The constituents of the essential oil from the leaf and wood of Chamaecyparis obtusa (SIEB. et ZUCC.) have been investigated; a sample of the commercial leaf oil was also examined. Elemol and eight monoterpenes were found in the leaf oil. This is the first recorded isolation of elemol from this species. The wood oil was found to contain γ-cadinene, calamenene, two cadinols, and seven monoterpenes. d-Longifolene, d-γ-cadi nene, calamenene, and thunbergene were identified in the commercial leaf oil.

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A convenient DTA apparatus using two matched thermistors was designed and was easily and inexpensively constructed. Because of sensitivity of the thermistors for detecting temperature difference and of the advantage of the double cell consisting of a inner tube and a jacket, the sample size is much reduced even to a few milligrams. The arrangement of the cell is also effective for making the base line flatten. Another characteristic point of the apparatus is that it permits direct viewing of the sample during the course of measurement. Since it is often desirable to compare peaks in the DTA curve with visual changes, the arrangement is found very useful for the study of phase reactions of organic materials. Tests concerning the experimental conditions show that analysis can be performed with accuracy and reproducibility. Applications were done for the studies of thermal behaviors of ammonium nitrate, bromo-diethylacetylurea and α-bromoisovalerylurea. Direct transformation of ammonium nitrate from the modification of IV to II was occasionally noticed. It was also confirmed that there was clear correspondence between the fall and rise of the DTA curve of copper sulfate pentahydrate and the changes in color observed with eye. As a general application of DTA, a simple method for evaluating the heat of transition was proposed. It is based on direct comparison of two peaks by conducting DTA with a mixture of the sample and the inert substance of known heat of transition. The heat of polymorphic transition of potassium nitrate at 128∼129° was found to be 1.20kcal./mol. by using benzoic acid as an internal standard. It is thought that the method will have wide application, especially to organic materials. Also, discrimination of pyrabital form the corresponding mixture of aminopyrine and barbital was successfully done by DTA. The curve of the former shows two peaks which is due to the stable eutectic liquefaction and to melting, while that of the latter exhibits in addition to these peaks, one pair of endothermic and exothermic ones which is attributed to the metastable eutectic liquefaction and to the molecular compound formation, respectively. These results will suggest that DTA is generally applicable to the detection of molecular compound between organic medicinals.

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Racemic and optically active N-(2-mercaptoethyl)ephedrines, 2-phenyl-3, 4-dimethyl-tetrahydro-4H-1, 4-thiazines, and their diastereomers were prepared, and their configurations were investigated. 2-Phenyl-3, 4-dimethyltetrahydro-4H-1, 4-thiazine, was obtained either by chlorination of N-(2-hydroxyethyl)ephedrine with thionyl chloride followed by cyclization with sodium sulfide, or by dehydration N-(2-mercaptoethyl)-l-and d-ψ-ephedrines with 80% sulfuric acid. Both reactions led to formation of threo-2-phenyl-3, 4-dimethyltetrahydro-4H-1, 4-thiazine. erythro-2-Phenyl-3, 4-dimethyltetra-hydro-4H-1, 4-thiazine was prepared from erythro-1-phenyl-2-methylaminopropanethiol and cthylene dibromide. When N-(2-mercaptoethyl)ephedrine was heated, formation of ephedrine due to partial splitting of 2-mercaptoethyl group was observed.

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Deoxydemethyllycoramine which is closely related in structure to galanthamine has been synthesized by an unambiguous sequence of reactions providing confirmative evidence for the structure of the alkaloid.

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The reaction products of nitrous acid on 5-amino-3, 4-dialkylisoxazoles (Ia, b, c) has been formulated as 4-(3, 4-dialkyl-5-isoxazolyl)azo-3, 4-dialkyl-5(4H)-isoxazolones (IVa, b, c) rather than the azoxy structure (II) which was originally proposed by Hanriot. To gain insight into this reaction mechanism, the behavior of o-, m-, and p-nitrobenzenediazonium chlorides on Ia has been also investigated.

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Two methods of synthesizing 1, 4, 6-triazaindene, which was isosteric to purine and to indole were described. The first method involves the ring-closure of 5-acylamido-6-methylpyrimidines. The second method involves the Claisen reaction of 5-nitro-6-methylpyrimidines followed by reductive condensation.

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1, 4, 6-Triazaindene and its derivatives corresponding to the naturally occurring purine bases were synthesized from the 1, 4, 6-triazaindenes reported in the preceding paper. The structures of these derivatives were confirmed by investigating them on their physico-chemical properties such as ultraviolet absorption and nuclear magnetic resonance spectra.

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When ubiquinone (35) (I) was irradiated with sunlight in ethanol or methanol, it was converted to some substances and the absorption at 275 mμ characteristic of homologues of ubiquinone decreased, the absorption around 240 mμ increasing. The reaction product was purified by chromatography on silicic acid to give nine fractions. In this case, when ethanol was used as solvent, acetaldehyde was formed, and when methanol was used, formaldehyde was produced. The same conversion was observed by irradiation with a mercury lamp. I was converted into the hydroquinone compound (II) in a sealed tube, in which the air was replaced by nitrogen.

