UA47128U - Process for the synthesis of fluoronitrobenzene sulfonyl chloride isomers - Google Patents

Abstract

A process for the synthesis of fluoronitrobenzene sulfonyl chloride isomers involves following stages:condensation of difluoronitrobenzene of formula (I):(I)with phenylmethanethiol to provide sulfanyl of formula (II):(II),chlorination of the prepared sulfanyl of formula (II) in the presence of water to provide fluoronitrobenzene sulfonyl chloride of formula (III):(III).

Description

Therefore, the task of the proposed useful model can be to create an inert atmosphere is the synthesis of fluoronitrobenzenesulfonyl chloride isomers, any inert gas is used that creates a red, using a simple synthesis technique, favorable conditions for the target reaction to occur, fluoronitrobenzenesulfonyl chlorides and available ex- for example, argon or nitrogen. moving substances The reaction of stage a) can proceed at temperature

The task is solved thanks to the temperature from 0°С to the boiling temperature using the synthesis of isomers of fluoronitrobenzene sulfonated solvent, but mainly the reaction of provonyl chloride, which includes the following stages: at room temperature to the temperature a) condensation of difluoronitrobenzene of the boiling formula of the solvent In any case, the choice (): reaction temperature depends on the reaction

Effectiveness of starting reagents.

As a chlorinating agent in stage b), elemental chlorine is used, which is obtained without

E (), medium, and is bubbled through the reaction solution, or hypochlorite solution. Simultaneously with the chlorination of the sulfur atom, its oxidation by chlorine with phenylmethanethiol occurs, with the formation of sulfanil and the formation of a sulfonyl chloride group. formula (I): The possibility of implementing the invention is confirmed by the following examples.

Examples

Example 1

Preparation of 4-nitro-2-(1), fluorobenzenesulfonyl chloride

E om OSI b) chlorination of the obtained sulfanil of formula (II) in the presence of water, with the formation of fluoronitrobenzenesulfonyl chloride of formula (I): 2

E At room temperature, 30.5 g of 1,2-difluoro-4-nitrobenzene was dissolved in 200 ml of DMF, 55.2 g of potassium carbonate was added, and 23.8 g of phenyl-50.SI (11) was added dropwise. methanethiol. Stirred at room temperature for 2 hours, then poured into water and

OM, the precipitate obtained was filtered and washed

In a preferred embodiment, the method is carried out with water. 730.4 g (yield T0096) was obtained /1- synthesis stage a) is carried out in the presence of a base. benzypsulfanyl-4-nitro-2-fluorobenzene as yellow

As a base in stage a) you can use a crystalline substance with a melting point of any suitable base that binds water fluoride- 12670. "H NMR (DMSO-aiv) 5 4.46 (s, 2H), 7.27-7 ,30 nu, which is formed during the reaction, for example, (t, 1H), 7.33-7.36 (t, 2H), 7.45-7.47 (d, 2H), 7.69-7, 72 sodium hydroxide, potassium hydroxide, sodium methoxide (t, 1H), 8.04-8.08 (m, 1H), triium, sodium ethoxide, potassium tert-butoxide, carbo-ZO, Ag 1-benzylsulfanyl-4- sodium nitro-2-nate, sodium hydrogencarbonate, fluorobenzene hydrogencarbonate were suspended in 400 ml of potassium formate, cesium carbonate or potassium carbonate, 2-tert-acid, and chlorine was blown until the absorption of butylimino-2-diethylamino-1,3-dimethylperhydrogen was complete. The solution was poured into 2 liters of water, extracted with 1,3,2-diazaphosphorine (BEMR), tert-butyliminochloroform, the extract was washed with tri(pyrrolidino)phosphorane bisulfite (PTPR), sodium hydride and sodium bicarbonate. , or amines, such as triethylamine, taken at boiling point - 145-1 52.9 at 2 mm Na. I get tributylamine, diisopropylethylamine, 2,6b-lutidine, 2AAG (6775) 4-nitro-2- or dimethylaminopyridine. In the preferred embodiment, fluorobenzenesulfonyl chloride. "H NMR (SOCI3) 5 of the invention, using calcium carbonate as a basis - 8.23-8.29 (m, ЗН). action. Example 2

As a solvent in stage a) can be used 2-nitro-3-thane is any suitable high-boiling organofluorobenzenesulfonyl chloride night solvent that does not react with the reagents used, for example, MO dimethylformamide, toluene, etc., or mixtures of the above-mentioned solvents.

