Methanesulfonyl chloride, sulfonylation

Methanesulfonic acid, sulfonylation of carbohydrates by, 239 Methanesulfonic anhydride, sulfonylation of carbohydrates by, 238 Methanesulfonyl chloride, sulfonylation agent for sugars, 236... 

Alkyl sulfonyl chlorides, having an a-hydrogen atom, react with enamines derived from aldehydes and cyclic ketones in the presence of triethylamine to give cyclic sulfones. Thus the enamine (22) gave the four-membered cyclic aminosulfone (143) on reaction with methanesulfonyl chloride (95). 

The formation of four-membered-ring sulfones and a-sulfonyl amides has also been applied to the reaction of methanesulfonyl chloride with ketene aminals and acetals (470-473). 

Ab initio SCRF/MO methods have been applied to the hydrolysis and methanol-ysis of methanesulfonyl chloride (334). ° The aminolysis by aromatic amines of sulfonyl and acyl chlorides has been examined in terms of solvent parameters, the former being the more solvent-dependent process.Solvent effects on the reactions of dansyl chloride (335) with substituted pyridines in MeOH-MeCN were studied using two parameters of Taft s solvatochromatic correlation and four parameters of the Kirkwood-Onsager, Parker, Marcus and Hildebrand equations. MeCN solvent molecules accelerate charge separation of the reactants and stabilize the transition... 

Section 7.8). Other classes of derivatives are thus most conveniently prepared from the sulfonyl chloride. Reaction with an alcohol leads to formation of a sulfonate ester. Two common sulfonyl chloride reagents employed to make sulfonate esters from alcohols arep-toluenesulfonyl chloride, known as tosyl chloride, and methanesulfonyl chloride, known as mesyl chloride (see Section 6.1.4). Note the nomenclature tosyl and mesyl for these groups, which may be abbreviated to Ts and Ms respectively. 

Substitution of fluorine for halogen in aromatic and alkyl sulfonyl halides can be carried out with or without using a solvent. An aqueous system such as 70 % aqueous potassium fluoride is also used because the rate of hydrolysis is much slower than the rate of fluorination as reported for the conversion of methanesulfonyl chloride (1) to methanesulfonyl fluoride (2).23... 

Selective sulfonylation of 1 A/i -tri-O-tritylsucrose (activated by Bu2SnO) with methanesulfonyl chloride in benzene afforded the 3-mesylated derivative, whereas the same process performed in toluene surprisingly provided the 4-mesylate in 50% yield. If triflic anhydride is used as the sulfonating reagent, the 4-triflate was obtained in 40% yield (Scheme 12).153... 

Methanesulfonyl chloride may be a new reagent to you. In the presence of a base (usually triethy-lamine, EtjN) it reacts with alcohols to give methanesulfonate esters, but the mechanism differs from the mechanism with TsCl. The first step is an elimination of HC1 from the sulfonyl chloride (this can t happen with TsCl, because there are no available protons) to give a sulfene. The sulfene is highly electrophilic at sulfur, and will react with any alcohol (including tertiary alcohols, which react very slowly with TsCl). Here are the two mechanisms compared, formation of toluenesuifonates (tosylates) reagents ROH + TsCl + pyridine... 

A [2 + 2] cycloaddition reaction between simple 1,1-enediamine and a sulfonyl chloride was also observed157-159. In the presence of a base, 1,1-dimorpholinoethy-lene (154) reacted with methanesulfonyl chloride (199) in ether or in tetrahydrofuran to give 3-morpholinothietane 1,1-dioxide (200) in good yield (equation 83). However, the reaction takes a different course in chloroform, leading to the conjugated 1,1-enediamine 201. Other reactants than 154 and 199 did not form cycloaddition products under the same conditions160. 

Sulfonic acids are converted to the corresponding acid halides in much the same way as carboxylic acids. Thionyl chloride is the best reagent for the preparation of methanesulfonyl chloride (83%). By heating with a large excess of thionyl chloride, however, p-toluenesulfonic acid is converted into its anhydride (87%). Benzenesulfonyl chloride is made in 80% yield by the action of either phosphorus pentachloride or phosphorus oxychloride at 180° on sodium benzenesulfonate. Chlorosulfonic and fluorosulfonic acids are used in the conversion of sodium p-chloro-benzenesulfonate to the corresponding sulfonyl halides (85 8S>%). ... 

