CS239405B1 - Process for preparing (E) -3- (hydroxymathylene) dihydro-2 (3H) -furanone sulfonates and carboxylates \ t - Google Patents

Abstract

The invention provides a method for preparing sulfonates and carboxylates of (E)-3-(hydroxymethylene)dihydro-2(3H)-furanone. Sulfonates and carboxylates of (E)-3-(hydroxymethylene)dihydro-2(3H)-furanone are prepared according to the invention by reacting the sodium salt of 3-(hydroxymethylene)dihydro-2(3H)-furanone with chlorides or bromides or anhydrides of carboxylic or sulfonic acids in solution under the catalysis of an organic nitrogen base such as a tertiary amine, pyridine, quinoline, etc. Sulfonates and carboxylates of (E)-3-(hydroxymethylene)dihydro-2(3H)-furanone are reactive compounds with extensive synthetic use; some of them have antitumor effects.

Description

The invention relates to a process for the preparation of (E) -3- (hydroxymethylene) dihydro-2 (3H) -furanone sulfonates and carboxylates.

Sulfonates and carboxylates of (E) -3- (hydroxymethylene) dihydro-2- (3H) furenone are reactive compounds with extensive synthetic uses, among them substances with antitumor activity. Preparations of these compounds described in the literature are either lengthy or do not yield yields above 50% or lead to the emission of (E) -a (Z) -isomers, which need to be laboriously resolved.

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According to the invention, the preparation of sulfonates and carboxylates of (E) -3- (hydroxymethylene) dihydro-2 (3H) -furanone of the formula I has been found

wherein X is acetyl, mono- to trichloroacetyl, mono- to tribromoacetyl, trifluoroacetyl, propionyl, butyroyl, isobutyroyl, cyclohexanecarbonyl, 1-edamantancarbonyl, benzoyl, 4-nitrobenzoyl, 4-fluorobenzoyl, 4-chlorobenzoyl, 4-bromobenzoyl, phenylacetobenzyl , trifluoromethanesulfonyl, benzenesulfonyl, 4-toluenesulfonyl, 4-bromobenzenesulfonyl, 1-naphthalenesulfonyl or 2-naphthalenesulfonyl, which are simple and give high yields of configuration-pure products in a short reaction time. Compounds of formula (X) may be prepared by reacting 3- (hydroxymethylene) dihydro-2 (3H) -furanone sodium salt with chlorides or bromides or anhydrides of carboxylic or sulfonic acids in solution to catalyze an organic nitrogen base such as a tertiary amine, pyridine quinoline and the like.

He did

3- (Hydroxymethylene) dihgdro-2 (3H) -furanone sodium salt (2.8 g) was dissolved in 30 ml of water with 2 g of triethylamine or 1.6 g of pyridine, 60 ml of acetone was added thereto, followed by stirring 0 0.02 mole of carboxylic or sulfonic acid chloride or bromide or anhydride, in the case of liquids without solvent, in the case of solids in solution in acetone-water (g: 1). After 30 minutes at room temperature, the pure corresponding <E) -3- (hydroxymethylene) dihydro-2 (3H) -furenone sulfonates or carboxylates of formula 1 were isolated from the mixture.

The following were prepared:

1a) (E) -3- (acetoxymethylene) dihydro-2 (3H) -furanone (compound of formula 1 wherein X is CH-jCO), m.p. 40.5-41.5 ° C, yield 75 lb) (E) -3- (benzoyloxymethylene) dihydro-2 (3H) -furanone (compound of formula I wherein X is C8H3CO), m.p. 5 DEG-152 DEG C., yield 95 ° s 1c) (S) - 3- (fenylacetoxymethylen) -dihydro-2 (3H) -furanone (compound of formula I wherein X is C ₆ H _{$ CH2} CO), mp 76-77 ° C, 83% yield ye:

1d) (E) -3- (methanesulfonyloxymethylene) dihydro-2 (3H) -furanone (compound of formula 1 wherein X is CH ₃ SO ₂ ), m.p. 19-120.5 ° C, yield 80 °;

(e) (E) -3- (Trifluoromethanesulfonyloxymethylene) dihydro-2 (3H) -furanone (compound of formula I wherein X is CP 2 SO 6), m.p. 41-42 ° C, yield 90 lf) (E) -3- (benzenesulfonyloxymethylene) dihydro-2 (3H) -furanone (compound of formula I wherein X is C8H4SO3), m.p. 82.5-83.5 ° C, yield 76% (g) (E) -3- (4-toluensulfonyloxymethylen) -dihydro-2 (3H) -furanone (compound of formula 1 wherein X is 4-CH.jC _of H ₂ SO _4), mp 116.5 to 117.5 ° C, yield 90%;

1h) (E) -3- (2-naphthalenesulfonyloxymethylan) dihydre-2 (3H) -furanone (compound of formula I wherein X is α-C ft ft ftSO SO), mp 105-106 ° C, yield 93%.

Claims (1)

A process for the general preparation of sulfenates and carboxylates of (E) -3- (hydroxymethylene) dihydro-2 (3H) -furanosulfonate I ox wherein X is acetyl, mono- to trichloroacetyl, mono- to tribromoacetyl, trifluoroacotyl, propionyl, butyroyl, isobutyroyl, cyclohexanecarbonyl 1-adamantanecarbonyl, benzoyl, 4-nitrobenzoyl, 4-fluorobenzoyl, 4-chlorobenzoyl, 4-bromobenzoyl, phenylacetyl, methanesulfonyl trifluoromethanesulfonyl, benzenesulfonyl, 4-toluenesulfenyl, 4-bromobenzenesulfonyl, 1-naphthalenesulfonyl or 2-naphthalenesulfonyl, The process of claim 3, wherein the sodium salt of 3- (hydroxymethylene) dihydro-2 (2H) -furanone is treated with chlorides or bromides or anhydrides of the corresponding carboxylic or sulfenic acids in a solution from catalysis of an organic nitrogen base such as a tertiary amine, pyridine or quinoline.