application 0 428 979 A2 discloses the carbonylation of allylic butenols and butenol esters using a rhodium catalysts and a hydrogen bromide or hydrogen iodide promoter under anhydrous conditions for the production of 3-pentenoic acid.
  • an allylic butenyl ether such as an alkyl crotyl ether or a corresponding mixture of butadiene and an alkanol will readily undergo carbonylation directly to a beta-gamma unsaturated carboxylic acid ester, such as alkyl-3-pentenoate, at high selectivity and high activity by use of a rhodium-containing catalyst in the presence of an iodide-containing promoter.
  • the present invention provides a process for the carbonylation of allylic butenyl ether or mixture of butadiene and an alcohol and the production of beta-gamma unsaturated carboxylic acid ester comprising the steps of:
  • the allylic butenyl ether is selected from the group consisting of methyl crotyl ether, 3-methoxybutene-l and mixtures thereof and the beta-gamma unsaturated carboxylic acid ester is methyl-3-pentenoate.
  • the carbonylation involves reacting butadiene and methanol and the beta-gamma unsaturated carboxylic acid ester is again methyl-3-pentenoate.
  • the iodide-containing promoter is selected from the group consisting of HI, A1I 3 , Snl 4 , Til 4 , Crl 3 , and CoI 2 and the rhodium-containing catalyst is dicarbonylacetylacetonate rhodium(I).
  • the process of the present invention involves a rhodium catalyzed carbonylation of an allylic butenyl ether to produce a beta-gamma unsaturated carboxylic acid ester wherein the rhodium-contaming catalyst is promoted by the use of HI, HBr or a metal halide salt.
  • the allylic butenyl ether being carbonylated is either an alkyl crotyl ether, a positional isomer thereof such as
  • 3-alkoxybutene-l or mixtures of the same are equivalent staring materials and such butadiene in the presence of an alkanol is to be considered an alternate starting material.
  • the following representative reaction showing a butadiene in the presence of methanol under catalytic reaction conditions producing the 3-methoxybutene-l intermediate (a positional isomer of methyl crotyl ether) which is then combines with carbon monoxide to produce methyl pentenoate is illustrative of the overall carbonylation.
  • Suitable allylic butenyl ethers are of the form
  • R 3 where one of the groups R , R , and R is methyl and the other two groups are H and wherein R 4 is a C ⁇ to Cio alkyl.
  • acceptable allylic compounds includes both cis and trans isomers, other positional isomers such as that illustrated by 3-alkoybutene-l and crotyl ester as well as mixtures of various allylic compounds.
  • butadiene in combination with a to do alkyl alcohol leads to in-situ ether formation and thus total equivalency relative to the use of allylic butenyl ether as starting material for the carbonylation reaction.
  • the reaction can be performed at a temperature in the range of
  • reaction temperature is between 90 °C and 150 °C and most preferably between 90 °C and 150 °C.
  • Suitable total pressures for the reaction are in the range 25 to
  • the pressure is between 100 and 2,000 psig with 200 to
  • the source of the carbon monoxide (CO) reactant for the present invention is not crucial. Commercially available grades of carbon monoxide are acceptable. As such, the carbon monoxide can contain inert impurities such as carbon dioxide, methane, nitrogen, noble gasses, and other hydrocarbon having up to four carbon atoms. Preferably the carbon monoxide also contains hydrogen typically at about a ten mole percent concentration relative to the carbon monoxide. At least 1 molar equivalent of carbon monoxide to allylic butenyl ether or butadiene is needed. Typically, an excess of CO is used.
  • inert impurities such as carbon dioxide, methane, nitrogen, noble gasses, and other hydrocarbon having up to four carbon atoms.
  • the carbon monoxide also contains hydrogen typically at about a ten mole percent concentration relative to the carbon monoxide. At least 1 molar equivalent of carbon monoxide to allylic butenyl ether or butadiene is needed. Typically, an excess of CO is used.
  • Suitable solvents for this process are those which are compatible with the reactants and the catalyst system under the reaction conditions.
  • Such solvents include aromatic hydrocarbon solvents, saturated halocarbon solvents, and mixtures thereof.
  • Carboxylic acid esters and lactones, such as methyl-3- pentenoate, valerolactone and the like, are also acceptable solvents.
  • Suitable aromatic hydrocarbon solvents include benzene, toluene, 1,2,4-trichlorobenzene and other C 2 to C alkyl substituted benzenes.
  • Suitable saturated halocarbon solvents include chlorinated and fluormated hydrocarbons such as methylene chloride, dichloroethane and chloroform as well as the so-called HCFC's including in particular HCFC-113 (FCC1 2 CF 2 C1) and HCFC-123 (CHC1 2 CF 3 ) or the like.
  • the most preferred solvents are toluene, HCFC-113 and HCFC- 123.
