Prins reaction on hindered substrates

Patent metadata

Field	Value
Publication number	US-9926249-B2
Application number	US-201515321880-A
Country	US
Kind code	B2
Filing date	Jul 1, 2015
Priority date	Jul 2, 2014
Publication date	Mar 27, 2018
Grant date	Mar 27, 2018

Abstract

The present invention relates to the field of organic synthesis and more specifically it concerns a process for the preparation of homoallylic alcohol derivatives as defined in formula (I) via a reaction of alkene of formula (II) with an aldehyde.

First claim

What is claimed is:

1. Process for the preparation of a compound of formula (I)

wherein R 1 represents a hydrogen atom or a C 1-8 alkyl group;
each R 2 , R 3 , R 4 , R 5 represent, when taken separately, independently from each other, a C 1-9 linear, branched or cyclic alkyl group optionally substituted by one to two C 1-5 alkyl groups and optionally comprising one or two functional groups of an ether, ester, carbonyl, amine, amide or alcohol group; R 2 and R 3 , when taken together, represent a C 4-11 linear, branched or cyclic alkanediyl group optionally comprising one or two functional groups of an ether, ester, carbonyl, amine, amide or alcohol group and/or R 3 and R 4 , when taken together, represent a C 2-9 linear, branched or cyclic alkanediyl group and/or R 4 and R 5 , when taken together, represent a C 4-9 linear, branched or cyclic alkanediyl group and/or R 2 and R 5 , when taken together, represent a C 2-9 linear, branched or cyclic alkanediyl group; and
R 6 represents a C 1-3 linear or branched alkyl group;

in the form of any one of its stereoisomers or a mixture thereof;
said process comprising the step of reacting a corresponding compound of formula (II)

wherein R 2 , R 3 , R 4 , R 5 and R 6 have the same meaning as in formula (I) with a compound of formula R 1 CHO, wherein R 1 has the same meaning as in formula (I).

2. A process according to claim 1 , wherein the compound of formula (II) are C 9 -C 20 compounds.

3. A process according to claim 1 , wherein the compound of formula (I) is compound of formula (III)

wherein n is 0 or 1;
each R 8 , R 9 , R 10 represent, when taken separately, independently from each other, a hydrogen atom or a C 1-6 linear, branched or cyclic alkyl group optionally substituted by one to two C 1-3 alkyl groups and optionally comprising one or two functional groups of an ether, ester, carbonyl, amine, amide or alcohol group;
each R 7 , R 11 , R 12 represent, when taken separately, independently from each other, a C 1-6 linear, branched or cyclic alkyl group optionally substituted by one to two C 1-3 alkyl groups and optionally comprising one or two functional groups of an ether, ester, carbonyl, amine, amide or alcohol group; R 7 and R 8 , when taken together, represent a C 3-9 linear or branched alkanediyl group optionally comprising one or two functional groups of an ether, ester, carbonyl, amine, amide or alcohol group and/or R 9 and R 10 , when taken together, represent a C 1-2 linear alkanediyl group and/or R 10 and R 11 , when taken together, represent a C 3-9 linear or branched alkanediyl group and/or R 8 and R 11 , when taken together, represent a C 1-3 linear or branched alkanediyl group; and
R 12 represents a C 1-3 linear or branched alkyl group;

in the form of any one of its stereoisomers or a mixture thereof.

4. A process according to claim 1 , wherein the compound of formula (II) is compound of formula (IV)

wherein n, R 7 , R 8 , R 9 , R 10 , R 11 and R 12 have the same meaning as in formula (III).

5. A process according to claim 1 , wherein the compound of formula (IV) is 1,1,4a,6-tetramethyl-5-methylenedecahydronaphthalene in the form of an essentially pure stereoisomer or in the form of a mixture of stereoisomers.

