WO2012098067A1 - Preparation of 4-acetoxy-2-methylbutanal by catalytic carbon carbon double bond hydrogenation - Google Patents

Preparation of 4-acetoxy-2-methylbutanal by catalytic carbon carbon double bond hydrogenation Download PDF

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WO2012098067A1
WO2012098067A1 PCT/EP2012/050544 EP2012050544W WO2012098067A1 WO 2012098067 A1 WO2012098067 A1 WO 2012098067A1 EP 2012050544 W EP2012050544 W EP 2012050544W WO 2012098067 A1 WO2012098067 A1 WO 2012098067A1
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process according
acetoxy
methyl
catalytic system
hydrogenation
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French (fr)
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Werner Bonrath
Jan SCHÜTZ
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DSM IP Assets BV
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Priority to KR1020137021444A priority Critical patent/KR101914806B1/en
Priority to JP2013549781A priority patent/JP6005064B2/en
Priority to CN201280005984.1A priority patent/CN103328431B/en
Priority to EP12700397.8A priority patent/EP2665698B1/en
Priority to ES12700397.8T priority patent/ES2616758T3/en
Priority to US13/980,118 priority patent/US8829231B2/en
Priority to BR112013018345-4A priority patent/BR112013018345B1/en
Publication of WO2012098067A1 publication Critical patent/WO2012098067A1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
    • C07C69/12—Acetic acid esters
    • C07C69/14—Acetic acid esters of monohydroxylic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/283—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds

Definitions

  • the present invention relates to a new way for the production of 4-acetoxy-2-m butanal.
  • 4-acetoxy-2-methyl-butanal which is the following compound of formula (I) is an important building block compound for the synthesis of organic compounds such as vitamin A, vitamin E, carotenoids and terpenoids.
  • the present invention relates to a process for the production of 4-acetoxy-2-methyl- butanal, which results in very good yields and selectivity. This process can also be carried at low temperature (room temperature).
  • the starting material for this process is 4-acetoxy-2-methyl-2-butenal, which resented by the following formula (II) which is hydrogenated selectively. This means that the carbon-carbon double bond is hydrogenated.
  • the present invention relates to a process for the production of 4-acetoxy- 2-methyl-butanal which comprises the hydrogenation of 4-acetoxy-2-methyl-2- butenal,
  • non-acid catalytic system is defined as follows:
  • An aqueous extract of the catalyst systems used in the process according to the present invention has a pH > 7.
  • the catalytic system can be a single compound or a mixture of compounds. When a mixture is used, then not all compounds have to have a pH (as an aqueous extract) of > 7, but the mixture has to fulfill this requirement.
  • the non-acid catalytic system comprises a heterogeneous Pd based catalyst.
  • the catalyst comprises a carrier material on which the Pd is brought on.
  • carrier materials are i.e. carbon (preferably in basic form), CaC0 3 and AI2O3 (preferably in basic form). Preferred is the use of a basic carrier.
  • modifiers which are basic. This is essential in those cases wherein the carrier material is not basic.
  • a modifier is chosen from the group of inorganic or organic bases.
  • Preferred modifiers are Na 2 C0 3 , Na(acetate), K(acetate), K2CO3 and Co(acetate) 2 .
  • More preferred are non-acidic catalytic systems, which comprise the use of a basic carrier (on which the Pd metal is brought on) without additional basic modifiers. Examples of such more preferred non-acidic catalytic systems are Pd/C (basic carbon), Pd/CaCOs, Pd/Al 2 0 3 (basic Al 2 0 3 ) and Pd, Pb/CaC0 3 .
  • the non-acid catalyst system is used in an amount of 0.25 weight-% (wt-%) to 10 wt-%, based on the total weight of 4-acetoxy-2-methyl-2-butenal.
  • the catalytic system is used in an amount of 0.5 wt-% to 8 wt-%, based on the total weight of 4-acetoxy-2-methyl-2-butenal.
  • the process can be carried out at temperature between 0 °C and 100 °C. Preferably the process is carried out at temperature between 10 °C and 50 °C. It is an advantage that the process according to the present invention can be carried out at low temperature (i.e. at room temperature, 20 °C to 25 °C).
  • the process is carried out in a polar solvent (or in a mixture of solvents).
  • the polar solvent can be protic or aprotic.
  • Suitable polar solvents do have a polarity of 1 -25 x 10 "30 Cm, preferred 4-18 x 10 "30 Cm.
  • the polarity of the solvents is determined according to commonly known methods.
  • Suitable solvents are alcohols, ethers, esters, ketones, carbonates and lactames. Examples of preferred solvents are Ci-C 6 -alcohols (such as methanol and ethanol) and propylene carbonate.
  • the process according to the present invention is usually carried out at 0.2 to 20 bar pressure, more preferably at 0.5 to 10 bar.
  • the isolation of the reaction product of the process according to the present invention is done by using conventional methods. It is also possible that the product of formula (I) is not isolated, but used in situ for further reaction procedures.
  • the catalytic system always comprises a basis carrier.
  • the hydrogenated compound, which is obtained, is citronellal (compound of formula (IV))
  • Table 2 Comparison experiments (hydrogenation of citral) using a non-acid catalytic system comprising a modifier.
  • the catalytic system incl. modifier
  • the catalytic system has been added in amount 8.6 wt-% Pd catalyst and 1 .7 wt-% basic modifier, based on the total amount of citral, the reaction temperature was 23 °C and the pressure was 10 bar, the reaction time was 60 minutes.
  • Table 3 Comparison experiments (hydrogenation of citral) using a non-acid catalytic system (with basic carrier and no modifier).
  • the catalytic system has been added in amount of 8.6 wt-%, based on the total amount of citral, the reaction temperature was 23 °C and the pressure was 10 bar, the reaction time was 60 minutes.

