Sulfonyl chloride, from sodium sulfonate

Sommelet reaction, 33, 93 Sorbic acid, 5-hydroxy-/3-methyl, J-lactone, 32, 57 Stannic chloride, 33, 91 Stearic acid, 34, 15 Stearone, 33, 84 cis-Stilbene, 33, 88 fraws-Stilbene, 33, 89 Stirrer, for caustic fusion, 30, 104, 105 seal for, 30, 54 Stobbe condensation, 30, 18 Styrene, 33, 72 34, 85 reaction with sulfuric acid, 35, 83 Styrene dibromide, 30, 73 Styrene oxide, 31, 3 0-Styrenesulfonyl chloride, 34, 85 Succinic acid, 34, 44 Succinic acid, < -benzhydrylidene-, a-ETHYL ESTER, 30, 18 CLNNAMYL-, 31, 85 DIPHENYL ESTER, 34, 44 HEPTANOYL-, DIETHYL ESTER, 34, 51 PHENYL-, 30, 83 Succinic anhydride, 34, 40 SUCCINONITRILE, a, -DIPHENYL-, 32, 63 Sulfide, methyl 2-thienyl, 35, 85 Sulfonation of styrene, 34, 85 Sulfonyl chloride, from sodium sulfonate, 34, 85... 

These results suggest that the starting material did not give sodium pyrrole-2-sulfonate, but 3-sulfonate 420 (Scheme 89), or that rearrangement occurred in the formation of sulfonyl chloride from pyrrole-2-sulfonate to afford pyrrole-3-sulfonyl chloride 421 or in a cyclization step of 2-substituted acid 426. 

Sodium sulfonate 1 has previously been prepared from NaHS03 and vinyltrimethylsilane using sodium nitrite/sodium nitrate as the radical initiator.3 In the submitters hands this protocol resulted in salt 1 as a pale tan powder in only 15-53% yield if 50% (v/v) aqueous methanol is employed as solvent. The yield of 1 could be increased to 63% if 22% (v/v) aqueous methanol is employed. An advantage of this method is the elimination of a potentially explosive perester as radical initiator. However, lower yields of 1 and the subsequent lower yield of the sulfonyl chloride 2 (53% for the sulfonylation, 35% overall from vinyltrimethylsilane) make this procedure less desirable than the method presented. The use of tert-butyl perbenzoate as the radical initiator4 not only provides 1 in a higher yield, but the subsequent conversion to 2 also proceeds in better yield. 

Pyridine-3-sulfonic acid is converted to the sulfonyl chloride with phosphorus penta-chloride and the 2-isomer results from treatment of the corresponding sodium sulfonate... 

Orthanilic acid was first made by the reduction of nitro-benzenesulfonic acid by ammonium sulfide.2 This reduction has also been carried out electrolyticallv, and by the use of iron or zinc.3 The acid has also been made by the rearrangement of phenylsulfamic acid,4 by the action of sodium hypobromite upon potassium o-carbaminebenzenesulfonate,5 by the reduction of the mixed nitrobenzenesulfonic acids followed by separation of the isomers,6 by the action of methyl alcohol upon o-nitro-phenylsulfurchloride,7 by the action of acid upon diacetyl diphenylsulfamide,8 by the debromination of />-bromoaniline-e-sulfonic acid,9 by the reduction of 1,2,6-aminothiophenolsulfonic acid,10 and by the hydrolysis and reduction of e-nitrobenzene-sulfonyl chloride, which was obtained from di-o-nitrophenyl-disulfide.11... 

Esters of aliphatic and aromatic sulfonic acids are conveniently prepared in high yields from alcohols and sulfonyl halides. A basic medium is required. By substituting sodium butoxide for sodium hydroxide in butanol, the yield of n-butyl p-toluenesulfonate is increased from 54% to 98%. Ethyl benzenesulfonate and nuclear-substituted derivatives carrying bromo, methoxyl, and nirro groups are prepared from the corresponding sulfonyl chlorides by treatment with sodium ethoxide in absolute ethanol the yields are 74-81%. Pyridine is by far the most popular basic medium for this reaction. Alcohols (C -Cjj) react at 0-10° in 80-90% yields, and various phenols can be converted to aryl sulfonates in this base. "... 

Mercaptopyrazine in aqueous hydrochloric or acetic acids was chlorinated to give the sulfonyl chloride which with excess liquid ammonia gave 2-sulfamoyl-pyrazine (1006, 1153). Direct sulfonation of the pyrazine ring has never been reported (819) but 2-sulfopyrazine (17) has been prepared from 2-chloropyrazine and aqueous sodium sulfite at 150° (819), and from 2-fluoropyrazine and aqueous sodium sulfite at reflux for 2 hours (882, 884). 2-Amino-3-mercaptopyrazine in aqueous sodium hydroxide with concentrated ammonia and sodium hypochlorite has been shown to give 2-amino-3-sulfamoylpyrazine (1101). 

Sulfonic acids and sulfonyl chlorides can also be prepared from sulfinic acids by oxidation with sodium permanganate (equation 590) [556] and chlorine in water (equation 591) [656], respectively. 

Sulfonyl and Sulfinyl Chlorides from Sulfonic and Sulfinic Acids. Alkyl or arylsulfonyl chlorides are prepared by heating the acid with thionyl chloride DMF catalyzes this reaction. (+)-Camphorsulfonyl chloride is produced in 99% yield without a catalyst. Use of the salts of sulfinic acids minimizes their oxidation p-toluenesulfinyl chloride is produced in about 70% yield from sodium p-toluenesulfinate dihydrate with excess thionyl chloride. Phosphorus(V) Chloride is more commonly used for this transformation. 

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