Some α-substituted-β-(5-nitrofuryl) acryloylaziridine derivatives were synthesized from the corresponding acyl halides, ethylene imine and triethylamine at 0-5°C5-Nitro-2-furylacryloylaziridine (1) was subjected to ring-opening reaction by treatment with an acid or base and was isomerized with sodium iodide in several solvents. Upon heating, furoylaziridine and furylacryloylaziridine were also isomerized with ease into furoyl-and furylacryloyl-oxazoline.
The reactions of Anti- and syn-isomers of f uran- and 5-nitrof uran-aldoximes were studied; these are (1) addition reactions tof isocyanates, (2) substitution reactions with acryloyl chloride in the presence of triethylamine, and (3) rearrangement reactions with the aid of zinc chloride or polyphosphoric acid at 120°C-130°C. Furan- and 5-nitrofuran-hydroxymic acid chlorides were obtained from the corresponding aldoximes and nitrosyl chloride in absolute ether at -20°C. The latteracid chloride was treated with a primary or secondary amine to give an aminoxime which was in tautomerism with its aminoalcoholic form. The former, however, gave only furoxan, dimer of the nitriloxide, under the same conditions. Severalother reactions involving the above mentioned hydroxymic acid chlorides were also studied.
The oxidation of 4, 4'-bisdimethylaminodiphenylmethane (1) with lead dioxide in diluted nitric acid has been studied. The main oxidation product was 4, 4'-bisdimethylaminobenzhydrol (2). N, N, N', N'-Tetramethylbenzidine (3) and a very amall amount of 4, 4'-bisdimethylaminobenzophenone were also detected as by-products. It was found that this oxidation took place over the surface of the oxidizing agent, and that the particle size of the oxidizing agent and the solubility of the reactants in the reaction medium showed marked effects on the reaction . In the oxidation of (1) nto (2) an equimolar amount of the oxidizing agent was found to be sufficient. In the oxidation of (2) into (3) however, a large excess of the oxidizing agent was required, because the (3) adsorbed on the surface of the lead dioxide retards and interferes with the oxidation of (2).
2, 3, 5, 6-Tetrachloroaniline was diazotized in a mixture of acetic acid and sulfuricacid according to the conventional procedures. The diazonium solution was then added dropwise into 700% sulfuric acid at 150-160°C, and the products were steamdistilled as soon as they were formed. Upon purification of the solids in the distillate, a small amount of colorless crystals (mp 212-213°C) showing a marked biological activity was obtained. This substance proved to be a new compound, 2, 3, 5, 6-tetrachlorophenylacetic acid. In the light of the fact that diazonium compounds usually decompose into phenols via diazonium ions, it is of interest to note that 2, 3, 5, 6-tetrachlorophenylacetic acid was obtained instead of 2, 3, 5. 6-tetrachlorophenol.
When 2, 3, 5, 6-tetrachlorobenzenediazonium hydrogen sulfate in acetic acid-sulfuric acid was decomposed in sulfuric acid at 150-160°C, 2, 3, 5, 6-tetrachlorophenylacetic acid and 1, 2, 4, 5-tetrachlorobenzene were obtained together with a large amount of resinous materials. On the other hand, 2, 3, 5, 6-tetrachlorobenzenediazonium salt was found to be converted into 3, 4, 6-trichlorobenzene-2-diazo-1-oxide at low temperatures (70-80°C) in acetic acid-sulfuric acid. The results obtained in the presence of a radical scavenger, ferric chloride, indicated that 2, 3, 5, 6-tetrachlorophenylacetic acid was produced via 2, 3, 5, 6-tetrachlorophenyl radical formed by homolytic decomposition of the diazonium salt at high temperatures (150-160°C), whereas a heterolytic reaction to form 2, 3, 5, 6-tetrachlorophenol scarcely occurred. The above mentioned diazo-oxide, which, might be formed even at high temperatures, actually decomposed at the melting point (117-118°C) to produce resinous materials.
Studies have been made to improve dyeing properties of cotton by introducing amino groups. The hydrolysis of an aminating agent, 2-amino-4, 6-dichloro-s-triazine(ADC), and the most suitable conditions for its treatment in an acetone -watermixture in the presence of sodium carbonate have been estaablished. It was noted that the hydrolysis of ADC was accelerated by the hydrogen chloride formed in the reaction. The hydrolysis in a sodium carbonate solution agreed with a second order reaction and the activation energy was calculated to be 19.5kcal/mol. When cotton was treated with ADC under the conditions of ADC 0.08 mol/l, sodium carbonate 0.16 mol/l, bath ratio 1:50, at 20°C for 24hr, aminized cottoncontaining 0.43% nitrogen was obtained . It was found that the cotton so treatedcould be dyed with acid dyes and its wash-fastness improved.
3-Acetoxy-2-naphthoic anhydride (ANA) was synthesized in good yield from 3-acetoxy-2-naphthoic acid and thionyl chloride in the presence of pyridine.A mixture of melamine and ANA dissolved in dioxane (D) was heated to ref lux to obtain N-(3-acetoxy-2-naphthoyl) melamine (1), which was identified in the form of a solvation product, (1).E1/2 D. In this reaction, N, N'-disubstituted melamine was also formed as by-product and identified in the form of its hydroxy derivative, N, N'-di-(3-hydroxy-2-naphthoyl) melamine. Upon hydrolysis with 10% aqueous pyridine, (1).1/2 D gave N-(3-hydroxy-2-naphthoyl) melamine (2). A possible use of (2) as grounder in azoic dyeing was studied.