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

Abstract

The present invention relates to a new way for the production of 4-acetoxy-2-methyl- butanal, wherein a non-acidic catalytic system is used.

Description

PREPARATION OF 4-ACETOXY-2-METHYLBUTANAL BY CATALYTIC CARBON CARBON DOUBLE BOND HYDROGENATION
The present invention relates to a new way for the production of 4-acetoxy-2-m butanal.
4-acetoxy-2-methyl-butanal, which is the following compound of formula (I)
Figure imgf000002_0001
is an important building block compound for the synthesis of organic compounds such as vitamin A, vitamin E, carotenoids and terpenoids.
Due to the complexness of the synthesis of organic compounds such as vitamin A, vitamin E, carotenoids and terpenoids it is desirable that the building block com- pounds (intermediates) are synthesized in an efficient manner. There is always a need for improved ways of such syntheses.
Until today, efficient hetero-catalytic selective hydrogenation of compounds containing the functional groups of a α,β-unsaturated aldehyde and an ester function is not known. Such compounds like those of formula (I) are very prone to saponify under the usual reaction condition.
Surprisingly it was found out that by the choice of the catalytic system a non-acidic catalytic system by-passes the saponification problem.
The present invention relates to a process for the production of 4-acetoxy-2-methyl- butanal, which results in very good yields and selectivity. This process can also be carried at low temperature (room temperature).
Surprisingly this hydrogenation does not work well for similar compounds like citral. The starting material for this process is 4-acetoxy-2-methyl-2-butenal, which resented by the following formula (II)
Figure imgf000003_0001
which is hydrogenated selectively. This means that the carbon-carbon double bond is hydrogenated.
Therefore the present invention relates to a process for the production of 4-acetoxy- 2-methyl-butanal which comprises the hydrogenation of 4-acetoxy-2-methyl-2- butenal,
wherein the hydrogenation is carried out by using a non-acid catalytic system.
In the context of the present invention the term non-acid catalytic system is defined as follows: An aqueous extract of the catalyst systems used in the process according to the present invention has a pH > 7. Preferably, the aqueous extract has a pH of > 7 (= basic catalytic system), more preferred the pH is > 7 and < 9.
The catalytic system can be a single compound or a mixture of compounds. When a mixture is used, then not all compounds have to have a pH (as an aqueous extract) of > 7, but the mixture has to fulfill this requirement.
The non-acid catalytic system comprises a heterogeneous Pd based catalyst. The catalyst comprises a carrier material on which the Pd is brought on. Such carrier materials are i.e. carbon (preferably in basic form), CaC03 and AI2O3 (preferably in basic form). Preferred is the use of a basic carrier.
It is also suitable to add at least one modifier, which is basic. This is essential in those cases wherein the carrier material is not basic. Such a modifier is chosen from the group of inorganic or organic bases. Preferred modifiers are Na2C03, Na(acetate), K(acetate), K2CO3 and Co(acetate)2. More preferred are non-acidic catalytic systems, which comprise the use of a basic carrier (on which the Pd metal is brought on) without additional basic modifiers. Examples of such more preferred non-acidic catalytic systems are Pd/C (basic carbon), Pd/CaCOs, Pd/Al203 (basic Al203) and Pd, Pb/CaC03.
The non-acid catalyst system is used in an amount of 0.25 weight-% (wt-%) to 10 wt-%, based on the total weight of 4-acetoxy-2-methyl-2-butenal. Preferably, the catalytic system is used in an amount of 0.5 wt-% to 8 wt-%, based on the total weight of 4-acetoxy-2-methyl-2-butenal.
