Preparation of 3-hydroxy-3,6-dimethylhexahydrobenzofuran-2-one and derivatives thereof

Patent metadata

Field	Value
Publication number	US-2019002424-A1
Application number	US-201615759135-A
Country	US
Kind code	A1
Filing date	Sep 12, 2016
Priority date	Sep 11, 2015
Publication date	Jan 3, 2019
Grant date	—

Abstract

The present invention relates to the synthesis of intermediate compounds which can be used in the synthesis of mint lactone and related compounds, including 3,6-dimethylhexahydrobenzofuran-2-ones, isomers, and other derivatives.

First claim

1 . A method of producing an α-hydroxylactone, comprising the steps of:
(a) forming a cyanohydrin intermediate from a hydroxy-ketone via cyanohydrin formation, wherein said cyanohydrin intermediate comprises a nitrile; and
(b) hydrolyzing and lactonizing said nitrile of said cyanohydrin intermediate in the presence of an aqueous acid to generate an α-hydroxylactone, wherein said α-hydroxylactone is 3-hydroxy-3,6-dimethylhexahydrobenzofuran-2-one.

2 . The method of claim 1 , wherein said hydroxy-ketone comprises 1-(2-hydroxy-4-methyl-cyclohexyl)ethanone).

3 . The method of claim 1 , wherein said cyanohydrin formation is performed using an aqueous mixture of a cyanide salt in the presence of ammonium chloride.

4 . The method of claim 3 , wherein said cyanide salt comprises sodium cyanide or potassium cyanide.

5 . The method of claim 3 , wherein a phase transfer catalyst is used to facilitate reaction with a nonaqueous phase during said cyanohydrin formation.

6 . The method of claim 1 , wherein the step of hydrolyzing said cyanohydrin intermediate is performed using a strong aqueous acid, wherein said aqueous acid comprises concentrated hydrochloric acid.

7 . An organoleptic compound chosen from formula (I) and formula (II) below:

optionally substituted derivatives thereof, and isomers thereof, wherein said organoleptic compound of formula (I) and formula (II) is derived from 3-hydroxy-3,6-dimethylhexahydrobenzofuran-2-one.

8 . The compound of claim 7 , wherein said organoleptic compound of formula (I) and formula (II) is used for enhancing a fragrance formulation.

9 . The compound of claim 7 , wherein said organoleptic compound of formula (I) and formula (II) is used for enhancing a flavoring formulation.

10 . A compound of general formula (III) below and/or an isomer thereof of formula (I) below and/or a polymeric derivative thereof:

wherein X is halogen, further wherein said compound is derived from an α-hydroxylactone.

11 . The compound of claim 10 , wherein said X is chlorine.

12 . A method of producing organoleptic compounds, comprising the steps of:
(a) providing an α-hydroxylactone compound having the following formula (IV):

(b) deoxygenating said α-hydroxylactone compound.

13 . The method of claim 12 , wherein said α-hydroxylactone compound is halogenated using a halogenating agent and then reduced to generate one or both of the isomers having the following formulas (V) and (VI):

14 . The method of claim 13 , wherein said α-hydroxylactone compound is deoxygenated via chlorination followed by reduction with zinc in presence of an acid.

15 . The method of claim 14 , wherein said acid is acetic acid.

16 . The method of claim 14 , wherein said chlorination is performed with thinoyl chloride or phosphorus trichloride.

17 . A method of producing isomers or derivatives of a compound having the following formula (VII):

(a) hydrogenating said compound in the presence of a base to obtain a mixture of isomers enriched with isomers comprising following formulas (VIII) through (XI):

18 . The method of claim 17 , wherein said base is introduced to said compound in advance of hydrogenation to promote ring-opening and isomerization.

19 . An organoleptic composition, comprising:
isomeric 3,6-dimethylhexahydrobenzofuran-2-one having at least 20% of a combination of isomers having following formulas (XII) and (XIII),

20 . A method of producing (R)-1-(4-methylcyclohex-1-en-1-yl)ethanone, comprising the steps of:
(a) providing a compound having the general formula (XIV):

(b) dehydrating said compound.

21 . The method of claim 20 , wherein said dehydration is catalyzed by an acid.

22 . The method of claim 21 , wherein said acid is a cationic resin.

23 . The method of claim 21 , wherein said dehydration is performed continuously.

24 . The method of claim 21 , wherein said dehydration is performed at an elevated temperature.

25 . The method of claim 24 , wherein said temperature is between 80° C. and 140° C.

26 . A method of producing mint lactone, comprising the steps of:
(a) providing an α-hydroxylactone of general formula (XV):

(b) eliminating the hydroxyl group of said α-hydroxylactone.

27 . The method of claim 26 , wherein the step of eliminating the hydroxyl group is performed by halogenating said α-hydroxylactone, and eliminating the halogen.

28 . The method of claim 26 , wherein the step of eliminating the hydroxyl group is performed using a strong acid at an elevated temperature.

29 . The method of claim 28 , wherein said strong acid is a phosphoric acid.

Assignees

• P2 Science Inc

Inventors

• Foley Patrick
• Yang Yonghua
• Salam Tania

Classifications

• C07C45/66

  by dehydration · CPC title

• A23V2002/00

  Food compositions, function of food ingredients or processes for food or foodstuffs · CPC title

• A23L27/88

  Taste or flavour enhancing agents · CPC title

• C07D307/83 Primary

  Oxygen atoms · CPC title

• A61K8/4973

  with oxygen as the only hetero atom · CPC title