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It was made clear that ubichromenol (35) (II) was one of the products of photochemical reaction of ubiquinone (35) (I). It was also found that I was converted to II in good yield with an aliphatic tertiary amine. Perhydroubichromanol (35)(III) and acetylubichromenol (35)(IV) were obtained as derivatives of II.

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It was Clarified that one of the photochemical reaction products of ubiquinone (35) (I) had the structure (II) where one of the double bonds of the isoprene side chain of I was conjugated with the quinone nucleus. It was named isoubiquinone (35). γ-Hydroxyisoubiquinone (35) (VII) was obtained by treating ubichromenol (35) (IV) with lithium aluminum hydride.

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It was made clear that one of the photochemical reaction produts of ubiquinone (35) (I) had the structure (II) in which one of the two methoxyls of I was converted to a hydroxyl. And it was named demethylubiquinone (35). II was converted to demethylubichromenol (35) (IV) by treating with triethylamine, and the position of the hydroxyls of II was decided from the fact that the two hydroxyls of IV gave a color reaction with phosphomolybdic acid, showing that they are in ortho-relation.

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The structure of a base-induced isomerization product of B-nor-6-oxo-5β-steroid(I) was assigned to be B-nor-6-oxo-5β, 8α-steroid (III) and conformation of the A-ring was also discussed on the basis of evidence obtained form nuclear magnetic resonance spectra.

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A-Ring conformations in B-nor-5α-cholestane-3β, 6α-diol (IV), the 3β-monoacetate (II), the 3, 6-dione (VI), 3β-acetoxy-B-nor-5α-and-5β-cholestan-6-one (III, XVIII) and 3β-hydroxy-B-nor-5β-cholestan-6-one (XVII) were discussed on the basis of evidence obtained from nuclear magnetic resonance spectra and conformational analysis.

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The naturtal l-β-hydrastine (Iβ) was epimerized to l-α-hydrastine (Iα). Iα was converted to(--)-canadine (VIII), througth ophiocarpine (VIα), whereas Iβ transformed into VIII through 13-epiophiocarpine (VIβ). The absolute configration of ophiocarpine and 13-epiophiocarpine are represented by VIα(13R : 13aR) and VIβ(13S : 13aR), respectively. Accordingly, the absolute configuration of l-α-hydrastine and l-β-hydrastine are also designated as Iα (αR : 1R)and Iβ(αS : 1R). respectively.

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The natural l-α-narcotine (Iα) and its epimer l-β-narcotine (Iβ) were stereospecifically converted into 1-(2-methyl-3, 4-dimethoxybenzyl)-6, 7-methylenedioxy-1, 2, 3, 4-tetrahydroisoquinoline (IV) and (-)-1-methoxycanadine (X), respectively. According to these results, the absolute configuration of Iα and Iβ were established as (αS : 1R) and (αS : 1R), respectively.

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Cinnoline 1-oxide (1) gave 4-nitrocinnoline 1-oxide (II) and a small amount of 5-nitrocinnoline 1-oxide (V) on warming with nitric and sulfuric acids, and gave 4, 5-dinitrocinnoline 1-oxide (IV) by using fuming nitric acid in sulfuric acid. The nitration of I with benzoyl nitrate afforded 3-nitrocinnoline 1-oxid (VI). I was converted into 4-chlorocinnoline (VIII) on the treatment with phosphoryl chloride.

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Diacetylenic compounds; 1, 7-diphenyl-1, 6-heptadiyne (I), N, N-bis(3-phenyl-2-propynyl) methylamine (III), bis(3-phenyl-2-propynyl) sulfide (VII) and bis(3-phenyl-2-propynyl) ether (IX) underwent intramolecular cyclization reaction by means of 14% solution of potassium tert-butoxide in tert-butyl alcohol in remarkably mild condition to aford naphthalene derivatives; 4-phenyl-2, 3-dihydro-1H-benz[f]indene (II), N-methy-4-phenyl-1, 3-dihydro-2H-benz[f]isoindole (IV), 4-phenyl-1, 3-dihydronaphtho[2, 3-c]thiophene(VIII) and 4-phenyl-1, 3-dihydronaphtho[2, 3-c]furan (X) respectively. The reaction mechanism of this cyclization was proposed.

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6-Phenyl-2, 4-dinitrophenol derivatives were prepared for their evaluation as herbicides. Some of these compounds were found to be promising.

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Carbanion reacted as nucleophilic reagent with quinazoline. Reaction of quinazoline with acetophenone in the presence of sodium hydroxide solution at room temperature afforded 2-(3, 4-dihydro-4-quinazolinyl)acetophenone. The mechanism for this reaction may be suggested as in Chart 1 in the text.

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