Die Konstitution der Desaurine

Abstract

1.37 bichromat und Platinchlorid fillen daraus braune bis schwarze Niederschlgge des Chromats bezw. Platinchlorid-Doppelsalzes der Thiazoniumbase. Beim Einleiten von Kohlendioxyd in die Htherische Losung der Base fiillt das Carbonat als dunkelbrauner, flockiger Niederschlag BUS. D r e s d e n ? 31. Dezember 1911. 17. C. K e l b e r und A. S o h w a r z : DieEonetitution der Desaurine.

Carbon Disulfide. II. Reaction with Active Methylene Compounds. The Structures of the Desaurins

“…Analogs of 5 were subsequently prepared by treatment of compounds of type ArCOCH2Ar1 and ArCOCH2CH, with carbon disulfide and base (15,16). Desaurins were also obtained by 41n this and subsequent structures no assignment of configuration is implied, unless specifically discussed.…”

“…Desaurins were also obtained by 41n this and subsequent structures no assignment of configuration is implied, unless specifically discussed. pyrolysis of the dibenzoyl derivatives or heavy metal salts of dithio acids of type 1 (16); pyrolysis of the acids themselves gave the desaurins, but in very poor yields. Recently, Gompper and Topfl (7a) have obtained desaurins directly from compounds of type 1 by treatment with acylating agents or with oxidizing agents (bromine, iodine, or ammonium persulfate).…”

“…This has been obtained in the case of the desaurin from acetophenone by a subsequent X-ray crystallographic study in collaboration with Nyburg and Mellor (28,29). The desaurin was prepared by the method of Kelber and Schwarz (16) and obtained by slow crystallization from toluene or nitrobenzene as small plates, m.p. 270-272.5' (dec.).…”

“…The formation of desaurins via thermal cleavage of diacyl derivatives of type 27 (16) [or the related alkyl derivatives (7a)l may well proceed via thioketene dimerization (e.g., eq. 4); a related pathway could also account for the formation of desaurins by treatment of compounds of type 1 with phthalyl chloride (7a).…”

Carbon Disulfide. III. Reaction with Active Methylene Compounds. The Infrared and Ultraviolet Spectra of the Desaurins

“…Recent X-ray crystallographic data have made it clear that for several of these compounds in the solid state the S-0 distance is considerably shorter than the sum of the van der Waals' radii of sulfur and oxygen (3.05 A),12 i.e., 6 (2.64 A) (3, 8), 12 (2.72 A) (8), 14 (2.70 A) (12), and 16 (2.63 A) (13).13 However, 3-methylthio-2-cyclohexenone (30), which perforce has an s-trans relationship between the sulfur atom and the carbonyl group, gives rise to a carbonyl-stretching band in its neat or solution i.r. spectrum at 5.98-6.01 p (26).…”