EP3898584A1 - Improved process to produce specific alpha,beta-unsaturated carboxylates - Google Patents

Improved process to produce specific alpha,beta-unsaturated carboxylates

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Publication number
EP3898584A1
EP3898584A1 EP19820771.4A EP19820771A EP3898584A1 EP 3898584 A1 EP3898584 A1 EP 3898584A1 EP 19820771 A EP19820771 A EP 19820771A EP 3898584 A1 EP3898584 A1 EP 3898584A1
Authority
EP
European Patent Office
Prior art keywords
formula
catalyst
process according
compound
reaction
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.)
Pending
Application number
EP19820771.4A
Other languages
German (de)
French (fr)
Inventor
Claude Alban FURER
Roman GOY
Jan Schuetz
Ralph Waechter
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.)
DSM IP Assets BV
Original Assignee
DSM IP Assets BV
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 IP Assets BV filed Critical DSM IP Assets BV
Publication of EP3898584A1 publication Critical patent/EP3898584A1/en
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
    • C07C403/06—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms
    • C07C403/12—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms by esterified hydroxy groups

Definitions

  • the present invention relates to a process for producing specific a, b-unsaturated carboxylates.
  • Ri is a Ci - C 4 -alkyl moiety, preferably -CH 3 or -CH CH 3 , and
  • R 3 is one of the following groups
  • R 4 is CH 3 or phenyl
  • a,b-unsaturated carboxylates are useful compounds. They can be used as such or they are useful intermediates to produce other compounds.
  • compound (la) is used as an intermediate in the production of Vitamin A acetate (via a reduction followed by an acetylation)
  • the new process to produce these compounds comprises a ruthenium catalyst.
  • the big advantage of the process according to the present invention is that the ruthenium catalyst can be recycled and reused whereby the activity of the catalyst is still excellent after it was reused a few times.
  • R5, R 6 , R7, and Re signify CH 3 , -OCH3, -N0 , halogen or -H, and
  • X and Y signify independently from each other an allylic moiety
  • q signifies an integer 1 , 2 or 3.
  • the catalyst of formula (IV’) is removed from the reaction mixture at the end of the reaction by filtration, wherein the filter cake, wherein the catalyst is present, is washed to remove all obtained product.
  • the present invention relates to a process (P) for the production of a compound of formula (I)
  • Ri is a Ci - C4-alkyl moiety, preferably -CH3 or -ChhChh, and
  • R 3 is one of the following groups
  • R4 is CH3 or phenyl
  • R5, Re, R7, and Re signify CH 3 , -OCH3, -N0 , halogen or -H, and
  • X and Y signify independently from each other an allylic moiety
  • q signifies an integer 1 , 2 or 3,
  • the present invention relates to a process (P1 ), which is process (P), wherein Ri is- CH 3 or -CH 2 CH 3
  • the present invention relates to a process (P2), which is process (P) or (P1), wherein
  • R 3 is one of the following groups
  • the present invention relates to a process (P3), which is process (P), (P1) or (P2), wherein
  • R 3 is one of the following groups
  • a very preferred catalyst is the one of formula (IVa) Therefore the present invention relates to a process (P3), which is process (P), (P1) or (P2), wherein
  • the substrate (starting material) to catalyst ratio (mol-based) is usually from 5000 : 1 to 10 : 1 , preferably from 1000 : 1 to 20 : 1.
  • the process according to the present invention is carried out without any solvents or in at least one apolar aprotic organic solvent.
  • paraffin oil a mixture of saturated aliphatic hydrocarbons
  • carboxylate esters such as ethyl acetate.
  • the process according to the present invention is usually carried out under very mild reaction condition.
  • the reaction temperature is usually between -5°C and 60°C. Preferably between 0° and 50°C.
  • the advantage of the new and inventive process is that the Ruthenium catalyst can be removed from the reaction mixture and reused.
  • the filtration can be carried by using any commonly known mean to carry out a filtration. Also the material of the filter is not essential.
  • Suitable solvents are usually chosen from the group consisting of, aliphatic, cyclic and aromatic hydrocarbons, and carboxylate esters.
  • the filter cake can be washed one or more times. If needed the washing can take place with different solvents.
  • the filter cake can be used as such in the next reaction.
  • the present invention relates to a process for the production of a compound of formula (I)
  • Ri is a Ci - C 4 -alkyl moiety, preferably -CH 3 or -CH CH3, and R 3 is one of the following groups
  • R 4 is CH 3 or phenyl
  • R3 has the meaning as defined above
  • R5, R6, R7, and Re signify CH 3 , -OCH3, -N0 , halogen or -H, and
  • X and Y signify independently from each other an allylic moiety
  • q signifies an integer 1 , 2 or 3,
  • the present invention relates to a process for the production of a compound of formula (I)
  • Ri is a Ci - C 4 -alkyl moiety, preferably -CH 3 or -ChhChh, and R 3 is one of the following groups
  • R4 is CH3 or phenyl
  • R 3 has the meaning as defined above.
  • the catalyst is recycled and usually re-used again after the reaction.
  • Example illustrates the invention further without limiting it. All per-centages and parts, which are given, are related to the weight and the tempera-tures are given in °C, when not otherwise stated.
  • Example 1 3-hydroxv-3-methyl-5-(2.6, 6-trimethylcyclohex- 1-en-1 -yl)penta-1, 4-dien- 1 -yl benzoate; re-use of Ru-catalyst by precipitation.

