SU242776A1 - - Google Patents

Description

METHOD OF OBTAINING ORGANIC COMPOUNDS The invention relates to the field of obtaining new physiologically active compounds. A method of producing compounds of the general formula where RI is an alkyl group with 1-6 carbon atoms or an aralkyl group with 7-9 carbon atoms, Ra and Rg is hydrogen, chlorine or brOM, and one of the substituents must be a halo, is proposed. is that the compound of the formula. 5 10 15 20 25 The compound is treated in an aqueous medium with potassium iodide and sodium pyrosulfate or phosphorous acid, the resulting product is affected by sodium sulfide IB alkaline medium, any known alkylating agent or aralkylating agent, and then reduced with hydrogen at the time of isolation. In the interaction of the starting compound with chlorosulfonic acid, a homogeneous product is obtained in the case that Ra and Rs are chlorine or 1 bromine. If, on the other hand, one of the substituents is hydrogen, then the resulting mixture is isomericus separated to isolate the desired compound. Or the mixture is diazotized and the resulting diazonium salt is treated with sulfuric anhydride in an organic solvent medium. Example 1. 2,4-D their lo-r-Za m in OTI 0a and 3 o l. a) 2,4-Dichloro-3-nitro-benzenesulfonyl chloride. 300 g of 2,6-dichloronitrobenzene are added to 550 ml of chlorosulfonic acid with stirring and room temperature. The resulting mixture is kept for 2 hours at an internal temperature of 145 ° C. Then the reaction mixture is poured onto 4 kg of ice, filtered 1 with + 5 ° C, washed thoroughly with water and dried. Crude 2,4-dichloro-3-nitrobenzenesulfonyl chloride is recycled nep) b) 2,2,4,4-tetrachloro-3,3-din 1 nitrodiffe- nyldrg sulfide.

A mixture of 480 g of 2,4-dichlor-3-nitrobenzenesulfonyl chloride, 27.5 g of potassium iodide, and 400 ml of water was stirred at 70 ° C (bahi temperature) until iodine was released. Then, over 3 hours, a solution of 418 g of hydroxy sulphite is poured; Sodium 720 ml of water is taim oi 6 rasm, so that some iodine is contained in the solution. After adding half the solution, the bath temperature is raised to 90 ° C. Upon completion of the reaction, the composition is cooled, filtered, washed with water and dried. After recrystallization from ethyl islet, pure 2,2,4,4-tetrachloro-3, 3-di-TrOт Diphenyl is obtained, and the sulfide with m.p. 180-182 ° C.

c) 2,4-Dichloro- | 3-Nitrothianisol.

To a suspension, 194 g of 2,2,4,4-tetra, and “lor-3,3-dinitrodi | fe1yldisulfide] ida in 800 ml of methanol are poured at room temperature for 0.5 hour with a 60% solution 19 , 8 g of sodium sulphide and 26.2 g of sodium hydroxide in 400 ml of water, then the solution is maintained at the ambient temperature for 0.5 hour, and at 55 ° C for 1 hour (bath temperature). The resulting solution is filtered, 600 ml of methanol and 200 ml of water are added to the solution, and then 136 ml of dimethylsulphate is added dropwise at room temperature with HI stirring. After half an hour, it is added dropwise and, with a slight cooling, 60 ml of a 30% aqueous solution of sodium hydroxide are stirred for another 15 minutes. Dilute with 2.7 l of water, filter, wash thoroughly with water, and dry. After recrystallizing from n-hexane, pure 2,4-dichloro-3-nitrothioanisole is obtained, mp. 100-102 ° C.

d) 2,4-Dichloro-3-aminothioanisol.

A mixture of 10 g of 2.4-D | Ichlor-ZchnitrotiOanizol-, 7, 1 g of iron dust and 20 ml of water and replenishing is carried out for 1 hour at llO ° C (bahium temperature). Pour 0.5 ml of concentrated hydrochloric acid and products stir for another 1 hour. After cooling, 100 ml of chloroform are poured in., Filtered, and the cold layer is separated. After drying over 1 m of sulfate, the stumps are evaporated, the residue is recrystallized from 50 ml of n-hexane. The resulting pure 2,4-dichloro-3-aminothioanisol has it. M. Pl. 51-54 ° C.

Example 2. 2,4-.D and chlo about p-Z and m and N about f enylbenzylsulfide.

