1002. The preparation of sulphinylhydrazides and their conversion into carboxylic acids and carboxylic acid derivatives

Abstract

A number of sulphinylhydrazides, RCO*NH*NSO, have been prepared. They are readily hydrolysed to the corresponding hydrazide, and, on heating, are converted into the carboxylic acid or acid chloride.

From Inert to Explosive, The Hydrolytic Reactivity of R−NSO Compounds Understood: A Computational Study

“…Despite the fact that N-sulfinylhydrazides can be regarded as the amido derivatives of N-sulfinylhydrazines, with one exception, they are known to react with water readily. 15,21 Benzyl-N-sulfinylhydrazide (PhCH 2 ÀCOÀNHÀNSO) was reported to be thermally and hydrolytically stable, which was attributed to the greater charge delocalization in its enol form compared to that in the enol form of the phenyl analog. 21 Even disregarding syn-anti isomerization of the NSO group, N-sulfinylhydrazides are rich in isomers.…”

“…15,21 Benzyl-N-sulfinylhydrazide (PhCH 2 ÀCOÀNHÀNSO) was reported to be thermally and hydrolytically stable, which was attributed to the greater charge delocalization in its enol form compared to that in the enol form of the phenyl analog. 21 Even disregarding syn-anti isomerization of the NSO group, N-sulfinylhydrazides are rich in isomers. The two enols (E E and E Z , where E or Z reflect the configuration of the C r ÀO r with respect to the NÀN R bond) and two ketones (K E and K Z ) are shown in Figure 1 for phenyl-N-sulfinylhydrazide (PhÀCOÀ NHÀNSO, PhSHd).…”

“…20 N-Sulfinylamides (RÀCOÀNdSdO) and -hydrazides (RÀCOÀNHÀNdSdO), with one exception, 21,22 and even though there is no quantitative comparison of their reactivity with that of other N-sulfinyl species, are also known to react readily with water. 15,21,22 Interestingly, whereas amides and hydrazides hydrolyze through nucleophilic attack of water on the carbonyl carbon, 23À26 their sulfinyl derivatives follow the same mechanism of hydrolysis as the N-sulfinylamines.…”

Syntheses and Characterization of Polyimidosulfate Complexes

“…A series of novel metal complexes of the S(NtBu)4 2-ligand could be synthesized Moreover, by defined hydrolyses with water, several interesting metal compounds could be obtained (3,4,9). Also, different metal cations could be coordinated in this way, which reflects the high flexibility of this ligand.…”

“…Oxidation state +IV is represented in the S-alkyl-iminosulfinamides, RS(NR')2 ¯ (A) [3] (Figure 1.1), which results from the addition of lithium organyls to the formal double bond of the sulfurdiimides (Figure 1.1). With R being an alkyl-or aryl group and R' an alkyl-, aryl-, or trimethylsilyl group many main group [3][4][5][6][7][8][9][10][11][12][13] and transition metal [11,14,15] complexes are known. Furthermore, iminosulfindiamides can be obtained (B, C and D).…”