NEW METHOD FOR OZONOLYSIS AND REDUCTIVE QUENCHING OF OZONIDES
The present disclosure pertains to improved methods of performing ozonolysis by reductive quenching of the intermediate ozonides using glyoxal as the reductant.
1 . A method for reductive quenching of primary and/or secondary ozonides to yield aldehyde and/or ketone products using glyoxal as the reducing agent, wherein the method comprises the step of treating an ozonide mixture (e.g., primary and/or secondary ozonides) with glyoxal (e.g., 40% aqueous glyoxal);
wherein the ozonide mixture is derived from the ozonolysis of a monounsaturated or polyunsaturated terpene, fatty acid, or fatty acid ester, or derived from the ozonolysis of an aliphatic or cyclic alkene.
2 . The method according to claim 1 , wherein the primary and/or secondary ozonides are dissolved or suspended in a solvent mixture, e.g., comprising one or more of water, a C 1-9 alkyl alcohol (e.g., tert-pentanol), C 1-12 carboxylic acid (e.g., propanoic acid, nonanoic acid), a C 1-3 alkyl C 1-12 carboxylic ester (e.g., ethyl acetate, methyl hexanoate), or a C 1-6 alkanediol (e.g., ethylene glycol), optionally an aqueous solvent mixture (e.g., water and an alcohol).
3 . The method according to claim 2 , wherein the solvent mixture does not comprise methanol, formic acid, or acetic acid.
4 . The method according to claim 2 , wherein the solvent mixture comprises water and an alcohol selected from isopropanol, s-butanol, t-butanol, isopentanol, s-pentanol, 3-methyl-2-butanol, 3-pentanol, tert-pentanol, cyclopentanol, 2-methyl-2-pentanol, and cyclohexanol.
5 . The method according to claim 2 , wherein the quenching is performed continuously on an ozonide mixture from a continuous ozonolysis operation.
6 . A method for performing ozonolysis with reductive quenching using glyoxal as the reducing agent, wherein the method comprises a first step of treating an alkene with ozone to form an ozonide mixture (e.g., primary and/or secondary ozonides), and a second step of treating the ozonide mixture from the first step with glyoxal (e.g., 40% aqueous glyoxal) to yield aldehyde and/or ketone products;
wherein the alkene is a monounsaturated or polyunsaturated terpene, fatty acid, or fatty acid ester, or wherein the alkene is an aliphatic or cyclic alkene.
7 . The method according to claim 6 , wherein the first step comprises the alkene dissolved or suspended in a solvent mixture, e.g., comprising one or more of water, a C 1-9 alkyl alcohol (e.g., tert-pentanol), C 1-12 carboxylic acid (e.g., propanoic acid, nonanoic acid), a C 1-3 alkyl C 1-12 carboxylic ester (e.g., ethyl acetate, methyl hexanoate), or a C 1 -6alkanediol (e.g., ethylene glycol), optionally an aqueous solvent mixture (e.g., water and an alcohol).
8 . The method according to claim 7 , wherein the solvent mixture does not comprise methanol, formic acid, or acetic acid.
9 . The method according to claim 7 , wherein the solvent mixture comprises water and an alcohol selected from isopropanol, s-butanol, t-butanol, isopentanol, s-pentanol, 3-methyl-2-butanol, 3-pentanol, tert-pentanol, cyclopentanol, 2-methyl-2-pentanol, and cyclohexanol.
10 . The method according to claim 6 , wherein the alkene is a monounsaturated or polyunsaturated terpene, optionally wherein the terpene is selected from pinenes, camphenes, elemenes, citronellol, citronellal, isopulegol, longifolene, isothujone, thujone, valencene, myrcene, dihydromyrcene, limonene, carvone, linalool, geraniol, terpineol, squalene, and nootkatone.
11 . The method according to claim 6 , wherein the alkene is a monounsaturated or polyunsaturated fatty acid or fatty acid ester.
12 . The method according to claim 11 , wherein the alkene is a fatty acid selected from erucic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gondonic acid, paullinic acid, nervonic acid, stearidonic acid, gamma-linolenic acid, eicosapentaenoic acid, arachidonic acid, docosatetraenonic acid, linolenic acid, linoleic acid, linoleaidic acid, myristoleic acid, sapienic acid, ricinoleic acid, and docosahexaenoic acid, or a C 3-12 alkyl ester thereof.
