CS202787B1 - Method of preparing d/u-up14c/arabinose - Google Patents

Description

SUMMARY OF THE INVENTION The present invention relates to a novel process for the preparation of D-ZU-a-arabinose by oxidative degradation of 4-nitrophenylhydrazone D- (U-C) -glucose.

Processes for the preparation of D-arabinose in which the starting compound is D-glucose and D-glucose, respectively. D-gluconic acid, or a suitable derivative thereof, is described in the literature by many / Wohl, respectively. Ruff or Weerman degradation, Hundadiecker reaction, disulfone degradation of aldoses, J. Stanek, M. Cerny, J. Kocourek, J. Paoak: Monosaccharides, Nakl. ČSAV, Praha 1960, decomposition of peroxo compounds prepared by the condensation reaction of per-O-acetylderivatives of D-gluconic acid chloride or bromoethyl ethyl-D-glucose with tert-butyl peroxide - M. Schulz, P. Berlin: Angew. Chem. 79,940 (1967), M. Schulz, H. Steinmau, Angew. Chem. gg., 918 (1963). For the production of sec-znečkovených _c h _n ižší of aldose aldose higher, the most commonly used oxidative degradation of an aldose under alkaline conditions, following the method of D-glucose is formed of d and arabic, which provides a reduction of a sodium amalgam D-arabinose. Simultaneously, parallel side reactions occur in this preparation process, and as a result a complex reaction mixture of carbohydrates is formed. On the other hand, the proposed process for the preparation of D-arabinose is substantially simpler in conversion and very suitable for milligram and resp. semimiligramové of the starting ^{4-1 *} Q_ _brand g] _Cova j D-glucose.

SUMMARY OF THE INVENTION The present invention is characterized in that the mixture of D-glucose and L-ZU-c / glucose is treated at 60 ° C for 3 hours with a 2% methanolic solution of 4-nitrophenylhydrazine,

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The resulting 4-nitrophenylhydrazone D-ZU-2-glucose is further degraded to D-ZU-1-arabinose in an alkaline ammonia solution in the presence of hydrogen peroxide and under the catalytic action of molybdenum ions.

An advantage of the proposed process for the preparation of D- (U-N-C) arabinose is that

- uses relatively available D / U-c / glucose,

- it is very simple to convert (the whole preparation process is carried out in a single tube, by successive addition of individual reagents),

- due to the simple reaction mixture formed, D- (U -) - arabinose is also easily isolated by paper chromatography,

- is suitable for milligrams resp. semimiligram quantities and

- the necessary chemicals are commercially available.

Execution example

A mixture of D-glucose / 10 mg / ZU- ^D-1 ^ / glucose / 10 .mu.Ci /, Voty / ml / 2% methanolic solution of 4-nitrophenylhydrazine / 2 mL / a and heated for 3 hours at 60 ° C. To the cooled solution were added 2.8% aqueous ammonia solution (2 ml), 0.5% sodium molybdate solution (1 ml) and 15% hydrogen peroxide (2 ml). The reaction mixture is allowed to stand for 20 h and then concentrated (bath temperature up to 30 ° C) to about 1/3 volume and chromatographed on Whatman No 1 papers using 5: 1: 4 1-butanol-ethanol-water elution system / flow rate for 20 h, temperature 20-23 ° C). The relative mobility related to arabinose (1.00) is 2.85 glucose for glucose and 2.85 for glucose and 4.62 (for ammonium aldonic acid and Starte) for 4-nitrophenylhydrazine.

From the radioactivity of the starting D / U-C / glucose after the reaction of glucose with 4-nitrophenylhydrazine in the D-glucose zone is 4.3%, in the 4-nitrophenylhydrazone D-glucose zone 86.4%} after oxidative degradation at Starte / ammonium salts aldonic acids / 27.2%, in the glucose zone 10.0% and arabinose 44.2% / t. j. 53% yield of D-ZU-α-arabinose relative to the starting D- (β-β-glucose) and glucose-1-α-α-d-glucose, respectively. 58.9% with respect to the regenerated D-ZU-C (glucose).

The invention is of importance for the preparation of D-ZU-arabinose having a high specific activity (200 µCi / mmol) which is a suitable and desirable export product.

Claims (1)

Process for the preparation of D-ZU- ¹ / arabinose, characterized in that a mixture of D-glucose and Dt / U-C / glucose is treated at 60 ° C for 3 hours with a 2% methanolic solution of 4-nitrophenylhydrazine, the resulting 4-nitrophenylhydrazone ZU- D ^ c / glucose is also in an alkaline solution of ammonia in the presence of a peroxide, consisting of: H catalyzed by molybdate ion degraded to DA! - ¹ ^ / arabinose.