US4623721A
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Synthesis of L-fructose and derivatives thereof
Assignee: Purdue Research Foundation
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Filing: 1984-05-23
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Granted: 1986-11-18
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Expires: 2004-05-23
Abstract
Abstract It is disclosed that L-fructose can be produced in high yield from L-sorbose. The process involves the inversion of the hydroxyl groups on carbon atoms C3 and C4 of L-sorbose to produce L-fructose. This inversion can be accomplished in simple, commercial equipment with the aid of common reagents. L-sorbose or an appropriately blocked derivative thereof is reacted so as to introduce or create a good leaving group, preferably mesyl or tosyl, at chiral carbon C3 thereby displacing the hydroxyl previously at that position. The leaving group is then displaced, preferably under alkaline conditions, in such a way that the hydroxyl oxygen atom at chiral carbon C4 attaches to chiral carbon C3, thereby displacing the leaving group while forming a 3,4-oxirane (epoxide) ring. The 3,4-oxirane ring forms in a downward position relative to the Haworth presentation thereby inverting chiral carbon C3 during formation of the 3,4-oxirane ring. The 3,4-oxirane ring is then opened under acidic or alkaline conditions to yield a sugar ring with a hydroxyl group in a position above the sugar ring at chiral carbon C4, and a hydroxyl group in a downward position at C3. Removal of any remaining blocking groups yields L-fructose. This may be accomplished by acid hydrolysis. There are also disclosed novel classes of compounds which act as intermediaries in the synthesis of L-fructose.
Inventors
- 👤 Chyi-Cheng Chen
- 👤 Roy L. Whistler
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-05 09:55
CPC Classifications
C; C07; C07H; C07H9/00; C07H9/02; C07H9/04; C07H3/00; C07H3/02
Claims Analysis
Total Claims: 17
Claim 1
Independent Claim
31 words
A 3,4-anhydro-L-sorbose having the formula: ##STR5## wherein R 1 represents a leaving group R 2 represents a (lower)alkyl group, or R 1 and R 2 taken together represent a blocking group.
Claim 2
Dependent Claim
31 words
A 3,4-anhydro-L-sorbose having the formula: ##STR5## wherein R 1 represents a leaving group R 2 represents a (lower)alkyl group, or R 1 and R 2 taken together represent a blocking group.
Claim 3
Dependent Claim
35 words
The compound of claim 1, wherein said leaving group is selected from the group of mesyl and tosyl, and said blocking group is selected from the group of isopropylidene, benzylidene, ethylidene, sec. butylidene and cyclohexylidene.
Claim 4
Dependent Claim
136 words
A process for producing a product wherein the C3 and C4 atoms are in the L-fructo configuration from an L-sorbose derivative comprising L-sorbose having a hydroxyl group attached to the C4 atom, and an L group attached to the C3 atom, wherein L is a leaving group that will be eliminated upon subjection to alkaline conditions, comprising the steps of (A) subjecting the L-sorbose derivative to alkaline conditions, thereby forming a 3,4-oxirane ring wherein the 3,4-oxirane ring is arranged in a downward position in relation to Haworth projection, in which the ring oxygen atom is to the right and behind the plane of the paper; and (B) subjecting the product formed in Step (A) to a condition selected from the group consisting of heated strong alkaline, and at least mild acidic, thereby opening the 3,4-oxirane ring.
Claim 5
Dependent Claim
136 words
A process for producing a product wherein the C3 and C4 atoms are in the L-fructo configuration from an L-sorbose derivative comprising L-sorbose having a hydroxyl group attached to the C4 atom, and an L group attached to the C3 atom, wherein L is a leaving group that will be eliminated upon subjection to alkaline conditions, comprising the steps of (A) subjecting the L-sorbose derivative to alkaline conditions, thereby forming a 3,4-oxirane ring wherein the 3,4-oxirane ring is arranged in a downward position in relation to Haworth projection, in which the ring oxygen atom is to the right and behind the plane of the paper; and (B) subjecting the product formed in Step (A) to a condition selected from the group consisting of heated strong alkaline, and at least mild acidic, thereby opening the 3,4-oxirane ring.
Claim 6
Dependent Claim
13 words
The process of claim 3, wherein the leaving group comprises mesyl or tosyl.