13 . The method according to claim 6 , wherein the alkene is a monounsaturated or polyunsaturated terpene (e.g., monoterpenes, diterpenes, sesquiterpenes).
14 . The method according to claim 13 , wherein the terpene is selected from pinenes, camphenes, elemenes, citronellol, citronellal, citronellene, methoxycitronellene (7-methoxy-3,7-dimethyloct-1-ene), hydroxycitronellene (2,6-dimethyloct-7-en-2-ol), 2,3,7-trimethyloct-7-en-2-ol, isopulegol, longifolene, isothujone, thujone, valencene, myrcene, dihydromyrcene, dihydromyrcenol, limonene, carvone, linalool, geraniol, terpineol, squalene, and nootkatone.
15 . The method according to claim 6 , wherein the alkene is an aliphatic or cyclic alkene (e.g., a monocyclic, bicyclic, or polycyclic cycloalkene), optionally monounsaturated, diunsaturated or polyunsaturated, and optionally substituted by one or more C 1-6 alkyl groups.
16 . The method according to claim 15 , wherein the alkene is selected from cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, cyclododecene, norbornene, and 2,3,4,5,6,7,8,9,10,11,12,13-dodecahydro-1H-cyclopenta[12]annulene, each optionally substituted by one or more C 1-6 alkyl groups (e.g., 2-methyl-2,3,4,5,6,7,8,9,10,11,12,13-dodecahydro-1H-cyclopenta[12]annulene).
17 . The method according to claim 6 , wherein the alkene is a fused bicyclic C 8-40 cycloalkene (e.g., C 8-40 , C 8-30 , C 8-20 , C 10-40 , C 10-30 , C 10-20 ) with a bridgehead double bond, optionally substituted by one or more C 1-6 alkyl groups, for example, a compound of the following formula:
wherein there are 0-5 groups R, and each R is independently C 1-6 alkyl, and n and m are integers independently selected from 1 to 17 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10)
18 . The method according to claim 1 , wherein the method provides one or more of nonanal, 9-oxononanoic acid, a 9-oxononanoic acid ester (e.g., C 1-6 alkyl ester) brassyl aldehyde, a brassyl aldehyde ester (e.g., C 1-6 alkyl ester), 6-hydroxy-2,6-dimethylheptanal, 6-methoxy-2,6-dimethylheptanal, and 3-methylcyclopentadecane-1,5-dione.
19 . The method according to claim 1 , wherein the method provides cyclooctane-1,5-dione, cyclononane-1,5-dione, cyclodecene-1,6-dione, cyclodecane-1,5-dione, cycloundecane-1,5-dione, cycloundecane-1,6-dione, cyclododecane-1,6-dione, cyclotridecane-1,5-dione, or cyclopentadecane-1,5-dione, each optionally substituted with 0-5 groups R (e.g., methyl).
20 . (canceled)
21 . (canceled)
22 . A product or composition comprising an aldehyde or ketone made according to the method of claim 1 .
23 . The method according to claim 1 , wherein the monounsaturated or polyunsaturated terpene is selected from the group consisting of pinenes, camphenes, elemenes, citronellol, citronellal, citronellene, methoxycitronellene (7-methoxy-3,7-dimethyloct-1-ene), hydroxycitronellene (2,6-dimethyloct-7-en-2-ol), 2,3,7-trimethyloct-7-en-2-ol, isopulegol, longifolene, isothujone, thujone, valencene, myrcene, dihydromyrcene, dihydromyrcenol, limonene, carvone, linalool, geraniol, terpineol, squalene, and nootkatone, and wherein the monounsaturated or polyunsaturated fatty acid or ester is selected from the group consisting of erucic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gondonic acid, paullinic acid, nervonic acid, stearidonic acid, gamma-linolenic acid, eicosapentaenoic acid, arachidonic acid, docosatetraenonic acid, linolenic acid, linoleic acid, and linoleaidic acid, or any ester thereof, and wherein the aliphatic or cyclic alkene is selected from cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, cyclododecene, norbornene, and 2,3,4,5,6,7,8,9,10,11,12,13-dodecahydro-1H-cyclopenta[12]annulene, each optionally substituted by one or more C 1-6 alkyl groups (e.g., 2-methyl-2,3,4,5,6,7,8,9,10,11,12,13-dodecahydro-1H-cyclopenta[12]annulene).