Substituted delta-lactones and methods of preparing same

Patent metadata

Field	Value
Publication number	US-10011582-B2
Application number	US-201515119539-A
Country	US
Kind code	B2
Filing date	Feb 18, 2015
Priority date	Feb 19, 2014
Publication date	Jul 3, 2018
Grant date	Jul 3, 2018

Abstract

The invention relates to substituted delta-lactones as well as to processes for synthesizing them, e.g., using fatty acids as starting material.

First claim

What is claimed is:

1. A method of producing a compound of formula A,

wherein the is a single bond or a double bond and R A is unsubstituted or substituted C 1 -C 10 alkyl, unsubstituted or substituted C 3 -C 20 cycloalkyl, unsubstituted or substituted C 2 -C 10 alkenyl, or unsubstituted or substituted aryl; the method comprising:
(i) when the compound of formula A is of formula I:

reacting a compound of formula II:

with ozone to obtain a compound of formula III;

wherein R 1 is unsubstituted or substituted C 1 -C 10 alkyl, unsubstituted or substituted C 3 -C 20 cycloalkyl, unsubstituted or substituted C 2 -C 10 alkenyl, or unsubstituted or substituted aryl and R 2 is H, unsubstituted or substituted C 1 -C 20 alkyl, or unsubstituted or substituted C 2 -C 20 alkenyl;
reacting the compound of formula III with a compound of formula IV:

in the presence of a metal to produce a reaction mixture, wherein Y is halo and R 3 is unsubstituted or substituted C 1 -C 20 alkyl unsubstituted or substituted C 2 -C 20 alkenyl, or unsubstituted or substituted aryl; and
optionally treating the reaction mixture with an acid and/or heat to obtain the compound of formula I wherein R 1 is unsubstituted or substituted C 1 -C 10 alkyl, unsubstituted or substituted C 3 -C 20 cycloalkyl, unsubstituted or substituted C 2 -C 10 alkenyl, or unsubstituted or substituted aryl; or alternatively,

(ii) when the compound of formula A is of formula V:

reacting a compound of formula VI

with ozone to obtain a compound of formula VII;

wherein R 5 is unsubstituted or substituted C 1 -C 20 alkyl or unsubstituted or substituted C 2 -C 20 alkenyl and R 6 is unsubstituted or substituted C 1 -C 10 alkyl;
reacting the compound of formula VII with a compound of formula VIII: R 4 —X (VIII) in the presence of a metal to produce a reaction mixture, wherein X is halo and R 4 is unsubstituted or substituted C 1 -C 10 alkyl, unsubstituted or substituted C 3 -C 20 cycloalkyl, unsubstituted or substituted C 2 -C 10 alkenyl, or unsubstituted or substituted aryl; and
optionally treating the reaction mixture with an acid and/or heat to obtain the compound of formula V wherein R 4 is unsubstituted or substituted C 1 -C 10 alkyl, unsubstituted or substituted C 3 -C 20 cycloalkyl, unsubstituted or substituted C 2 -C 10 alkenyl, or unsubstituted or substituted aryl.

2. The method of claim 1 , wherein the compound of formula A is of formula I wherein R 1 is unsubstituted or substituted C 1 -C 10 alkyl, unsubstituted or substituted C 3 -C 20 cycloalkyl, unsubstituted or substituted C 2 -C 10 alkenyl, or unsubstituted or substituted aryl, and the method comprises:
reacting a compound of formula II:

with ozone to obtain a compound of formula III;

wherein R 1 is unsubstituted or substituted C 1 -C 10 alkyl, unsubstituted or substituted C 3 -C 20 cycloalkyl, unsubstituted or substituted C 2 -C 10 alkenyl, or unsubstituted or substituted aryl and R 2 is H, unsubstituted or substituted C 1 -C 20 alkyl, or unsubstituted or substituted C 2 -C 20 alkenyl;
reacting the compound of formula III with a compound of formula IV:

in the presence of a metal to produce a reaction mixture, wherein Y is halo and R 3 is unsubstituted or substituted C 1 -C 20 alkyl unsubstituted or substituted C 2 -C 20 alkenyl, or unsubstituted or substituted aryl; and
optionally treating the reaction mixture with an acid and/or heat to obtain the compound of formula I.

3. The method of claim 2 , R 1 is unsubstituted C 1 -C 10 alkyl or unsubstituted C 2 -C 10 alkenyl.

4. The method of claim 2 , wherein R 2 is C 1 -C 10 alkyl or C 2 -C 10 alkenyl, each substituted with COOR a , in which R a is H or unsubstituted or substituted C 1 -C 10 alkyl.

5. The method of claim 2 , wherein the compound of formula II is ricinoleic acid or an ester thereof.

6. The method of claim 2 , wherein the compound of formula III is 3-hydroxynonanal or 3-(R)hydroxynonanal.

7. The method of claim 2 , wherein the compound of formula I is 6-hexyl-5,6-dihydro-2H-pyran-2-one or (R)-6-hexyl-5,6-dihydro-2H-pyran-2-one.

8. The method of claim 2 , wherein the compound of formula IV is ethyl bromoacetate or ethyl chloroacetate.

9. The method of claim 2 , wherein the reaction of the compound of formula II with ozone is carried out in the presence of a solvent.

10. The method of claim 2 , wherein the reaction of the compound having the formula II with ozone is carried out in the absence of a solvent.

11. The method of claim 1 , wherein the compound of formula A is of formula V wherein R 4 is unsubstituted or substituted C 1 -C 10 alkyl, unsubstituted or substituted C 3 -C 20 cycloalkyl, unsubstituted or substituted C 2 -C 10 alkenyl, or unsubstituted or substituted aryl, and the method comprises:
reacting a compound of formula VI

with ozone to obtain a compound of formula VII;

wherein R 5 is unsubstituted or substituted C 1 -C 20 alkyl or unsubstituted or substituted C 2 -C 20 alkenyl and R 6 is unsubstituted or substituted C 1 -C 10 alkyl;
reacting the compound of formula VII with a compound of formula VIII: R 4 —X (VIII) in the presence of a metal to produce a reaction mixture, wherein X is halo and R 4 is unsubstituted or substituted C 1 -C 10 alkyl, unsubstituted or substituted C 3 -C 20 cycloalkyl, unsubstituted or substituted C 2 -C 10 alkenyl, or unsubstituted or substituted aryl; and
optionally treating the reaction mixture with an acid and/or heat to obtain the compound of formula V.

12. The method of claim 11 , wherein R 4 is unsubstituted C 1 -C 10 alkyl or unsubstituted C 2 -C 10 alkenyl.

13. The method of claim 11 , wherein the compound of formula VI is a fatty acid ester.

14. The method of claim 13 , wherein the compound of formula VI is a component of meadowfoam seed oil.

15. The method of claim 11 , wherein the compound of formula VII is methyl 5-oxopentanoate.

16. The method of claim 11 , wherein the compound of formula V is 6-allyltetrahydro-2H-pyran-2-one.

17. The method of claim 11 , wherein the compound of formula VIII is 3-bromoprop-1-ene or 3-chloroprop-1-ene.

Assignees

• P2 Science Inc

Inventors

• Foley Patrick
• Yang Yonghua

Classifications

• C07D309/32 Primary

  having two double bonds between ring members or between ring members and non-ring members · CPC title

• C07D309/30

  Oxygen atoms, e.g. delta-lactones · CPC title