DD143253A1 - PROCESS FOR THE PRODUCTION OF AZIRIDINE DERIVATIVES - Google Patents

Abstract

The invention relates to a process for the preparation of aziridine derivatives of general formula I and II from 2-cyanoaziridine and ketones. The aim of the invention is to produce these compounds in yields of approximately 80%. This is achieved by drying the ketones used until completely free of water before use and adding alkali metal alkylate in catalytic amounts to prepare the compounds of general formula II. - Formulas I and II -

Description

20 35 2

Process for the preparation of aziridine derivatives

Field of application of the invention

The invention relates to a process for the preparation of aziridine derivatives of the general formulas I or II from 2-cyano-aziridine and ketones. These compounds have a cancerostatic and immunostimulating action.

Characteristic of the known technical solutions

DDR patent No. 128 615 describes aziridine derivatives synthesized from 2-cyano-aziridine and carbonyl compounds by hydration of a nitrile group and aminal formation. Yields when working with acetone are 29 %, when using cyclohexanone depending on the Ar / beitsweise 12 to 27 %, even with the addition of catalytically active substances such as aliphatic amines, the yields are not higher than 30 %. The method is thus completely inadequate for the technical realization.

Object of the invention

The invention is based on the object of developing a process for the preparation of aziridine derivatives from 2-cyano-aziridine and ketones, in which the yields are considerably higher, so that it is suitable for top conduction in practice.

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Explanation of the essence of the invention

This object is achieved by according to the invention, the ketone used dried before use until complete freedom from water and distilled immediately before the start of the experiment. It is advantageous. Acetone over diphosphorus pentoxide for about 3 hours and cyclohexanone over calcium chloride for about 24 hours to dry. It has furthermore been found that aziridine derivatives of general formula II are formed with the addition of catalytic amounts of alkali metal citrate solution of 2-cyano-aziridine and the anhydrous ketones (reaction equations see Appendix).

The 2-cyano-aziridine used can be prepared according to DDR patent specification 107,679.

The final products are obtained in yields of over 80 % .

Exemplary embodiments Example 1

A mixture of 10 mmol (0.68 g) of 2-cyanaziridine and 10 mmol (0.98 g) of anhydrous cyclohexanone, which was dried over calcium chloride and then distilled, was allowed to stand at room temperature for 14 days. After addition of seed crystals, after 1 additional 6 days 1 g (86 % of theory) of 1-5 cyano

Melting point: 187-189 ° C (from toluene).

Example 2

A mixture of 10 mmol (0.68 g) of 2-cyanaziridine, 10 mmol (0.58 g) of anhydrous acetone, which was dried over diphosphorus pentoxide and then distilled, and 0.2 ml of anhydrous triethylamine is allowed to stand at room temperature for 10 days and receives 0.7 g (71 % of theory) of 2- ^ 2 "cyanaziridinyl- (l) 7- ² - ^ 2-carbamoyl-aziridinyl ~ (lj | 7-propane, melting point: 151-155 ° C (from acetone).

2 0 3 5 20

Example 3.

A mixture of 20 mmol (1.36 g) of 2-cyanaziridine and 80 mmol (4.64 g) of anhydrous acetone, which was dried over diphosphorus pentoxide and then distilled, was added under ice-cooling with 3 drops of 2N sodium methylate solution. The mixture is allowed to stand at room temperature for 2 days and evaporated in vacuo. The solid obtained is sublimed in vacuo and recrystallized. This gives 2.1 g (83 % of theory) of 3,3-Dimethylaziridino ^, 2-c7imidazolidin-5-one, m.p .: 119 - 121 ⁰ C (from gasoline),

Example 4

A mixture of 20 mmol (1.36 g) of 2-cyano-aziridine and 80 mmol (7.84 g) of anhydrous cyclohexanone, which was dried over calcium chloride and then distilled, was added under ice-cooling with 3 drops of 2N sodium methylate solution. After working up analogously to Example 3 to obtain 2.9 g (87 % of theory) Spiro ^ äziridino (l, 2-c) imidazolidin-3, l'-cyclohexar ^ -one, melting point: 154 - 155 ° C (from Petrol).

Claims (2)

invention claim l. ^A process for the preparation of aziridine derivatives of the general formulas I or II from 2-cyano-aziridine and ketones, characterized in that the ketone used is dried and distilled before use until it is completely free from water, 2. The method according to item 1, characterized in that the Heretellung of compounds of the general formula II alkali metal is added in catalytic amounts. For this ^ ^ pages formulas Z0 3 5 2 investment CN CONH ₀ L, J ² CN O C 7 / / H - alkylate \ / J \ / ^N \ _P ^ ^NH (II N H R e is lower alkyl, where the substituents may optionally be closed to the saturated or unsaturated ring