Claim 7
Dependent Claim
14 words
The process of claim 3, wherein Step (A) is carried out at room temperature.
Claim 8
Dependent Claim
16 words
The process of claim 3, wherein Step (B) ia carried out under heated strong alkaline conditions.
Claim 9
Dependent Claim
21 words
The process of claim 6, wherein said conditions include heating the product to a temperature of from 50° C. to boiling.
Claim 10
Dependent Claim
17 words
The process of claim 3, wherein Step (B) is carried out using at least mild acidic conditions.
Claim 11
Dependent Claim
42 words
The process of claim 3, wherein the L-sorbose derivative is produced from a starting material selected from the group consisting of L-sorbose, methyl L-sorbofuranoside, 1,2-O-isopropylidene-L-sorbofuranose, 1,2-O-isopropylidene-L-sorbopyranose, 2,3-O-isopropylidene-L-sorbofuranose, 2,3-O-isopropylidene-L-sorbopyranose, 1,3-O-isopropylidene-L-sorbofuranose, 1,3-O-isopropylidene-L-sorbopyranose, 1,2:4,6-di-O-isopropylidene-L-sorbofuranose, 2,3:4,6-di-O-isopropylidene-L-sorbofuranose, 1,3:4,5-di-O-isopropylidene-L-sorbofuranose, methyl 4,5-O-isopropylidene-L-sorbofuranoside, ethyl 4,6-O-isopropylidene-L-sorbofuranoside, methyl 1,3:4,6-di-O-isopropylidene-L-sorbofuranoside, and ethyl 1,3:4,6-di-O-isopropylidene-L-sorbofuranoside.
Claim 12
Dependent Claim
38 words
The process of claim 3, wherein the L-sorbose derivative is produced by a process wherein L-sorbose is reacted in the presence of a divalent catalyst to produce a compound having blocking groups in the 1,2 and 4,6 positions.
Claim 13
Dependent Claim
13 words
The process of claim 10, wherein the divalent catalyst is SnCl 2 .
Claim 14
Dependent Claim
23 words
The process of claim 11, wherein the blocking groups are selected from the group consisting of isopropylidene, benzylidene, ethylidene, sec. butylidene and cyclohexylidene.
Claim 15
Dependent Claim
148 words
A process for producing L-fructose from L-sorbose comprising the steps of (A) reacting L-sorbose in the presence of a divalent catalyst to yield a product having blocking groups in the 1,2 and 4,6 positions, (B) reacting the product of Step (A) with methanesulfonyl chloride or toluenesulfonyl chloride, (C) reacting the product of Step (B) with acid to remove the 4,6 position blocking group, (D) reacting the product of Step (C) with a base, thereby forming a 3,4-oxirane ring, wherein the 3,4-oxirane ring is arranged in a downward position in relation to Haworth projection, in which the ring oxygen atom is to the right and behind the plane of the paper, (E) heating the product of Step (D) to from 50° to boiling, thereby opening the 3,4-oxirane ring, and (F) subjecting the product of Step (E) to acid hydrolysis to remove the 1,2 position blocking group, thereby yielding L-fructose.
Claim 16
Dependent Claim
148 words
A process for producing L-fructose from L-sorbose comprising the steps of (A) reacting L-sorbose in the presence of a divalent catalyst to yield a product having blocking groups in the 1,2 and 4,6 positions, (B) reacting the product of Step (A) with methanesulfonyl chloride or toluenesulfonyl chloride, (C) reacting the product of Step (B) with acid to remove the 4,6 position blocking group, (D) reacting the product of Step (C) with a base, thereby forming a 3,4-oxirane ring, wherein the 3,4-oxirane ring is arranged in a downward position in relation to Haworth projection, in which the ring oxygen atom is to the right and behind the plane of the paper, (E) heating the product of Step (D) to from 50° to boiling, thereby opening the 3,4-oxirane ring, and (F) subjecting the product of Step (E) to acid hydrolysis to remove the 1,2 position blocking group, thereby yielding L-fructose.
Claim 17
Dependent Claim
37 words
The process of claim 13, wherein step (A) is carried out by reacting L-sorbose, in the presence of tin (II) chloride catalyst and a solvent, with a compound selected from the group consisting of 2,2-dimethoxypropane and acetone.
References Cited (Backward Citations)
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