P-Tolylsulfonylmethyl isocyanide

The synthesis of p-tolylsulfonylmethyl isocyanide is described in this Volume. The light-brown compound, m.p. 111-114°, was used without further piu ification. 

C=N, C=S, C=C, and N N containing substrates. Thus oxa2oles, imidazoles, thiazoles, p rrroles, and 1,2,4-triazoles have been prepared, respectively. Furthermore, p-tolylsulfonylmethyl isocyanide has found use in a one-step conversion of ketones into cyan-idea and in a two-step synthesis of a-hydroxyaldehydes from ketones. ... 

Synthetic applications of organosulfur reagents are expanding rapidly. Stable sulfuranes are included for the first time in BIS[2,-2,2-TRIPLUORO-l-PHENYL-l-(TRIFLUOROMETHYL)ETHOXY] diphenyl SULFURANE and DIETHYLAMINOSULFUR TRI-FLUORIDE. The latter is used to transform an alcohol to a fluoride in p-NITROBENZYL FLUORIDE. The direct homologation of a ketone to a nitrile by use of p-TOLYLSULFONYLMETHYL ISOCYANIDE is illustrated in 2-ADAMANTANECARBONITRILE. Reagents with... 

The van Leusen reaction forms 5-substituted oxazoles through the reaction of p-tolylsulfonylmethyl isocyanide (1, TosMIC) with aldehydes in protic solvents at refluxing temperatures. Thus 5-phenyloxazole (2) is prepared in 91% yield by reacting equimolar quantities of TosMIC and benzaldehyde with potassium carbonate in refluxing methanol for 2 hrs. ... 

Substituted oxazoles through the reaction of p-tolylsulfonylmethyl isocyanide (TosMIC) with aldehydes in protic solvents at refluxing temperatures. 

A solution of 50 g. of p-tolylsulfonylmethyl isocyanide in 150 ml. of dichloromethane is placed on a 40 x 3 cm. column containing about 100 g. of neutral alumina slurried in dichloromethane. A nearly colorless solution (ca. 700 ml.) is collected over about 1 hour. This solution is evaporated to dryness on a rotary evaporator, providing 42-47 g. of white p-tolylsulfonylmethyl isocyanide, m.p. 113-114 (dec.). 

Earlier workers reported the silver(I)-catalyzed reaction of an aldehyde with p-Tolylsulfonylmethyl Isocyanide (eq 4). The (/ )-(/ )-dihydrooxazolines formed can be reduced with Lithium Aluminum Hydride to provide a facile route to a-alkyl-p-(N-methylamino)ethanols in good to excellent yield. 

Related Reagents. 7V,7V Diethylaminoacetonitrile Dimethyldithiocarbamoylacetonitrile (4a/ )-(4aa, 7Q, 8a )-Hexa-hydro-4,4,7-trimethyl-4i l,3-benzoxathiin 2-Lithio-l,3-dithi-ane Nitromethane 1,1,3,3-Tetramethylbutyl Isocyanide p-Tolylsulfonylmethyl Isocyanide 2-(Trimethylsilyl)thiazole. 

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