The process can be carried out at temperature between 0 °C and 100 °C. Preferably the process is carried out at temperature between 10 °C and 50 °C. It is an advantage that the process according to the present invention can be carried out at low temperature (i.e. at room temperature, 20 °C to 25 °C).
The process is carried out in a polar solvent (or in a mixture of solvents). The polar solvent can be protic or aprotic. Suitable polar solvents do have a polarity of 1 -25 x 10"30 Cm, preferred 4-18 x 10"30 Cm. The polarity of the solvents is determined according to commonly known methods. Suitable solvents are alcohols, ethers, esters, ketones, carbonates and lactames. Examples of preferred solvents are Ci-C6-alcohols (such as methanol and ethanol) and propylene carbonate. The process according to the present invention is usually carried out at 0.2 to 20 bar pressure, more preferably at 0.5 to 10 bar.
The isolation of the reaction product of the process according to the present invention is done by using conventional methods. It is also possible that the product of formula (I) is not isolated, but used in situ for further reaction procedures.
The following examples serve to illustrate the invention. All percentages are given in weight percentages and the temperatures are given in °C. Examples Example 1
In a glass autoclave 4-acetoxy-2-methyl-2-butenal (20.0 g, 140.7 mmol), methanol (200.0 g), palladium on charcoal (1720 mg, 5 % palladium), and sodium carbonate (340.0 mg, 3.21 mmol) were added. The closed autoclave was agitated (1000 rpm) at 21 °C for 45 min. The hydrogen pressure was set to 0.5 bar. GC-area% showed a yield of 4-acetoxy-2-methyl-butanal of 95.2 % (100.0 % conversion).
Example 2
In a glass autoclave 4-acetoxy-2-methyl-2-butenal (1 .0 g, 7.03 mmol), methanol (10.0 g), palladium on charcoal (86 mg, 5% palladium), and sodium carbonate (17.0 mg, 0.16 mmol) were added. The closed autoclave was agitated (1000 rpm) at 23°C for 37. The hydrogen pressure was set to 0.5. GC-area% showed a yield of 4- acetoxy-2-methyl-butanal of 99% (100.0% conversion).
Examples 3 to 6
The following examples have been carried out in analogy to Example 2 (with the exemption that no modifier has been added). The catalytic system always comprises a basis carrier.
Table 1 : Examples 3 to 6
Figure imgf000006_0003
Examples 7 to 12 (comparison examples)
To demonstrate that the process according to the present invention is surprising, the following comparison tests have been made. Instead of using 4-acetoxy-2-methyl-2- butenal as a starting material the structurally similar compound citral (compound of formula (III))
Figure imgf000006_0001
The hydrogenated compound, which is obtained, is citronellal (compound of formula (IV))
Figure imgf000006_0002
The same reaction conditions have been used as for the process according to the present invention.
Table 2: Comparison experiments (hydrogenation of citral) using a non-acid catalytic system comprising a modifier. The catalytic system (incl. modifier) has been added in amount 8.6 wt-% Pd catalyst and 1 .7 wt-% basic modifier, based on the total amount of citral, the reaction temperature was 23 °C and the pressure was 10 bar, the reaction time was 60 minutes.
Figure imgf000007_0001
Table 3: Comparison experiments (hydrogenation of citral) using a non-acid catalytic system (with basic carrier and no modifier). The catalytic system has been added in amount of 8.6 wt-%, based on the total amount of citral, the reaction temperature was 23 °C and the pressure was 10 bar, the reaction time was 60 minutes.
Figure imgf000007_0002
The reactions do not lead to the same excellent yields as for the hydrogenation of 4- acetoxy-2-methyl-2-butenal.

