O-Toluenesulfonyl chloride

Other disazo dyes with good substantivity and high wet-fastness properties on polyamides are Acid Red 114 (40), made by coupling o-toHdine to phenol which is then coupled to G-acid, followed by reaction of the phenoHc hydroxyl group with -toluenesulfonyl chloride, and Acid Blue 113 (41) (metanilic acid — 1-naphthylamine — 8-anilino-1-naphthalenesulfonic acid). 

In the reaction with enamino ketones derived from dimedone (e.g., 49) p-toluenesulfonyl chloride gives the chloroiminium cation (138) isolated as the perchlorate. This indicates that initial O sulfonation is followed by addition of chloride ion and subsequent expulsion of tosylate (42) in a manner similar to the trichloroacetyl chloride reaction with 49 (Section IV.A). 

A mixture of 200 grams of 2-benzoyloxyethanol in 2 liters of pyridine at -5°C is treated with 275 grams of p-toluenesulfonyl chloride and the resulting mixture is stirred at O C for 2 hours. Water is added slowly at O " to 5°C. Extracting with chloroform, washing the extract with dilute hydrochloric acid, water and potassium bicarbonate, and evaporating the solvent leaves benzyloxyethyl p-toluenesulfonate. 

Deoxy-D-jcylo hexose 6-(dihydrogen phosphate) (21) has also been synthesized (2) the reaction sequence makes use of 3-deoxy l 2,5 6-di-O-isopropylidene D-galactofuranose (16), a compound that can be easily prepared from D-glucose (2, 60). The mono-isopropylidene derivative (17) formed by partial hydrolysis of the di-ketal is converted into the 6-tosylate (18) by reaction with one molar equivalent of p-toluenesulfonyl chloride. From this the epoxide (19) is formed by reaction with sodium methoxide. Treatment of the anhydro sugar with an aqueous solution of disodium hydrogen phosphate (26) leads to the 6-phosphate (20)... 

Alcohols react with p-toluenesulfonyl chloride (tosyJ chloride, p-TosCl) in pyridine solution to yield alkyl tosylates, ROTos (Section 11.1). Only the 0-H bond of the alcohol is broken in this reaction the C—O bond remains intact, so no change of configuration occurs if the oxygen is attached to a chirality center. The resultant alkyl tosylates behave much like alkyl halides, undergoing both SN1 and Sjsj2 substitution reactions. 

Ji-Toldaldehyde, 2-bromo-, 46,13 />-ToJuenesult onamide, alkylation with o-xylylene dibromide, 47, 111 -Toluenesulfonvlbromide, 45, 88 -Toluenesulfonyl chloride m prepara tion of methvl isocyanide, 46,... 

R)-Cyanohydrins react with toluenesulfonyl chloride, methanesulfonyl chloride or 4-nitrobenzenesulfonyl chloride without loss of stereochemical purity, and the 2-sulfonyloxy-nitrile reacts with a variety of Sn2 reactions to give a variety of products, such as 2-fluoro nitrile [64], 2-azidonitrile [65] and /V- p h t h a I o yl - p rot e c te d 2-aminonitrile [66], 2-acetoxy nitrile [66], and 2-mercapto nitrile [67]. Hydrogenation of 2-sulfonyloxynitriles with LiAIH4 in good chemical yields and high ee afforded 2-monosubstituted (S)-aziridines [68]. 

Trimethylbenzenesulfonyl chloride has been shown21 to be much more selective for the monosulfonylation of a vicinal secondary diol (for example, methyl 4,6-O-benzylidene-a-D-gluco-pyranoside) than p-toluenesulfonyl chloride, and, apparently, 2,4,6-triisopropylbenzenesulfonyl chloride exhibits an even higher selectivity.22... 

Miiller and Vargha65 reported that treatment of 1,6-di-O-benzoyl-D-mannitol (29) with p-toluenesulfonyl chloride gave 2,5-anhydro-l,6-di-0-benzoyl-3,4-di-0-p-tolylsulfonyl-D-glucitol (67). The formation of this compound may be the result of a favored p-toluenesulfonyla-tion at the 2(5)-hydroxyl group, followed by intramolecular cycliza-tion and subsequent esterification by the excess of the reagent. This... 

Buchanan and co workers71 found that treatment of the 7 3 mixture of the D-altro (68) and D-alio (69) hept-l-ynitol derivatives obtained from 2,3,5-tri-O-benzyl-D-ribofuranose and ethynylmagnesium bromide with 2.2 equivalents of p-toluenesulfonyl chloride at 60° gives the 1-D-ribofuranosylethyne derivatives (70 and 71) in 52 and 13%... 

Piroxicam Piroxicam, 1,1 -dioxid-4-hydroxy-2-methyl-iV-2-pyradyl-2//-1,2-benzothiazine-3-carboxamide (3.2.78), is synthesized from saccharin (3.2.70). Two methods for saccharin synthesis are described. It usually comes from toluene, which is sulfonated by chlorosulfonic acid, forming isomeric 4- and 2-toluenesulfonyl chlorides. The isomeric products are separated by freezing (chilling). The liquid part, 2-toluenesulfonyl chloride (3.2.68) is separated from the crystallized 4-toluenesulfochloride and reacted with ammonia, giving 2-toluenesul-fonylamide (3.2.69). Oxidation of the product with sodium permanganate or chromium (VI) oxide in sulfuric acid gives saccharin—o-sulfobenzoic acid imide (3.2.70) [123-126]. 

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