The continued use of pyridine as the usual solvent for sulfonyla-tions is justified by the well known catalytic effect of pyridine on esterification of alcohols. A discussion of such reactions has been presented by Foster and coworkers in which the possibility is considered that complexes of pyridine with sulfonyl chlorides are responsible for the catalytic effect of pyridine. In a study of the reaction of l,2 5,6-di-0-isopropylidene-a-D-glucofuranose with methanesulfonyl chloride, the corresponding 3-methanesulfonate was formed in 88% yield widi pyridine as solvent, but in only 45% yield with triethylamine or tributylamine. In some methanesulfonylations of methyl glycopyranosides, mixtvures of pyridine and triethylamine, and of pyridine and N,2V-dimethylformamide, have been used " to... 

Preparative Methods The enantiopure sulfonamide la is prepared via sulfonylation of (7 ,7 )-l,2-diaminocyclohexane 2 in the presence of an excess of triethylamine (eq 1). Use of excess amine base is essential for obtaining a high yield of the bis-sulfonamide. Synthesis of related bis-sulfonamides is easily accomplished by substituting the desired sulfonyl chloride in the former procedure. Recrystallization of the bis-sulfonamide la from hexane/ethyl acetate and drying over P2O5 allows for isolation of the analytically pure reagent. Methanesulfonyl chloride and (7 ,/ )-l,2-diaminocyclohexane 2 are commercially available from a number of sources. However it should be noted that racemic 1,2-diaminocyclohexane 2 can be resolved via formation of the tartrate salt. Typically, the diamine can be obtained in >99 1 enantiomeric ratio (er) after two crystallizations from water. Determination of the enantiopurity of the diamine is accomplished via formation of the bis-3-toluyl amide and anal-... 

The former names arc preferred, but the latter are allowed. The variant to be used in any particular case depends on the circumstances. Thus, sulfuryl is u.sed in inorganic radicofunctional nomenclature and sulfonyl is used in organic substitutive nomenclature. (That is, organic chemists tend to speak of methanesulfonyl chloride, MeSO CI. while inorganic chemists speak of sulfuryl chloride. 

Sulfenes generated from sulfonyl chlorides and tertiary amines do not react with simple alkenes or dienes however, the sulfene generated from (trimethylsilyl) methanesulfonyl chloride (112) and caesium fluoride affords the [4+2] cycloadduct (113) with cyclopentadiene (114) (Scheme 73). 

Methanesulfonyl chloride is the largest-volume alkanesulfonyl chloride. Benzenesulfonyl chloride is the only aromatic sulfonyl halide with significant commercial production, primarily as a feedstock for the manufacture of A-butyl benzenesulfonamide. All sulfonyl chlorides are poorly water soluble, which limits their hydrolysis except at elevated temperatures or in the presence of a homogenizing agent such as a cosolvent, surfactant or phase-transfer agent. 

Sulfonyl chlorides have extensive uses in organic synthesis in the preparation of sulfonamides and sulfonate esters. Methanesulfonyl chloride is a key raw material in the synthesis of critical components for photographic color developing formulations, as well as for herbicides and pharmaceuticals. 

When methanesulfonyl chloride was allowed to react with 2,3,4,6-tetra-O-ben-zylglucopyranose and collidine in dichloromethane, the a-glucopyranosyl chloride was isolated regardless of whether the quaternary ammonium bromide was included. Addition of methanol to the reaction mixture resulted in the formation of an anomeric mixtiue of methyl glycosides. Similar results were obtained with toluenesulfonyl chloride, although it was noted that the initial sulfonylation was somewhat slower [8,9]. The use of tosyl chloride in the dehydrative coupling of alcohols with pyranoses was later revisited by Szeja and his coworkers, with the difference that aqueous... 

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