Intermediates and process for the preparation of sandalwood oil building blocks

Patent metadata

Field	Value
Publication number	US-9879203-B2
Application number	US-201515529300-A
Country	US
Kind code	B2
Filing date	Nov 16, 2015
Priority date	Dec 2, 2014
Publication date	Jan 30, 2018
Grant date	Jan 30, 2018

Abstract

The present invention concerns a process for the preparation of an oxidized terpenes fraction which proved to be particularly useful in the preparation of sandalwood oil building blocks.

First claim

The invention claimed is:

1. A composition of matter consisting in an oxidized terpenes fraction (I) comprising:
from 15 to 40% w/w of 3-((1S,2R,4R)-2-methyl-3-methylenebicyclo[2.2.1]heptan-2-yl)propanal, of formula

wherein the bold and hatched line indicate an absolute configuration;
from 1 to 8% w/w of 3-((1S,2S,4R)-2-methyl-3-methylenebicyclo[2.2.1]heptan-2-yl)propanal, of formula

wherein the bold and hatched line indicate an absolute configuration;
from 40 to 60% w/w of 3-((1S,3R,4S)-2,3-dimethyltricyclo[2.2.1.0 2,6 ]heptan-3-yl)propanal, of formula

wherein the bold and hatched line indicate an absolute configuration; and
from 5 to 20% w/w of 3-((1S,5S,6R)-2,6-dimethylbicyclo[3.1.1]hept-2-en-6-yl)propanal, of formula

wherein the bold and hatched line indicate an absolute configuration;

the w/w ratio being relative to the total weight of the oxidized terpenes fraction (I).

2. The composition of claim 1 , wherein said composition comprises:
from 20 to 35% w/w of the compound of formula (I-A);
from 1 to 5% w/w of the compound of formula (I-B);
from 40 to 55% w/w of the compound of formula (I-C); and
from 10 to 20% w/w of the compound of formula (I-D).

3. The composition of claim 1 , wherein said composition comprises:
a w/w % ratio (I-C)/(I-D) comprised between 4/1 and 2/1; and/or
a w/w % ratio (I-C)/(I-A) comprised between 3/1 and 1/1.

4. The composition of claim 1 , wherein said compounds (I-A), (I-B), (I-C) and (I-D) have an e.e. of at least 80%.

5. A process for the preparation of a composition of matter, as defined in claim 1 , comprising reacting:
a sesquiterpene hydrocarbons fraction (II) comprising
i) from 10 to 30% w/w of (1S,2R,4R)-2-methyl-3-methylene-2-(4-methylpent-3-en-1-yl)bicyclo[2.2.1]heptane (also known as (−)-β-santalene), of formula

wherein the bold and hatched line indicate an absolute configuration;

ii) from 1 to 6% w/w of (1S,2S,4R)-2-methyl-3-methylene-2-(4-methylpent-3-en-1-yl)bicyclo[2.2.1]heptane (also known as (+)-epi-β-santalene), of formula

wherein the bold and hatched line indicate an absolute configuration;

iii) from 20 to 50% w/w of (2S,4S,7R)-1,7-dimethyl-7-(4-methylpent-3-en-1-yl)tricyclo[2.2.1.0 2,6 ]heptane (also known as (+)-α-santalene), of formula

wherein the bold and hatched line indicate an absolute configuration; and

iv) from 20 to 40% w/w of (1S,5S,6R)-2,6-dimethyl-6-(4-methylpent-3-en-1-yl)bicyclo[3.1.1]hept-2-ene (also known as (−)-α-trans-bergamotene), of formula

wherein the bold and hatched line indicate an absolute configuration;

the w/w ratio being relative to the total weight of the sesquiterpene hydrocarbons fraction (II)
with ozone under reductive conditions.

6. The process of claim 5 , wherein said sesquiterpene hydrocarbons fraction (II) comprises:
a w/w % ratio (II-C)/(II-D) comprised between 2/1 and 1/2; and/or
a w/w % ratio (II-C)/(II-A) comprised between 3/1 and 1/1.

7. The process according to claim 5 , wherein said reductive conditions are performed with an alkaline sulfite or a C 2-6 dialkyl sulfide.

8. The process of claim 5 , wherein said sesquiterpene hydrocarbons fraction (II) is obtained in a previous step wherein a terpene synthase is contacted with farnesyl-diphosphate (FPP) to produce said sesquiterpene hydrocarbons fraction (II).

9. A method for preparing a sandalwood oil building block comprising utilizing the oxidized terpenes fraction (I) of claim 1 as a starting material for preparing a sandalwood oil building block.

10. The method of claim 9 , wherein the sandalwood oil building block is a composition of matter comprising:
a) from 20 to 35% w/w, of (−)-(Z)-β-santalol;
b) from 1 to 8% w/w, of (−)-(Z)-epi-β-santalol;
c) from 40 to 80% w/w, of (+)-(Z)-α-santalol; and
d) from 3 to 25% w/w, of (Z)-α-trans-bergamotol.

11. The method of claim 9 , wherein the sandalwood oil building block is a composition of matter comprising:
a) from 20 to 30% w/w, of (−)-(Z)-β-santalol;
b) from 2 to 6% w/w, of (−)-(Z)-epi-β-santalol;
c) from 45 to 65% w/w, of (+)-(Z)-α-santalol; and
d) from 5 to 20% w/w, of (Z)-α-trans-bergamot

Assignees

• Firmenich & Cie

Inventors

• Knopff Oliver
• Fonteny Fabien

Classifications

• C11B9/0046 Primary

  containing only two condensed rings · CPC title

• C07C47/115

  containing condensed ring systems · CPC title

• C07C47/225

  containing rings other than six-membered aromatic rings · CPC title

• C07C45/40 Primary

  by oxidation with ozone; by ozonolysis · CPC title

• C11B9/0042

  compounds containing condensed hydrocarbon rings · CPC title