6. A process according to claim 1 , wherein compound of formula R 1 CHO is paraformaldehyde.

7. A process according to claim 1 , wherein temperature at which the reaction can be carried out is comprised in the range between 160° C. and 230° C.

8. A process for the preparation of a compound of formula (I)

wherein R 1 represents a hydrogen atom or a C 1-8 alkyl group;
each R 2 , R 3 , R 4 , R 5 represent, when taken separately, independently from each other, a C 1-9 linear, branched or cyclic alkyl group optionally substituted by one to two C 1-5 alkyl groups and optionally comprising one or two functional groups of an ether, ester, carbonyl, amine, amide or alcohol group; R 2 and R 3 , when taken together, represent a C 4-11 linear, branched or cyclic alkanediyl group optionally comprising one or two functional groups of an ether, ester, carbonyl, amine, amide or alcohol group and/or R 3 and R 4 , when taken together, represent a C 2-9 linear, branched or cyclic alkanediyl group and/or R 4 and R 5 , when taken together, represent a C 4-9 linear, branched or cyclic alkanediyl group and/or R 2 and R 5 , when taken together, represent a C 2-9 linear, branched or cyclic alkanediyl group; and
R 6 represents a C 1-3 linear or branched alkyl group;

in the form of any one of its stereoisomers or a mixture thereof;
said process comprising the step of reacting a corresponding compound of formula (II)

wherein R 2 , R 3 , R 4 , R 5 and R 6 have the same meaning as in formula (I)
with a compound of formula R 1 CHO, wherein R 1 has the same meaning as in formula (I),
wherein the process is carried out in the presence of a carboxylic derivative of a C 2-8 carboxylic acid, C 4-16 carboxylic anhydride or a mixture of said carboxylic acid and said carboxylic anhydride.

9. A process according to claim 1 , wherein the process is carried out in the presence of a solvent.

10. A process according to claim 8 , wherein the compound of formula (II) are C 9 -C 20 compounds.

11. A process according to claim 8 , wherein the compound of formula (I) is compound of formula (III)

wherein n is 0 or 1;
each R 8 , R 9 , R 10 represent, when taken separately, independently from each other, a hydrogen atom or a C 1-6 linear, branched or cyclic alkyl group optionally substituted by one to two C 1-3 alkyl groups and optionally comprising one or two functional groups of an ether, ester, carbonyl, amine, amide or alcohol group;
each R 7 , R 11 , R 12 represent, when taken separately, independently from each other, a C 1-6 linear, branched or cyclic alkyl group optionally substituted by one to two C 1-3 alkyl groups and optionally comprising one or two functional groups of an ether, ester, carbonyl, amine, amide or alcohol group; R 7 and R 8 , when taken together, represent a C 3-9 linear or branched alkanediyl group optionally comprising one or two functional groups of an ether, ester, carbonyl, amine, amide or alcohol group and/or R 9 and R 10 , when taken together, represent a C 1-2 linear alkanediyl group and/or R 10 and R 11 , when taken together, represent a C 3-9 linear or branched alkanediyl group and/or R 8 and R 11 , when taken together, represent a C 1-3 linear or branched alkanediyl group; and
R 12 represents a C 1-3 linear or branched alkyl group;

in the form of any one of its stereoisomers or a mixture thereof.

12. A process according to claim 8 , wherein the compound of formula (II) is compound of formula (IV)

Assignees

• Firmenich & Cie

Inventors

• Knopff Oliver
• Fonteny Fabien

Classifications

• C07C33/14

  containing six-membered rings · CPC title

• C07C2601/16

  the ring being unsaturated · CPC title

• C07C29/44 Primary

  increasing the number of carbon atoms by addition reactions, i.e. reactions involving at least one carbon-to-carbon double or triple bond (C07C29/16 takes precedence) · CPC title

• C07C2101/16

  Chemistry & Metallurgy · mapped topic

• C07C33/02

  Acyclic alcohols with carbon-to-carbon double bonds · CPC title