Synthesis of aliphatic alcohols as aroma chemicals

Patent metadata

Field	Value
Publication number	US-11286224-B2
Application number	US-201816755308-A
Country	US
Kind code	B2
Filing date	Oct 4, 2018
Priority date	Oct 13, 2017
Publication date	Mar 29, 2022
Grant date	Mar 29, 2022

Abstract

The present invention relates to a method for preparing a compound of formula (I). The present invention also relates to compounds of formula (A) or a compound in the form of a stereoisomer. The present invention further relates to the use of a compound of formula (A) as aroma chemical.

First claim

The invention claimed is:

1. A method for preparing a compound of formula (I)

wherein
is a single or a double bond,
wherein formula (I) comprises
the compound of the formula (Ia)

the compound of the formula (Ib)

and
the compound of the formula (Ic)

and stereoisomers thereof;
whereby m is 0; R 1 , R 3 , R 4 and R 5 , identical or different, are selected from the group consisting of H, C 1 -C 4 -alkyl and C 3 -C 4 -cycloalkyl;
whereby m is 1, 2 or 3 and R 1 , R 2 , R 3 , R 4 and R 5 , identical or different, are selected from the group consisting of H, C 1 -C 4 -alkyl and C 3 -C 4 -cycloalkyl;
comprising at least the steps of:
a) providing a compound of formula (IIa),

whereby m is 0; R 3 , R 4 and R 5 , identical or different, are selected from the group consisting of H, C 1 -C 4 -alkyl and C 3 -C 4 -cycloalkyl;
whereby m is 1, 2 or 3; R 2 , R 3 , R 4 and R 5 , identical or different, are selected from the group consisting of H, C 1 -C 4 -alkyl and C 3 -C 4 -cycloalkyl;
b) subjecting the compound of the formula (IIa) to a compound selected from peroxyacids and peroxides to obtain a compound of formula (IIb),

c) reacting the compound of the formula (IIb) with a compound of formula (IIc),
R 1 CH 2 MgX  formula (IIc),

wherein R 1 is selected from the group consisting of H, C 1 -C 4 -alkyl and C 3 -C 4 -cycloalkyl; X is Br, Cl or I, to obtain a compound of formula (IId),

whereby m is 0; R 1 , R 3 , R 4 and R 5 , identical or different, are selected from the group consisting of H, C 1 -C 4 -alkyl and C 3 -C 4 -cycloalkyl;
whereby m is 1, 2 or 3 and R 1 , R 2 , R 3 , R 4 and R 5 , identical or different, are selected from the group consisting of H, C 1 -C 4 -alkyl and C3-C4-cycloalkyl;
d) subjecting the compound of formula (IId) to a dehydration reaction to obtain the compound of the formula (I).

2. The method of claim 1 for preparing compound of formula (I′)

wherein
is a single or a double bond,
wherein formula (I′) comprises
the compound of the formula (Ia′)

the compound of the formula (Ib′)

and
the compound of the formula (Ic′)

and stereoisomers thereof;
wherein R 1 , R 2 , R 3 , R 4 and R 5 , identical or different, are selected from the group consisting of H, C 1 -C 4 -alkyl and C 3 -C 4 -cycloalkyl;
comprising at least the steps of:
a) providing a compound of formula (IIa′),

wherein R 2 , R 3 , R 4 and R 5 , identical or different, are selected from the group consisting of H, C 1 -C 4 -alkyl and C 3 -C 4 -cycloalkyl;
b) subjecting the compound of the formula (IIa′) to a compound selected from peroxyacids and peroxides to obtain a compound of formula (IIb′),

c) reacting the compound of the formula (IIb′) with a compound of formula (IIc′),
R 1 CH 2 MgX  formula (IIc′),

wherein R 1 is selected from the group consisting of H, C 1 -C 4 -alkyl and C 3 -C 4 -cycloalkyl; X is Br, Cl or I, to obtain a compound of formula (IId′),

wherein R 1 , R 2 , R 3 , R 4 and R 5 , identical or different, are selected from the group consisting of H, C 1 -C 4 -alkyl and C 3 -C 4 -cycloalkyl;
d) subjecting the compound of formula (IId′) to a dehydration reaction to obtain the compound of the formula (I′).

3. The process according to the claim 1 , wherein steps (b), (c) and (d) and/or steps (b) and (c) and/or steps (c) and (d) are carried out in a single pot.

4. The process according to the claim 1 , wherein the peroxyacid in step b) is selected from the group consisting of peroxymonosulfuric acid, peroxyphosphoric acid, peroxyacetic acid, peroxyformic acid, peroxytrifluoroacetic acid, potassium peroxymonosulfate, sodium perborate, peroxynitric acid and peroxybenzoic acid.

5. The process according to the claim 4 , wherein the peroxybenzoic acid is metachloroperoxybenzoic acid.

6. The process according to the claim 1 , wherein the peroxide in step b) is selected from the group consisting of hydrogen peroxide.

7. The process according to claim 1 , wherein step d) is carried out in the presence of an acid.

8. The process according to claim 7 , wherein the acid is selected from the group consisting of methanesulfonic acid, phosphoric acid, p-toluenesulfonic acid, formic acid, sulfuric acid, hydrochloric acid and acetic acid.

9. A compound of the formula (A.a2), (A.b2), (A.c2), (A.a3), (A.b3) or (A.c3),

and stereoisomers thereof.

10. A composition comprising at least one compound selected from the mixture of compounds of the formulae (A.a2), (A.b2), (A.c2), (A.a3), (A.b3) or (A.c3) according to claim 9 .

11. An aroma the compound of the formula A

wherein
is a single or a double bond,
wherein formula A comprises
the compound of the formula (A.a),

the compound of the formula (A.b),

and
the compound of the formula (A.c)

wherein R 1 , R 2 and R 5 , identical or different, are selected from the group consisting of H, C 1 -C 4 -alkyl and C 3 -C 4 -cycloalkyl;
R 4 is selected from the group consisting of H, C 2 -C 4 -alkyl and C 3 -C 4 -cycloalkyl;
R 3 is H;
and stereoisomers thereof, with a proviso that when R 1 is H or methyl then at least one of the R 2 , R 4 and R 5 is not H.

12. The use aromatic chemical according to claim 11 , wherein
i) the at least one compound selected from the compound of the formulae (A.a1), (A.b1) and (A.c1), is used for preparing a fragrance and/or aroma having a n

Assignees

• Basf Se

Inventors

• Hickmann Volker
• Hindalekar Shrirang
• Gupte Nitin
• Ardekar Sadanand
• Siegel Wolfgang
• Swaminathan Vijay Narayanan
• Pelzer Ralf

Classifications

• C07B2200/09

  Geometrical isomers · CPC title

• C07C33/025 Primary

  with only one double bond · CPC title

• C07D313/04

  not condensed with other rings · CPC title

• C11B9/0015

  containing oxygen as the only heteroatom · 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