The reaction is carried out as described in Example 1 (c). The following amounts are taken: 9.5 g of 4,4,4-tetrachloro-3,3-dinitrodiphenyl disulfide, 600 g of methanol, 15.3 g of sulfur dioxide (bo-nsh), 20.3 g of sodium hydroxide at 310. water and 127 ml of chloride: bvnzila. Dilute with 500 ml of water, filter, wash and dry. After recrystallization from 400 ml of ethanol, pure 2,4-dichloro-3-nitrophenyl benzyl sulfide is obtained, m.p. 92-99 ° C.

Restoration was carried out as described in Example 1 (d). 152 g of 2,4-dichloro-Znitrophenylbenzyl sulfide, 81 g of iron powder (dust), 600 ml of water and 5.7 ml of concentrated hydrochloric acid are used. After recrystallizing the residue after distilling off the chloroform from 100 ml of ethanol, pure 2,4-di, chloro-3-aminophenyl | L bepsyl sulfide is obtained, m.p. 59-61 ° C.

example 3. 2,4-D И1Х l about r-ZA. m and N. o.fen and l and 3 about b at t and l with at l f f and d.

From 2,2,4,4-tetrachloro-3,3-dinitrodiphenyl disulfide, according to the procedure described in example 1 (IB), the disulfide is cleaved and

then alkylating with isobutyl bromide-2, 4-dichloro-3 - nitrophenyl isobutyl sulfide, m.p. 152 ° C (at a residual pressure of 0.2 mm Hg. Art.). Reduction of 2,4-di1-chloro-3-nitrophenyl iso-butyl sulfide described in Example 1 (g)

2,4-dichloro-3-ami-1NOINISIS butylsulyfide, t. bale is obtained by the method. , 115 ° С (residual

pressure 0.1 mm Hg. Art.).

Example 4. 4-hl о.р-3-a m Inoti oann 3 O l.

An iB solution of 50 2 4-chloro-3-nitrothioanisole, 8.8 ml of concentrated hydrochloric acid and 150 ml of methanol are added over a period of 0.5 hour while being transferred and at an oil temperature

baths 100 ° C iron dust pordi-mi (only 44.7 g) and continue to boil for 5 hours. The reaction mixture is alkalinized with 15 ml of a concentrated solution of sodium hydroxide, methanol is distilled off under vacuum. To the residue after

120 ml of water and 150 ml of chloroform are poured over the flasks and filtered. The chloroform layer is separated, washed with water, evaporated and distilled off under vacuum. The main fractions of 4-chloro-3-am1Inoothianisol boils at 158-

160 ° С (residual pressure 12 Л1М рт. Ст.).

Pr. And mep 5. 2-h l about m and n about t and about and n and 3 about l.

a) 2-Chloro-3-nitrobenzenesulfonyl chloride.

In a mixture of .100 g of 2-chloro-3-nitroaniline with

1020 ml of concentrated hydrochloric acid, with stirring at 0 ° C: a solution of 48.4 g of nitrate, sodium chloride in 175 ml of water is added dropwise for 0.5 hour and incubated for 15 minutes. Cold diazo solution rush

(for each, mp, m) for 1 hour to a solution of 16.2 g of copper chloride, 39 ml of water and 1200 ml of glacial acetic acid, which contains 28% of sulfurous anhydride, and 25–30 ° C (the temperature inside the reaction masses) and

aging, they are 15 minutes. The reaction mixture is poured into 3200 ml of ice water, the precipitate is filtered off and dried. After recrystallization from three times of 0 isome of isopropyl ether, pure 2-chloro-3-nitrobenzenesulfonyl chloride is obtained, m.p. 76-78 ° C.

stirring for 1 hour and internal temperature of 85 ° C, a solution of 97.5 g of 2-chloro-3-nitroben Zol ultrachloride in 5 ml of glacial acetic acid, then incubate for 1.5 hour at an internal temperature of 95 ° C to complete the reaction. After rising, 950 ml of water is cooled, filtered and dried. After double-non-recrystallization (each time), a pure 2, 2-dichlorop-3, 3 dinitrodipheny, ldisulfide, t. L. Is obtained from a threefold volume of 4-methylpentane 1H-2-ol. 179-18GS.

c) -2-Chloro-3-nitrothioanisole.

