Process for the preparation of polysantol-type compounds

Patent metadata

Field	Value
Publication number	US-10807941-B2
Application number	US-201716301756-A
Country	US
Kind code	B2
Filing date	Jun 1, 2017
Priority date	Jun 3, 2016
Publication date	Oct 20, 2020
Grant date	Oct 20, 2020

Abstract

The present invention relates to the field of organic synthesis and more specifically it concerns a novel compound of formula (I). The invention additionally relates to a process for preparing a compound of formula (III) using the compound of formula (I) as an intermediate, wherein the process involves elimination of the R3(X)nC(═O)O functional group of the compound of formula (I).

First claim

The invention claimed is:

1. A compound of formula (I)

in the form of any one of its stereoisomers or a mixture thereof, and wherein R1 is a C5-11 branched alkyl or a C6-11 alicyclic group optionally comprising an ether functional group, R2 is a hydrogen atom or a methyl group, n is 0 or 1; X is a NR3 group, or oxygen atom; and R3 is, independently, a hydrogen atom or a C1-6 alkyl group or an aryl group.

2. The compound according to claim 1 , characterized in that the compound is of formula

in the form of any one of its stereoisomers or a mixture thereof, wherein n, X, R2 and R3 have the same meaning as defined in claim 1 , and the dotted line is a carbon-carbon single or double bond.

3. The compound according to claim 1 , characterized in that the compound is of formula

in the form of any one of its stereoisomers or a mixture thereof, wherein R2 and R3 have the same meaning as defined in claim 1 , and the dotted line is a carbon-carbon single or double bond.

4. The compound according to claim 1 , characterized in that the compound is an acetate or propionate of 3,3-dimethyl-4-oxo-1-(2,2,3-trimethylcyclopent-3-en-1-yl)pentan-2-yl, 1-(2,2-dimethyl-3-methylenecyclohexyl)-3,3-dimethyl-4-oxopentan-2-yl, 3,3-dimethyl-4-oxo-1-(2,2,3-trimethylcyclohex-3-en-1-yl)pentan-2-yl or 3-methyl-4-oxo-1-(2,2,3-trimethylcyclopent-3-en-1-yl)pentan-2-yl.

5. Process for the preparation of a compound of formula (III)

in the form of any one of its stereoisomers or a mixture thereof, wherein R1 is a C5-11 branched alkyl or a C6-11 alicyclic group optionally comprising an ether functional group, and R2 is a hydrogen atom or a methyl group;
comprising the step of eliminating an R3(X)nC(═O)O functional group from a compound of formula (I)

wherein R1 is a C5-11 branched alkyl or a C6-11 alicyclic group optionally comprising an ether functional group, R2 is a hydrogen atom or a methyl group, n is 0 or 1; X is a NR3 group, or oxygen atom; and R3 is, independently, a hydrogen atom or a C1-6 alkyl group or an aryl group;
wherein the elimination step is a pyrolysis.

6. The process according to claim 5 , characterized in that the pyrolysis is performed at a temperature between 400 and 600° C.

7. The process according to claim 5 , characterized in that the process further comprises the step of preparing compound of formula (I) from compound of formula

in the form of any one of its stereoisomers or a mixture thereof, wherein R1 is a C5-11 branched alkyl or a C6-11 alicyclic group optionally comprising an ether functional group, and R2 is a hydrogen atom or a methyl group.

8. The process according to claim 7 , characterized in that the process further comprises the step of preparing the compound of formula (V) by an aldol condensation between iso-propyl methyl ketone or propyl methyl ketone and R1CH2CHO wherein R1 is a C5-11 branched alkyl or a C6-11 alicyclic group optionally comprising an ether functional group.

9. The process according to claim 5 , characterized in that the compound of formula (III) is of formula

wherein R2 is a hydrogen atom or a methyl group and the dotted line is a carbon-carbon single or double bond.

10. The process according to claim 5 , characterized in that the compound of formula (III) is selected from the group consisting of 3,3-dimethyl-5-(2,2,3-trimethylcyclopent-3-en-1-yl)pent-4-en-2-one, 3-methyl-5-(2,2,3-trimethylcyclopent-3-en-1-yl)pent-4-en-2-one, 5-(2,2-dimethyl-3-methylenecyclohexyl)-3,3-dimethyl pent-4-en-2-one and 3,3-dimethyl-5-(2,2,3-trimethylcyclohex-3-en-1-yl)pent-4-en-2-one.

11. The process according to claim 7 , characterized in that compound of formula (V) is of formula

wherein R2 is a hydrogen atom or a methyl group and the dotted line is a carbon-carbon single or double bond.

12. The process according to claim 11 , characterized in that the process further comprises the step of preparing the compound of formula (VI) by the aldol condensation between α-campholenic aldehyde and iso-propyl methyl ketone or methyl ethyl ketone.

13. The process according to claim 7 , characterized in that the compound of formula (V) is selected from the group consisting of 4-hydroxy-3,3-dimethyl-5-(2,2,3-trimethylcyclopent-3-en-1-yl)pentan-2-one, 4-hydroxy-3-methyl-5-(2,2,3-trimethylcyclopent-3-en-1-yl)pentan-2-one, 5-(2,2-dimethyl-3-methylenecyclohexyl)-4-hydroxy-3,3-dimethylpentan-2-one and 4-hydroxy-3,3-dimethyl-5-(2,2,3-trimethylcyclohex-3-en-1-yl)pentan-2-one.

Assignees

• Firmenich & Cie

Inventors

• Knopff Oliver

Classifications

• C11B9/0026

  compounds containing an alicyclic ring not condensed with another ring · CPC title

• C11B9/0019 Primary

  carbocylic acids; Salts or esters thereof · CPC title

• C07C2601/16

  the ring being unsaturated · CPC title

• C07C69/14

  of monohydroxylic compounds · CPC title

• C07C2601/14

  The ring being saturated · CPC title