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

Abstract

The present invention relates to a process for producing specific α,β-unsaturated carboxylates.

Description

IMPROVED PROCESS TO PRODUCE SPECIFIC a.b-UNSATU RATED CARBOXYLATES
The present invention relates to a process for producing specific a, b-unsaturated carboxylates.
The specific a,b-unsaturated carboxylates which are aimed to be produced are represented by the following formula (I)
wherein
Ri is a Ci - C4-alkyl moiety, preferably -CH3 or -CH CH3, and
R3 is one of the following groups
wherein
R4 is CH3 or phenyl
(the * is showing where the bond is localized).
These specific a,b-unsaturated carboxylates are useful compounds. They can be used as such or they are useful intermediates to produce other compounds. For example compound (la) is used as an intermediate in the production of Vitamin A acetate (via a reduction followed by an acetylation)
Therefore due to the importance of such important intermediates, there is always a need for excellent methods of producing such compounds.
The new process to produce these compounds comprises a ruthenium catalyst. The big advantage of the process according to the present invention is that the ruthenium catalyst can be recycled and reused whereby the activity of the catalyst is still excellent after it was reused a few times.
Most of the che compounds of formula (I) are not known from the prior art. The process to produce these compounds is the following:
A compound of formula (II)
wherein the Ri, R and R3 have the same meanings as defined above for the compound of formula (I)
in the presence of at least one catalyst of formula (IV) wherein
R5, R6, R7, and Re signify CH3, -OCH3, -N0 , halogen or -H, and
X and Y signify independently from each other an allylic moiety, and
q signifies an integer 1 , 2 or 3.
After the termination of the reaction (1 st cycle) the catalyst of formula (IV) has been transformed into the following form of formula (IV’)
The newly formed catalyst of formula (IV’), wherein all the substituents have the same meanings as defined above, can be isolated from the reaction product and it can be reused easily and it is still active after a series of cycles.
The catalyst of formula (IV’) is removed from the reaction mixture at the end of the reaction by filtration, wherein the filter cake, wherein the catalyst is present, is washed to remove all obtained product.
Therefore the present invention relates to a process (P) for the production of a compound of formula (I)
wherein
Ri is a Ci - C4-alkyl moiety, preferably -CH3 or -ChhChh, and
R3 is one of the following groups
wherein
R4 is CH3 or phenyl
(the * is showing where the bond is localized), wherein
a compound of formula (II)
wherein the Ri , R2 and R3 have the same meanings as defined above for the compound of formula (I)
in the presence of at least one catalyst of formula (IV)
wherein
R5, Re, R7, and Re signify CH3, -OCH3, -N0 , halogen or -H, and
X and Y signify independently from each other an allylic moiety, and
q signifies an integer 1 , 2 or 3,
and wherein in next step (after the reaction has ended) the catalyst is removed from the reaction mixture by filtration.
Preferred are compounds of formula (I), wherein Ri is-CHs or -CH2CH3.
Therefore the present invention relates to a process (P1 ), which is process (P), wherein Ri is- CH3 or -CH2CH3
Preferred are compounds of formula (I), wherein
Therefore the present invention relates to a process (P2), which is process (P) or (P1), wherein
Preferred are compounds of formula (I), wherein
R3 is one of the following groups
Therefore the present invention relates to a process (P3), which is process (P), (P1) or (P2), wherein
R3 is one of the following groups
Most preferred to be produced are the following compounds of formula (G) - (I’””)
A very preferred catalyst is the one of formula (IVa) Therefore the present invention relates to a process (P3), which is process (P), (P1) or (P2), wherein
the catalyst of formula (IVa)
is used.
