SU421197A3 - METHOD FOR OBTAINING 2-IMINO-1,3-DITHIAN-DERIVATIVES - Google Patents

Description

one

The invention relates to a method for producing 2-imino-1,3-dithian derivatives not described in the literature of general formula I

R

.N-)

/

R

where RI is a straight or branched alkyl group with 1-5 carbon atoms;

Ra is hydrogen, straight or branched alkyl group with 1-5 carbon atoms,

or their salts, which can be used in agriculture as biologically active substances.

A known method for the preparation of iminodithiols, the nitrogen atom of which is bound to a hydrocarbon radical, is heating ethylene monocarbonate with an isocyanate containing a hydrocarbon radical, or a thiourea containing one or two hydrocarbon radicals, for example alkyl, aryl, aralkyl or cycloalkyl.

A method for the preparation of compounds of the general formula I or their salts is proposed, in that the compound of the general formula II

ZCH-z-CHlNRiRjl-CHzZ

where RI and RS are as indicated;

Z is a leaving group, for example a halogen or tosylate, preferably chlorine,

subjected to interaction with the salt of cyanimine thiomethylthiol carbonate formula III

Mes

,

/

where Me is a cation, preferably potassium, followed by isolation of the target product in free form or in the form of a salt by known methods.

The process for the preparation of compounds of general formula I is carried out as follows.

Two equivalents of the compound of general formula III are dissolved in a suitable solvent, e.g. alcohol, and preferably at elevated temperature, e.g. 70-75 °, and stirred with a compound of general formula II in a suitable solvent, e.g. alcohol, for -20 minutes The reaction mixture is stirred for 10 minutes at 70-75 ° C, cooled is given, filtered from precipitated salt and treated in a well-known way. Salts of compounds of formula I are prepared by pressing the corresponding acid in a suitable solvent to the corresponding compound of formula I.

From the salts of the compound of formula I, the corresponding compounds can be obtained in the form of crystalline substances by reacting them with an alkali.

Example 1. 2-Cyanimino-5-dimethylamino, 3-dithian.

. 214 g (1.26 mol) of potassium cyanimothiomethylthiol carbonate in 600 ml of alcohol is heated to 70-75 °. A solution of 0.635 mol of 1,3-dichloro-2-dimethylaminopropane, prepared from 122 g (0.635 mol) of 1,3-dichloro-2-dimethylaminopropane hydrochloride in 400 ml of alcohol and 35.2 g (0.63 mole) KOH in 200 ml of alcohol and after filtering out the precipitated KC1, for 20 minutes at 70-75 ° C. Stir further for 10 minutes at the same temperature and cool to room temperature. Potassium chloride is filtered off and the filtrate is evaporated under a water-jet pump under vacuum at 50 °. The oily residue is dissolved in 500 ml of chloroform, washed twice with water, using 200 ml of water each, and dried with sodium sulfate. After evaporation of the solvent in vacuo at 50 °, 40 ml of diethyl ether are added to the oily residue and cooled to 0 °. With this, 2-cyanimino-5-dimethylamino-1, 3-dithiane crystallizes out. Sucked off, washed with an additional small amount of ether or alcohol and get a clean connection with so pl. 98.5 °.

Calculated,%: C 41.8; P 5.5; N 20.9; S 31.9.

CrHiiNsSa (mol. C. 201.3)

Found,%: C 41.5; H 5.6; N 21.0; S 32.2.

Example 2. Oxalate 2-cyanimino-5-dimethylamino-1, 3-dithiane. 50 g (0.25 mol) of 2-cyanimino-5-dimethylamino-1, 3-dithiane are dissolved with stirring at 50 ° in 200 ml of alcohol and 22.5 g (0.25 mol) of oxalic acid in 100 ml are added alcohol. Oxalate falls out. After cooling to room temperature, the solvent is filtered off with suction. Oxalate still falls out when the mother liquor is evaporated to a volume of about 50 ml. After drying under vacuum at 50 ° C, the 2-cyanimino-5-dimethylamino-1, 3-dithianal oxalate melts at 154 °. Calculated,%: C 37.1; H 4.5; N 14.4; S 22.0.

C7HiiN3S2-C2H2O4 (mol. C. 291.34) Paideno,%: C 37.0; H 4.8; N 14.8; S 22.4.

Subject invention

The method of obtaining 2-imino-1,3-dithian derivatives of General formula I

S /

where RI is a straight or branched alkyl group with 1-5 carbon atoms;

R2 is hydrogen, a straight or branched alkyl group with 1-5 carbon atoms,

or salts thereof, characterized in that the compound of general formula II

zCH7-CH (KTliU2) -CH2Z

where RI and R2 have the indicated value;

Z is a leaving group, for example a halogen or tosylate,

subjected to interaction with the salt of cyanimine thiomethylthiol carbonate of General formula P1

Mes

C N-CHN

SNL5

where Me is a cation,

with the subsequent selection of the target product in free form or in the form of a salt.