Atactic polypropylene was treated with chlorine gas in solution. The structure of the chlorinated polypropylene was investigated by means of infrared spectrophotometry. The chlorination in the sunlight proceeded by a chain reaction mechanism. Higher chlorinated products containing about 40% of chlorine were obtained under adjusted reaction conditions. The reactivity of the hydrogen atom in polymer was found to be in the order of CH<CH2<CH3. As the solvent, carbon tetrachloride and chloroform were more favorable than dichloroethane and trichloroethane. The chlorination in the presence of iodine or heavy metal in the dark seemed to undergo partially through ionic reaction mechanism, and the extent of chlorination rather decreased. In these cases, the methylene group in the polymer chain was most suspectible to the attack of chlorine. Crystallinity of polypropylene decreased with increase of the degree of chlorination.
The condensation of aromatic nitriles with 4-aminoazobenzene by AlCl3 gave the following amidines having azo group N- (4-phenylazo) phenylbenzamidine (1a), N- (4-phenylazo) phenyl-m-toluamidine (1b), N- (4-phenylazo) phenyl-p-toluamidine (1c), p-chloro-N- (4-phenylazo) phenylbenzamidine (1d) and N- (4-phenylazo) phenyl-2-naphthamidine (1e). ArC=NH-NH-_??_-N=N-_??_ Ar=C6H5 (1a), m-CH3C6H4 (1b), p-CH3C6H4 (1c), p-ClC6H4 (1d), 2-C10H7 (1e) The HCl-adducts of the above amidines were converted into the corresponding 2-aryl-5-phenylazobenzimidazole [(2a), (2b), (2c) and (2d)] by N'-chlorination by sodium hypochlorite and the subsequent dehydrochlorination by NaHCO3. ArC=N-NH-_??_-N=N-_??_ Ar=C6H5 (2a), m-CH3C6H4 (2b), p-CH3C6H4 (2c), p-ClC6H4 (2d) Upon treatment with N, N-dimethylformamide dimethylacetal, the above amidines gave the corresponding N-dimethylaminomethylidene-N'- (4-phenylazo) phenylamidine [(3a), (3b), (3c), (3d) and (3e)]. ArC-N=CHN (CH3) 2=N-_??_-N=N-_??_ Ar=C6H5 (3a), m-CH3C6H4 (3b), p-CH3C6H4 (3c), p-ClC6H4 (3d), 2-C10H7 (3e) The corresponding N'- (4'-phenylazo) benzoyl-N- (4-phenylazo) -phenylamidine [(4a), (4b), (4d) and (4e)] were also obtained by the condensation of p-phenylazobenzoyl chloride with the aid of NaHCO3. ArC=NCO-_??_-N=N-_??_-NH-_??_-N=N-_??_ Ar=C6H5 (4a), m-CH3C6H4 (4b), p-ClC6H4 (4d), 2-C10H7 (4e) (1a), (1b), (1c), (2a), (2b), (2c), (3a), (3b), (3c), (4b) and (4d) dyed acetate fiber yellow or light yellow.
Synthesis of phenylditolylphosphine by means of the Friedel-Crafts reaction was investigated, and the isomer ratio of the product was determined. Phenylphosphonous dichloride reacted with a large excess of toluene in an autoclave at 210220°C in the presence of aluminum trichloride, giving phenylditolylphosphine (1). On the other hand, ditolylphosphinous chloride-aluminum trichloride complex (2), which was obtained by the reaction between toluene and phosphorus trichloride in the presence of aluminum trichloride, was converted to ethyl ditolylphosphinite (3) by treatment with ethanol and triethylamine. Another crop of phenylditolylphosphine (1′) was obtained from the phosphinite by treatment with phenylmagnesium bromide. These phoshines were mixtures of isomeric phenylditolylphosphines having two tolyl groups at ortho, meta, and/or para positions. In this study, the ratios of the isomers were also analyzed by comparing their liquid-gas chromatograms and infrared spectra with those of authentic samples.