The malonic acid synthesis is usually performed in the presence of strong bases.In the present study, however, it was found that the reaction readily took placewhen aweak base such as sodium bicarbonate was used in polar organic solvents, such as dimethyl formamide and dimethyl sulfoxide. Ethyl malonate was thus treated with benzyl chloride in dimethyl formamide in the presence of sodium bicarbonate at125.. for 1 hr to obtain the mono-and di-benzylmalonates. Similar reactions also occured in dimethyl sulfoxide, but not in cyclohexanone, cyclohexanol, and n-butanol.Other active methylene compounds such as methyl acetoacetate and other chlorides such as ethyl monochloroacetate were slso used too establish the versatility of the reaction. The effects of the water added to the solvent were also investigated.
The reaction between dicyanodiamide and a cyano compound to form 2-substituted-4, 6-diamino-s-triazine has been applied to a vinyl polymer containing nitrilegroups. When polyacrylonitrile (PAN) was used as a starting polymer, naphthylidenetyperings were formed in addition, to fhe expected triazine structure as a result of the competitive reaction Thus, it was possible to introduce triazine rings up to only13.3 mol % despite the presence of a large number of cyano groups.Essentially no triazine ring was formed when an acrylonitrile-styrene copolymer containing less than 20 mol % acrylonitrile was treated with dicyanodiamide. Thecontent of the intraduced turiazine ring was in creased as the acrylonitrile content was raised. Thus, approximately 30 mol % triazine rings were introduced to the polymer when the nitrile content was 77.6 mol %. Some consideration on theseresults were given.
5-Fluoro-2-nitroaniline-4-sulfonic acid (1) was obtained by the reaction of 2, 4-difluoro-5-nitrobenzenesulf onie acid (2) with ammonia . A series of new reactive azo dyes of general formula (3) and (3)' were then synthesized by the combination of diazotized (1) and azo components, such as G-, J-, H-, N.W.-acids, N-acetyl derivatives of J-, .A-, H-acids, and derivatives of 1-phenyl-3-methy1-5-pyrazolones, etc. These dyes dyed cellulosic fibers in the presence of alkali by chemical combination, and the fabrics so obtained were very fast against washing and soaping.(Ar=residual group of azo component. Di=residual group of diazo component)
Azo-, anthraquinone-, and phthalocyanine-type acid dyes containing an amino group were condensed with (1) or (2) in order to obtain new reactive dyes of general formula (3) and (4).(D=residual group of color component)These dyes contain two types of reactive groups; one, the 2-chloroethane sulfonyl group, and the other, the active halogen on the benzene ring. They dyed cotton in the presence of alkali by chemical combination, and the dyes of (3) type combined with cellulosic fibers through both of the reactive groups under mild dyeing conditions. Dyed fabrics thus obtained were very fast against acid and alkali.
When the conventional alkali fusion techniques are applied to the alkylated benzenesulf onic acids, the corresponding phenols are obtained in relatively low yields(p-methyl 69%, p-ethyl 58%, p-isopropyl 54%). In the present study, conditions for the alkali fusion of aromatic sulfonic acid salts containing methyl-, ethyl-, and isopropyl-groups in the para or ortho position have been studied in detail. The optimum conditions for the sodium hydroxide fusion of unsubstituted sodium benzenesulfonate were first established. These conditions were successfully applied to the fusion of alkyl substituted sulf onates effecting improved yields. Thus, pethyl-and p-isopropyl-phenols were obtained in yields of 92 and 88%, respectively, with potassium hydroxide. When sodium hydroxide was used, p-methyl-, omethyl-, p-ethyl-, and p-isopropyl-phenols were obtained in yields of 95, 93, 82, and 71%, respectively. This indicates that the reactivities are affected by the type of substituent. Though p-substituted sulfonates are hardly soluble in fused sodium hydroxide, sodium p-toluenesulf onate becomes soluble at about 365... Thus, the treatment at high temperatures for a short time is recommended for the improvement of the yield.