UA47127U - Fluoronitrobenzene sulfonyl chloride isomers - Google Patents

Abstract

Fluoronitrobenzene sulfonyl chloride isomers of formula (I):(I),wherein,when NOgroup is in position 2 relative to SOCl group, fluorine atom is in 3,4 or 5 position of benzene ring;when NOgroup is in position 4 relative to SOCl group, fluorine atom is in position 2 of benzene ring; andwhen NOgroup is in position 5 relative to SOCl group, fluorine atom is in position 3 of benzene ring.

Description

E E

S- O.S S. ZO, SI

M M

2 What 2 what where when the MO" group is in the 2nd position from In the preferred embodiment of the method, the fluorine atom is in the 3, 4 synthesis, stage a) is carried out in the presence of a base. or 5 position; As a base in stage a) you can use when the MO" group is in the 4th position from any suitable base that binds fluoride to the 5О2СІ group, the fluorine atom is in the 2nd position, which is formed during the reaction, for example , position; and sodium hydroxide, potassium hydroxide, methoxide, when the MO" group is in the 5th position of sodium, sodium ethoxide, potassium tert-butoxide, carbonic 5О2СІ group, the fluorine atom is in 3 of sodium nat, potassium carbonate, sodium hydrogencarbonate, position potassium bicarbonate, cesium carbonate or carbonate

Synthesis of isomers of fluoronitrobenzenesulfo-potassium, 2-tert-butylimino-2-diethylamino-1,3-nyl chloride of formula (I), dimethylperhydro-1,3,2-diazaphosphorine (BEMR),

E tert-butylimino-tri(pyrrolidino)phosphorane (PTPR), sodium hydride or potassium hydride, or amines such as triethylamine, tributylamine, diisopropylethylamine, 2,6-lutidine or dimethylaminopyridine. Mostly

In the second embodiment of the invention, potassium carbonate is used as a basis.

O.M As a solvent in stage a) can be used; () any suitable high-boiling organic solvent, which does not react with the MO» group is in the 2 position of the reagents used, for example, the 5О2СІ group, the fluorine atom is in the 3,4 dimethylformamide, toluene etc., or mixtures of mention- or 5 position of the benzene ring; they are higher than solvents. when the MO» group is in the 4th position of the 5О2СІ group can be used as a solvent in stage b), the fluorine atom is in the 2nd position of the benzene ring; and with water and which does not react with alcohol, when the "MO" group is in the 5 position of the reactants, for example, bearing the 5О2СІ group, the fluorine atom is in the 3 methylene chloride, acetic acid, formic acid position of the benzene ring, includes the following and others, or mixtures of the solvents mentioned above. stages: To create an inert atmosphere, any inert gas can be used to create a) condensation of difluoronitrobenzene of the formula ("in favorable conditions for the target reaction to occur,

For example, argon or nitrogen.

The reaction of stage a) can take place at a temperature from 0°C to the boiling point of the solvent used, but the reaction is mainly

This is done at a temperature from room temperature to the boiling point of the solvent. In any case, the choice

OM of the reaction temperature depends on the reactivity (1) of the starting reagents. with phenylmethanethiol, with the formation of sulfanil. Formula (I) is used as a chlorinating agent in stage b): elemental chlorine, obtained directly, is bubbled through the reaction solution or hypochlorite solution. Simultaneously with chlorination

At the sulfur atom, it is oxidized by chlorine with the formation of a sulfonyl chloride group.

Synthesis of the fluoronitrobenzenesulfonyl chloride isomer of the formula (I),

And Z E

OM x (I) b) chlorination of the obtained sulfanil of formula (II) in the presence of water, with the formation of fluoronitrobenzenesulfonyl chloride of formula (1): OM ; ()

ground, washed with sodium thiosulfate solution. It was dried and distilled in a vacuum, obtaining when the MO" group is in the 2 position of 21g (5195) 2-nitro-3-fluorobenzenesulfonyl chloride, bearing the 5О2СІ group, the fluorine atom is in the 5 position, which crystallized upon standing. Recrystallization - the position of the benzene ring; shafts from hexane, obtaining yellow crystals with a temperature of 51-522С. "H NMR (SOCI3) of 0 tafluorobenzenesulfochloride with a mixture of nitric 7.75-7.78 (m, 1H), 7.83-7.87 (m, 1H), 8.03-8.04 (d, sulfuric acid 18).

The feasibility of the invention is confirmed by the following examples. Preparation of Z-nitro-5-

