Sulphurdi-imines

Sulphurdi-imines.— Appel and Kohnke have reported two methods for the synthesis of symmetrical sulphurdi-imines. In the first, treatment of an alkyl amine with bromine and hydrogen sulphide afforded 60% yields of di-imine. In the second, treatment of the alkyl amine with chlorine and then with bis(dimethylamino)sulphide resulted in 80% yields of di-imine. Leandri et al have effected an JT-ray crystallographic determination of the structure of the bis-p-tolyl imine (100 R = p-tolyl) and have found 

The sulphurdi-imines are hydrolysed in acidic media to sulphur dioxide and two equivalents of amine. Oxidation with ozone afforded a nitrocompound and sulphinylamine. Pyrolysis of the diphenyl derivative (100 R = Ph) gave azobenzene, but pyrolysis of the di-t-butyl derivative (100 R = t-butyl) resulted in an intramolecular elimination to isobutylene, hydrogen sulphide, and ammonia. The bis-tosyl imine (100 R = toluene-p-sulphonyl) reacted with diamines (1,2----------1,6-) in an 

Sekara, and P. Rumpf, Bull. Soc, chim. France, 1971, 286. 

Imino-oxysnlphuranes.—Ohashi et al. and Colonna and Stirling have reported a new method for the preparation of sulphoximines involving the lead tetra-acetate oxidation of an amine or amide in the presence of a sulphoxide. Thus, iV-aminophthalimide and optically active benzyl-p-tolyl sulphoxide afforded the optically active sulphoximine (103) in 89% yield.  

Schmidbaur and Kammel have elaborated on the earlier conversion of sulphoxides into sulphoximines by hydrazoic acid, including further conversion of the parent sulphoximine into N-alkylated derivatives. Johnson and his co-workers have devised two routes to sulphonimidoyl 

Sulphurdi-imines.—Grunwell and Baker have carried out additional CNDO/2 calculations on the — N=S=N— system based on the u.v. spectra. Howeyer, they were unable to demonstrate conclusively that d-orbitals were necessary in order to explain the tt-tt electronic transition energies. Previously, X-ray analysis had demonstrated that in the solid state 

Leandri, V. Busetti, G. Valle, and M. Mammi, Chem. Comm., 1970, 413. 

Ditosylsulphurdi-imine acts as an oxidizing agent, converting hydro-quinone into quinone, thiophenol into diphenyl disulphide, hydrazobenzene into azobenzene, and 1,4-dihydronaphthalene into naphthaiene. The same di-imine reacted with dimethylaminotrimethylstannane such that the latter reagent added separately across each S=N bond. The same reagent reacted with tetrasulphur tetranitride to form the di-imine (131), which reacted with 

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The sulphurdi-imine complexes [PdCl2(RNSNRXPhMe2As)] (R = Me, Et, Pr , or Bu ) exist in the isomeric forms (18) and (19), with (18) the more favoured. Moreover, isomer (18) was found to participate in intermolecular exchange reactions, whereas isomer (19) in which non-bonded Pd -H—C interactions between the metal and the unco-ordinated end of the sulphurdi-imine are present, does not undergo... 

R. Meij, T. A. M. Kaandorp, D. J. Stufkens, and K. Vrieze,/. OrganometalUc Chem., 1977, 128, 203. Fluxional sulphurdi-imine complexes. 

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