Substituted delta-lactones and methods of preparing same
The invention relates to substituted delta-lactones as well as to processes for synthesizing them, e.g., using fatty acids as starting material.
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.
18. The method of claim 11 , wherein the reaction of the compound of formula VI with ozone is carried out in the presence of a solvent.
19. The method of claim 11 , wherein the reaction of the compound having the formula VI with ozone is carried out in the absence of a solvent.
20. A compound of formula I produced by the method of claim 1 .
21. A compound of formula V produced by the method of claim 11 .
22. The method 13 , wherein the compound of Formula VI is a fatty acid ester wherein R 5 is unsubstituted C 14 alkyl.