New methods for the production of chloropicrin have been developed. C2-C3 chloro-olefins were nitrated, and the resultant nitrated oils were chlorinated with an alkali hypochlorite at a temperature below 60°C. The following three processes gave satisfactory results. (1) Trichloroethylene was nitrated with a nitrating mixture at 030°C, and the product chlorinated to obtain chloropicrin in 59.5% yield. (2) In the process of (1), dinitrogen tetroxide was used as a nitrating agent to obtain chloropicrin in 62.3% yield. (3) Allyl chloride was nitrated with dinitrogen tetroxide at 030°C, and the product chlorinated to obtain chloropicrin in 64.0% yield. It was further confirmed that chloronitroacetyl chloride and nitryl chloride were the principal products in the nitration of trichloroethylene with a mixed acid. Chloronitroacetyl chloride was converted quantitatively to chloropicrin upon treatment with an alkali hypochlorite.
p-Vinylphenyl glycidyl ether (1), a new vinyl epoxy monomer, was synthesized in 11.1% yield from p-vinylphenol and epichlorohydrin. (p-Vinylphenyl)-methanesulfonate and (p-vinylphenyl)-benzenesulfonate were also synthesized, and their polymers prepared. (1) was bulk-polymerized into a new epoxy resin (3) with intrinsic viscosity of 0.81 dl·g-1 (dioxane, 30°C). (1) and (3) appeared to be useful for casting or heat adhesion. By treatment of poly-p-vinylphenol with benzenediazonium chloride, a colored polymer containing azo groups was obtained, and with cinnamoyl chloride, a photosensitive polymer was formed.
A mixture of acetonitrile and chlorine in a molar ratio of 1/0.021.21 was heat-treated at 500800°C in a silica tube in the presence of diluent nitrogen. The liquid products were analyzed by gas chromatography, mass spectroscopy, and infrared spectroscopy to identify malononitrile, fumaronitrile, maleonitrile, βchloropropionitrile, cis-and trans-monochlorodicyanoethylenes, cis-and trans-dichlorodicyanoethylenes, and monochloroacetonitrile.
The reaction pathways in the bromination and protodebromination of 3-phenanthrols have been studied. When 3-phenanthrol (1) was treated with bromine in carbon tetrachloride at 0°C in the presence or the absence of anhydrous sodium carbonate, 4-bromo-3-phenanthrol (2) or 9-bromo-3-phenanthrol (3) was obtained, respectively. In contact with dry hydrogen bromide, (2) was readily isomerized into (3). When this isomerzation reaction of (2) was conducted in the presence of 2-phenanthrol (4), 1-bromo-2-phenanthrol (5) was also obtained. These facts suggest the following reaction scheme. (2)+HBr _??_ (1)+Br2→ (3)+HBr (4) →→ (5)+HBr (2) and 2, 4, 9-tribromo-3-phenanthrol (6) were also prepared from (1) and 2, 9-dibromo-3-phenanthrol (7), respectively, by the reaction with N-bromo-tert-butylamine. When heated with hydrogen bromide, (6) was debrominated to give (7) and free bromine. The structures of (2) and (6) were determined by converting into respective known compounds.
N-Substituted guanamines have been synthesized from substituted biguanides and carboxylic acid chlorides or esters. In the present study, it has been found that carboxylic acids and their esters, amides, and nitriles react with biguanides or their hydrochlorides to yield guanamines in good yields when polyphosphoric acid is used as a solvent. Some new guanamines were thus synthesized from C2-C16 aliphatic carboxylic acids and phenylbiguanide. Some of their physical properties were also reported.