DE404174C - Process for the preparation of unsaturated derivatives of cyanamide - Google Patents

Description

Process for the preparation of unsaturated derivatives of cyanamide. It is known that the metal atom in salts of cyanamide is replaced by organic Can replace leftovers. O. Diels and R. Gollmann describe (see reports of the German chemical society vol. 44, p. 3158) the conversion of the cyanamide into the cyanimidodicarboxylic acid ester by means of chlorocarbonic acid ester in the presence of sodium hydroxide solution. In the same way They carried out cvanamide using dimethyl sulfate in an aqueous alkaline solution in dimethyl cvanamide above. Extensive attempts have also been made. Traube and Alfred Engelhardt (see reports a. a. O. Vol. Q.q., p. 3149) where it is shown that cyanamide sodium and Cyanamide calcium in alcoholic solution with haloalkylene in dialkyl cyanamide derivatives can be transferred; so became diethyl cyanamide, diisoamyl cyanamide and dibenzyl cyanamide won. If you now work according to the same method with allyl haloids and substituted ones Allyl haloids, the diallyl cyanamide derivatives are obtained in an unfavorable yield, because much of the allyl halide is altered in other ways. On the other hand succeeds here the representation of the diallylcyanamide derivatives is very smooth; when you are in the present Allyl haloids act on cvanamide salts of water with strong turbines. The reaction can take place at ordinary temperature or at a little elevated temperature be made. Comparative tests showed that the saturated alkyl haloids do not react or react very slowly under these conditions.

Mird z. B. 1 mol. Sodium cyanamide in aqueous solution with 2 mol. Propyl bromide shaken for 48 hours at ordinary temperature, the reaction product can be removed almost all of the propyl bromide used can be recovered unchanged. Even when heated, no reaction occurs in the aqueous solution.

Similar to the allyl haloids, other unsaturated aliphatic or aromatic-aliphatic haloids behave, in particular those which have the grouping CRRI = CH. CH, Hlg contain (R and R1 = M-hydrogen, alkyl or aryl), such as. B. Isoprene hydrobromide (CH3) 2C = CH- CH, Br, styrene bromide, C, H; CH = CH - CH, Br, geranyl chloride, (CH,), = CH - CH, - CH, - C (CHz) = CH - CH2 Cl.

The process products should be used as starting materials for the production of Medicinal products serve. Example.

A solution of zoo g of 83% sodium cyanamide (1 mol.) In zoo ccm of water is shaken or turbinated for 48 hours with 242 g of allyl bromide (2 M01.), Expediently with initial cooling. After this time the supernatant 01 is lifted and thus the Diallvlcvanamid as a colorless liquid, bp. 95 'at 9 mm was obtained in a yield of 85 percent.

When using allyl chloride, in order to achieve rapid conversion, heat to 40 '.

In the above example, if the allyl bromide is replaced by the equivalent Amount of dimethyl allyl bromide or styryl bromide, tetramethyldiallylcyanamide is obtained or distyrylcyanamide.

The tetramethyldiallylcyanamide forms a colorless liquid that boils at 1413 to 142 'at 13 mm pressure, the distyrylcyanamide is a colorless substance with a melting point of 82'.

It is known that alkylene haloids, especially allyl haloids, in many cases are distinguished from the alkyl haloids by increased reactivity (see e.g. patent specification 268z58). However, from the known facts on the influence of the solvent on the reactivity of the allyl haloids in the sense of the present invention do not extract anything.

Claims (1)

PATENT CLAIM: Process for the preparation of unsaturated derivatives of the cyanamide, characterized in that one unsaturated aliphatic or aromatic aliphatic haloids with cyanamide salts in the presence of water in the cold or reacts with heating.