Toluene sulfinic acid

Os(II) complexes of tosylmethylisocyanide react with aldehydes and ketones in the presence of sodium methoxide, producing cyclic carbene complexes (66). Compound 32 undergoes a rapid reaction with benzal-dehyde and NaOMe, yielding the oxazol-2-ylidene complex 33 and eliminating p-toluene sulfinic acid (66) ... 

Tolylmercuric chloride has been prepared from />-toluene-sulfinic acid and mercuric chloride,1 from /)-toluenesulfochloride and mercury diphenyl at 1200,2 by treating />-tolueneboric acid with mercuric chloride,3 by the direct mercuration of toluene with mercuric acetate,4 from -tolylmercuric nitrate and hydrochloric acid,5 from hydrochloric acid and / -tolylmercuric hydroxide formed by the oxidation of mercury di-/>-tolyl,6 and from mercury di-/>-tolyl by heating with mercuric chloride in alcohol.7... 

Redox initiators have been proposed. The initiation system is composed from iron sulfate, dibenzoyl peroxide, and a reductant. Of the latter, hydroxyacetone, 2-hydroxy-2-phenylacetophenone, ascorbic palmitate, and toluene sulfinic acid are among the most economical. The reaction conditions are such that the cyclic oxida-... 

Early results with crotyl chloride and the sodium salt of toluene sulfinic acid in the presence of DIOP gave the allyl sulfone in 88% ee and with a ratio of 5.3 1 for the regioisomers favoring the chiral product [113]. A BPPFA analogue com-... 

Indole was prepared by Baeyer in 186610 isoindole did not appear until 1972, when three groups in swift succession obtained it by independent routes. Fenton and Ingold3 had attempted in 1928 to eliminate toluene-sulfinic acid from 2-tosylisoindoline, but hydrolysis had prevailed. Some... 

Potassium tert-butoxide produces the elimination of /7-toluene sulfinic acid (/7-MePhS02H). 

Sodium tin oxide. See Sodium stannate Sodium 4-toluenesulfinate Sodium toluene-4-sulfinate. See Sodium p-toluenesulfinate Sodium p-toluenesulfinate CAS 824-79-3 EINECS/ELINCS 212-538-5 Synonyms Benzenesulfinic acid, 4-methyl-, sodium salt Sodium 4-methylbenzenesulfinate Sodium 4-toluenesulfinate Sodium toluene-4-sulfinate Sodium-p-toluene sulfinic acid Sodium p-tolylsulfinate p-Toluenesulfinic acid, sodium salt Ciassification Sulfinate Empiricai C7H7Na02S... 

Sodium-p-toluene sulfinic acid. See Sodium p-toluenesulfinate,... 

The tosyl group could alternatively be eliminated during the reaction when a base, such as l,8-diazabicyclo[5.4.0]undec-7-ene (DBU), was present, as is the case for the photolysis of 1,2-diaryl-l-tosylstilbenes that led to phenanthrenes or their heterocyclic analogues in one step (Scheme 14.15, path h). These results were consistent with a mechanism involving a base-induced ehmination of p-toluene-sulfinic acid from 9-tosyl-4a,4b-dihydrophenanthrene as intermediate, formed by photochemical cyclization of the starting ethene [88]. 

The reaction of the sulfenic acid has also been reported with other sulfur nucleophiles when treatment of the sulfoxide (106) with p-toluene-sulfinic acid afforded the thiosulfonate (163) (Allen et al., 1974). Under the reaction conditions only the a,p-unsaturated isomer was isolated. 

The reaction of peroxyesters, hydroperoxides or peroxides, which are more storage stable than BP, with tertiary amines is generally too slow to give a sufficiently rapid cure for acrylic resins. Composite mixes containing t-butyl perbenzoate, -butyl hydroperoxides or dicumyl peroxide-tertiary amines do not harden for days. Many other redox systems have been suggested for vinyl polymerizations, only a few have been employed in dental resins. Substitution of 2 toluene sulfinic acid or sulfinic acid derivatives for tertiary amines yields colorless products (38-42). Most of these compounds have poor shelf-life. They readily oxidize in air to sulfonic acids which do not activate polymerization. Lauroyl peroxide in conjunction with a metal mercaptide (such as the zinc hexadecyl mercaptide) and... 