  • the process of this invention where the starting material is a methoxybutene may be run in the absence of solvent.
  • the rhodium catalyst can be provided from any source or by any material which will produce rhodium ions under the carbonylation reaction conditions.
  • rhodium metal rhodium salts
  • rhodium oxides rhodium carbonyl compounds
  • organorhodium compounds coordination compounds of rhodium, and mixtures thereof.
  • specific examples of such compounds include, but are not limited to, RhCl 3 , RI 3 , Rh(CO) 2 I 3 , Rh(CO)I 3 , Rh 4 (CO) 12 , Rh 6 (CO) 16 ,
  • Rh(acac) 3 Rh(CO) 2 (acac), Rh(C 2 H 4 ) 2 (acac), [Rh(C 2 H 4 ) Cl] 2 , [Rh(CO) 2 Cl] 2 ,
  • rhodium catalyst examples include rhodium(I) compounds such as Rh(CO) 2 (acac), [Rh(CO) 2 Cl] 2 , [Rh(COD)Cl] 2 , Rh(COD)(acac), and rhodium iodide compounds such as Rhl 3 and Rh(CO) 2 I 3 .
  • rhodium- containing compound is Rh(CO) 2 (acac).
  • Suitable concentrations of rhodium in the reaction are in the range of 0.005 to 0.50 % by weight of rhodium metal based on the reaction medium.
  • concentration of rhodium is in the range of 0.02 to 0.20 wt%.
  • the rhodium which may be pre-formed or generated in situ, must be promoted by HI, HBr or a metal halide, preferably by HI or a metal iodide, to achieve a satisfactory rate and selectivity to pentenoate ester.
  • suitable promoters are the acid halides as well as halides of Groups IIB, III A, IIIB, IVA, IVB, VIB, VII, VIII of the periodic table.
  • Preferred promoters are those where the halide is iodide, such as but not limited to HI, A1I 3 , Snl , Til 4 ,
  • the molar ratio of promoter to rhodium can be in the range of about 1:1 to about 50:1. Although high selectivities to the desired methyl-3- penetoate can be obtained even at low promoter to rhodium ratios, the rate of formation of methyl-3-pentenoate on a per Rh basis decreases significantly when the molar ratio of promoter to rhodium is less than 1. This decrease in reaction rates, coupled with the high cost of rhodium makes it more economical to use promoter to rhodium ratios greater than 1 : 1. Similarly, the molar ratio of promoter to rhodium must be less than about 50 to obtain reasonable yields of the unsaturated ester. Preferably, the molar ratio of promoter to rhodium is between about 10 and about 30.
  • Reaction times can be varied and depend on choice of reactants, solvent, catalyst and promoter as well as their respective concentration and reaction conditions such as temperature and pressure. Residence times of the order of about 1 minute to about 20 hours are acceptable.
  • the reaction of the present invention may be carried out in a batch or continuous mode.
  • the products can be isolated and recovered by any of the techniques generally known in the art including by example but not limited thereto, extraction, distillation or the like.
  • the conversion data reported is based on quantitative measurement of the relative amount of the primary or limiting reactant (e.g., 3-methoxybutene-l or alternatively butadiene) that is not consumed by chemical reaction.
  • the selectivity to the desired methyl- 3-pentenoate (M3P) is based on and reported as the amount of methyl ester produced relative to the amount of the primary reactant consumed by the reaction.
  • M3P methyl- 3-pentenoate
  • Hastelloy-C autoclave A 120 mL mechanically stirred Hastelloy-C autoclave was charged with 0.258 grams (0.1 mmole) of dicarbonylacetylacetonate rhodium(I), 1.63 grams (4.0 mmole) of anhydrous aluminum iodide and 72.1 grams (83.4 mL) toluene.
  • the reaction vessel was pressurized to 400 psig with a 90/10 mixture of CO and hydrogen.
  • the solution was heated to a temperature of 120 °C and the carbonylation reaction was initiated by injecting a solution of 8.6 grams (100 mmole) of 3-methoxybutene-l and 1.0 grams of ortho- dichlorobenzene (ODCB, internal GC standard) in 5 grams of toluene.
  • ODCB ortho- dichlorobenzene
  • the total pressure was then adjusted to 700 psig with the 90/10 CO/H 2 .
  • Carbon monoxide and H (90/10 ratio) were continuously fed to the autoclave from a reservoir so as to maintain the total pressure constant at 700 psig.
  • Samples were removed at intervals for GC analysis on a DBFFAP 30 M J&W Scientific capillary GC column. The analysis showed that 62.5% of the methoxybutene charged was converted in the first hour and the selectivity to methyl-3- pentenoate (M3P; cis and trans isomers) was 93.9%. After 4 hours the conversion was 98% and the selectivity to M3P was 93%.