The substrate (starting material) to catalyst ratio (mol-based) is usually from 5000 : 1 to 10 : 1 , preferably from 1000 : 1 to 20 : 1.
The process according to the present invention is carried out without any solvents or in at least one apolar aprotic organic solvent.
All reactants are added together and mixed. The reaction mixture is heated to the temperature at which the transition metal-based catalytic rearrangement reaction occurs, to provide a resulting mixture.
As solvents there can be used in the scope of the present invention in general apolar aprotic organic solvents, especially aliphatic, cyclic and aromatic hydrocarbons, such as, for example, C7-Cio-alkanes, Cs-Cycycloalkanes, benzene, toluene and naphthalene as well as mixtures of such solvents with one another, e.g. paraffin oil (a mixture of saturated aliphatic hydrocarbons). As well as carboxylate esters, such as ethyl acetate.
The process according to the present invention is usually carried out under very mild reaction condition. The reaction temperature is usually between -5°C and 60°C. Preferably between 0° and 50°C.
As stated above the advantage of the new and inventive process is that the Ruthenium catalyst can be removed from the reaction mixture and reused.
This is done by filtration. The filtration can be carried by using any commonly known mean to carry out a filtration. Also the material of the filter is not essential.
Usually the filter cake is washed with the same solvent as the reaction was carried out.
It is also possible to carry out the reaction without any solvent, in that case a suitable solvent as stated above is used to wash the filter cake Suitable solvents are usually chosen from the group consisting of, aliphatic, cyclic and aromatic hydrocarbons, and carboxylate esters.
The filter cake can be washed one or more times. If needed the washing can take place with different solvents.
After the washing step, the filter cake can be used as such in the next reaction.
Therefore the present invention relates to a process for the production of a compound of formula (I)
wherein
Ri is a Ci - C4-alkyl moiety, preferably -CH3 or -CH CH3, and R3 is one of the following groups
R4 is CH3 or phenyl
(the * is showing where the bond is localized), wherein
a compound of formula (II)
wherein the Ri, R and R3 have the same meanings as defined above for the compound of formula (I) in the presence of at least one catalyst of formula (IV’), which is recycled from the reaction mixture,
wherein
R3 has the meaning as defined above
R5, R6, R7, and Re signify CH3, -OCH3, -N0 , halogen or -H, and
X and Y signify independently from each other an allylic moiety, and
q signifies an integer 1 , 2 or 3,
and wherein in next step (after the reaction has ended) the catalyst is removed from the reaction mixture by filtration.
Therefore the present invention relates to a process for the production of a compound of formula (I)
wherein
Ri is a Ci - C4-alkyl moiety, preferably -CH3 or -ChhChh, and R3 is one of the following groups
wherein
R4 is CH3 or phenyl
(the * is showing where the bond is localized), wherein
a compound of formula (II)
wherein the Ri , R and R3 have the same meanings as defined above for the compound of formula (I)
in the presence of at least one catalyst of formula (IVa’), which is recycled from the reaction mixture, wherein
R3 has the meaning as defined above.
The catalyst is recycled and usually re-used again after the reaction.
The following Example illustrates the invention further without limiting it. All per-centages and parts, which are given, are related to the weight and the tempera-tures are given in °C, when not otherwise stated.
Examples
Example 1 : 3-hydroxv-3-methyl-5-(2.6, 6-trimethylcyclohex- 1-en-1 -yl)penta-1, 4-dien- 1 -yl benzoate; re-use of Ru-catalyst by precipitation.
