Methyl methanesulfonyl chloride

Manufacture. Methanesulfonyl chloride is made commercially either by the chlorination of methyl mercaptan or by the sulfochlorination of methane. The product is available in 99.5% assay purity by Elf Atochem NA in the United States or by Elf Atochem SA in Europe. 

Manufacture. Methanesulfonic acid is made commercially by oxidation of methyl mercaptan by chlorine in aqueous hydrochloric acid to give methanesulfonyl chloride which is then hydrolyzed to MSA. 

Dehydro-6a-methyl-9a-fluorohydrocortisone Methanesulfonyl chloride Sodium iodide Sodium thiosulfate... 

To a stirred solution of 186 mg (0.568 mmol) of methyl 2-hydroxy-2- 2-oxo-5-[(Z)-6-trimcthylsilyl-4-hex-cnyl]pyrrolidinyl acetate in 4.5 mL of acetonitrile, under a nitrogen atmosphere at -30 C, is added 0.095 mL (0.68 mmol) of triethylamine. After 15 min, 0.050 mL (0.64 mmol) of methanesulfonyl chloride is added, and the reaction mixture is allowed to warm to 20 "C and then refluxed for 20 h. After cooling... 

Epiberberine and berberine were stereoselectively converted to fumaritrine (421) and its analog via 8,14-cycloberbines 216). The cycloberbine 432, derived from epiberberine (431) in the established way, was treated with p-toluenesulfonic acid in methanol and then with methyl iodide to give stereoselectively the cis-fused indenobenzazepine 433 in excellent yield (Scheme 86). Deoxygenation of the hydroxyl group in 433 was accomplished by treatment with methanesulfonyl chloride and subsequent reduction with sodium borohydride in dimethoxyethane to give (+ )-fumaritrine (421) (216). 

On treatment with 30 equivalents of methanesulfonyl chloride in N,N-dimethylformamide for 8 days at 65°, methyl /3-maltoside gave a mixture of methyl 3,6-dichloro-4-0-(6-chloro-6-deoxy-a-D-glucopyranosyl)-3,6-dideoxy-/3-D-allopyranoside, isolated in 46%... 

While the vast majority of the chemistry of thiolsulfonates involves reactions in which the sulfenyl sulfur acts as an electrophilic center and is attacked by nucleophiles, one example has been reported (Douglass, 1959) in which this same sulfur acts as a nucleophile. Methyl methanethiolsulfonate undergoes a very slow reaction with methanesulfenyl chloride that leads to the formation of methanesulfonyl chloride and dimethyl disulfide. The mechanism is believed... 

A somewhat similar isomerization was observed with the sultam 5-methylimino-4-phenyl-l,3,4-dithiazolidine 1-dioxide (17 i = H). On heating at 60°C in the presence of benzoyl chloride, rearrangement into the isomeric 5-phenylimino-4-methyl-l,3,4-dithiazolidine 1-dioxide (19, 1 = H) was found (Scheme IV.ll). As intermediate can be proposed the amidinium salt 18 (78JOC4951). Furthermore, NMR-controlled test tube experiments revealed that this rearrangement also occurs under influence of aluminum trichloride and methanesulfonyl chloride. Also, the 2-phenyl derivative 17 (R = CeHs) could be isomerized it required heating in acetone with m-dichlorobenzoic acid as catalyst (Scheme IV.ll). 

The conversion of sterically hindered carboxylic acids to A-methoxy-A-methyl amides can be efficiently carried out with methanesulfonyl chloride, 3 equivalents of triethy-lamine and A-methoxy-A-methylamine. Yields for this process range from 59% to... 

Mercaptobenzimidazole, 56 2-Mercaptobenzoxazole, 57 Methanesulfonic acid, 58 Methanesulfonyl chloride, S8 Methanol, 31 Methyl acrylate, 65 Methylamine, 60 Methylaniline, 62... 

Methanesulfonyl chloride has been prepared by the chlorination of methyl thiocyanate, S-methylthiourethan, sodium methyl thiosulfate or S-methylisothiuronium sulfate from sodium methanesulfonate by the action of phosphorus penta-chloride, phosphorus oxychloride, or benzotrichloride from methanesulfonic acid by the action of phosphorus pentachloride or by the reaction of methylmagnesium iodide with sulfuryl chloride. ... 

