WO2000046176A1 - Procede de preparation d'esters d'acide 3-alcenique et catalyseur permettant de mettre en oeuvre ledit procede - Google Patents

Procede de preparation d'esters d'acide 3-alcenique et catalyseur permettant de mettre en oeuvre ledit procede Download PDF

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Publication number
WO2000046176A1
WO2000046176A1 PCT/EP2000/000670 EP0000670W WO0046176A1 WO 2000046176 A1 WO2000046176 A1 WO 2000046176A1 EP 0000670 W EP0000670 W EP 0000670W WO 0046176 A1 WO0046176 A1 WO 0046176A1
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WO
WIPO (PCT)
Prior art keywords
catalyst
alkyl
group
acid esters
reaction
Prior art date
Application number
PCT/EP2000/000670
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German (de)
English (en)
Inventor
Dietmar Barth
Justin Wolf
Helmut Werner
Martin Schäfer
Michael Schulz
Original Assignee
Basf Aktiengesellschaft
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 Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to EP00904974A priority Critical patent/EP1149064A1/fr
Priority to JP2000597249A priority patent/JP2002536351A/ja
Publication of WO2000046176A1 publication Critical patent/WO2000046176A1/fr

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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
    • C07C67/38—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by addition to an unsaturated carbon-to-carbon bond

