Oxidation of santalene to santalol
AssigneeIsobionics B.V.
InventorsDominique Callant, Paul Alsters, Karin Dautzenberg, Angela Gonzalez De Castro, Robert Trokowski
Life of this patent
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Abstract
The invention relates to a process for the oxidation of santalene to santalol. The starting material is in particular a mixture comprising alpha-santalene, beta-santalene, epi-beta-santalene, trans-alpha-bergamotene and beta-bisabolene. The oxidation of the santalenes occurs via an intermediate chloro-santalene compound. Substitution of the chloro-substituent by acetate yielded the mixture of the corresponding santalyl acetates, which were hydrolyzed to yield the corresponding mixture of santalols.
Claims12
A process for the synthesis of a mixture of compounds of Formula (Ia), Formula (Ib), Formula (Ic), Formula (Id) and Formula (Ie),
- wherein R=a, b, c, d or e;
- and wherein Formula (Ia) corresponds to Formula (I) where R is a, Formula (Ib) corresponds to Formula (I) where R is b, Formula (Ic) corresponds to Formula (I) where R is c, Formula (Id) corresponds to Formula (I) where R is d, and Formula (Ie) corresponds to Formula (I) where R is e,
- the method comprising
- (1) chlorinating a mixture of compounds of Formula (II) by combining the starting compounds of Formula (II) with an acid and an aqueous NaOCl solution, wherein the mixture of compounds of Formula (II) comprises the compounds of Formula (IIa), Formula (IIb), Formula (IIc), Formula (IId) and Formula (IIe)
- wherein Formula (IIa) corresponds to Formula (II) where R is a, Formula (IIb) corresponds to Formula (II) where R is b, Formula (IIc) corresponds to Formula (II) where R is c, Formula (IId) corresponds to Formula (II) where R is d, and Formula (IIe) corresponds to Formula (II) where R is e,
- to a mixture of intermediates of Formula (IIIa), Formula (IIIb), Formula (IIIc) and Formula (IIIe) and a di-chlorinated and/or a tri-chlorinated analogue of intermediate of Formula (IIId)
- wherein Formula (IIIa) corresponds to Formula (III) where R is a, Formula (IIIb) corresponds to Formula (III) where R is b, Formula (IIIc) corresponds to Formula (III) where R is c, Formula (IIId) corresponds to Formula (III) where R is d, and Formula (Ille) corresponds to Formula (III) where R is e,
- wherein the chlorinating step comprises
- converting the starting compounds of Formula (IIa), Formula (IIb), Formula (IIc) and Formula (IIe) to the intermediates of Formula (IIIa), Formula (IIIb), Formula (IIIc) and Formula (IIIe);
- and
- introducing two or three chloro-substituents on the starting compound of Formula (IId) to yield the di-chlorinated and/or tri-chlorinated analogue of the intermediate of Formula (IIId);
- conversion of (2) converting a mixture of intermediates of Formula (IIIa), Formula (IIIb), Formula (IIIc) and Formula (IIIe) to a mixture of compounds of Formula (Ia), Formula (Ib), Formula (Ic) and Formula (Ie) by
- reacting the intermediate of Formula (III) with a carboxylate R′—COO− to form the corresponding carboxylate ester of Formula (IV), wherein the carboxylate is selected from the group consisting of acetate, formate, propionate, butyrate, valerate, benzoate, pivalate, and mixtures thereof
- and hydrolyzing the carboxylate ester of Formula (IV) to obtain the mixture of compounds of Formula (Ia), Formula (Ib), Formula (Ic) and Formula (Ie),
- wherein the di-chlorinated and/or tri-chlorinated analogue of the intermediate of Formula (IIId) is removed from the mixture prior to or during the conversion of intermediates of Formula (IIIa), Formula (IIIb), Formula (IIIc), and Formula (IIIe) to the mixture of compounds of Formula (Ia), Formula (Ib), Formula (Ie) and Formula (Ie).
A compound of Formula (III)
- wherein R=e;
A mixture of compounds of Formula (III) comprising compound of Formula (IIIa), compound of Formula (IIIb), compound of Formula (IIIc) and compound of Formula (IIIe) and comprising a di-chlorinated and/or a tri-chlorinated analogue of the intermediate of Formula (IIId)
- wherein R=a, b, c, d or e:
Dependencies are inferred from the claim text.