For suspension 60.4 g of 2,2-dichloro-3,3-dilitrodiphenyl disulfide: in 240 ml of methanol, a solution of 22.4 g of sodium sulfide nonhydrate and 10.6 g of sodium hydroxide in 160 ml is poured over 15 minutes at 20 ° C water and maintained at 50 ° C (internal temperature) 45 min. Then the solution is filtered from the insoluble part and 50 ml of dimethyl sulfate is poured into the filtrate for 0.5 hour with stirring and at a room temperature. After 0.5 hour, pour in 24 ml of concentrated pacTBOipa sodium hydroxide and 1100 ml of water, cool to 0 ° C, filter and dry. After recrystallizing from eight times the volume of isopropanol, pure 2-chloro-3-nitrothioanisole is obtained, mp. 94-96 ° C.

d) 2-Chloro-3-aminothio-1 Nizol.

To a mixture of 59 g of iron powder (dust), 5 ml of concentrated hydrochloric acid and 90 ml of water at 130 ° C (bath temperature) are poured over 1 hour while stirring a solution of 55.7 g of 2-chloro-3-nitrothioanyl 130 in 280 ml of ethanol and continue to heat for another 1 hour. The reaction mixture is evaporated; the residue after evaporation is treated with 250 ml of chloroform and; filtered; and after separation of the chloroform layer, it is washed with water and evaporated. As a result of the recrystallization of the residue (after evaporation) from nine times of petroleum ether (in the ratio 1: 2, the petroleum ether is boiling low), pure 2-chloro-3-aminothioanisol is obtained, m.p. 45-47C.

Example 6. 2,4-D and br o m-3-amine oEoan from OwT,

a) 2,4-Di | bromo-3-nitrobenzenesulfonyl chloride. iB 396 ml of chlorosulfonic acid

stirring at room temperature and 314 g of 2,6-dibr0mnitr0 | benzene and the mixture is kept for 2 hours at 145 ° C (temperature in the flask). Then poured on 4 kg of ice, filtered at 3 ° C, carefully. Wash with water and dry. The substance is dissolved in 330 ml of chloroform, 1 l of n-hexane is added, the o.ch is cooled and filtered. The resulting pure 2,4-dibromo-3-nitrobenzenesulfachlo. Is melted at 116-118 ° C.

b) 2,24,4-Tetrabrom-3,3-dinitrodiphenyl disulfide.

bath) until iodine is released. Then, for 5 hours at a internal temperature of 70–9.0 ° C, a solution of 304 g of sodium sulfate in 550 ml of water is poured so that there is always a certain amount of iodine in the solution. At the end of the silving, the mixture is kept for 30 minutes at (temperature, bani,), cooled, filtered, thoroughly washed with water, and dried. After recrystallization, pure 2.2H, 4tetrabrom-3, i3 - dinitrodiphenyl disulfide, m.p. i 35-237 C.

c) 2,4-Dibromo-, 3-nitroti.oanisole.

To a suspension of 98.3 g of 2,2,4,4-tetrabromo-3,3-dinitrodiphenyl disulfide in 700 ml of methanol at room temperature are poured in for 0.5 hour with a 607 o. Solution of 7.2 g of sodium sulfide and 9.5 g of sodium hydroxide in 145 ml of water, then give half an hour at room temperature and 1 hour at 70 ° C (bath temperature) to bring the reaction to completion. The resulting solution is filtered, the filtrate is diluted with 150 ml of methanol and then with stirring and 40 ° C (internal temperature), vl. Gives 49 ml of dimethyl sulfate. After 0.0 hours, add 23 ml of 30% caustic soda solution under low cooling and continue stirring for 15 minutes. Diluted with 1 liter of water, filtered, thoroughly, washed

water and dry. After recrystallization from 907 o ethanol, pure 2,4-dibromo-, 3-nitroT (Oanisole, mp 102-104 ° C) is obtained.

g) 2,4-Di bromo-3-aminothioanisol.

A mixture of 75.5 g of 2,4-dibrom-3-nitrothio. Anisole, 50 and iron dust and. A ml of water is stirred at (bath temperature), and 105 ml of concentrated hydrochloric acid are poured in over 1 hour and 45 minutes and the mixture is heated for 4 hours. Cool, add 300 ml of chloroform and 155 ml of concentrated ammonia and filter.

The chloroform layer is separated, dried over

magnesium sulfate and evaporated. Sediment after

evaporation is recrystallized from ethanol and.

get pure 2,4-dibromo-3-aminothioanisol, t. pl. .

Subject invention

50

Method of obtaining organic compounds of the general formula

55

Sr,

ti

60 7 must be halogen, characterized in that the compound forms 5 g where R 2 and C 3 are as defined above, are reacted with chlorosulfoic acid with subsequent treatment (The obtained 1p ETN product with potassium iodide and sodium pyrosulfate or a phosphoric acid, alkylated or in araline. and hydrogen IB is release.