Definitions

  • the invention relates to a process for the preparation of 3-alkenoic acid esters by catalytic reaction of dienes with alkyl formates.
  • the invention further relates to a catalyst which is particularly suitable for the process.
  • 3 -alkenic acid esters are versatile intermediates. From 3-pentenoic acid ester e.g. Adipic acid ester or 6-oxohexanoic acid ester produced. These substances in turn serve as intermediates in the production of nylon 6 or nylon 6,6.
  • DE-B 30 40 432 discloses a process for the preparation of 3-alkenoic acid esters by catalytic carbonylation of a diene with carbon monoxide (CO) and an alcohol, which is based on a cobalt carbonyl catalyst which is in a solvent, consisting of at least two N-heterocycles.
  • the use of solvents requires a complex separation step.
  • work is carried out at comparatively high pressures (300 bar).
  • US-A 5 495 041 relates to a similar process for the preparation of pentenoic acid esters, in which a catalyst consisting of palladium, a pentenoic acid and a phosphine derivative is used.
  • a disadvantage of this process is the low selectivity and the relatively large amount of catalyst used.
  • WO 97/29069 discloses a process based on the following reaction sequence: Chlorobutene + CO ⁇ S »pentenoic acid chloride (I),
  • Ratio can only be achieved in practice by complex multi-stage reaction.
  • a one-stage reaction procedure on the other hand, it is very difficult to maintain the ratio, since the acid chloride is formed only as an intermediate. If the alcohol is added in a deficit, reactive acid chloride accumulates in the reaction mixture, the separation of which, as in
  • Keim and Becker The addition of methyl formate to butadiene in the presence of PdCl 2 and HC1 is described in Keim and Becker (Journal of Molecular Catalysis 54, 1989, pages 95-101). Keim and Becker only achieved an unsatisfactory yield on pentenoic acid ester of 10-15% at a CO pressure of 80 bar. Only moderate selectivities can be achieved with this catalyst system. In addition, the handling and recycling of HC1 is also very problematic. It is therefore an object of the invention to provide a process for the preparation of 3-alkenyl acid esters which can be carried out without solvent or in which only the starting materials act as solvents, which makes the addition of HC1 unnecessary and which has a higher selectivity than the known processes . Furthermore, the process should also be able to be carried out at lower pressures than previously known processes.
  • the object is achieved by a process for the selective production of 3-alkenoic acid esters by adding alkyl formates to dienes in accordance with the general reaction equation I.
  • W ⁇ to R independently of one another either hydrogen or -CC 3 o-alkyl, C 6 -C 30 aryl, C 7 -C 30 alkylaryl, C 5 -C 12 cycloalkyl or C r C 21 alkyl-C 6 -C 9 mean cycloalkyl and R 7 is a d-Cso-alkyl radical in the presence of CO with a partial pressure of at least 10 bar (1 MPa).
  • a catalyst is provided according to the invention for carrying out the method according to the invention.
  • This catalyst contains a) a Pd compound and b) one or more compounds of the type MCl n , where M has one of the following meanings:
  • R ⁇ to Rs are preferably hydrogen or methyl.
  • R 7 preferably represents an unbranched d-C ⁇ -alkyl group, especially an unbranched Cj-C o -alkyl group such as methyl, ethyl, n-propyl, n-butyl.
  • the CO required to build up the CO support pressure can be obtained by decomposing an alkyl formate how methyl formate is provided, especially since the required minimum CO partial pressure of 10 bar (IMPa) is very low. CO partial pressures from 10 to 150 bar, preferably from 15 to 100 bar, are preferred.
  • the alkyl formates which can be used according to the invention are obtained on a large scale by carbonylation of alcohols and can be transported to the place of use more cheaply than CO.
  • Methyl formate can also be obtained directly from methanol in high yields (see Applied Catalysis 57, 1990, pages 1-30).
  • the process according to the invention does not require any additional inert solvents, ie the educts listed in I function at most as solvents. Due to the comparatively high volatility of the alkyl formates, there are cost advantages in working up compared to processes in which the corresponding alcohol or other solvent is used.
  • the catalyst according to the invention contains a palladium compound, in particular a Pd salt.
  • Pd salts are preferably used, in particular Pd ⁇ halides, especially Pd" chlorides such as PdCl 2 or PdCl 2 (PhCN) 2 or Na 2 [PdCl 4 ].
  • the catalyst according to the invention also contains a compound of the type MCl n or a mixture of various compounds of this type.
  • M can be an alkaline earth metal ion such as Mg 2+ , Ca 2+ , Sr 2+ and Ba 2+ , with Mg 2+ and Ca 2+ being preferred.
  • M can also be a metal ion of the 4th group (also called IV. Subgroup, according to: Nomenclature of Inorganic Chemistry, VCH Weinheim, ISBN 3-527-29340).
  • the 4th group includes Ti 4+ , Zr 4+ and Hf 4 "1" , with Ti 4+ being preferred.
  • M can be an ion of a metal of the 6th group (formerly: subgroup VI). These metals include Cr, Mo and W. Within the scope of the invention, the metals can assume oxidation states III, V or VI. Mo v is preferred.
  • the ratio of palladium to MCl n preferably corresponds to 1/1 to 1/100, especially 1/3 to 1/30.
  • the ratio of diene to palladium is preferably 1/1 to 1/10000, especially 1/20 to 1/1000.
  • the ratio of palladium to alkyl formate is preferably between 1/100 and 1/10000, especially between 1/1000 and 1/5000. If the reaction is carried out batchwise, these ratios are set before the start of the reaction. If the reaction is carried out continuously, these molar ratios should remain steady to adjust.
  • the reaction temperature is usually in the range from 60 to 120 ° C.
  • the method according to the invention has a better selectivity than the known methods. It also makes it possible to dispense with HC1 as a cocatalyst. In this way, the handling problems associated with the use of HC1 are eliminated. However, in contrast to the aforementioned organic bases containing nitrogen or phosphorus, HC1 does not interfere with the process according to the invention.
  • the catalyst additionally contains CuCl 2 or FeCl 3 .
  • the molar ratio of palladium to CuCl 2 or FeCl 3 is preferably 1/1 to 1/200, especially 1/5 to 1/50.
  • the method according to the invention is carried out without supplying HC1.
  • Ri to R ⁇ is hydrogen. So butadiene is used as a starting material.
  • R 1 is methyl and R to R $ are hydrogen. So isoprene is used as a starting material.
  • R has the meaning methyl, ethyl, propyl or butyl. These alkyl radicals are preferably unbranched. The use of methyl formate as starting material is particularly preferred.
  • the catalyst has no basic organic compounds containing nitrogen or phosphorus, such as triphenylphosphine. This would usually affect his activity.
  • the catalyst according to the invention can have different compounds of the MCl n type, preferably not more than three, especially not more than two.
  • the total number of different chloride salts which the catalyst contains is preferably not more than five, especially not more than four.
  • the compounds of the MCl ⁇ type can also be used in the form of easy-to-handle adducts such as TiCl 4 (HCO 2 CH 3 ) 2 , ZrC ⁇ 4 (HCO 2 CH 3 ) 2 or HfCl 4 (HCO 2 CH 3 ) 2 .
  • the metal ion is Hf * + or Mo 5+ .
  • Another embodiment of the catalyst according to the invention contains MgCl and another compound of the type MCl n , where M is Ti 4+ , Zr 4+ or Hf 4 *.
  • the resulting catalyst thus contains, for example, PdCl 2 , MgCl 2 , and one of the salts TiCL, ZrCl 4 or HfCl 4 .
  • Another embodiment of the catalyst according to the invention additionally contains CuCl 2 .
  • M has the meaning of Mg 2+ , Ti 4+ , Zr 4+ or Hf + . So it is for example PdCl 2 / CuC MgCl 2 ; PdCl 2 / CuCl 2 / TiCl 4 ; PdCl 2 / CuCl 2 / ZrCl 4 or PdCl 2 / CuCV HfC-.
  • Another embodiment of the catalyst according to the invention additionally contains FeCl 3 .
  • the invention is described in more detail below by the example.
  • Tests up to 15 bar were carried out in 25 ml glass autoclaves, tests at higher pressures in a 250 ml stainless steel autoclave with a glass insert.
  • the reaction pressure remained constant after the reaction temperature was reached.
  • the composition of the reaction gas was checked by GC analysis in the experiments for the addition of MeFo to butadiene.
  • the gas analysis was taken after the reaction mixture had cooled. The gas was released to normal pressure. Percentages relate to the amount of substance (mol%).
  • Comparative Examples 1 and 2 show that with PdCl 2 alone as a catalyst, significant amounts of product of value can only be obtained in the presence of large amounts of alcohol. Yield and selectivity are, however, significantly lower than in the examples according to the invention.
  • a comparison of comparative examples 7 and 9 with example 8 according to the invention shows that the catalyst according to the invention enables higher yields and selectivities than the known combination of HC1 with PdCl 2 .
  • Examples 13 and 14 show the influence of the alcohol corresponding to the formate (here methanol, MeOH) on the activity of the catalysts according to the invention: small amounts, as are present in commercially available alkyl formates, do not interfere, larger amounts of the alcohol have an inhibiting effect.
  • Comparative example 15 shows that the catalysts according to the invention have no activity in the carbonylation of dienes, as would have been expected if MeFo were cleaved back into MeOH and CO.
  • Comparative Example 16 illustrates the inhibitory effect of basic organic compounds containing nitrogen or phosphorus. Table:

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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

Procédé de préparation sélective d'esters d'acide 3-alcénique par ajout de formiates d'alkyle à des diènes selon l'équation de réaction générale (I), selon laquelle R1 à R6 signifient indépendamment les uns des autres hydrogène ou alkyle C1-C30, aryle C6-C30, alkylaryle C7-C30, cycloalkyle C5-C12 ou alkyle-C1-C21-cycloalkyle-C6-C9 et R7 est un reste alkyle C1-C30, en présence de CO à une pression partielle d'au moins 10 bar (1 MPa), à l'aide d'un catalyseur. Ledit catalyseur contient (e) un composé Pd et (f) un ou plusieurs composés du type MCln, M ayant l'une des significations suivantes: un ion de métal alcalino-terreux avec n=2, un ion métallique du groupe 4 (sous-groupe IV) avec n=4, un ion du groupe 6 (sous-groupe VI) avec n=3, 5 ou 6 en présence d'une base contenant du phosphore ou de l'azote.
PCT/EP2000/000670 1999-02-03 2000-01-28 Procede de preparation d'esters d'acide 3-alcenique et catalyseur permettant de mettre en oeuvre ledit procede WO2000046176A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP00904974A EP1149064A1 (fr) 1999-02-03 2000-01-28 Procede de preparation d'esters d'acide 3-alcenique et catalyseur permettant de mettre en oeuvre ledit procede
JP2000597249A JP2002536351A (ja) 1999-02-03 2000-01-28 ３−アルケン酸エステルの製法および該方法を行うための触媒

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19904200.4 1999-02-03
DE1999104200 DE19904200A1 (de) 1999-02-03 1999-02-03 Verfahren zur Herstellung von 3-Alkensäureestern und ein Katalysator zur Durchführung des Verfahrens

Publications (1)

Publication Number Publication Date
WO2000046176A1 true WO2000046176A1 (fr) 2000-08-10

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Country Status (4)

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EP (1) EP1149064A1 (fr)
JP (1) JP2002536351A (fr)
DE (1) DE19904200A1 (fr)
WO (1) WO2000046176A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1106590B2 (fr) † 1999-12-09 2018-01-10 Safeguard Chemicals Ltd. Méthode pour le traitement de béton et de maçonnerie

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011089008B4 (de) * 2011-12-19 2017-08-24 Evonik Degussa Gmbh Verfahren zur Herstellung von Estern aus Formiaten und olefinisch ungesättigten Verbindungen

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0092350A1 (fr) * 1982-04-12 1983-10-26 Exxon Research And Engineering Company Procédé pour la conversion des oléfines en acides ou esters carboxyliques en employant des composés solubles d'iridium
EP0140673A2 (fr) * 1983-10-28 1985-05-08 BP Chemicals Limited Préparation d'acides carboxyliques et d'esters
EP0219948A1 (fr) * 1985-08-29 1987-04-29 The British Petroleum Company p.l.c. Procédé pour la préparation d'esters

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0092350A1 (fr) * 1982-04-12 1983-10-26 Exxon Research And Engineering Company Procédé pour la conversion des oléfines en acides ou esters carboxyliques en employant des composés solubles d'iridium
EP0140673A2 (fr) * 1983-10-28 1985-05-08 BP Chemicals Limited Préparation d'acides carboxyliques et d'esters
EP0219948A1 (fr) * 1985-08-29 1987-04-29 The British Petroleum Company p.l.c. Procédé pour la préparation d'esters

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1106590B2 (fr) † 1999-12-09 2018-01-10 Safeguard Chemicals Ltd. Méthode pour le traitement de béton et de maçonnerie

Also Published As

Publication number Publication date
DE19904200A1 (de) 2000-08-10
EP1149064A1 (fr) 2001-10-31
JP2002536351A (ja) 2002-10-29

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