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Trichothecin is the isocrotonic ester of the ketonic alcohol, trichothecolone. On the basis of its properties and those of degradation products, obtained by oxidation, alkaline fission, and dehydrogenation, the alternative structures (I; R=H) and ( 11), of which the former is preferred, are proposed for trichothecolone. On treatment with hot potassium hydroxide, trichothecolone gives an isomer, isotrichothecolone. Some properties and derivatives of the latter are described.TRICHOTHECIN is an antifungal substance, produced by the fungus Trichothecium roseurn Link.1 Some of its chemical and biological properties have been de~cribed.~-~ It is an ester, Cl,H,O5, giving on hydrolysis isocrotonic acid and a ketonic alcohol, trichothecolone, C,,H,04.Trichothecin was readily hydrogenated at atmospheric pressure with palladiumcharcoal, two mols. of hydrogen being absorbed to give the non-crystalline tetrahydrotrichothecin. This uptake was accounted for by saturation of one ethylenic double bond in the isocrotonic ester group and a second ethylenic double bond in the trichothecolone part of the molecule. Trichothecin contained a reactive carbonyl group, which was retained in tetrahydrotrichothecin. Kuhn-Roth determinations showed that trichothecin has at least three C-methyl groups. No methoxyl group was detected. The infrared spectrum of trichothecin had bands a t 1670 (up-unsaturated ketone), 1710 and 1177 (a@unsaturated ester), and 1650 cm.-l (attributed to ethylenic unsaturation). Absence of a band in the region of 3400 cm.-l indicated absence of hydroxyl groups which was confirmed by indifference of trichothecin, even under the most vigorous conditions, to acetic anhydride or benzoyl chloride. There was no indication of benzenoid absorption in the spectrum.

The nitrates of mono-, di-, and tri-methylamine, mono-, di-, and triethylamine, ethanolamine, glycine , aniline, and benzylamine have been prepared, and their heats of combustion determined. The heats of solution of mono-and tri-methylamine nitrates in water have also been determined. THE object of the present work was to prepare a series of amine nitrates and examine the effect of alteration of structure on a variety of their physical properties. Unfortunately the work was not completed, and only the heat of combustion of all the salts prepared was determined, as well as the heat of solution of two of them in water.Early work on amine nitrates is due to Franchimont (Rec. Truv. chim., 1883, 2, 329), van Romburgh (ibid., 1886, 5, 246), and Walden (cf. Chem. Centr., 1914, I, 1800). More recently, Willis (Trans. Furuduy SOC., 1947, 43, 97) has prepared the nitrates of a number of cyclic bases, and determined their heats of combustion, but only one of the compounds investigated by him, aniline nitrate, has been studied by us. EXPERIMENTAL.Pre$aration of Amine Nitrates.-An aqueous solution of the base was neutralised with 70% nitric acid, the water removed by distillation in vucuo, alone and with alcohol, and the product recrystallised from absolute alcohol.The m. p.s are several degrees higher than those previously recorded, probably because many of the salts are very hygroscopic. No further comment is necessary, except for ethanolamine nitrate, which was prepared by Gabriel (Bey., 1888, 21, 2668) by saturating an aqueous solution of vinylamine with nitric acid, whereas we found that this precaution to prevent formation of the nitric ester is unnecessary, and that the pure nitrate can be M. p.s and analyses are given in Table I.

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The preparation and properties of the chlorohydrin and epoxide from cis-1 : 2 : 3 : 6-tetrahydrophthalic anhydride and several of its dialkyl esters are described. Reactions of the anhydride with chlorine and bromine, and preparation of the jmide are reported.