Any suitable solvent that is miscible with water and that does not react with the 1,3-burnable reagents used at room temperature to the solution can be used as a solvent in stage b), e.g. , difluoro-2g-nitrobenzene In 200 ml of DMF were added methylene chloride, acetic acid, formic acid, 21.6 g of potassium carbonate and added dropwise while cooling, etc., or a mixture of the solvents mentioned above. Jenny with water 23.4 g of phenylmethanethiol. The solution was stirred for 2 hours, filtered and the filtrate

triturated to dryness to obtain 4bg (9395) 1- was and washed with water and dried over anhydrous benzylsulfanyl-2-nitro-3-fluorobenzene as red magnesium sulfate Then evaporated under vacuum and no oil. 2096 disubstituents are present in the NMR spectrum. 7bg (50495) of the C-nitro-5 product was obtained. fluorobenzenesulfonyl chloride. "H NMR (SOSIz) 6

The obtained mixture was dissolved in 200 ml of methylene - 8.12-8.14 (m, 1H), 8.35-8.36 (m, 1H), 8.7 (s, 1H). chloride and 200 ml of water. Then, chlorine was passed through Example 4 until the end of the reaction (TLC). The organic layer was separated and washed with sodium fluorobenzenesulfonyl chloride sodium thiosulfate solution. It was dried and distilled in a vacuum, obtaining E 21g (5195) of 2-nitro-3-fluorobenzenesulfonyl chloride, which crystallized on standing. It was recrystallized from hexane to obtain yellow crystals with a melting point of 51-527С. "H NMR (SOSI»z) 5 7.75-1.18 (m, 1H), 7.83-7.87 (m, 1H), 8.03-8.04 (d, MO, 1H). AXIS

Example C : no : And c.

Obtaining Z-nitro-5-| At room temperature, difluoro-2-orbenzenesulfonyl chloride of nitrobenzene was dissolved in zOml D; potassium carbonate solution was added and 3.9 g of phenylmethanethiol was added dropwise. It was stirred at room temperature for 2 hours, then poured into water. The obtained precipitate was filtered and washed with water, dried. 7 Ag (90965) 1-od OCI of benzylsulfanyl-2-nitro-4-fluorobenzene was obtained as yellow. with. . And in crystalline substance with a melting point

At room temperature, 51g of 1,3-difluoro-5 1042C, "H NMR (DMSO-4v) 5 4.37 (s, 2H), 729-743 of nitrobenzene was dissolved in ZbOml of DMF, added (m, 5H), 7.67 -7.68 (t, 1H), 7.77-7.79 (m, 1H), 8.08- 69.5 g of potassium carbonate and added dropwise 39.8 g of phenyl-8 09 ( c) ' ' sho ' ' sho methanethiol. Stirred at a temperature of 1007C with 5 g of 59.5 g of 1-benzylsulfanyl-2-nitro-4- for 10 hours. The mixture was cooled, filtered, and fluorobenzene was dissolved in a mixture of 300 ml of water and the filtrate Evaporated to dryness to obtain 78 g of BOOMLl. r o and washed with water and a saturated solution of thiosul-2095 disubstituted product. I: I and I sodium phate. Then evaporated and distilled. Boiling point. 166g 1-benzylsulfanyl-3-nitro-5-o o 27, 150-15572; at 2mm Sun. 31g (57905) of 2-fluorobenzene was dissolved in a mixture of 200 ml of methylene x- : : 4 and I nitro-4-fluorine benzenesulfonyl chloride. "NN NMR of chloride and 200 ml of water. Through the mixture at a good SOS) 5 757-765 well. 8.30-8 34 (Kk. 1H with stirring, chlorine was blown to saturation. Pis- ( z) 6 7.57-7.65 (m, 2H), 8.30-8.34 (Kk, 1H). At the end of the reaction, the organic layer separates

Computer typesetting by M. Lomalov 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