SU786890A3 - Method of preparing substituted thioureidobenzene - Google Patents

Description

at room temperature with stirring, after which the mixture is heated and kept under reflux for 1 hour. Then the mixture containing the formed ethoxycarbonyl isothiocyanate is cooled to room temperature and 6.8 g (0.04 mol) is added to the cooled mixture with stirring N, M-dimethyl-o-phenylenediamine. Next, the reaction mixture is stirred at room temperature for 30 minutes and poured into water. Filter the mixture, rinse the obtained crystals with water and dry. 11.3 g (0.04 mol) of 1- (N, H-dimethylamino) -2- (3-ethoxycarbonyl-2-thioureido) -benzene crystals, raw in the degree of purity, are obtained. The crystals have a melting point of 110 ° C. After recrystallization from an aqueous solution of methanol, light yellow crystals are obtained. 111- 113 ° C. Found,%: C 53.75; H 6.42; 15.85. Cf2H, 7 N302 H 6.37j Calculated,%; C 53.93, N 15.73. and p and m 4. 4. 1-Benzylideneamino-2- (3-methoxycarbonyl-2-thioureido) benzene. 10.4 g (0.11 mol) of methyl chloroformate is gradually added to 11 g (0.11 mol) of dry potassium thiocyanate dissolved in 30 ml of acetone, at room temperature with stirring, after which the mixture is kept. 30 min under the action of the reverse refrigerator. The mixture containing the obtained methoxycarbonyl isothiocyanate is cooled and maintained at a temperature below –5 ° C on a cooling mixture. A solution of 19.6 g (0.10 mol) of 2-benzylide aminoaniline in 30 ml of acetone is added dropwise to this mixture, and the reaction mixture is kept at a temperature below -5 C on the cooling mixture with stirring. The reaction mixture is then kept at room temperature for 30 minutes with stirring. By adding about 200 ml of water to the mixture, light yellow crystals are obtained, a precipitate is formed. The mixture is filtered using suction, the resulting crystals are washed with water and dried. After recrystallization from ethanol, 25 g of crystals are obtained, having a decomposition temperature of 145-146 seconds. Found,%: C 61.37; H 4.75; N 13.37; S 10.25 C 16 H, 5 N., 025 Calculated,%: C 61.34; H 4.79; N 13.42, S I0.22j. EXAMPLE 5. 1- (3-N, N-Dimethylthiocarbamoyl-2-thioureido) -2- {3-methoxycarbanil-2-thioureido) -beneol. 20 ml of an acetone solution containing 7.3 g (0.05 mol) of freshly prepared dimethylthiocarbamoylisothiocyanate are added dropwise to 11.3 g (0.05 mol) of 2- (3-methoxy-parbonyl-2-tiopyreido) -aniline in 50 ml acetone, and the reaction mixture is maintained at a temperature below the cooling mixture with stirring, then kept at room temperature for 1 h with stirring. Then, acetone was distilled off from the mixture under reduced pressure, and the residue was washed with water. Using recrystallization from ethanol, 12 g of crystals with a decomposition temperature of 148-149 ° C are obtained from the residue. Found,%: C 41.85, H 4.60, N 18.85 :, S 25.80 s, 50283 Calculated,%: C 41.94, H 4.58; H 18.87 S 25.88. Compounds obtained by the proposed method can be converted into the corresponding salts by addition of the corresponding acids. Some of the typical compounds obtained are listed in the table, with the values of the melting point or decomposition temperature (p) for each of the compounds.

2- (3-Methoxycarbonyl-2-thioureido) -aniline

184-185 (p)

2- (3-Ethoxycarbonyl-2-thioureido) aniline

162-162, 5 (p)

Achn-c-mn-c-o-ccC CH-j, 2- (3-iso-propoxy-carbochenyl-2-thioureido) aniline

137-138

Table continuation

Continuation of the table HH-.C-1IH-C-OC2H NH-CII j About UH - (- lfH-C-0 (J2H $ (i IfH-CO-CH II KH-C-litH-jj-OtiHs 0 TsTH-C -OCaHg 1-Benzamido-2- (3-ethoxycarbonyl-2-thioureido) benzene 192-193 1-methoxycarbonamido-2- (3-ethoxycarbonyl-2-thioureido) benzene 1b8-170 (p) 1-Ethoxycarbonamido-2- ( 3-methoxycarbonyl-2-thioureido) benzene 147-149 (p)

Table continuation

148-149 (p)

159-160 (p)

145-146

183-183,5 (p)

$ o

1- {4-Netoxybenzylideneamino)

IIb.

O-ifH-d-oclHj -2- (3-methoxycarbonyl-2-thiopeido) benzole

tО

-1GN-С-0} 2Н5

1- (3-Nitrobenzylideneamino) -2- (3-ethoxycarbonyl-2-thioureido) benzene

Claims (1)

Invention Formula The method of obtaining substituted ureidobenzene of the general formula HH-C-SH-tf-OKi Z 159-159,5 (p) 185 (p) where X is hydrogen, chlorine, methyl, nitropyclic Z is or -N R alkyl Cc-C, Rj is hydrogen, methyl, R is hydrogen, methyl, form 1l, Cjj is alkylcarbonyl, cyclopropylcarbonyl, benzoyl. C C-alkoxycarbonyl, alkylaminocarbonyl, thioformyl, unsubstituted or Cd-alkyl, amine noothiocarbonyl, 3,3, -dimethylureidothiocarbonyl, .3,3-dimethiLioureidothiothiocarbonyl, unsubstituted or substituted by chlorine, nitro or methoxy, benzal, thyroid, thiocarbonyl, unsubstituted or substituted by chlorine, nitro or methoxy, benzyl, thyroid, thiocarbonyl, unsaturated or Since the substituted aniline of the general formula where X and 2 - have the indicated values, is reacted with the substituted carbonyl isothiocyanate of the general formula. SdK-c-ORt where R.J - have the indicated meanings, followed by isolation of the desired product as a base or salt. Priority by featured. 06/18/68 at X is hydrogen, chlorine, methyl or nitro, Rt is methyl, ethyl, RjR, KZ-BODODorod or Rg is aborigine and Rj is methyl, R 2 and Yaz are hydrogen and R3 is methyl. hydrogen, R ,,; R2-water RJ-aminothioxycarbonyl, methyl amy noocarbonyl, ethyl, hydrogen, Rj-hydrogen, Cj-Cd-alkylaminocarbonyl, ethoxycarbonyl, R-methyl, X-hydroelectric, Z -N R2 Rji R and hydrogen, methyl, hydrogen Z-- NR R RHH Rj, hydrogen or R2 water and Rj-cyclopropylcarbonyl, benzoyl, formyl, Cj | C-alkylaminothiocarbonyl, 3,3-dimethylthioureidothiocarbonyl, 3,3-dimethylureidothiocarbonyl, thio formyl,. - N Poison, Poison - unsubstituted or benzal, or benzene, nitro or methoxy group, benzal, 0 -04-SKYLE. formations, at examination 57723, 67 (prototype)