Methane sulfonyl chloride

On dehydration, nitro alcohols yield nitro-olefins. The ester of the nitro alcohol is treated with caustic or is refluxed with a reagent, eg, phthaUc anhydride or phosphoms pentoxide. A mil der method involves the use of methane sulfonyl chloride to transform the hydroxyl into a better leaving group. Yields up to 80% after a reaction time of 15 min at 0°C have been reported (5). In aqueous solution, nitro alcohols decompose at pH 7.0 with the formation of formaldehyde. One mole of formaldehyde is released per mole of monohydric nitro alcohol, and two moles of formaldehyde are released by the nitrodiols. However, 2-hydroxymethyl-2-nitro-l,3-propanediol gives only two moles of formaldehyde instead of the expected three moles. The rate of release of formaldehyde increases with the pH or the temperature or both. 

Methane Sulfonyl Chloride (MSC)—Properties, Reactions and Applications, Technical Bulletin S-104, Elf Atochem North America, Philadelphia, Pa. 

The thiocyanatohydrin must be acylated in a second step to provide substrates for thiirane syntheses. The most convenient acylating agent, methane-sulfonyl chloride, has been used to prepare thiiranes at the 1,2 (A-nor)-, " 2,3-, 3,4-, " 5,6-, ll,12-, o 14,15- ° and 16,positions of steroids in high yield, e.g., conversion of (126) to (129). 

The dienamine (148) can react in two ways with methane sulfonyl chloride. In one a 1,4 Diels-Alder-type addition gives 149 in the other way the initially formed product reacts further to give the bis-cyclic sulfone (150) (102,103). 

To a stirred solution of 9a-fluoro-11(3,17,21 -trihydroxy-160 -methyI-pregna-1,4-diene-3,20-dione (10 g, 25.5 mmol) in 20 ml pyridine and 12 ml acetone at -10°C, a cold solution of methane sulfonyl chloride (3 ml, 38,5 mmol) in 8 ml acetone was added dropwise. The addi-... 

Acetic anhydride Methane sulfonyl chloride Chlorine... 

To 6a-fluoro-16a-hydroxy-hydrocortisone 21-acetate, described by Mills et al, J. Am. Chem. Soc., volume 81, pages 1264 to 1265, March 5, 1959, there was added acetic anhydride in dry pyridine. The reaction mixture was left at room temperature overnight and was then poured with stirring into ice water. The resulting precipitate was filtered, washed with water and crystallized from acetone-hexane to give 6a-fluoro-16a-hydroxy-hydrocortisone-16a,21-diacetate. This was reacted with methane-sulfonyl chloride in dimethyl formamide in the presence of pyridine at 80°C for 1 hour. The mixture was cooled, diluted with water and extracted with ethyl acetate. The extract was washed with water, dried over anhydrous sodium sulfate and the ethyl acetate was evaporated. By recrystallization of the residue from acetone-hexane there was obtained 6a-fluoro-A <" -pregnadiene-16o ,17a,21-triol-3,20-dione 16a,21 diacetate. 

CK-Hvdroxy-9CK-fluorohydrocortlsone acetonide Methane sulfonyl chloride Lithium chloride... 

The carbonyl chloride reactant was prepared by reacting 2-imidazolidone with methane sulfonyl chloride then that product with phosgene. The mixture was stirred for 10 minutes at 0°C and subsequently further stirred at room temperature until no further addition of triethylamine was necessary to maintain a pH value of 7 to B. 150 parts by volume of water were added and the tetrahydrofuran was largely removed in a rotary evaporator at room temperature. 

Similar reaction of 2,3,l, 3, 4, 6 -hexa-0-acetylsucrose with methane-sulfonyl chloride in N,N-dimethylformamide gave two products, which were separated on silica gel and characterized as 1,3,4,6-tetra-O - acetyl-/3 - D - fructofiiranosyl 2,3 - di - O - acetyl - 4,6 - dichloro -4,6 -... 

Thietene is also called thiete. It can be synthesized by treating methane-sulfonyl chloride (mesyl chloride) with trimethylamine and trapping the... 

Mannitol hexanitrate is obtained by nitration of mannitol with mixed nitric and sulfuric acids. Similarly, nitration of sorbitol using mixed acid produces the hexanitrate when the reaction is conducted at 0—3°C and at —10 to —75°C, the main product is sorbitol pentanitrate (117). Xylitol, ribitol, and L-arabinitol are converted to the pentanitrates by fuming nitric acid and acetic anhydride (118). Phosphate esters of sugar alcohols are obtained by the action of phosphorus oxychloride (119) and by alcoholysis of organic phosphates (120). The 1,6-dibenzene sulfonate of D-mannitol is obtained by the action of benzene sulfonyl chloride in pyridine at 0°C (121). To obtain 1,6-dimethanesulfonyl-D-mannitol free from anhydrides and other by-products, after similar sulfonation with methane sulfonyl chloride and pyridine the remaining hydroxyl groups are acetylated with acetic anhydride and the insoluble acetyl derivative is separated, followed by deacetylation with hydrogen chloride in methanol (122). Alkyl sulfate esters of polyhydric alcohols result from the action of sulfur trioxide—trialkyl phosphates as in the reaction of sorbitol at 34—40°C with sulfur trioxide—triethyl phosphate to form sorbitol hexa(ethylsulfate) (123). 

The thiocyanatohydrin must be acylated in a second step to provide substrates for thiirane syntheses. The most convenient acylating agent, methane-sulfonyl chloride, has been used to prepare thiiranes at the 1,2 (A-nor)-,148... 

The sulfone derivative of Achiwa s BPPM (5, 6) was prepared from the free base and methane sulfonyl chloride. 

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