Toluene sulfonylation

Pivalates. The selective pivaloylation of sucrose with pivaloyl (2,2-dimethylpropionyl) chloride has been thoroughly investigated (56). The reactivity of sucrose toward pivaloylation was shown to be significantly different from other sulfonic or carboxyflc acid chlorides. For example, reaction of sucrose with four molar equivalent of toluene-/)-sulfonyl chloride in pyridine revealed, based on product isolation, the reactivity order ofO-6 0-6 > 0-1 > 0-2 (57). In contrast, a reactivity order for the pivaloylation reaction, under similar reaction conditions, was observed to be 0-6 0-6 > 0-1 > 0-4. 

A/-phenyl-AT-(p-toluene-sulfonyl)-/) -phenylenediamine Dihjdroquinolines [100-93-6] (37) RU Ururoyal Chemical... 

In this method, an oligoethylene glycol is treated with 0.3 eq. of sodium bromoace-tate in methanol. The resulting monocarboxylic acid salt is then treated with toluene-sulfonyl chloride, sodium carbonate and dioxane. After heating the reaction mixture at 50° for an hour, the product was obtained either by Kugelrohr distillation or extraction. The two compounds produced in the reaction below (i.e., n = 1 and n = 2) were formed in 38% and 42% yields respectively . 

The aromatic sulfonyl chlorides which have no a-hydrogen and thus cannot form sulfenes give acylic sulfones. Thus 1-piperidinopropene on reaction with benzene sulfonyl chloride (9J) gave 2-benzenesulfonyl-l-piperidinopropene (153). Similarly the enamine (28) reacts with p-toluene-sulfonyl chloride to give the 2-p-toluenesulfonylcyclohexanone (154) on hydrolysis (/OS). 

Benz[/]isoindole (125), recently prepared from the p-toluene-sulfonyl derivative (124), proved to be too unstable for isolation, but eould be trapped in solution as the Diels-Alder adduct (127). The corresponding 1-phenyl derivative (126) was also prepared and, aecording to spectral measurements, reacts with maleic anhydride to give the product (128) derived by additive substitution. This subsequently rearranged to the adduct (129). The same behavior is observed in the reaction of (126) with V-phenylmaleimide. This provides the first clear indication that substitution products from isoindole derivatives and dienophiles can be converted into the normal addition products. 

Qi-Hydroxy-17-methyltestosterone p-Toluene sulfonyl chloride Hydrogen fluoride... 

Endo-amlnoborneol HCI o-Methyl-N-p-toluene sulfonyl urea... 

The suspension is dissolved by the addition of 20 ml of 1 N caustic soda. The alkaline solution is extracted with ether, acidified with dilute hydrochloric acid and filtered. The precipitate is washed with water and recrystallized from alcohol/water to yield 1-(p-toluene-sulfonyl)-3-(2-endo-hydroxy-3-endo-bornyl)-urea having a melting point of 193° to 195°C. 

Nitroimidezole sodium i 3-Chloroethyl morpholine p-Toluene sulfonyl chloride... 

Bis-Chloroethyl toluene sulfonyl amide Manufacturing Process... 

The starting materials for the overall process are phenylacetonitrile with bis-chloroethyl toluene sulfonyl amide. These react to give a product which hydrolyzes to normeperidine (4-carboethoxy-4-phenylpiperidine). Condensation of that material with benzoylethylene gives the ketone /3-(4-carboethoxy-4-phenylpiperidino)propiophenone. 

Methyl a-D-mannopyranoside was treated in succession with p-toluene-sulfonyl chloride, carbonyl chloride, and benzoyl chloride, and, without isolating the intermediates, there was obtained in 37% yield methyl 4-0-l enzoyl-2,3-O-carbony 1-6-0-(p-tolylsulfonyl ) -D-mannoside. The tos-yloxyl group of the latter was replaced by iodine, and hydrogenation of the 6-iodo derivative in the presence of a nickel boride catalyst gave methyl 4-0-benzoyl-2,3-0-carbonyl-6-deoxy- -D-mannoside. Treatment of the latter with hydrogen bromide in acetic acid gave crystalline 4-0-benzoyl-2,3-0-carbonyl-6-deoxy-a-D-mannosyl bromide (8) (16). The... 

Whereas aryl Grignard compounds afford good yields of sulfones with sulfonyl fluorides298 299, phenyllithium is mainly chlorinated by a-toluene-sulfonyl chloride on the other hand, the corresponding fluoride yields only a trace of the expected mono-sulfonylation product, while the main product is 26 obtained by twofold sulfonylation300 (equation 61). 

Reduction, carboxyl groups, 56,83 Reduction of a,0-unsaturated p-toluene-sulfonyl-hydrazones to alkenes, 59,42 Reductive alkylation, 56,52 Reductive cleavage, 56, 101 Resolution of amines, 55,80, 83 Rexyn 201,55,4 Rhodium(III) oxide, 57, 1 Ring contraction, 56, 107 Ring expansion of cycloalkanones to cycloalkenones, 59, 113... 

Chloroethyl)polystyrenes and (iodoethyl)polystyrenes are each prepared from the alcohol by common reagents in a single step without complications, but one-pot procedures fail to produce completely pure bromide, which must be prepared from the tosylate by assisted halide exchange (57). The preparation of (toluenesulfonyloxyethyl)polystyrene itself, if performed in ice-cold pyridine as for the free analogue (64, 65), required a week to complete (67) if quaternary ammonium and other side-products (68) are to be avoided. In contrast, with non-nucleophilic diisopropylamine (69) as acid acceptor instead of pyridine, (hydroxyethyl)polystyrene and toluene-sulfonyl chloride need only be refluxed in carbon tetrachloride for a few hours to give the desired tosic ester as sole product in quantitative yield (57). 

Studies of the thermodynamics of formation of complexes of zinc with 2,2 -bipyridine in the presence of halide and thiocyanate ions in DMF has been carried out.205 The zinc complexes of 2,2 -bipyridine with A-(benzenesulfonyl)glycine and A-(toluene- -sulfonyl)glycine were synthesized and infrared data implied a structural analogy with the cadmium complexes. This suggests that the zinc promotes sulfonamide nitrogen deprotonation in the amino acid ligands in the solid state.206... 

Figure 8 Partial MALDI-TOF spectrum from PMMA generated by ATRP with p-toluene sulfonyl chloride as initiator (inset shows theoretical isotope distribution for lithiated 13-mer of 6). (Peak labelled 7 arises from post-source decay of 7 [10].)...

This procedure represents the most convenient synthesis of 3(5)-aminopyrazole. It employs readily available starting materials and gives excellent yields in all steps.5,6 />-Toluene-sulfonyl chloride can be replaced by other arenesulfonyl chlorides. 3-Imino-l-arylsulfonylpyrazolidines can be alkylated with dimethyl sulfate or with alkyl 7>-toluenesulfonates in dimethyl-formamide to give salts of l-alkyl-2-arylsulfonyl-5-amino-4-... 

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