Tosyl hydrazone chloride

The Hurd-Mori 1,2,3-thiadiazole synthesis is the reaction of thionyl chloride with the N-acylated or tosylated hydrazone derivatives 1 to provide the 1,2,3-thiadiazole 4 in one simple step. ... 

Other papers of interest in this section report transamination of camphor-3-carbothioamides with secondary cyclic amines, reaction of camphorquinone with dimethyl /S-ketoglutarate, the use of fenchone (212 X=0) in alkene formation from Grignard reagents, bromination of 2-e/itfo-6-endo-dibromobornane to yield 2,3,6-endo-tribromoborn-2-ene, and camphor-enol trimethylsilyl ether formation by quenching the reaction mixture of butyl-lithium and camphor tosyl-hydrazone with trimethylsilyl chloride. ... 

Glyoxalines s. Imidazoles Glyoxalyl chloride tosyl-hydrazone as reactant 26,201 Glyoxylic acids... 

XPhos Aiyl sulfonates, tosyl hydrazones SPhos Aryl chlorides ... 

In general, the reaction can be performed between 0-60°C with the majority of the reactions being run at room temperature. The reactivity of the hydrazones with either the acyl or tosyl leaving group with thionyl chloride depends on the substrate. However, the acylated hydrazones generally provide gaseous by-products where as the tosyl chloride reaction products have to be separated from the reaction mixture. 

Thiadiazoles (57) are produced by the reaction of fV-substituted hydrazones (58 R1, R2 = alkyl, aryl, H R3 = acetyl, ester, tosylate, etc.) with thionyl chloride.67... 

A parallel synthesis of 1,2,3-thiadiazoles employing a catch-and-release strategy has been reported using the Hurd-Mori reaction. A polymer-bound tosyl hydrazide resin reacted with a-methylene ketones to afford a range of sulfonyl hydrazones. Treatment of these sulfonyl hydrazones with thionyl chloride causes 1,2,3-thiadiazole formation and cleavage of the resin in one step <1999JOC1049>. 

Although introduced over 40 years ago, Hurd and Mori s synthesis of 1,2,3-thiadiazoles remains the most widely used for the synthesis of 1,2,3-thiadiazoles. The simplicity of the method has contributed to its popularity. A variety of ketones and aldehydes have been converted into their corresponding hydrazones (tosyl and acyl), and thioamides have been converted into thio-carbazonate esters. The carbonyl derivatives are then treated with thionyl chloride to yield 1,2,3-thiadiazoles in high yields. When one is faced with the task of synthesizing new 1,2,3-thiadiazoles, Hurd and Mori s method should always receive attention. 

Diazo compounds have previously been prepared by a variety of methods. Some of these methods Include hydrazone oxidations, the reaction of diazomethane with acid chlorides,4 the reaction of activated methylene compounds with tosyl azide, decomposition of N-nitroso compounds, ... 

Azide synthesis (2, 415). In the definitive paper3 describing the conversion of primary amines into azides by a diazo transfer reaction, methyllithium is preferred to methylmagnesium chloride as the base. The reaction has been extended to hydrazones. Thus, when the hydrazones of benzophenone, fluorenone, and acetophenone are treated with methylmagnesium chloride and then with tosyl azide, the corresponding diazoalkanes are obtained in about 20% yield. 

Other methods for the synthesis of l,4-dihydro-l,2,4,5-tetrazines 9 which can be explained by intermediate formation of nitrile imines 8 are the photolysis of 1,2,3-triazoles 2181 and sydnones 3,182 reaction of tetrazoles 4180 with tosyl chloride, elimination of pyridine from the pyridinium compounds 5,189-190 of hydrogen chloride from the hydrazonic acid chlorides 1 s.3-i88 or elimination 0f sulfinate from the a-sulfonyl hydrazone 7.189... 

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