Process for the manufacture of D-erythrose

Details Process for the manufacture of D-erythrose Process for the manufacture of D-erythrose

1997-09-09

2001-10-09

Wilson, James O. (Department: 1623)

Organic compounds -- part of the class 532-570 series

Organic compounds

Carbohydrates or derivatives

C536S018500

Reexamination Certificate

active

06300494

ABSTRACT:

The subject of the present invention is a process for the manufacture of D-erythrose.
More specifically, the subject of the present invention is a process for the manufacture of D-erythrose from gluconic acid, which process is catalysed by ions of a metal selected from the group consisting of cobalt, nickel and ruthenium and takes place in the aqueous phase.
Processes for the manufacture of D-erythrose are already known.
Among these, mention may firstly be made of that developed by Ruff (Ber., 32, 3674 (1899); 33, 1799 (1900)), which consists in oxidizing calcium D-arabinonate in the presence of aqueous hydrogen peroxide solution. Such a process exhibits the major disadvantage of using arabinonic acid, which is not a common commercially available product, as starting material.
Other processes for the manufacture of D-erythrose have followed, such as the oxidation of D-glucose in the presence of lead tetraacetate, known under the name of the Perlin method (Perlin A. S., Methods Carbohydr. Chem., 1962, 1, 64), or the acid hydrolysis of 2,4-O-ethylidene-D-erythrose obtained by the oxidation with periodate of 4,6-O-ethylidene-D-glucose (Schaffer R., J. Am. Chem. Soc., 81 (1959), 2838; Barker R. and MacDonald D. L., J. A. Chem. Soc., 82 (1960), 2301).
D-Erythrose is not of great interest in itself but would be in particular a very important synthetic intermediate if it came to pass that it could be produced on a large scale and at a low cost.
This is because a simple additional stage of hydrogenation of D-erythrose makes it possible easily to obtain erythritol, which is a polyol which can be employed in many food applications and in particular as non-cariogenic and low-calorie substitute for sucrose.
For this reason, another subject of the present invention is a process for the manufacture of erythritol starting from D-erythrose obtained in accordance with the process of the invention.
Although widespread in nature and having formed part of the human diet from time immemorial, erythritol has for a long time been ignored by the food industry, because of the difficulties encountered in obtaining it in a financially viable way.
In the pharmaceutical industry, erythritol can be oxidized to L-erythrulose, a molecule which has an advantageous functionality conferring on it the possibility of being used in the synthesis of biologically active compounds.
Studies which have been carried out on processes for the manufacture of erythritol have, taken as a whole, been divided into two main routes: chemical synthesis and fermentative biosynthesis.
None of the known chemical synthesis techniques, such as reduction of meso-tartrate, oxidation/reduction of 4,6-O-ethylidene-D-glucose and hydrogenation of starch dialdehyde hydrolysates (T. Dola and T. Sasaki, Bio-Industry, (1988), 5, (9), 32), has been able, however, to achieve a true industrial dimension.
Although markedly more numerous than in chemical synthesis, studies carried out on fermentation techniques are in the great majority of cases concerned with the production of erythritol as a secondary constituent.
These studies have been devoted to the production of erythritol by the yeasts Debaryomyces (U.S. Pat. No. 2,986,495), Pichia (U.S. Pat. No. 2,986,495), Candida (U.S. Pat. No. 3,756,917), Moniliella (Antonie van Leeuwenhoek, 37 (1971), 107-118), and Aureobasidium (JP-A 61/31,091).
The results provided to date by studies on the fermentation of erythritol nevertheless bring out a certain number of disadvantages, such as foaming during fermentation, the rate of fermentation, the extent of the byproducts and especially the poor yield, which further jeopardise the possibilities of the industrialization thereof.
There thus existed a need to develop a high-performance process for the manufacture of D-erythrose (and thus of erythritol by hydrogenation of the D-erythrose thus obtained) which does not exhibit the limitations and/or the disadvantages of the prior art.
It was while working on this research theme that the Applicant Company developed a new process for the manufacture of D-erythrose by the chemical route from gluconic acid or its salts. The process in accordance with the invention goes back to the principle of the method described by Ruff nearly a century ago.
This method makes it possible, in a general way, to convert an aldonic acid containing n carbons to an aldose containing (n-1) carbons, by virtue of the combined action of ferric ions and of aqueous hydrogen peroxide solution. However, the aldose yields are very modest.
Thus, the conversion of gluconic acid to D-arabinose is carried out according to this method.
A few improvements have subsequently been introduced by R. C. Hockett and C. S. Hudson (J. Amer. Chem. Soc., 56, 1632-1633, (1934) and ibid., 72, 4546, (1950)) and by the document U.S. Pat. No. 3,755,294. Arabinose yields of 60%, starting from gluconic acid, are described therein. Progress has been accomplished by V. Bilik (CZ-232647, (1983)) by using cupric (Cu(II)) ions as catalysts. Yields of the order of 70% are achieved after a laborious purification.
Identical results were recently obtained with a mixture of ferric and ferrous ions as catalysts (CZ-279002, (1994)).
Finally, under specific conditions, the document EP-A 0,716,067 reports yields of certain aldoses of 78%.
During a widescale investigation of the Ruff reaction, the Applicant Company has discovered that cobalt, nickel and ruthenium salts catalysed the reaction of gluconic acid with aqueous hydrogen peroxide solution to give, surprisingly, D-erythrose and not, as might have been expected, D-arabinose. Two carbon atoms are thus lost with respect to the starting aldonic acid.
Thus, according to the invention, the process for the manufacture of D-erythrose is characterized in that an aqueous solution of a salt of gluconic acid is brought into contact with hydrogen peroxide in the presence of a salt of a metal selected from the group consisting of cobalt, nickel and ruthenium.
A first advantage in such a process, in comparison with the fermentation processes of the prior art, is obviously that it avoids all the restrictions and problems related to the fermentation techniques as mentioned above.
A second advantage of the process in accordance with the invention lies in the fact that it is extremely easy to implement since both the starting material and the reagents are readily accessible.
A third advantage of the process in accordance with the invention is that D-erythrose is obtained with a very good yield close to stoichiometric.
Another advantage of the process in accordance with the invention is that it readily finds a place in industry, in particular the food industry, because it uses water as solvent, which is an undeniable advantage both as regards toxicity and as regards safety.
The process of the invention makes use of a salt of gluconic acid.
In the present invention, salt of gluconic acid is understood to mean gluconic acid in the free form, in the lactone form or in the form of a mixture of these two forms, in the form of salts or in the form of esters. Thus, for example, calcium gluconate, sodium gluconate or &dgr;-gluconolactone are entirely suitable.
Gluconic acid is obtained in a known way by oxidation of glucose. This oxidation stage can be carried out either by the chemical route or by the microbiological route.
The preferred chemical route in the context of the invention consists in oxidizing glucose using air or oxygen in alkaline medium and using palladium catalysts.
A particularly preferred process is that which has been described in United States Patent U.S. Pat. No. 4,845,208, of which the Applicant Company is an assignee, which consists in using, as oxidation catalyst, palladium attached to active charcoal and doped with bismuth.
It is also possible to envisage the oxidation of glucose by the electrolytic route or using hypobromite. It is also possible to oxidize glucose by the microbiological route using Gluconobacter or Aspergillus.
The process of the invention is preferably implemented, in water, with a content of salt of gluconic ac

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