Process

Patent metadata

Field	Value
Publication number	US-2025353805-A1
Application number	US-202218716728-A
Country	US
Kind code	A1
Filing date	Dec 20, 2022
Priority date	Dec 22, 2021
Publication date	Nov 20, 2025
Grant date	—

Abstract

Described herein are methods for making intermediates useful in the production of fragrance ingredients starting from myrcene. In particular, methods for making geranyl chloride, (E)-6,10-dimethylundeca-1,5,9-triene and (E)-6,10-dimethylundeca-5,9-dien-1-yne are described. Methods for making other intermediates in the process are also described.

First claim

1 . A method producing a purified form of geranyl chloride, a compound of Formula (I),

wherein the method comprises:
(i) a halogenation step comprising chlorinating a compound of Formula (II)

 with
 a) a chloroformate to produce a first reaction mixture comprising a compound of Formula (I) and a carbamate, or
 b) an acid chloride to produce a first reaction mixture comprising a compound of Formula (I) and an amide,
and
(ii) a distillation step, the distillation step comprising distilling a mixture comprising the first reaction mixture to produce a separated portion of the distillation mixture comprising a purified form of the compound of Formula (I) as compared to the first reaction mixture; and
wherein Q is a a monovalent residue selected from N(methyl) 2 , N(ethyl) 2 , N(n-propyl) 2 , N(isopropyl) 2 , N(benzyl) 2 , N(CH 3 )CH 2 CH 2 NR 2 (CH 3 ), N-methyl-N-ethyl-amine,

and wherein
n is selected from 1, 3 and 4; and
A is selected from O and NR 2 wherein R 2 is selected from H and geranyl

2 . The method of claim 1 wherein the chloroformate is a compound of the Formula (VI),

wherein R′ is selected from C 1 -C 6 alkyl groups which may be optionally substituted, such that the carbamate has the formula Q-C(═O)OR′.

3 . The method of claim 1 wherein the acid chloride is a compound of Formula (VII),

wherein R″ is selected from selected from Cl, —C(O)Cl, phenyl wherein the phenyl ring is optionally substituted with one group selected from methyl, methoxy, halogen, C 1 -C 10 alkyl (linear or branched) and —C(O)Cl, bicyclic aromatic systems and tricyclic aromatic systems, such sat the amide has the formula Q-C(═O)R″.

4 . The method of any one of claims 1 to 2 wherein carbamate has a higher boiling point than the compound of Formula (I) and the compound of Formula (I) is distilled from distillation mixture into one or more distillate fractions.

5 . The method of any one of claims 1 to 2 wherein the carbamate has a lower boiling point than the compound of Formula (I) and the carbamate is distilled from the distillation mixture into one or more distillate fractions.

6 . The method of any preceding claim wherein the separated portion has a higher molar or weight ratio of the compound of Formula (I) to carbamate than the molar or weight ratio, respectively, of the compound of Formula (I) to carbamate in the first reaction mixture.

7 . A method of producing a compound of Formula (IV),

wherein the method comprises:
(i) a halogenation step comprising chlorination of a compound of Formula (II) with
a) a chloroformate to produce a first reaction mixture comprising a compound of Formula (I) and a carbamate, or
b) an acid chloride to produce a first reaction mixture comprising a compound of Formula (I) and an amide

 wherein Q is a a monovalent residue selected from N(methyl) 2 , N(ethyl) 2 , N(n-propyl) 2 , N(isopropyl) 2 , N(benzyl) 2 , N(CH 3 )CH 2 CH 2 NR 2 (CH 3 ), N-methyl-N-ethyl-amine,

 and wherein
 n is selected from 1, 3 and 4; and
 A is selected from O and NR 2 wherein R 2 is selected from H and geranyl;
and
(ii) a distillation step, the distillation step comprising distilling a mixture comprising the first reaction mixture to produce a separated portion of the distillation mixture comprising a purified form of the compound of Formula (I) as compared to the first reaction mixture; and
(iii) contacting the separated portion with a nucleophile to produce a compound of formula (IV) wherein R 1 is selected from furyl, phenyl, C 1 -C 10 alkyl, C 2 -C 10 alkyl comprising at least one double bond or triplet bond, C 1 -C 10 alkyl-OH, C 2 -C 10 alkyl-OH comprising at least one double bond or one triplet bond, and —CH 2 -C≡C-Si-(R 3 ) 3 wherein each R 3 is selected independently from C 1 -C 5 alkyl.

8 . The method of claim 7 wherein the chloroformate is a compound of the Formula (VI),

wherein R′ is selected from C 1 -C 6 alkyl groups which may be optionally substituted, such that the carbamate has the formula Q-C(═O)OR′.

9 . The method of claim 7 wherein the acid chloride is a compound of Formula (VII),

wherein R″ is selected from selected from selected from Cl, —C(O)Cl, phenyl wherein the phenyl ring is optionally substituted with one group selected from methyl, methoxy, halogen, C 1 -C 10 alkyl and —C(O)Cl, bicyclic aromatic systems and tricyclic aromatic systems, such that the amide has the formula Q-C(═O) ″.

10 . The method of claim 7 , wherein the nucleophile is an organometallic reagent, for example, an allyl magnesium halide or an alkynyllithium.

11 . The method of claim 7 , wherein the produced compound of Formula (IV) is a compound selected from 6,10-dimethylundeca-5,9-dien-1-yne (e.g. (E)-6,10-dimethylundeca-5,9-dien-1-yne) and 6,10-dimethylundeca-1,5,9-triene (e.g. (E)-6,10-dimethylundeca-1,5,9-triene).

12 . A compound of Formula (I),

obtained by or obtainable by a method of any of claims 1 to 6 .

13 . A compound of Formula (IV),

obtained or obtainable by a method of any one of claims 7 to 11 .

14 . A compound of claim 13 , wherein the compound is selected from 6,10-dimethylundeca-5,9-dien-1-yne (e.g. (E)-6,10-dimethylundeca-5,9-dien-1-yne) and 6,10-dimethylundeca-1,5,9-triene (e.g. (E)-6,10-dimethylundeca-1,5,9-triene).

Assignees

• Givaudan Sa

Inventors

• Schroeder Fridtjof
• Lovchik Martin

Classifications

• C07C7/04

  by distillation · CPC title

• C07C1/326

  the hetero-atom being a magnesium atom · CPC title

• C07C2/86

  by condensation between a hydrocarbon and a non-hydrocarbon · CPC title

• C07C17/093

  by replacement by halogens · CPC title

• C07C17/383 Primary

  by distillation · CPC title