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Published online by Cambridge University Press: 17 January 2013
Some years ago I commenced an examination of the behaviour of the so-called olefines towards certain compound halogens. I was induced to this by the conviction that the bodies resulting from the union of a group of unequally chemico-negative elements with an olefine, would place an instrument of great power into the hands of systematic chemists, especially of synthesists. My expectations have been more than realized. The few olefines which I have examined in their relation to compound chemico-negative groups have given rise to a series of new bodies remarkable alike for their great number and for the elegance and importance of the reactions attending their formation and recompositions.
page 612 note * I. Chem. Soc. Quart. Jour., vol. xii. p. 109. Ann. der Ch. u Ph., cxiii. p. 266; Annales de Ch. et Phys., vol. lix. p. 461.
II. Chem. Soc. Quart. Jour., vol. xiii. p. 35. Ann. der Ch. u Ph., cxvi. p. 234.
III. Chem. Soc. Quart. Jour., vol. xiii. p. 129.
page 612 note † From Messrs Simpson, Maule, and Nicholson.
page 612 note ‡ M. Wurtz (Ann. de Ch. et Phys., vol. lix.), in referring to the bodies (1), (2), (3), (4), (9), (10), remarks,—
“SCl2 correspondant à SO2 etant diatomique, il en résulte en effet que SC12 − Cl c'est à dire SCl doit être monatomique. Vous ferons remarquer, néanmoins, que l'on peut envisager la constitution de ces composées d'une autre manière, en supposant qu'ils renferment le groupe diatomique,
“Sulphure d'ethylène (C4 H4 S2)“ et
“Sulphure d'amylène (C10 H10 S2)“ correspondant aux oxydes. Ces groups en se combinant à 2 atomes de chlore forment les deux chlorures suivants—
Dichlorure de Sulphethylène (C4 H4 S2)“ Cl2
Dichlorure de Sulphamylène (C10 H10 S2)“ Cl2
“Quant aux chlorure C10 H10 S2 Cl nous doublons son equivalent et nous representons sa constitution par la formule
“On sait que 2 atomes d'oxyde d'ethylène peuvent se réunir pour se combiner à 1 atom d'eau. II n'est pas done extraordinaire que 2 atomes de sulphure d'amylène de reunissent pour se combiner a 2 atomes de chlore. Si cette manière de voir est exacte on doit representer la constitution de l'oxyde de disulphamyléne et cette de hydrate d'oxyde de disulphamylène par les formules
With regard to the first portion of M. Wurtz's remark relative to the bichlorosulphides, I have to observe that the body SCl2 has not been shown to exist, and, therefore, how its atomicity would be affected by a withdrawal of chlorine is a premature speculation.
Further, if the diatomic olefines are combined with two atoms of sulphur (“corresponding to the oxides”), why do they combine with two more atoms of halogen? Not, I think, because they have two stages of saturation, as M. Wurtz's view would indicate, but because halogen groups may have the same index of saturation as simple halogens. In this manner
Concerning the bisulphochlorides, there is perhaps as much reason for doubling their formulæ as for doubling that of water; and so for the bisulphoxide.
M. Wurtz's proposed formula for the hydrated bisulphoxide of amylen, viz.,
I cannot interpret, unless it belong to the class of “mixed types.”
On the other hand, we may regard it as
which, I insist, is more congenial to analogy.
But, in truth, if the function of a formula be to express potential recomposition, these bodies eminently show the insufficiency of a single formula.
page 615 note * Chem. Soc. Quart. Jour., vol xiii.
page 616 note * I may not here discuss the composition of the sulphocyanides. Whether they be isotypic with the cyanates or the cyanides, or whether such a distinction be at all a substantial one, is here a matter of secondary importance.
page 623 note * I only find one example of this last recoraposition, namely, the formation of nitronapthaline by the action of NO4 upon napthaline described by Laurent.
page 625 note * Dr M. Simpson has already announced the formation of bicyanide of ethylen, and the derivation therefrom of succinic acid.
page 630 note * The physical properties of this body, and the large quantity of liquid which water separates rom it, seem to point to its being a compound of chloride of zinc, with bisulphide of œnanthyl.
page 630 note † Bisulphide of ethyl boils circa 150° C. If Kopp's law hold good, a successive increment of 19° C. for every C2 H2 would point to 245° C. as the boiling point of bisulphide of œnanthyl. But in the cases of other bisulphides, a common increment of 33 would more nearly represent experimental results. Hence it is possible that this substance may only be an isomer of bisulphide of œnanthyl.