P-toluenesulfonyl hydrazine

Isolation. Diimide has been isolated by low-temperature (-196°, liquid Nj) condensation of the pyrolysis products of the lithium derivative of p-toluenesulfonyl hydrazine (2). This is prepared by the reaction of tosyl hydrazine with lithium bis-(trimethylsilyl) amide in benzene at room temperature. Pyrolysis of (2) is carried out under high vacuum (< I0" torr). 

CYCLIC CARBONATES Performic acid. CYCLIC DISULFIDES Lead acetate. CYCLIC KETONES p-Toluenesulfonyl-hydrazine. 

OLEFINS N,N-Dimethylformamide dimethyl acetal. Iron pentacarbonyl. 0-4-Methylphenyl chlorothioformate. Naphthalene-Sodium. Potassium hexachloro-tungstate. Sodium methylsulfinylmethyl-ide. Sodium sulfide. p-Toluenesulfonyl-hydrazine. Trimethyl phosphite. Triphenylphosphine. 

The preparation of azido diazo substrates 17a and 17b proved to be feasible (Scheme 3). A three-step, one-pot procedure modified from the literamre converted isatin to azido acid 14 in 84% yield. Treating 14 with p-toluenesulfonyl hydrazine in hot acetic acid afforded hydrazone 15 in 81 % yield. The latter was reacted with thionyl chloride at 80 °C for 1 h in benzene. Removal of excess thionyl chloride and finally recrystallization yielded the stable acyl chloride 16 in 71% yield. Condensations of 16 with 10a or 10b... 

A mixture of 2.0 g (R)-3-ethyl-l-[2-(17/-indol-3-yl)ethyl]-2,4-dioxo-3-piperidinepro-panoic acid methyl ester (5.4 mmol) and 2.0 g (/7-toluenesulfonyl)hydrazine (10.8 mmol) in 10 mL MeOH was refluxed for 2 days then an additional 1.0 g (p-toluenesulfonyl)hydrazine (5.4 mmol) in 2.0 mL MeOH was added. The operation was repeated every 48 h over 10 days. The mixture was then concentrated under reduced pressure, and the residue was chromatographed on silica gel using hexane/ EtOAc (1 1) to give 2.30 g pure (R)-3-ethyl-l-[2-(17/-indol-3-yl)ethyl]-2-oxo-4-[[(4-methylphenyl)sulfonyl]hydrazono]-3-piperidinepropanoic acid methyl ester as a yellow amorphous solid, in a yield of 80%. 

This elegant and versatile synthesis of acetylenic ketones and aldehydes through fragmentation of a,/3-epoxy-ketones with p-toluenesulfonyl hydrazine was developed by ). Shreiber, D. Felix, A. Eschenmoser, M. Winter, F. Gautschi, K. H. Shulte-Elte, E. Sundt, G. Ohioff, J. Kalvoda, H. Kaufmann, P. Wieland and G. Anner, Helv. Chim. Acta, 50, 2101 (1967). 

Conversion of ketone 437 to hippocasine (105) was accomplished by Bom-ford-Stevens reaction via the following reaction sequence. Successive treatments of 437 with hydrazine, p-toluenesulfonyl chloride, and then lithium tert-butylamine gave hippocasine (105). The reaction occurred exclusively in the desired direction. Treatment of hippocasine (105) with methanolic hydrogen peroxide gave hippocasine oxide (106) (Scheme 54). 

Tetrazolo[l,5-a]pyridines have been prepared from either the corresponding halopyridine and sodium azide in the presence of acid with spontaneous electrocyclic ring closure, or by nitrosation of the appropriate 2-hydrazinopyridines (71T5121,76JOC1073) as shown in Scheme 70. The reaction of 2-nitroaminopyridines with hydrazine under the influence of Raney nickel (72JHC461) and 2-aminopyridines with p-toluenesulfonyl azide (79JHC1567) are two other useful routes to tetrazolo[l,5-a]pyridines. 

There are three isomeric structures for diimide, N2H2 cis- and fran -diimide (1 and 2), and 1,1-diimide (aminonitrene 3), Diimide has been generated and trapped at low temperatures from the gas-phase electric discharge of hydrazine, and by the thermal decomposition of metal salts of p-toluenesulfonyl hydrazide. A careful analysis of the available spectroscopic data has indicated the formation and presence only of (2). ° 1,1-Diimide (3) has been recently generated by the low temperature photochemi-... 

Other reactions. The preparation of an acid hydrazide from an acid is illustrated by the reaction of p-toluenesulfonyl chloride with hydrazine hydrate in Iclrtihydro-... 

Umezawa and coworkers synthesized neamine from paromamine. Treatment of peracetylated paromamine with methanolic methoxide gave tri-N-acetylparomamine. Selective p-toluenesulfonylation of its primary hydroxyl group, followed by replacement of the p-tolylsulfonyloxy group by an azido group, amination by catalytic reduction, and finally, N-de-acetylation with hydrazine, afforded neamine (83). 

Reactions induced by ultrasonic irradiation of methyl 9,12-dioxostearate with hydrazines in water in the presenee of acidic alumina gave high yields of pyridazine fatty esters directly (95). The synthesis of novel piperidine- [25] and pyridine- [26] containing long-chain fatty ester derivatives has been reported starting from methyl wo-ricinoleate, 9-hydroxy-18 l(12Z) (96). Allylic amination of methyl oleate with bis(A-p-toluenesulfonyl)sulfodiimide gave a mixture of methyl ll-amino-(iV-p-toluenesulfonyl)-18 l(9 ) and methyl 8-amino-(Af-p-toluenesulfonyl)-18 l(9 ) (97). 

With regard to the reaction above (5A.42), recall the abbreviation Ts = tosyl or p-toluenesulfonyl (i.e., P-CH3-C6H4-SO2-). The hydrazones (as the products with hydrazine are called) lend themselves to a number of unique transformations, of which we will discuss the Wolff-Kishner reduction and the Shapiro reaction. 

Synonyms Benzenesulfonic acid, 4-methyl-, hydrazide Hydrazine, p-tolylsulfonyl- p-Toluenesulfonhydrazide p-Toluenesulfonic acid, hydrazide p-Toluenesulfono-hydrazide p-Toluenesulfonyl hydrazide N-Toluolsulfonyl hydrazine Tolylsulfonyl hydrazine Tosyl hydrazide... 

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