3-Methyl-1-(2,6,6-trimethylcyclohex-1 -en-1-yl)pent-1 -en-4-yn-3-ol (1.75 g, 7.5 mmol) and benzoic acid (1.37 g, 1 1.25 mmol, 1.5 eq.) were dissolved in ethyl acetate (10 mL) under argon atmosphere. In a counter flow of argon, 0.274 g (0.45 mmol) of the ruthenium catalyst of formula (IVa) were added. After stirring for 24 h at 0 °C (Table 1), n-heptane (10 mL) was added. All volatiles were removed in vacuo at 0 °C. Heptane (10 mL) was added twice and was removed in vacuo. The residue was suspended in heptane (50 mL) and cooled to -10 °C. The suspension was stirred for 2 h at -10 °C under argon atmosphere. The suspension was filtered, and the filter cake washed with heptane (10 mL). The mother liquor was concentrated in vacuo. The crude product was obtained as yellow-brown oil in 71 % yield (3.02 g, 60 % purity), containing 6.3 mg of the ruthenium catalyst of formula IV’b)
The filter cake was dissolved in ethyl acetate under argon and the yellow solution was concentrated in vacuo. The residue was dissolved in ethyl acetate (10 mL), cooled to 0 °C and 3-methyl-1-(2,6,6-trimethylcyclohex-1 -en-1-yl)pent-1 -en-4-yn-3-ol (1.75 g, 7.5 mmol) and benzoic acid (1.83 g, 15 mmol, 2 eq.) were added. The reaction mixture was stirred at 0 °C for 24 h. All volatiles were removed in vacuo at 0 °C. Heptane (10 ml) was added twice and was removed in vacuo. The residue was suspended in heptane (50 mL) and cooled to -10 °C. The suspension was stirred for 2 h at -10 °C under argon atmosphere. The suspension was filtered, and the filter cake washed with heptane (10 mL). The mother liquor was concentrated in vacuo. The crude product was obtained as yellow-brown oil in 78% yield (3.51 g, 57 % purity), containing 35 mg of the ruthenium catalyst of formula (IV’ b)).
Example 2: 3-hydroxv-3-methyl-5-(2, 6, 6-trimethylcyclohex- 1-en-1 -yl)penta-1,4-dien-1 -yl adamantoate; re-use of Ru-catalyst by organic-solvent-nanofiltration .)
3-Methyl-1-(2,6,6-trimethylcyclohex-1 -en-1-yl)pent-1 -en-4-yn-3-ol (4.54 g, 20 mmol) and adamantanecarboxylic acid (5.46 g, 30 mmol, 1.5 eq.) were dissolved in anhydrous ethyl acetate (20 mL) under argon atmosphere. In a counter flow of argon, 0.488 g (0.8 mmol) of the ruthenium catalyst of formula (IVa) were added. After stirring for 2 h at 20 °C the yellow solution was transferred under a counter nitrogen flow into the filtration apparatus fitted with a preconditioned membrane (MWCo 600) and the system was brought under pressure (20-50 barg nitrogen). The flux of filtrate was continuously monitored. Once 20 mL solution had permeated through the membrane the pressure of the system was released. The filtrate was concentrated in vacuo. The crude product was obtained as yellow-brown oil (2.35 g, results Table 1), containing no ruthenium catalyst
To the retentate (which contains the catalyst of formula (IV’c)
in the filtration apparatus was added under a counter nitrogen stream again 3-methyl-1 -(2,6,6- trimethylcyclohex-1 -en-1-yl)pent-1 -en-4-yn-3-ol (4.54 g, 20 mmol) and adamantanecarboxylic acid (5.46 g, 30 mmol, 1.5 eq.) dissolved in anhydrous ethyl acetate (20 mL) under nitrogen atmosphere. After stirring for 2 h at 20 °C-the system was brought under pressure (20-50 barg) and the flux of filtrate was continuously monitored. Once 30 mL solution had permeated through the membrane the pressure of the system was released. The filtrate was concentrated in vacuo. The crude product was obtained as yellow-brown oil (9.75 g, results Table 1), containing no ruthenium catalyst of formula (IV’c). This filter/fill procedure was repeated until no further catalyst activity was observed.
After the 10. addition of 3-methyl-1-(2,6,6-trimethylcyclohex-1 -en-1-yl)pent-1 -en-4-yn-3-ol (4.54 g, 20 mmol) and adamantanecarboxylic acid (5.46 g, 30 mmol, 1.5 eq.) dissolved in anhydrous ethyl acetate (20 mL) reaction mixture was concentrated in vacuo (without a filtration step). The crude product was obtained as yellow-brown oil (16.18 g, results Table 1), containing no ruthenium catalyst of formula (IV’c). After overall addition of 200 mmol 3-methyl- 1 -(2,6,6-trimethylcyclohex-1-en-1-yl)pent-1-en-4-yn-3-ol, a conversion of 79 % as well as yield of 78.3 % was obtained.
Table 1

