SU466681A3 - Method for preparing carbamate ketoxime derivatives - Google Patents

Description

This invention relates to a process for the preparation of carbamate ketoxime derivatives of general formula I, which are not described in the literature.

L

R

11 4

AT:

RftJ-ti-C-x

carbamyl, acyl, the lower alkyl or alkenyl radicals being substituted by X;

Rg is hydrogen, lower alkyl, while Re, RD and N in the group NRsRg can form a heterocyclic ring.

A known method for the preparation of carbamate derivatives of the general formula wherein R, Ri, R2 and Rs are as defined above, followed by isolation of the desired product by a known procedure. The proposed method for the preparation of compounds of the general formula I is that the compound of the general formula 0-C-N-. I II R O p I II S where Ri-RT are as defined above; Y is a halogen, is reacted with a compound of the general formula HX, where X has the above values, in the presence of an acceptor HY, where Y has the above value, followed by isolation of the target product in a known manner. The compounds obtained according to the inventive method have a high biological activity. In the examples below, all percentages, proportions, and proportions are by weight. Example 1. 3,3-Dimethyl-2-methylcarbamyloximino-1- (pyrrolidinyl) -butane. To a solution of 12.6 g of 1-bromo-3,3-dimethyl-2-methylcarbamyloxy-aminobutane in 100 ml of anhydrous ether, 7.8 g (0.11 mol) of pyrrolidine are added dropwise. The mixture was stirred at room temperature for 1 hour and heated to reflux for 0.5 hour, then cooled and washed with water. The ether solution is separated, dried, and after removing the solvent, 11.8 g of fragrant oil is obtained, which, on standing, hardens into a fragrance, mp. 43-48 ° C. The properties of this and similar compounds obtained by the proposed method are shown in the table. Example 2. 1-Bromo-3,3-dimethyl-2-butanoxime. To a solution of 69 g (1.0 mol) of hydroxylamine hydrochloride in 100 ml of water is added in an ice bath 90 g (0.5 mol) of 1-bromo-3,3 dimethyl-2-butanone. After pouring 100 ml of 95% ethanol, the mixture is stirred for 16 hours and then warmed to room temperature. The resulting white paste is filtered, the solid precipitate is washed with water and dried. 55 g of the expected compound are obtained, mp. 111 -112X. Paydeno,%: N 7.1; Br 42.4. SbP12NVgO. Calculated,%: N 7.1; Br 42.4. Example 3. 3,3-Dimethyl-1-nitro-2-butanoxime. To a solution of 18.2 g (0.26 mol) of sodium nitrate in 130 ml of dimethyl sulfoxide, 29 g (0.15 mol) of 1-bromo-3,3-dimethyl2-butanone oxime were added in portions. Due to the slightly exothermic reaction, external cooling is necessary to maintain the temperature at 27 ° C. Then, continuing to stir, an additional amount of solvent is added. After stirring for 20 hours, the mixture was poured into ice-water and a solid residue was obtained, which was collected on a filter. By recrystallization from the hot benzene-petroleum ether mixture, 10 g of a solid substance with mp. 115-120 With get 7 g of white crystals with so pl. 124-125 ° C. Paideno,%: C 45; H 7.8. Sbp121 20z. Calculated,%: C 45; And 7.6. Example 4. 3,3-Dimethyl-2-methylcarbamylamino-1-methylsulfinylbutane. 9 g of metallic sodium (0.042 mol), 60 ml of water and 25 ml of methanol are mixed and after cooling to 0 ° C, 8.7 g (0.04 mol) of 3,3-dimethyl-2-methylcarbamyloxymino-1- are added in portions methylthiobutane. After stirring at 0-10 ° C for 18 hours, the mixture is warmed to room temperature, then the volatiles are evaporated on a rotary evaporator, and the resulting residue is extracted with ethyl acetate. The dry extract is evaporated to give 9 g (96%) of the desired compound as a viscous yellow oil. Found,%: C 45.2; P 7.5. S9P18M2Oz5. Calculated,%: C 46.1; P 7.7.

The subject matter of the invention.

The method of obtaining carbamate ketoxime derivatives of general formula

KO-1 "

. f 11

II RS to

where X is -SRs, S (0) R8, SOsRs, ORs, OSOsRg, NRsRg, NOz, CN, SCN, N3 or halogen;

Ri is hydrogen, substituted or unsubstituted lower alkyl, alkenyl, alkynyl or X;

Ra, Rs and R4 are hydrogen, substituted or unsubstituted lower alkyl, alkenyl, alkynyl.

moreover, R2 and Ra can form a cycloaliphatic ring;

Rs is hydrogen, substituted or unsubstituted lower alkyl, alkenyl, quinil or X, and when Rs and X -ORe, SRs, S (0) R8, S., NRsRg, TO Rs together with X forms a heterocyclic ring;

Rs and R are hydrogen, lower alkyl, alkenyl, alkyl;

Rs is hydrogen, lower alkyl, alkenyl, alkynyl, substituted or unsubstituted aryl, carbamyl, acyl, and lower alkyl or alkenyl radicals can be substituted with X;

Rg is hydrogen, lower alkyl, while Rs, Rg and N in the NRgRg group can form a heterocyclic ring. 9, characterized in that the compound of the general formula. -D ® I II „1Г О о. (II. 1 i 5 510 where Ri-R have the above values; 10 Y is halogen; react with a compound of the general formula HX, where X has the above values, in the presence of the HY accentor, where Y has the above value, followed by isolation of the target product in a known manner. Priority to features: 08/04/71 with X -ORg, NRaRg, CN, SCN, N02, SRg, S (O) iR8, SOaRs. 02.24.72 with X -SRs, OSOaRs, N3.