Method for preparing an insect repellent agent

Patent metadata

Field	Value
Publication number	US-12096770-B2
Application number	US-202017625928-A
Country	US
Kind code	B2
Filing date	Jul 10, 2020
Priority date	Jul 10, 2019
Publication date	Sep 24, 2024
Grant date	Sep 24, 2024

Abstract

The present invention relates to a method for preparing p-menthane-3,8-diol, characterised in that it comprises the following steps:
a. preparation of an aqueous solution comprising between 0.05% and 5% by mass, preferably between 0.05% and 2% by mass, preferentially between 0.05% and 1% by mass, even more preferentially between 0.05% and 0.5% by mass of an ammonium salt, the said ammonium salt being characterised in that it is selected from the group formed by an amino acid ammonium salt, and in particular an amino acid hydrochloride, a vitamin B ammonium salt, and in particular a vitamin B hydrochloride, an ammonium salt of an amino acid ester, and an ammonium salt of a vitamin B ester, or is defined by the following formula (I):

wherein R 1 represents a benzyl, optionally substituted, or R 1 represents an alkyl, either linear or branched, optionally cyclical, saturated or unsaturated, optionally substituted, comprising from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms, preferentially from 2 to 4 carbon atoms, and R 2 , R 3 and R 4 represent a hydrogen or a methyl group, and X represents a chlorine atom, bromine atom or an OR′ group, R′ being an alkyl group comprising from 1 to 10 carbon atoms,
b. adding of citronellal to the aqueous solution obtained in the step a), and obtaining a mixture;
c. stirring and heating of the mixture obtained in the step b);
d. decanting of the reaction medium obtained at the end of step c) and obtaining at least two phases; and
e. separation of the said at least two phases obtained in the step d), and obtaining at least one aqueous phase and at least one organic phase, the said organic phase comprising at least p-menthane-3,8-diol.

First claim

The invention claimed is:

1. A method for preparing p-menthane-3,8-diol, comprising the following steps:
a. preparing an aqueous solution comprising between 0.05% and 5% by mass of an ammonium salt, said ammonium salt being selected from the group consisting of an amino acid ammonium salt, a vitamin B ammonium salt, an ammonium salt of an amino acid ester, and an ammonium salt of a vitamin B ester, or is defined by the following formula (I):

wherein R 1 represents a benzyl, optionally substituted, or R 1 represents an alkyl, either linear or branched, optionally cyclical, saturated or unsaturated, optionally substituted, comprising from 1 to 10 carbon atoms, and R 2 , R 3 and R 4 represent a hydrogen or a methyl group, and X represents a chlorine atom, bromine atom or an OR′ group, R′ being an alkyl group comprising from 1 to 10 carbon atoms;
b. adding of citronellal to the aqueous solution obtained in the step a), and obtaining a mixture;
c. stirring and heating of the mixture obtained in the step b);
d. decanting of the reaction medium obtained at the end of step c) and obtaining at least two phases; and
e. separating said at least two phases obtained in the step d), to obtain at least one aqueous phase and at least one organic phase, said organic phase comprising at least p-menthane-3,8-diol.

2. The method according to claim 1 , wherein the amino acid ammonium salt derivative comprises at least one COOR ester functional group, R being an alkyl, either linear or branched, comprising from 1 to 10 carbon atoms.

3. The method according to claim 1 , wherein the amino acid ammonium salt is selected from the group consisting of hydrochlorides of histidine, guanine and glycine.

4. The method according to claim 1 , wherein the group R 1 is a saturated linear alkyl group, comprising from 1 to 10 carbon atoms, and further comprising a carboxylic acid functional group.

5. The method according to claim 1 , wherein the ammonium salt is selected from the group consisting of O-methylated histidine dihydrochloride, guanine hydrochloride, O-methylated glycine hydrochloride, vitamin B1 dihydrochloride, vitamin B6 hydrochloride, and 2-trimethylammonioacetate hydrochloride.

6. The method according to claim 1 , wherein the citronellal is used in the form of an essential oil.

7. The method according to claim 1 wherein the organic phase obtained at the end of step e) further comprises at least one compound selected from the group consisting of citronellal, isopulegol and an acetal, said acetal being produced by reaction between citronellal and p-menthane-3,8-diol.

8. The method according claim 1 , wherein the organic phase obtained at the end of step e) further comprises at least one compound selected from the group consisting of linalool, citronellol and geraniol.

9. The method according to claim 1 , wherein the method further comprises a step f) of adding at least one compound selected from the group consisting of citronellol, geraniol, terpineol and caryophyllene to the organic phase comprising p-menthane-3,8-diol obtained in the step e).

10. A composition obtained by the method according to claim 1 , comprising: at least 70 mole % of p-menthane-3,8-diol relative to the total number of moles of the composition; citronellal and an acetal; and optionally isopulegol; said acetal being produced by reaction between citronellal and p-menthane-3,8-diol.

11. The composition according to claim 10 , wherein the composition comprises from 70 to 98 mole % of p-menthane-3,8-diol.

12. The composition according to claim 10 , wherein the composition comprises, relative to the total number of moles of the composition:
from 70 to 98 mole % of p-menthane-3,8-diol;
from 0.1 to 40 mole % of citronellal;
from 0.1 to 20 mole % of acetal; and optionally
from 1 to 30 mole % of isopulegol.

13. The composition according to claim 10 , wherein the composition further comprises from 0.1 to 10 mole % of terpineol.

14. The composition according to claim 10 , wherein the composition further comprises from 0.1 to 10 mole %.

15. The composition according to claim 10 , wherein the composition further comprises from 0.1 to 15 mole % of linalool.

16. The composition according to claim 10 , wherein the composition further comprises from 0.1 to 40 mole % of citronellol.

17. The composition according to claim 10 , wherein the composition further comprises from 0.1 to 40 mole % of geraniol.

18. Method of repelling at least one hematophagous arthropod from a target of the hematophagous arthropod, comprising applying on said target the composition according to claim 10 .

19. The method according to claim 18 , wherein the hematophagous arthropod is selected from the group consisting of mosquitoes, ticks and midges.

20. The method according to claim 18 , wherein the hematophagous arthropod is a mosquito.

Assignees

• Centre Nat Rech Scient
• Univ Montpellier
• Centre Nat Rech Scient

Inventors

• Grison Claude
• Stanovych Andrii

Classifications

• C07C29/86

  by liquid-liquid treatment · CPC title

• C07C29/56

  by isomerisation · CPC title

• A01N31/04

  Oxygen or sulfur attached to an aliphatic side-chain of a carbocyclic ring system · CPC title

• A01N31/02

  Acyclic compounds · CPC title

• A01N27/00

  Biocides, pest repellants or attractants, or plant growth regulators containing hydrocarbons · CPC title