The orientation in the ring opening reactions of epichlorohydrin and epibromohydrin with phosphorus oxychloride and phosphorus oxybromide has been studied. The IR and NMR spectra of the reaction products were compared with those of the authentic phosphates. It was found that the “normal” opening of the oxirane ring occurred exclusively or predominantly, at least, in all cases studied. Thus, tris- (1, 3-dihalo-2-propyl) phosphates were obtained in a good yield. Major factors affecting the direction of ring opening are discussed.
An oligomer of trans-2, 5-dimethyl piperazine oxamide containing amino terminal groups was synthesized as a precursor of block copolymers characterized by moisture regain properties. A low temperature solution polymerization method was applied using trans-2, 5-dimethyl piperazine and oxalyl chloride. In order to attain the desired degree of polymerization, a solvent was used in such a way that polydimethyl piperazine oxamide precipitated as the polymerization proceeded. The expected oligomer containing amino terminal groups was obtained by using excess trans-2, 5-dimethyl piperazine as a hydrogen chloride acceptor.
1, 3-Dipolar cycloaddition reaction of diazomethane with 5-nitro-2-furylacrylic acid gave 4- (5'-nitro-2'-furyl) -3-carbomethoxypyrazoline (3), mp 184485°C, in 80% yield. A similar reaction with 5-nitro-2-furylpropiolic acid afforded the corresponding isomeric mixture of the 2-pyrazole derivatives in 25% yield. (1) was refluxed in toluene to afford 2- (5'-nitro-2'-furyl) -cyclopropane carboxylate, mp 144 145°C, in 88% yield.
The possibility that 2-alkoxy-1, 3-dioxolane might be attacked by nucleophilic reagent to form 2-substituted-1, 3-dioxolane prompted us to conduct this set of studies. Thus, 2-methoxy-1, 3-dioxolane was treated with Grignard reagents and heated to form the corresponding 2-alkyl- or 2-aryl-1, 3-dioxolanes, as follows : O-CH2-CH2-O-CH-OCH3+RMgX→O-CH2-CH2-O-CH-R R=C6H5 (24% yield), o-CH3C6H4 (39%), m-CH3C6H4 (16%), p-CH3C6H4 (19%), p-ClC6H4 (9%), o-CH3OC6H4 (15%), m-CH3OC6H4 (15%), p-CH3OC6H4 (9%), n-C3H7 (10%), n-C4H9 (13%), CH2=CH-_??_- (6%) Similarly, p-vinylphenylmagnesium chloride gave 2-(p-vinylphenyl)-1, 3-dioxolane (VPD). This was bulk polymerized by 2, 2'-azobisisobutyronitrile to give a polymer with intrinsic viscosity of 0.18 dl. g-1 in dioxane at 30°C. Possible initial processes of the radical polymerization and the simultaneous crosslinking reactions of VPD were discussed based on the infrared spectra of the product polymers.
The reactions of substituted phenoxides with carbon dioxide in N, N-dimethylformamide (DMF) were studied. In the phenoxides containing a methyl-, amino-, hydroxyl-, or chlorine-substituent, the carboxyl groups were introduced into the para-position as well as ortho-position. This unusual Kolbe-Schmidt type reaction hardly occurred in meta-substituted phenoxides. In DMF, with the exception of o- and p-aminophenoxides, the carboxylation was effected under rather mild conditions. Phenol derivatives containing a nitro-, sulfo-, carbamoyl-, or carboxyl-group underwent such reaction with difficulty. Though a hydroxy acid was obtained in a low yield from 8-hydroxyquinoline, β-naphthol and pyrroles were fully devoid of reactivity.