The preparation of 1,2,3,5-dithiadiazolium chlorides from the reaction of nitrile sulphides with thiazyl chloride

Abstract

. Adamantyl-1,3,4-oxathiazol-2-one has been prepared for the first time and from it 1-adamantyl nitrile sulphide has been generated. Characterisation data are presented, including the X-Ray crystal structure of the oxathiazolone. (Crystal data for C,,H,,NO,S: monoclinic, space group F'2,/c, a = 11.334(2) A, b = 7.344(1) A, c = 14.373(2) A, P = 107.74(1)", V = 1139.5(3) AS, Z = 4, R = 0.042). The planar heterocyclic ring is similar to structures observed in the gas phase for other oxathiazolone derivatives. The nitrile sulphide was reacted with dimethyl-acetylene dicarboxylate in situ to give an isothiazole derivative. On a prtparC l'adamantyl-l,3,4-oxathiazol-2-one pour la premikre fois et on l'a utilise pour gCnCrer la sulfure de l-adamantyl nitrile. On prCsente les donntes ayant semi ?i sa caractCrisation, y compris la structure de l'oxathiazolone determinee par diffraction des rayons X. Les donntes cristallines pour C,,H,,NO,S sont les suivantes: cristaux monocliniques, groupe d'espace [Traduit par la Rtdaction]

Adamantane-based nitrile sulfides: the generation of the synthetic equivalent of the first bis(nitrile sulfide)

“…The heterocycles are planar, partially delocalized (la and lb) or fully delocalized ( l c and Id) .rr systems as described previously (3 bond distances and angles consistent with those reported for methylacetyl groups in similar compounds (3). It is noted, however, that in lc, Id, and 2b the plane of the ester group next to the adamantane moiety is twisted out of the plane of the heterocycle to which it is attached, while the second ester group, which is more distant from the adamantane moiety, essentially lies in the plane of the heterocycle.…”

“…Indeed, the actual reaction of l a and l c gives a quantitative yield of l e and S8 and is in agreement with previous studies that indicated that nitrile sulfides, while highly reactive to nitrile T systems, give higher yields with aromatic nitriles or those bearing strongly electron-withdrawing substituents (17). In previous work it was shown by theoretical calculations and the established pattern of reactivity that the aromatic nitrile sulfides have extensively delocalized T systems that may stabilize the 1,3-dipole (3). If this is a reliable analysis, then an aromatic ring may be a more suitable platform for the generation of bis(nitri1e sulfides) in polymerization reactions.…”

“…These reactions may provide higher yields at lower concentrations and subsequent investigations on the reaction of l a with inorganic .rr systems will examine this possibility. The recovered yield of the reaction of a monosubstituted adamantane with DMAD was reported to be 27% (3). If the two heterocycles in l a react completely independently, then the percent yield of the total reaction would be expected to be the square of the yield of an individual cycloaddition reaction (predicted yield -7%).…”

“…3. The generation of a series of heterocyclic compounds by reaction of l a with inorganic n systems is now practical.…”

The selective complexation of adamantane nitriles by tungsten pentacarbonyl

“…They are typically generated in situ from precursor oxathiazolone heterocycles such as 2 in the presence of a dipolarophile to give five-membered ring heterocycles. We have reported the first systematic X-ray crystallographic analysis of the precursor ring and the cycloadducts from the reaction of adamantane -nitrile sulphide with the alkyne and thiazyl triple bonds and explored the chemistry of the first bis(nitrile sulfide) (5).…”