Process for preparing procyanidin(4-6 or 4-8) oligomers and their derivatives
AssigneeMars, Incorporated
InventorsLeo J. Romanczyk, Jr., Alan P. Kozikowski, Werner Tueckmantel
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Abstract
A process is disclosed for the production of polyphenol oligomers having n polyphenol monomers, n being an integer from 2-18. The process includes coupling of a protected polyphenol, having protected phenolic hydroxyl groups, with a C-4 functionalized polyphenol monomer. The protected polyphenol may be a protected polyphenol monomer or a protected polyphenol oligomer having 2-17 monomers. Advantageously, polyphenol monomers forming the polyphenol oligomers may be the same or different.
Claims17
A process for the preparation of a procyanidin (4→8) dimer, comprising the steps of:
- (a) protecting each phenolic hydroxyl group of an epicatechin monomer to form a protected epicatechin monomer,
- (b) oxidizing the 4-position of the protected epicatechin monomer to form a protected dimer derivatized at the 4-position with a C2-C6 alkoxy group having a terminal hydroxy group;
- (c) coupling the derivatized, protected epicatechin monomer with a protected catechin monomer or protected epicatechin monomer to form a protected procyanidin (4→8) dimer;
- and
- (d) deprotecting the protected procyanidin (4→8) dimer.
A process for the preparation of a procyanidin (4→8) oligomer, having n monomeric units, where n is 3 to 18, which process comprises the steps of:
- (a) protecting each phenolic hydroxyl group of an epicatechin monomer to form a protected epicatechin monomer;
- (b) oxidizing the 4-position of the protected epicatechin monomer to form a protected epicatechin monomer derivatized at the 4-position with a C2-C6 alkoxy group having a terminal hydroxyl group;
- (c) coupling the derivatized, protected epicatechin monomer with a protected catechin monomer or a protected epicatechin monomers to form a protected procyanidin (4→8) dimer;
- (d) coupling additional protected epicatechin monomer(s) derivatized at the 4-position with a C2-C6 alkoxy group having a terminal hydroxyl group, or additional protected catechin monomers derivatized at the 4-position with a C2-C6 alkoxy group having a terminal hydroxyl group to form a protected procyanidin (4→8) oligomer having the desired number of monomeric units;
- and
- (e) deprotecting the protected procyanidin (4→8) oligomer.
A process for the preparation of a procyanidin (4→6) dimer, comprising the steps of:
- (a) protecting each phenolic hydroxyl group of an epicatechin monomer to form a protected epicatechin monomer;
- (b) oxidizing the 4-position of the protected epicatechin monomer to form a protected epicatechin monomer derivatized at the 4-position with a C2-C6 alkoxy group having a terminal hydroxyl group;
- (c) blocking the 8-position of a protected catechin monomer or of a protected epicatechin monomer by introducing a halogen;
- (d) coupling the derivatized, protected epicatechin monomer with the blocked, protected catechin monomer or the blocked, protected epicatechin monomer to form a blocked, protected procyanidin (4→6) dimer;
- and
- (e) deblocking and deprotecting the procyanidin (4→6) dimer to form the (4→6) dimer.
A process for the preparation of a procyanidin (4→6) oligomer, having n monomeric units, where n is 3-18, which process comprises the steps of:
- (a) protecting each phenolic hydroxyl group of an epicatechin monomer to form a protected epicatechin monomer;
- (b) oxidizing the 4-position of the blocked, protected epicatechin monomer to form a protected epicatechin monomer derivatized at the 4-position with a C2-C6 alkoxy group having a terminal hydroxyl group;
- (c) blocking the 8-position of a protected catechin monomer or of a protected epicatechin monomer by introducing a halogen;
- (d) coupling the derivatized, blocked, protected epicatechin monomer with a blocked, protected catechin monomer or with a blocked, protected epicatechin monomer to form a blocked, protected procyanidin (4→6) dimer;
- (e) coupling the blocked, protected epicatechin dimer with additional blocked, protected epicatechin monomers (a) derivatized at the 4-position with a C2-C6 alkoxy group having a terminal hydroxyl group or with additional blocked, protected catechin monomer(s) derivatized at the 4-position with a C2-C6 alkoxy group having a terminal hydroxyl group to form a blocked, protected procyanidin (4→6) oligomer having the desired number of monomeric units;
- and
- (f) deblocking and deprotecting the blocked, protected procyanidin (4→6) oligomer.
The process of 7, wherein the protic acid is hydrochloric acid.
The process of 7, wherein the Lewis acid is selected from the group consisting of:
- titanium tetrahalides, aluminum trihalides, boron trihalides and triaryl silyls.
Dependencies are inferred from the claim text.