The reaction conditions for the synthesis of 1, 7-dicyanoheptene-3 from 1, 7-dichloroheptene-3 or 1, 4, 7-trichloroheptane which was obtained through ring opening reaction of 3-(2-tetrahydrofuryl) propanol with hydrogen chloride have been investigated. When 1, 7-dichloroheptene-3 was treated with sodium cyanide by using 70-80% methyl cellosolve, ethyl cellosolve, DMSO, or methanol as a solvent, 1, 7-dicyanoheptene-3 was obtained in 90-96% yield. When this reaction was conducted in an aqueous medium containing a quarternary ammonium salt type cationic surface active agent, the yield dropped to 70%. Catalytic vapor phase reaction between 1, 7-dichloroheptene-3 and hydrogen cyanide at high temperatures in the presence of granular active carbon impregnated with metal chlorides resulted in the formation of only olefins. 1, 7-Dicyanoheptene-3, however, was obtained in 25% yield upon treatment of the 1, 7-drehloro-olefin with hydrogen cyanide in liquid ammonia. Using sodium cyanide, it was possible to convert 1, 4, 7-trichloroheptane selectively into 1, 7-dicyano-4-chloroheptane, which was then dehydrochlorinated at 250-280°C. in uacuo to give 1, 7-dicyanoheptene-3 in 73% yield.

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1, 7-Diaminoheptane has been synthesized from 1, 7-dichloroheptene-3 through ammonolysis followed by hydrogenation. For the formation of the desirable primary amine in the ammonolysis reaction, the following conditions have been proved favorable: use of liguid ammonia with or without a small amount of water or an organic solvent rather than aqueous ammonia, use of an excessive amount of ammonia, reaction temperatures above 80°C, in case of aqueous ammonia and above 60°C, in case of liquid ammonia, the effects of temperature upon yield being small over the range 100-140°C, and efficient agitation to ensure thorough contact of the reactants. The maximum yield of 1, 7-diaminoheptene-3, however, was 72-73%. Attempts to improve the yield resulted in the formation of secondary and tertiary polyamine by-products. 1, 7-Diaminoheptene-3 thus obtained was readily hydrogenated into 1, 7-diaminoheptane in 96% yield in the presence of Raney nickel catalyst under the atmospheric pressure as well as under pressure. Condensation polymerization of 1, 7-diaminoheptene-3 and that of 1, 7-diaminoheptane with urea proceeded smoothly and white solid polyureas with good spinning properties were obtained. The former polyurea showed m.p. 216°C, d²⁰4 1.13 and the latter, m.p. 260°C, d²⁰ 1.12. The melting point of the polyurea obtained from 1, 9-noname. thylenediamine fell between that of the two polymers, and the specific gravity of the former was approximately 5% less than that of the latter two. The fiber of 1, 7-diaminoheptene-3 polyurea as well as that of 1, 7-diaminoheptane polyurea showed a slightly better dyeing properties with acidic and dispersing dyes than 1, 9-nonamethylenediamine polyurea, though other properties of those three types of fiber were alike.

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The synthesis of benzene-polycarboxylic acids of growing demand for theproduction of synthetic fiber and plastics has been investigated using m-xylene as a starting compound. The present study has been directed to establish the synthesis conditions and yields for mesitylene (2) and isodurene (3) through the Friedel-Crafts reaction of m-xylene (1); 4-chloromethyl-m-xylene (4) and 4, 6-dichloromethylm-xylene (5) through chloromethylation of (1); and 2-chloromethylmesitylene (6) and 2, 4-dichloromethylmesitylene (7) through chloromethylation of (2). Trimesic acid, trimellitic acid, pyromellitic acid, prehnitic acid, and benzenepentacarboxylic acid were obtained via potassium permanganate oxidation of (2), (4), (5), (6), and (7), respectively, and the effects of the reaction time on the yields have also been studied.

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An attempt was made to synthesize .ε-caprolactam directly from cyclohexanoneand a primary nitroparaffin, the latter being used as a source of hydroxylamine. When nitromethane, nitroethane, or nitropropane was treated with sulfuric acid in a molar ratio of 1:5 at 125-130°C, hydroxylamine sulfate was formed in a yield above 90%. The reaction mixture thus prepared was then treated with cyclohexanone at 120-125°C. Oxime formation and the Beckmann rearrangement proceeded smoothly, and .ε-caprolactam was obtained in a good yield.

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2-Methylanthraquinone and 2, 3-dimethylanthraquinone were synthesized through the Diels-Alder reaction of 1, 4-naphthoquinone with isoprene and 2, 3-dimethylbutadiene, respectively. Eighteen types of dispersing dyes were then prepared from those two compounds and their dyeing qualities tested with Acetate and Tetoron. The colors of dyed cloth varied from orange to blue. The 2-methyl derivatives showed better dyeing qualities over the 2, 3-dimethyl analogs. Their fastness against sunlight was comparatively better in Acetate, and that in Tetoron was of 2-3 grade in most cases. The fastness against friction and washing was excellent particularly in the 2, 3-dimethyl derivatives.

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A series of dispersing dyes containing a β-methyl group and an α-amino group have been synthesized in such a way that those substituents are not located in adjacent positions to each other on the ring structure. The starting compounds employed were the Diels-Alder adducts obtained from 2, 3-dimethylbutadiene with naphthazarine and with 5-nitro-2, 3-dichloronaphthoquinone. Their dyeing qualities for Acetate and Tetoron were then tested. It has been reported that the presence of a methyl group in an adjoining position to the amino group lowers the fastness against sunlight due to increased electron density at the amino group. The dyes prepared in the present study thus showed improved fastness of 4-6 grade for Acetate, that for Tetoron being around 3 grade. They also revealed excellent resistance against washing and sublimation, though their dyeing qualities remained almost the same as that of 2-methylanthraquinone derivatives. Shift of the maximum absorption peak toward the longer wave length was noted in ethanol when the methylanthraquinones were compared with anthraquinone derivatives containing no methyl group.

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