During a study of azonitrones (70), Forrester and Thomson showed that reaction with toluene-p-sulfinic acid resulted in nitrogen evolution and formation of the hydroxamic acid (66) together with the pyrrolidone (71) and the amidine (72). These workers suggested the following reaction course. Although the yield of hydroxamic acid was high, the method is not likely to be of preparative value. 

The tosyl compound reacts with aldehydes in the presence of potassium carbonate to yield 5-alkyl- or 5-aryl-oxazoles, the intermediate dihydrooxazoles (which can be isolated) eliminating toluene-p-sulfinic acid (Scheme 30). Use of acyl chlorides in place of aldehydes leads to 4-tosyloxazoles (288). Furthermore, alkylation of tosylmethyl isocyanide with an alkyl halide RfX, followed by treatment with an aldehyde R2CHO, yields a 4,5-disubstituted oxazole (289). A related reaction is that of A-tosylmethyl-iV -tritylcarbodiimide with aromatic aldehydes under phase-transfer catalysis to yield 2-tritylaminooxazoles which are readily converted into 2-amino-5-aryloxazoles (equation 117) (81JOC2069). 

Employing a 5-endo-dig cyclization process catalyzed by />-toluenesulfonic- or sulfinic acid, the amino esters 8 were smoothly converted to the pyrroles 9 in refluxing toluene. Both acid catalysts gave comparable results in terms of yield <03SL2258>. 

Toluene-p-sulfonylmethyl isocyanide (32) ( Tosmic ) reacts in a base-induced cycloaddition (in protic medium) with aldimines. Toluene-p-sulfinic acid is eliminated to yield 1,5-disubstituted imidazoles (33 = H) in... 

Tosylmethyl isocyanide anion reacts with a,P-unsaturated esters, ketones or sulfones with loss of toluene-sulfinate. Isocyano-acetates react with a,P-unsaturated nitro-compounds with loss of nitrous acid. 

Benzene-, toluene-, and halobenzene-sulfinic acids, as well as sulfinobenzoic acids, amongst others, have been prepared by this procedure. 

Knoevenagel and Polack733 have given directions for the preparation of aromatic sulfinic anhydrides by the action of acetic anhydride on a suspension of the dry sulfinic acid in a little acetic acid. The reaction is catalysed by sulfuric acid or a 0.1% solution of iron(m) chloride in glacial acetic acid or acetic anhydride. Benzene-, / -toluene-, / -xylene-, pseudocumene-, mesitylene-, and / -bromo- and / -iodo-benzene-sulfinic anhydride have been obtained in this way. 

Esterification of p-toluenesulfinic acid vkith (li ,2S,5i )-(—)-menthol (1) is not stereoselective, producing a diastereoisomeric mixture of (5)- and (7 )-menthyl p-toluene sulfinate esters (2), (S) (R) 2 1) (Scheme 2.1) [4]. Repeated recrystallization gave diastereoisomerically pure (5)-(—)-menthyl p-toluene sulfinate in 30% yield. 

Depending on the solvent, different reaction products form when alkenes react with iodine in presence of cerium(IV) triflate 1,2-hydroxy iodides in water, 1,2-alkoxy iodides in alcohols and 1,2-acetoxy iodides in acetic acid (Iranpoor and Shekarriz, 2000). Treatment of a mixture of styrene and sodium p-toluene sulfinate in anhydrous acetonitrile with CAN af-... 

Glutamic acid (140b) served as the starting material for the synthesis of (7i ,85)-(+)-disparlure (536a) by Iwaki et al (252) (Scheme 95). The final product was ca. 94% optically pure. Mori et al. (253) obtained (536 a) in >98% optical purity in their synthesis, which began with L-(+)-tartaric acid (557) (Scheme 96). A shorter stereospecific synthesis of (536a) (>99% pure) has been reported recently by Farnum et al. (254) from L-(-)-menthyl-p-toluene sulfinate (566) (Scheme 97). 

More rigorous evidence supporting the inversion in the transesteiifi-cation of sulfinates was provided by kinetic measurements in which the rate of the acid-catalyzed racemization of (+)-methyl p-toluene-sulflnate 65 in methanol was compared with that of isotopic methoxy-methoxy exchange under exactly the same conditions. 

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