SU448643A3 - The method of obtaining-metallozidov - Google Patents

Description

and, if the Ac radical has values other than Ri, 2, Cs, then they are cleaved or acylated with free hydroxy groups and the desired product is isolated by known techniques.

The decomposition reaction is preferably carried out in a solvent, for example, ethylene chloride or benzene, and in the presence of a salt or oxide of a heavy metal, for example silver oxide, silver carbonate or mercury cyanide (li), at temperatures above the boiling point of the solvent used or in the presence of a tertiary organic solvent. base, such as pyridine or 2,6-lutidine, preferably at -50 ° C. An excess of the base used can also be used as a solvent. Subsequent cleavage of acyl radicals from compounds of formula (i) is preferably carried out hydrolytically, for example, in the presence of an acid or a base and at temperatures not below the boiling point of the solvent used, for example, at UOC.

The radiolabeled compound of general formula I, in which RI-Rs are hydrogen atoms, can be again acylated, preferably at room temperature or with cooling with the appropriate anhydride or acid halide in pyridine or the corresponding carboxylic acid in the presence of dicyclohexylcarbodiimide.

The original genins of general formula (II) are known.

The triacyl-a-b-talomethylosyl halide used as a starting material of the general formula (III) is obtained from the corresponding tetraacyl-a-b-talomethylose by an exchange decomposition reaction with hydrogen chloride or hydrogen bromide in glacial acetic acid.

Example 1. Sp-a-b-talomethyloside-5p, 14 rdioxy-19-oxo-card-20 (22) -enolide. A. 0.202 g (0.5 mol) of D-strophanthidine, dissolved in 20 ml of ethylene chloride, 0.54 g (1 mmol) of tribenzoyl-a-b-talomethylosyl bromide, dissolved in 2 ml of ethylene chloride, and 0.26 g (1 mmol a) mercury cyanide (II) 3 hours move in a nitrogen atmosphere at room temperature. Upon completion of the reaction (set using thin layer chromatography), the mixture is washed with 3% sodium bicarbonate solution, the organic phase is dried over sodium sulfate and concentrated to dryness in vacuo.

The resulting tribenzoyl-3p-ia-L metalomethyl-5p derivative, 14p - dihydroxy-19 - oxocard-20 (22) -enolide has a value of 0.5 (CPS; LM mixture of methyl ethyl ketone and xylene i: i).

B. The obtained tribenzoyl derivative is dissolved in 50 ml of methanol, 5 ml of a 10% aqueous solution of potassium carbonate is added to it and saponified at room temperature. After neutralization 2 n. acetic acid the reaction mixture is concentrated to dryness

under vacuum, and the residue purified by column chromatography on silica gel (0.2-0.0 mm) with a mixture of chloroform and methanol 9: 1.

Yield 0.14 g (51% of theory); m.p. 247- Rf 0.4 (KGHF; LM: methyl ethyl ketone).

Example 2. 3 | e-a-b-talomethylosyl-14 | 3-hydroxy-card-20 (22) -epolide.

0.1 g (0.5 mmol) of digitoxigenin, 0.54 g (1 mmol) of tribenzoyl-a-b-talomethyllosyl bromide, and 0.26 g (I mmol) of mercury cyanide (II) are reacted in the same way as in Example 1.

output 0.12 g (56% of theory); m.p. 235-, RI 0.25 (KGHF; a mixture of methyl ethyl ketone and xylene 5: 2).

Example 3. Sp-a-b-talomethylosyl-14 | p-hydroxy-1u-oxo-0ufa-4,; 0,22-trpenolide.

0.2 g (0.5 mmol) of silliglaucosidine, 0.54 g (1 mmol) of tribenzoyl-a-b-talomethylosyl bromide, and 0.26 g (1 mmol) of mercury cyanide P are reacted in a manner similar to Example 1.

Yield 0.14 g (52% of theory); m.p. 120- (substance is amorphous); Rf 0.15 (COPR; mixture of methyl ethyl ketone and xylene 5: 2).

Example 4. Sp-a-b-talomethylosyl-14 | 3-hydroxy-bufa-4, 20,22-trnenolide.

0.19 g (0.5 mmol) of scilarinine A, 0.54 g (1 mmol) of tribenzoyl-cc-b-talomethyllosylbromide and 0.26 g (1 mmol) of mercury cyanide (II) are reacted in a manner similar to Example 1.

Intake of 0.13 g (49% of theory); m.p. 200-205 ° C; Rf 0.5 (KGHP; a mixture of ethyl acetate and ethanol 95: 5).

Example 5. Sp - (2,3,4 - triacetyl-a-b-talomethylosyl) -5p, 14p-dioxy-19 - oxo-card-20 (22) -enolide.

/ s-Strofantidine and triacetyl-a-b-talomethylosyl bromide are reacted as in Example 1. So pl. 142-145 ° C (substance amorphous); Rf 0.6 (KGHP; LM; a mixture of methyl ethyl ketone and xylene 5: 2).

Example 6. Sp- (2,3,4-tripropionic-a-LTalomethyl) -5 | 3,14-dioxy - 19-oxo-card20 (22) -enolide.

At 0.75 g (1.3 mmol) of Zr-a-talometilosyl-5p, 14 | 3-dioxy-19-oxo-card-20 (22) enolide, dissolved in 10 ml of pyridine, 2 ml of propiophoic anhydride are added . Upon completion of the reaction (set by thin layer chromatography) the reaction temperature rises to room temperature. The reaction solution was poured into ice water and extracted twice with chloroform. The combined extracts are washed to neutral medium, and after sodium sulfate, the leaves are concentrated to dryness under vacuum.

Yield 0.91 g (94% of theory); m.p. 120-130 ° C (the substance is amorphous); Rf 0.7 (KGIiP; LM; mixture of methyl ethyl ketone and xylene 5: 2); “ID -29.9 ° (c 1; chloroform).

PRI me R 7. Sp - (2,3,4-tritytyl-a-L-ta