SU501668A3 - The method of obtaining derivatives of 2-aminobenzylamine - Google Patents

Description

(54) METHOD FOR PRODUCING 2-AMINOBENZSH1AMIN DERIVATIVES

The proposed method allows to obtain the desired products with a yield of up to 82%.

Compounds of the general formula NaK used as starting products. is clear

U o u "

NH-C

I/

where Hal and RI have the indicated meanings, are - new, and can be obtained by benzoxing 2 - aminobenzaldehyde of the formula HctC. SSS

where Hal and RI have the indicated meanings by oxidizing compounds of the general formula

Us (,. (.

2 days

 NH-C-Q

where Hal and Rj have the indicated meanings, and X is a hydroxy group or a chlorine, bromine or iodine atom, by reacting compounds of the formula 3 CHO

where Hal and RI have the indicated meanings, Y is a halogen volume, with benzamide.

Example. N (2 - amino 3,5 ibromobenzyl) hydrochloride - .N - methyl -. trans 4 - aminoiklohexanol.

5 g of 2 - amino 3,5 - dibromobenzaldehyde, 5.75 trans - 4 - methylamino - cyclohexanol and 2 mi of tetravic acid are heated to 200 ° C for 30 minutes, during which the water formed is distilled off. Then add the same amount of amine and ferric acid and heat for 1.5 more hours. The reaction product is dissolved in 0.5 L of dilute ammonia and 50 ml of chloroform. The chloroform phase is separated and the aqueous phase is extracted by shaking with 50 ml of chloroform. The combined chloroform phases are dried. The residue is dissolved in 30 ml of ethanol and acidified with ethanolic hydrochloric acid. After the addition of a small amount of simple ether, the hydrochloride crystallizes out.

Output. 6.3 g (82% of theory, t.pcs.216.5-217.5 ° C (decomposition).

PRI mme R 2. N - (2 - amino - 3,5 dibromobenzyl) - trans - 4 - aminocyclohexanol hydrochloride.

5 g of 2-amino-3,5-dibromobenzaldehyde, 5.75 g of trans-4-amino-cyclohexanol and 2 ml of formic acid are heated to 200 ° C for 30 minutes while the formed water is distilled off. The same amount of amine and formic acid are then added and heated for another 1.5 hours. The reaction product is dissolved in 0.5 l of diluted ammonia and 50 ml of chloroform. The chloroform phases are dried. The residue is dissolved in 200 ml of 2N. hydrochloric acid solution, boil some

reflux, provide activated carbon, alkalinize with concentrated ammonia and extract twice with shaking with 50 ml of chloroform each time. . The combined chloroform phases are concentrated to dryness. The residue is dissolved in 30 ml of ethanol and acidified with a hydrochloric acid ethanol solution. After adding a small amount of ether, the hydrochloride crystallizes out. Output 4.5 g (60.6% of theoretical),

T.PL. 233-234 ° C (decomposition).

PRI me R 3. N - (2.-Amino-3,5-dibromobenzyl) -N-methylcyclohexylamine is prepared from 2-amino-3,5-dibromobenzaldehyde and N. - methylcyclohexylamine according to example 1.

I Temperature pl. hydrochloride 232-235 ° O (decomposition).

Example4. N- (2-amino-3,5-dibromobenzyl) -N-methyl-cis-3-amino-cyclohexanol is obtained from 2-amino-3.5-dibromobenzaldehyde and cis-3-methylamino-cyclohexanol in Example 1.

Temperature pl. hydrochloride 207-208 ° C (decomposition).

PRI me R 5. N - (2 - benzoylamino - 4-chlorobenzyl) - N - methylglycine-propylamine.

10.4 g (0.04 mol) of 2-benzoylamino-4 chlorobenzaldehyde and 26.0 g (0.2 mol) of sarcosinisopropylamine are mixed dropwise with 7.64 ml (0.2 mol) of 98% formic acid, heating to about 60 ° C. Then the reaction mixture is heated to 150 ° C for 5 hours. After cooling, another 0.2 mol of formic acid and 0.2 mol of sarcosinisopropylamine are added. After holding the mixture for 5 hours at 150 ° C, it is cooled, 0.2 mol of formic acid and sarcosinisopropylamine is added and heated for another 8 hours to 150 ° C. The cold mixture is displaced from about 200 ml of 2N: solution caustic soda and extracted with chloroform. The organic phase is washed with water, dissolved over magnesium sulphate and evaporated in vacuo. A brown oil is obtained which is purified chromatographically. The oily residue, obtained after ynapHBai-ftiH, is crystallized by dissolving approximately 10 ml of isopropanol. Cool strongly (ice / methanol), filter, crystallize from 10 ml of isopropanol.

Yield 6.1 g (40.8% of theory); T.PL. 140-142 ° C.

PRI me R 6. N - (2 beoyoylamino - 6 bromobenzyl) .- N - methylglycine morphine-get

IE 2 - benzoylamino - 6 - bromobenzaldehyde and

sarcosine morpholide in Example 5; m.p. 159-1b1 ° C.

Example 7. N- (2-benzoylamino-6 chlorobenzyl) -N-methyl glycine morpholide.

2.6 g 2 - benzoylamino - 6 chlorobenzaldehyde,

15.8 g sarcosinmorphrolide and 4.6 ml formic acid

acids are heated to 150 ° C for 2.5 hours.

The cooled reaction product is dissolved in 20 ml.