  • M3P methyl-3- pentenoate
  • the first order rate constant for the formation of M3P was 1.02 hr 1 , corresponding to a space-time yield (STY) of 734 mmole M3P per liter per hour.
  • Example 1 The experiment in Example 1 was repeated except that the 3-methoxybutene-l was replaced with a 70/30 mixture of l-methoxybutene-2 (methyl crotyl ether) and 3-methoxybutene-l, the iodide to rhodium ratio was increased from 12/1 to 18/1 and the temperature was increased to 130°C.
  • the GC analysis showed a methoxybutene conversion of 85.8% after 30 minutes and a selectivity to M3P of 82%. After 60 minutes the conversion was 97% and the selectivity to M3P was 84.6%.
  • the first order rate constant for the formation of M3P was 2.96 hr "1 , corresponding to a space-time yield (STY) of 2,135 mmole M3P per liter per hour.
  • Example 3 Carbonylation of 3 -Methoxybutene- 1 using a Rhodium Catalyst and aqueous HI Promoter: A 25 mL glass lined pressure vessel was charges with 5 mL of a solution containing 5.9 grams (69 mmol) of 3-methoxybutene-l (3MB1), 0.258 grams (1.0 mmol) of dicarbonylacetylacetonate rhodium(I), 1.34 grams (6.0 mmol) of 57% aqueous HI solution, and 1.00 grams of o-dichlorobenzene (internal gas chromatograph standard) in 100 mL of toluene.
  • 3-methoxybutene-l 3-methoxybutene-l
  • the pressure vessel was freed from air by purging first with nitrogen (twice) and then with carbon monoxide containing 10 mol% hydrogen (twice). The vessel was then pressurized to 500 psig of 90/10 CO/H 2 and heated to 120 °C with agitation for 3 hours. The heat was shut off, the pressure vessel was allowed to cool to room temperature and the excess gases were vented. The product was analyzed by gas chromatography on a DBFFAP 30 M J&W Scientific capillary GC column. The results of the analysis are summarized below: Before esterification mmol/100 mL
  • Methoxybutene conversion was 94.0%, selectivity to methyl-3-pentonate (M3P) was 84.8% and selectivity to 3-pentenoic acid was 13.9%. Product accounting was 99%.
  • M3P methyl-3-pentonate
  • Example 3 In a manner analogous to the procedure employed in Example 3, an additional run was performed except that 0.064 grams of methanol (MeOH) per 100 grams of methoxybutene (2 equivalents per 100 equivalents) was added.
  • MeOH methanol
  • Table 1 The resulting data for this example as well as the corresponding data from Example 1 are presented in Table 1.
  • Example 5 The procedure employed in Example 4 was repeated except that 0.19 grams of methanol per 100 grams of methoxybutene (6 equivalents per 100 equivalents) was added. The resulting data are presented in Table 1.
  • Example 4 The procedure employed in Example 1 was repeated except that the toluene solvent was replaced with the halocarbon HCFC-123 (CHC1 2 CF 3 ). The resulting data are presented in Table 1.
  • Example 7 The procedure employed in Example 1 was repeated except that the toluene solvent was replaced with the halocarbon HCFC-123 (CHC1 2 CF 3 ). The resulting data are presented in Table 1.
  • Example 8 The procedure employed in Example 5 was repeated except that the aqueous HI promoter was replaced with an equivalent amount of A1I 3 (2 equivalents of A1I 3 per g-atom of Rh). The resulting data are presented in Table 1.
  • Example 8 The procedure employed in Example 5 was repeated except that the aqueous HI promoter was replaced with an equivalent amount of A1I 3 (2 equivalents of A1I 3 per g-atom of Rh). The resulting data are presented in Table 1.
  • Example 8 The procedure employed in Example 5 was repeated except that the aqueous HI promoter was replaced with an equivalent amount of A1I 3 (2 equivalents of A1I 3 per g-atom of Rh). The resulting data are presented in Table 1.
  • Example 8 The procedure employed in Example 5 was repeated except that the aqueous HI promoter was replaced with an equivalent amount of A1I 3 (2 equivalents of A1I 3 per g-atom of Rh). The resulting data are presented in Table 1.
  • Example 8 The procedure employed in Example 5 was repeated except that the aqueous
  • Example 3 The procedure employed in Example 3 was repeated except that the toluene solvent was replaced with the halocarbon HCFC-113 (FCC1 2 CF 2 C1). The resulting data are presented in Table 1.
  • Example 9 The procedure employed in Example 3 was repeated except that the toluene solvent was replaced with the halocarbon HCFC-113 (FCC1 2 CF 2 C1) and the aqueous HI promoter was replaced with an equivalent amount of Til 4 (2 equivalents of Til 4 per g-atom of Rh).
