A synthesis of 1, 9-nonamethylenediamine was attempted by use of furfural andacetaldehyde, and this report deals with the condition of synthesis of 3-(2-furfuryl) acrolein in the following synthetic scheme. Furfural+ acetaldehyde→3-(2-furyl) acrolein→3-(2-tetrahydrofuryl) propanol-1→1, 7-dichloropentene-3→1, 7-dicyanopentene-3→ 1, 9-nonamethylenediamine. The concentration of alkali, amount of water and the effect of temperature in the preparation of 3-(2-furyl)acrolein was investigated to seek the optimal condition under which the yield amounted to 91%. The heat of exothermic reaction was found to be 12.8 Kcal/mol. According to the reaction traced by bromine addition method, it was found that the velocity of formation of 3-(2-furyl) acrolein was proportional to the product of the concentration of alkali, of furfural and of acetaldehyde, and that its activation energy was 21.9 kcal/mol.
The reactivity of various azetidinium chlorides and azetidinium sulf onates wereinvestigated and it was found that these compounds were so reactive as expected, and had interesting properties. Especially, azetidinium sulf onates, derived from methylamine and piperazine, consumed sodium thiosulfate rapidly, and showed astrong anticancerous effect.
Cancer inhibitors may be mentioned as one of the most urgently needed chemicals at present. It was found that a certain amino acid showed carcinogenic inhibition. In this report, the synthesis of sulfur-containing amino acids, especially of dichloroacetyl derivatives are described. Methionine, its oxidized substances and its esters, cysteine, cystine and its esters were selected as starting materials. Their acylations were made by (A) Schotetn-Baumann's method and (B) by Kameda's method. The results indicated that the sulfur-containing amino acids in general gave higher yield and higher purity of objective compounds in the B method than in the A method, while the synthesis was easier by use of the A Method in case of esters.
A vaper phase catalytic reaction of aromatic acids and ammonia was investigated. It was found that acidic sites of solid acids ready for alkali poisoning accelerated the process of formation of aromatic amides. It was found that activated carbon, vanadium oxide and molybdenum oxide showed the activity for formation of aromatic nitriles. The normal active state of vanadium oxide and molybdenum oxide, respectively, was found to be V2O3 and MoO2. The lowering of the activity of vanadium catalyst can be explained due to the deposition of carbonaceous matter, but in case of molybdenum catalyst, it was found to be due to the formation of lower oxide by the reduction of molybdenum oxide in the current of ammonia.
For the preparation of tetrahalophthalic anhydride with a vapor phase catalytichalogenation of phthalic anhydride, the thermal halogenation and the activities of various halogenation catalysts were investigated. The velocity of thermal bromination was slower than that of thermal chlorination and the decomposition reaction occurred more easily in the former. Solid acids, such as alumina gel, silica gel, etc., accelerated the chloronation, especially with decomposition giving mainly hexachlorobenzene. Activated carbon gave hexachlorobenzene and pentachlorobenzoic acid in case of chloriantion and gave hexabromobenzene, in case of bromination. Among metal chloride type catalysts, ferric chloride showedespecially high chlorination activity and gave tetrachlorophthalic anhydride in the yield of 54 mol%.
Reaction of 2, 4-dichloro-6-isothiocyanate-s-triazine with amines, such as monomethylamine, dimethylamine, diethylamine, n-butylamine, isopropylamine, morpholine, aniline and diphenylamine, gave new compounds, N-(2, 4-dichloro-s-triazinyl)-N-alkyl (or phenyl)ureas, and the same reaction with methanol, ethanol, isopropyl alcohol, n-butanol and benzyl alcohol gave new compounds 2, 4-dichloro-s-triazinylthionecarbamic acid esters. The properties of these new compounds and the conditions for their preparation were clarified. Also, the reactivity of isothiocyanate in this triazine ring was found to be not so high as that of isocyanate.