Examples of fluorobenzenesulfonyl chloride

Example 1 E

Preparation of 4-nitro-2-fluorobenzenesulfonyl chloride

IS

OO O, M 50,

At room temperature, 51 g of 1,3-difluoro-5-

100 ml of nitrobenzene was dissolved in 100 ml of DMF, 69.5 g of potassium carbonate was added, and 39.8 g of phenyl was added dropwise. At room temperature, 30.5 g of 1,2-difluoro-4-methanethiol. Stirred at a temperature of 100" nitrobenzene was dissolved in 200 ml of DMF, added over 10 hours. The mixture was cooled, 55.2 g of potassium carbonate was filtered and 23.8 g of phenyl was added dropwise, and the filtrate was evaporated to dryness, obtaining 78 g of methanethiol. It was stirred at room temperature (8095) 1-benzylsulfanyl-3Z-nitro-5-fluorobenzene ture for 2 hours, then poured into water and I as a yellow-red oil. In the NMR spectrum, the resulting precipitate was filtered off and washed with 2095 disubstituted product. water. 30.4 g was obtained (yield 10096) 1- 166 g of i-benzylsulfanyl-3-nitro-5-fluorobenzene benzylsulfanyl-4-nitro-2g-fluorobenzene as yellow was dissolved in a mixture of 200 ml of methylene chloride and 200 ml of a crystalline substance with the melting point of water. Through the mixture with good stirring 12626. IN NMR (DMSO -dv) b 4.46 (c, 2H), 7.27-7.30 chlorine was blown to saturation. After completion (t, 1H), 7.33-7.36 (t, 2H), 7.45- 7.47 (d, 2H), 7.69-7.72 reactions, the organic layer was separated and washed (t, 1H), 8.04-8.08 (m, 1H) with water and 50.4 g of 1-benzylsulfanyl-4-nitro-2- was stirred over anhydrous magnesium sulfate. Then it was evaporated under vacuum and distilled. Ode-fluorobenzene was suspended in 400 ml of formic acid, 76 g (504905) of 3-nitro-5-acid was added and chlorine was blown until the end of absorption of fluorobenzenesulfonyl chloride. "H NMR (SOCI3) 5 with chloroform, the extract was washed with bisulfite" Example A what! ! ME of sodium and sodium bicarbonate. Evaporated and distilled. Preparation of 2-nitro-4- at Tbop. - 145-152.9 at 2MM Na. 24 Ag (6796) of 4-nitro-2-E fluorobenzenesulfonyl chloride was obtained. "H NMR (SOSIv). 5 8.23-8.29 (m, ZN).

Example 2

Preparation of 2-nitro-3-fluorobenzenesulfonyl chloride MO,

IS

MO, AXIS

At room temperature, 5 g of 1,4-difluoro-2-nitrobenzene was dissolved in 3 ml of DMF, 50.SI ag of potassium carbonate was added, and 3.9 g of phenylmethane-2-thiol was added dropwise. Stirred at room temperature

At room temperature to a solution of Zog 1.3- for 2 hours, then poured into water. The resulting precipitate was added to difluoro-g-nitrobenzene in 200 ml of DMF, filtered and washed with water, 27.6 g of potassium carbonate and added dropwise while cooling. 23.4 g of phenylmethanethiol was obtained with 7 Ag (9096) 1-jenny water. The solution of pebenzylsulfanyl-2-nitro-4-fluorobenzene as yellow was stirred for 2 hours, filtered and the crystalline substance with a melting point was dried to dryness, obtaining H (Z - og 1 5 benzylsulfanyl-2-nitro-3-fluorobenzene as red B) me vv, 7 vad s, (m NU 8 Ov. not oil. In the NMR spectrum, there are 2096 disubstituted-8 bo (d c) ' ' sho ' ' sho product, the mixture was dissolved in 200 ml of methylene- 59.5 1 -benzylsulfanyl-2-nitro-4: fluorobenzene was dissolved in a mixture of 300 ml of water and chloride and 200 ml of water. Then chlorine was passed to 500 ml of methylene chloride and the excess of the end of the reaction (TLC) was blown off. The organic layer was separated

chlorine The solution was poured into water, the organic layer was a mixture of 13 ml of nitric acid, which was washed with water and a saturated solution of thiosuldimite (P 1.5 g/ml) and 2 bml of 9595 sulfuric acid sodium phata. Then evaporated and distilled. Tkip P -1.83). The mixture is cooled in an ice bath to 150-155 C at 2 mm No. 3 g (5755) of 2-weight was obtained and, with stirring, portions of: 4-nitro-4-fluorobenzenesulfonyl chloride were added. NOyaMe 0.05M of 3-fluorobenzenesulfonyl chloride. After pre- (SOSIv) 2 7.57-7.65 (m, 2H), 8.30-8.34 (k, 1H). giving the entire amount of the starting substance is reactive

Example 5 | the mass was stirred at 0-52C for 2 hours, and

Obtaining | 2-nitro-5- then at a temperature of 207C for another 4 hours. After fluorobenzenesulfonyl chloride, this reaction mass with intensive mixing

E was carefully poured into 200 g of crushed ice in the bath, the resulting solution was extracted with diethyl ether (3 x 100 ml). The combined organic fractions were washed with water, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced

AXIS pressure. Bg (yield 5095) of 2-nitro-5-fluorobenzenesulfonyl chloride was obtained, which, if necessary

MO can be recrystallized from hexane. "N

NMR (SOCI3) δ 7.63-7.66 (m, 1H), 7.98-8.05 (m, 2H).

Computer typesetting A. Krulevskyi Signature Circulation 28 approx.

Ministry of Education and Science of Ukraine

State Department of Intellectual Property, str. Urytskogo, 45, Kyiv, MSP, 03680, Ukraine

SE "Ukrainian Institute of Industrial Property", str. Glazunova, 1, Kyiv - 42, 01601