  • the resulting data are presented in Table 1. Table 1
  • Example 10 The procedure employed in Example 3 was repeated for a series of six additional runs except that the iodide promoter was varied and the resulting product was esterified with methanol to determine total carbonylation selectivity including dibasic esters (DBE's; esters of adipic acid, 2- methylglutaric and ethylsuccinic acids). The results are summarized in Table 2.
  • DBE's dibasic esters
  • a 25 mL glass lined pressure vessel was charges with 5 mL of a solution containing 5.4 grams (100 mmol) of butadiene, 1.34 grams (6.0 mmol) of 57% aqueous HI, 3.2 grams methanol (100 mmole), 0.258 grams (1.0 mmol) of dicarbonylacetylacetonate rhodium(I), and 1.00 grams of o-dichlorobenzene
  • Example 17-27 The procedure employed in Example 16 was repeated for a series of eleven additional runs except that the iodide promoter, the temperature, and the solvent were varied. The results are summarized in Table 3.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé de carbonylation de butényl éther allylique (notamment le méthyl crotyl éther, 3-méthoxybutène-1 et leurs mélanges) ou de mélange de butadiène et d'alcool (p. ex, le méthanol) et de production de esters d'acide carboxylique béta-gamma insaturés (p. ex., le méthyl-3-penténoate) au moyen d'un catalyseur contenant du rhodium (p. ex., le dicarbonylacetylacétonate rhodium(I) ou analogue) activé par un composé contenant du iodure (p.ex., HI, AlI3, SnI4, TiI4, CrI3, et CoI2 ou analogue). Un tel procédé est particulièrement utile dans la production de monomères difonctionnels et d'intermédiaires dans la synthèse de l'acide adipique. La réaction représentative (a), dans laquelle un butadiène est en présence du méthanol dans des conditions de réaction catalytique permettant de produire l'intermédiaire 3-méthoxybutène-1 (un isomère positionnel de méthyl crotyl éther) qui est ensuite combiné avec un monoxyde de carbone afin d'obtenir un méthyl penténoate, illustre bien la carbonylation dans sa globalité.
PCT/US1999/028247 1998-12-18 1999-11-30 Procede de preparation d'esters insatures beta-gamma Ceased WO2000037411A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CA002347451A CA2347451A1 (fr) 1998-12-18 1999-11-30 Procede de preparation d'esters insatures beta-gamma
EP99962928A EP1140770A1 (fr) 1998-12-18 1999-11-30 Procede de preparation d'esters insatures beta-gamma
KR1020017007611A KR20010101275A (ko) 1998-12-18 1999-11-30 베타-감마 불포화 에스테르의 제조 방법
JP2000589483A JP2002533308A (ja) 1998-12-18 1999-11-30 β−γ不飽和エステルの調製方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US21540998A 1998-12-18 1998-12-18
US09/215,409 1998-12-18

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WO2000037411A1 true WO2000037411A1 (fr) 2000-06-29

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EP (1) EP1140770A1 (fr)
JP (1) JP2002533308A (fr)
KR (1) KR20010101275A (fr)
CN (1) CN1331668A (fr)
CA (1) CA2347451A1 (fr)
ID (1) ID28976A (fr)
WO (1) WO2000037411A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101318898B (zh) * 2008-07-03 2011-08-31 浙江大学 合成反式α-酰基-β,γ-不饱和羧酸酯的方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0217407A2 (fr) * 1985-10-03 1987-04-08 QUANTUM CHEMICAL CORPORATION (a Virginia corp.) Carbonylation d'éthers alkyliques en esters
EP0428979A2 (fr) * 1989-11-13 1991-05-29 E.I. Du Pont De Nemours And Company Procédé de carbonylation des butènols allyliques et des esters butènoliques
DE19510324A1 (de) * 1995-03-22 1996-09-26 Basf Ag Verfahren zur Herstellung von 3-Pentensäureestern durch Carbonylierung von Alkoxybutenen

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0217407A2 (fr) * 1985-10-03 1987-04-08 QUANTUM CHEMICAL CORPORATION (a Virginia corp.) Carbonylation d'éthers alkyliques en esters
EP0428979A2 (fr) * 1989-11-13 1991-05-29 E.I. Du Pont De Nemours And Company Procédé de carbonylation des butènols allyliques et des esters butènoliques
DE19510324A1 (de) * 1995-03-22 1996-09-26 Basf Ag Verfahren zur Herstellung von 3-Pentensäureestern durch Carbonylierung von Alkoxybutenen

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CA2347451A1 (fr) 2000-06-29
KR20010101275A (ko) 2001-11-14
JP2002533308A (ja) 2002-10-08
EP1140770A1 (fr) 2001-10-10
CN1331668A (zh) 2002-01-16
ID28976A (id) 2001-07-19

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