A solution of 72.08 g (0.19 mol) of 5-bromo-l-pentanyl acetate in 1.4 L of MeOH was treated with 38 mL of a 1.0 molar solution of tetrabutylammonium hydroxide and the mixture was stirred at room temperature for 3.0 h, 3.0 mL of AcOH was added and the solution was evaporated at 35°C. The residue was dissolved in 400 mL of EtOAc and the solution was washed with saturated NaHC03, brine, dried, and evaporated to give 60.45 g (94% yield) of the intermediate hydroxy ester (an analytical sample may be obtained by crystallization from 70% EtOAc in hexane, m.p. 58-61°C. A stirred solution of 60.25 g of the hydroxyester in 700 mL of EtOAc was cooled to 5°C and treated with 75.5 mL (3 equiv.) of triethylamine and 32.6 mL (2.35 equiv.) of methanesulfonyl chloride. The mixture was stirred at 6°C for 2.0 h, transferred to a separatory funnel and washed sequentially with water, 2 N HCI, and brine. Concentration of the EtOAc to ca. 300 mL and dilution cooled to 0°C and treated with 75.5 mL (3 equiv.) of triethylamine and 32.6 mL (2.35 equiv.) of methanesulfonyl chloride. The mixture was stirred at 6°C for 2.0 h transferred to a separatory funnel and washed sequentially with water, 2 N HCI, and brine. Concentration of the EtOAc to ca. 300 mL and dilution with 250 mL of hexane led to crystallization (0°C, 18 h). The product was collected by filtration and washed with some cold hexane - EtOAc (1 1) to give 66 g (84% yield) of methyl (R,S)-6-acetyl-3,4-dihydro-7-[5-[(methylsufonyl)oxy]pentyloxy]-2H-l-benzopyran-2-carboxylate m.p. 73-76°C. 

To a stirred solution of 9a-fluoro-lip,17,21-trihydroxy-16a-methyl-pregna-l,4-diene-3,20-dione (lOg, 25.5 mmol) in 20 ml pyridine and 12 ml acetone at -10°C, a cold solution of methanesulfonyl chloride (3 ml, 38.5 mmol) in 8 ml acetone was added dropwise. The addition was completed within about 3 hours and the mixture was then left standing in the cold for a further IV2 hours after which 200 ml cold water were added. The resulting precipitate was separated by filtration and washed with water to give 11.5 g (96% of theoretical yield) of dexamethasone 21-mesylate, melting point 208°C to 210°C (decomposition). 

Methyl 2-(2-iodophenyl)propanoate Tetrabutylammonium chloride Diethyl 1,1-cyclopropanedicarboxylate Vinyl magnesium bromide Methyl magnesium chloride Borane-tetrahydrofuran complex Diisopropylethylamine Methanesulfonyl chloride... 

To a solution of 2-(2-(3(S)-(3-(2-(7-chloro-2-quinolinyl)ethenyl)phenyl)-3-hydroxypropyl)phenyl)-2-propanol in THF was dissolved in THF (1 mL) and DMF (1 mL) at -40°C was added diisopropylethylamine (2.2 mmol) and then methanesulfonyl chloride (2.2 mmol). The mixture was stirred 2 hours with slow warming to -30°C. The methyl l-(thiomethyl)cyclopropaneacetate (2.3 mmol) was added to the cloudy reaction mixture followed by dropwise addition of potassium tert-butoxide/THF solution (4.4 mmol). The reaction mixture was stirred at -30°C for 3.5 hours before quenching it with 25% aq NH40Ac. Extraction with EtOAc, washing the organic layer with brine and evaporation of the solvents left a residue that was purified by flash chromatography (5%-10% EtOAc in toluene) giving 658 mg (53%) of methyl l ((((R) (3 (2-(7-chloro-2-quinolinyl)ethenyl)phenyl)-3-(2-(2-hydroxy-2-propyl)phenyl)propyl)thio)methyl)cyclopropaneacetate. 

Boron trifluoride diethyl etherate l,8-Diazabicyclo[5.4.0]undec-7-ene 4-Toluenesulfonic acid Methanesulfonyl chloride N,N-Diisopropylethylamine Chloromethyl methyl ether Potassium hydroxide Ammonium chloride Dimethylaminophenol 2-(Diethylamino)ethyl(bicyclohexyl)-l-carboxylate... 

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