Claims

Claims
1 . A process of production of 4-acetoxy-2-methyl-butanal which comprises the hydrogenation of 4-acetoxy-2-methyl-2-butenal in a polar solvent, wherein the hydrogenation is carried out by using a non-acid catalytic system.
2. Process according to claim 1 , wherein the process is carried out in a polar solvent (or in a mixture of solvents).
3. Process according to claim 2, wherein the polar solvent is protic or aprotic.
4. Process according to claim 2 or 3, wherein the polar solvent has a polarity of 1 -25 x 10"30 Cm, preferred 4-18 x 10"30 Cm.
5. Process according to any of claims 2 to 4, wherein the solvent is chosen from the group consisting of alcohols, ethers, esters, ketones, carbonates and lac- tames.
6. Process according to any of the preceding claims wherein the catalytic sys- tern comprises a heterogeneous Pd based catalyst.
7. Process according to any of the preceding claims wherein the catalytic system comprises a basic modifier.
8. Process according to any of the preceding claims, wherein the basic modifier is chosen from the group consisting of Na2C03, Na(acetate), K(acetate), K2CO3 and Co(acetate)2.
9. Process according to claim 5, wherein the catalytic system comprises a basic carrier.
10. Process according to any of the preceding claims, wherein the non-acid catalytic system is used in an amount of 0.25 wt-% to 10 wt-%, based on the total weight of 4-acetoxy-2-methyl-2-butenal, preferably 0.5 wt-% to 8 wt-%.
1 1 . Process according to any of the preceding claims, wherein the reaction temperature is between 0 °C and 100 °C (preferably 10°C - 50°C).
12. Process according to any of the preceding claims, wherein process is carried out at 0.2 to 20 bar pressure, preferably at 0.5 to 10 bar.
PCT/EP2012/050544 2011-01-19 2012-01-16 Preparation of 4-acetoxy-2-methylbutanal by catalytic carbon carbon double bond hydrogenation Ceased WO2012098067A1 (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
KR1020137021444A KR101914806B1 (en) 2011-01-19 2012-01-16 Preparation of 4-acetoxy-2-methylbutanal by catalytic carbon carbon double bond hydrogenation
JP2013549781A JP6005064B2 (en) 2011-01-19 2012-01-16 Preparation of 4-acetoxy-2-methylbutanal by catalytic carbon-carbon double bond hydrogenation
CN201280005984.1A CN103328431B (en) 2011-01-19 2012-01-16 Method for preparing 4-acetoxy-2-methylbutyraldehyde by catalytic carbon-carbon double bond hydrogenation
EP12700397.8A EP2665698B1 (en) 2011-01-19 2012-01-16 Preparation of 4-acetoxy-2-methylbutanal by catalytic carbon carbon double bond hydrogenation
ES12700397.8T ES2616758T3 (en) 2011-01-19 2012-01-16 Preparation of 4-acetoxy-2-methyl-butanal by catalytic hydrogenation of carbon double bonds with carbon
US13/980,118 US8829231B2 (en) 2011-01-19 2012-01-16 Preparation of 4-acetoxy-2-methylbutanal by catalytic carbon carbon double bond hydrogenation
BR112013018345-4A BR112013018345B1 (en) 2011-01-19 2012-01-16 CATALYTIC CARBON-CARBON DOUBLE CONNECTION HYDROGENATION

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JP2015520177A (en) * 2012-06-05 2015-07-16 ディーエスエム アイピー アセッツ ビー．ブイ． Process for producing 4-alkanoyloxy-2-methylbutanoic acid

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GB201501593D0 (en) * 2015-01-30 2015-03-18 Cambrex Karlskoga Ab New compounds and processes
CN113603592B (en) * 2021-06-29 2023-05-30 万华化学集团股份有限公司 A kind of preparation method of 2-methyl-4-acetoxy-2-butenal with thermal stability
CN114000170B (en) * 2021-12-01 2023-03-24 万华化学集团股份有限公司 Method for preparing 4-acetoxyl-2-methyl-2-butene-1-aldehyde
CN116283522B (en) * 2023-03-13 2025-09-16 上虞新和成生物化工有限公司 Synthesis method of 4-acetoxyl-2-methyl butyraldehyde

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KR101914806B1 (en) 2018-11-02
JP6005064B2 (en) 2016-10-12
BR112013018345A2 (en) 2016-10-04
BR112013018345B1 (en) 2019-02-26
CN103328431B (en) 2015-05-06
US20140081042A1 (en) 2014-03-20
EP2665698B1 (en) 2016-11-30
KR20140010038A (en) 2014-01-23
CN103328431A (en) 2013-09-25
JP2014510713A (en) 2014-05-01
US8829231B2 (en) 2014-09-09

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