Chemistry: molecular biology and microbiology – Micro-organism – tissue cell culture or enzyme using process... – Preparing compound containing saccharide radical
Patent
1982-08-30
1984-04-03
Shapiro, Lionel M.
Chemistry: molecular biology and microbiology
Micro-organism, tissue cell culture or enzyme using process...
Preparing compound containing saccharide radical
435105, 536 11, 536124, 536125, C12P 1924, C12P 1902, C07H 308
Patent
active
044408544
DESCRIPTION:
BRIEF SUMMARY
TECHNICAL FIELD
This invention relates to organic chemical synthesis and, in particular, synthesis of 6-deoxy sugars.
BACKGROUND OF THE INVENTION
The 6-deoxy sugars constitute particularly useful starting materials for the preparation of 4-hydroxy-2,5-dimethyl-2,3-dihydrofuran-3-one, better known by the name of FURANEOL.RTM. (registered trademark of Firmenich SA, Geneva). M. Matsui et al. [see Chem. Abstr., 91, 20309q (1979)], for example, have described the method for converting 6-deoxy-D-glucose into FURANEOL. Although the yields observed during this conversion were very satisfactory, the method of Matsui suffers from a major drawback, i.e., the high cost of the starting material whose preparation requires four reaction steps. This invention concerns an original solution to this problem. We have found that 6-deoxy-D-fructose and 6-deoxy-L-sorbose, of the following formulas respectively ##STR1## can be converted into FURANEOL in excellent yield, with the conversion taking place in the presence of an organic nitrogen base and a carboxylic acid, under reaction conditions similar to those described by Matsui.
SUMMARY OF THE INVENTION
This invention concerns a process for the preparation of 6-deoxy-D-fructose and/or 6-deoxy-L-sorbose characterized by the fact that the following steps are carried our consecutively: the presence of an enzymatic system composed of aldolase and triose phosphate isomerase in aqueous medium at pH 7.0, and concerns a process for the preparation of 6-deoxy-D-fructose and/or 6-deoxy-L-sorbose which consists of treating 1.3-dihydroxyacetone phosphate of the formula ##STR2## with D- and/or L-lactaldehyde in the presence of an enzymatic system composed of aldolase and triose phosphate isomerase in equation medium at pH 7.0, and hydrolyzing the monophosphate salt thus obtained.
This invention finally concerns a process for the preparation of 6-deoxy-D-fructose and/or 6-deoxy-L-sorbose which consists of treating 1.3-dihydroxyacetone with D- and/or L-lactaldehyde in the presence of an anionic exchange resin.
The processes described above can be illustrated by the reaction scheme below: ##STR3## Definition of abbreviations: 6-DF=6-deoxyfructos; 6-DF-1-P=6-deoxyfructose-1-phosphate
The first step of the procedures making use of aldolase and triose phosphate isomerase (TPI) formally constitutes an example of aldol condensation. This reaction proceeds in a perfectly selective manner and does not require the protection of other functional groups present in the molecule. The required reaction conditions are also particularly mild (pH 7.0-room temperature), and it follows that the industrial application of the aforementioned procedures for the preparation of 6-deoxy-D-fructose or 6-deoxy-L-sorbose can be visualized directly. The enzymatic system chosen was immobilized on a solid support in accordance with the method described in J. Am. Chem. Soc., 102, 6324 (1980). The aldolase and the triose phosphate isomerase are commercial enzymes.
The D- and L-lactaldehyde were prepared from L- and D-threonine by reaction with ninhydrin according to the method described in J. Biol. Chem., 241, 3028-35 (1966).
The 1,3-dihydroxyacetone phosphate (DHAP) can be obtained either by enzymatic phosphorylation of 1,3-dihydroxyacetone (DHA) using ATP and the monopotassium salt of phosphoenolpyruvate, or by the chemical phosphorylation of the same DHA using POCl.sub.3. Fructose-1,6-diphosphate, in the form of its sodium or dicalcium salt, is a commercial product. If necessary, it can be purified before its use by a treatment using an anionic exchange resin, for example, of the type DOWEX 1. The particular purification method used is described in detail in the examples which follow.
As indicated above, one of the procedures which consists of the reaction between 1,3-dihydroxyacetone and lactaldehyde is carried out in the presence of an anionic exchange resin.
For this purpose, AMBERLITE.RTM. (see The Merck Index, 9th Edition, Merck & Co. Inc., USA, Sec. 386) Type IRA-400 is preferably used.
The deoxyfuranoses prep
REFERENCES:
Matsui et al., Chemical Abstracts 91:20309q, 1979.
Kaufmann et al., Chemical Abstracts 68:39963v, 1968.
Mazenod Francois P.
Whitesides George M.
Wong Chi-Huey
Engellenner Thomas J.
Shapiro Lionel M.
Smith, Jr. Arthur A.
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