Polythiols as cis/trans isomerization catalysts for unsaturated compounds

Patent metadata

Field	Value
Publication number	US-9765002-B2
Application number	US-201314651510-A
Country	US
Kind code	B2
Filing date	Dec 18, 2013
Priority date	Dec 18, 2012
Publication date	Sep 19, 2017
Grant date	Sep 19, 2017

Abstract

The present invention relates to a process of a cis/trans isomerization of an unsaturated compound A being selected from the group consisting of unsaturated ketones, unsaturated ketals, unsaturated aldehydes, unsaturated acetals, unsaturated carboxylic acids, esters of an unsaturated carboxylic acid and amides of an unsaturated carboxylic acid using polythiol as cis/trans isomerization catalyst. It has been observed that the isomerization is very efficient and fast.

First claim

The invention claimed is:

1. A process for the cis/trans isomerization of an unsaturated compound A of formula (I) or (II) or an acetal or ketal thereof:

wherein Q stands for H or CH 3 and m and p stand independently from each other for a value of 0 to 3 with the proviso that the sum of m and p is 0 to 3, and wherein
a wavy line represents a carbon-carbon bond which is linked to the adjacent carbon-carbon double bond so as to have said carbon-carbon double bond either in the Z or in the E-configuration, and wherein
the substructures in formula (I) and (II) represented by s1 and s2 can be in any sequence; and wherein
the double bond having dotted lines ( ) in formula (I) and (II) represent either a single carbon-carbon bond or a double carbon-carbon bond; and wherein
the symbol represents a stereogenic centre, wherein
the process the steps of:
a) providing a cis or a trans isomer of the unsaturated compound A;
b) adding a polythiol to the cis or trans isomer of the unsaturated compound A provided according to step a) to form a mixture thereof; and
c) heating the mixture of the polythiol and the cis or trans isomer of the unsaturated compound A to a temperature of between 20° C. and the boiling point of the unsaturated compound A in the presence of a polar solvent thereby leading to a mixture of cis/trans isomers of the unsaturated compound A.

2. The process according to claim 1 , wherein the polythiol is present in an amount between 1 and 20% by weight relative to the amount of the unsaturated compound A.

3. The process according to claim 1 , wherein the polythiol is a compound of formula (X):

wherein n1 represents an integer from 1 to 4,
m1 represents an integer from 2 to 8, and
A represents an aliphatic m1-valent hydrocarbon group of the molecular weight of between 28 g/mol and 400 g/mol.

4. A process for producing specific cis and trans isomers, respectively, from a mixture of cis and trans isomers of an unsaturated compound A of formula (I) or (II) or an acetal or ketal thereof:

wherein Q stands for H or CH 3 and m and p stand independently from each other for a value of 0 to 3 with the proviso that the sum of m and p is 0 to 3, and wherein
a wavy line represents a carbon-carbon bond which is linked to the adjacent carbon-carbon double bond so as to have said carbon-carbon double bond either in the Z or in the E-configuration, and wherein
the substructures in formula (I) and (II) represented by s1 and s2 can be in any sequence; and wherein
the double bond having dotted lines ( ) in formula (I) and (II) represent either a single carbon-carbon bond or a double carbon-carbon bond; and wherein
the symbol represents a stereogenic centre, wherein
the process comprises the steps of:
i) providing a mixture of cis and trans isomers of the unsaturated compound A, wherein the cis isomers of the unsaturated compound A are present in the mixture in an amount by weight w cis and the trans isomers of the unsaturated compound A are present in the mixture in an amount by weight w trans ;
ii) adding a polythiol to the mixture of cis and trans isomers of the unsaturated compound A;
iii) heating the mixture of cis and trans isomers of the unsaturated compound A to a temperature T iso1 , which is the boiling point of an isomer I lbp which has a lowest boiling point of the mixture of cis and trans isomers of the unsaturated compound A provided according to step i);
iv) distilling off the isomer I lbp and collecting the isomer I lbp ;
v) conducting cis/trans isomerization of an isomer I lbp having a higher boiling point than the boiling point of the isomer I lbp in the presence of the polythiol added to the mixture according to step ii); and
vi) after the step v), repeating the steps iii), iv) and v); and wherein
the weight of the collected isomer I lbp is more than the weight w cis of the cis isomer of the unsaturated compound A in the mixture in the case where the collected isomer I lbp is a cis isomer of the unsaturated compound A; or
the weight of the collected isomer I lbp is more than the weight w trans of the trans isomer of the unsaturated compound A in the mixture in the case where the collected isomer I lbp is a trans isomer of the unsaturated compound A; and wherein
each of the weight w cis and weight w trans of the cis and trans isomers of the unsaturated compound A, respectively, in the mixture is 0 gram to 10 tons, with the proviso that the ratio of the weight w cis and the weight w trans is larger than 70/30 or smaller than 30/70 with the proviso that not both w cis and w trans are 0 grams.

5. The process of claim 4 , wherein the weight of the collected isomer I lbp isomer is more than 80% by weight, of a sum of the weight w trans and the weight w cis .

6. A process for producing specific cis and trans isomers, respectively, from a mixture of cis and trans isomers of an unsaturated compound A of formula (I) or (II) or an acetal or ketal thereof:

wherein Q stands for H or CH 3 and m and p stand independently from each other for a value of 0 to 3 with the proviso that the sum of m and p is 0 to 3, and wherein
a wavy line represents a carbon-carbon bond which is linked to the adjacent carbon-carbon double bond so as to have said carbon-carbon double bond either in the Z or in the E-configuration, and wherein
the substructures in formula (I) and (II) represented by s1 and s2 can be in any sequence; and wherein
the double bond having dotted lines ( ) in formula (I) and (II) represent either a single carbon-carbon bond or a double carbon-carbon bond; and wherein
the symbol represents a stereogenic centre, wherein
the process comprises the steps of:
a) providing a mixture of cis and trans isomers of the unsaturated compound A, wherein the cis isomers of the unsaturated compound A are present in the mixture in an amount by weight w cis and the trans isomers of the unsaturated compound A are present in the mixture in an amount by weight w trans ;
b) adding a polythiol to the mixture of cis and trans isomers of the unsaturated compound A;
c) heating the mixture of cis and trans isomers of the unsaturated compound A to a temperature T iso1 , which is the boiling point of an isomer I lbp which has a lowest boiling point of the mixture of cis and trans isomers of the unsaturated compound A provided according to step i);
d) distilling off the isomer I lbp ;
e) isolating a specific isomer I lbp which has a higher boiling point than the boiling point of the isomer I lbp from a remainder of step d) and collecting the isomer I hbp ;
f) conducting cis/trans isomerization of the isomer I lbp and the remainder of step e) in the case there is a remainder after step e) in the presence of the polythiol added according to step b); and
g) after the step f), repeating the steps c), d), e) and f), wherein
the weight of the collected isomer I hbp is more than the weight w cis of the cis isomer of the unsaturated compound A in the mixture in the case where the collected isomer I hbp is a cis isomer of the unsaturated compound A; o

Assignees

• Dsm Ip Assets Bv

Inventors

• Stemmler René Tobias
• Greiner Nadine

Classifications

• C07D319/06 Primary

  not condensed with other rings · CPC title

• C07C45/82

  by distillation · CPC title

• C07C45/67

  by isomerisation; by change of size of the carbon skeleton · CPC title

• C07C43/313 Primary

  containing halogen · CPC title

• C07C41/60

  Preparation of compounds having [IMAGE cpc-sch-C07C-0959.gif] groups or[IMAGE cpc-sch-C07C-0960.gif] groups · CPC title