Claims

Claims
1. Process for the production of a compound of formula (I)
wherein
Ri is a Ci - C4-alkyl moiety, preferably -CH3 or -CH CH3, and
R3 is one of the following groups
wherein
R4 is CH3 or phenyl
(the * is showing where the bond is localized), wherein a compound of formula (II)
is reacted with a compound of formula (III) wherein the Ri, R2 and R3 have the same meanings as defined above for the compound of formula (I)
in the presence of at least one catalyst of formula (IV)
wherein
R5, Re, R7, and Re signify CH3, -OCH3, -N0 , halogen or -H, and
X and Y signify independently from each other an allylic moiety, and
q signifies an integer 1 , 2 or 3,
and wherein in next step (after the reaction has ended) the catalyst is removed from the reaction mixture by filtration.
2. Process according to claim 1 , wherein
Ri is-CHs or -CH2CH3.
3. Process according to claim 1 or claim 2, wherein
4. Process according to any of the preceding claims, wherein R3 is one of the following groups
5. Process according to any of the preceding claims, wherein the catalyst of formula (IVa)
is used.
6. Process according to any of the preceding claims, wherein the substrate (starting material) to catalyst ratio (mol-based) is usually from 5000 : 1 to 10 : 1 , preferably from 1000 : 1 to 20 : 1.
7. Process according to any of the preceding claims, wherein the process is carried out without any solvents.
8. Process according to any of claims 1 to 5, wherein the process is carried out in at least one apolar aprotic organic solvent.
9. Process according to claim 8, wherein the solvent is chosen from the group consisting of, aliphatic, cyclic and aromatic hydrocarbons, and carboxylate esters.
10. Process according to any of the preceding claims, wherein the process is carried out at a temperature of from -5°C to 60°C.
11. Process according to any of the preceding claims, wherein the filter cake is washed with a solvent chosen from the group consisting of, aliphatic, cyclic and aromatic hydrocarbons, and carboxylate esters.
12. Process for the production of a compound of formula (I)
wherein
Ri is a Ci - C4-alkyl moiety, preferably -Ch or -ChhChh, and
R3 is one of the following groups
wherein
R4 is CH3 or phenyl
(the * is showing where the bond is localized), wherein
a compound of formula (II)
wherein the Ri , R2 and R3 have the same meanings as defined above for the compound of formula (I)
in the presence of at least one catalyst of formula (IV’), which is recycled from the reaction mixture,
wherein
R3 has the meaning as defined above
R5, R6, R7, and Re signify CH3, -OCH3, -N0 , halogen or -H, and
X and Y signify independently from each other an allylic moiety, and
q signifies an integer 1 , 2 or 3,
and wherein in next step (after the reaction has ended) the catalyst is removed from the reaction mixture by filtration.
EP19820771.4A 2018-12-20 2019-12-17 Improved process to produce specific alpha,beta-unsaturated carboxylates Pending EP3898584A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP18214430 2018-12-20
PCT/EP2019/085498 WO2020127158A1 (en) 2018-12-20 2019-12-17 Improved process to produce specific a,b-unsaturated carboxylates

Publications (1)

Publication Number Publication Date
EP3898584A1 true EP3898584A1 (en) 2021-10-27

Family

ID=64746347

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Application Number Title Priority Date Filing Date
EP19820771.4A Pending EP3898584A1 (en) 2018-12-20 2019-12-17 Improved process to produce specific alpha,beta-unsaturated carboxylates

Country Status (3)

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EP (1) EP3898584A1 (en)
CN (1) CN113195451A (en)
WO (1) WO2020127158A1 (en)

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Publication number Priority date Publication date Assignee Title
EP4168420B1 (en) * 2020-06-19 2024-11-13 DSM IP Assets B.V. Improved process to produce specific alfa, beta-unsaturated carboxylates

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1442014B1 (en) * 2001-10-31 2007-03-21 DSM IP Assets B.V. Manufacture of retinoids
JP2004180505A (en) * 2002-11-29 2004-07-02 Mitsubishi Rayon Co Ltd Method for producing unsaturated carboxylic acid ester
WO2006025182A1 (en) * 2004-08-30 2006-03-09 Sanyo Chemical Industries, Ltd. PROCESS FOR PRODUCTION OF α,β-UNSATURATED CARBOXYLIC ESTERS AND α,β-UNSATURATED CARBOXYLIC ESTERS

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CN113195451A (en) 2021-07-30

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