Syntheses and reactions of functional polymers. XCVII. Chemical activation and functionalization of poly(γ-methyl-L-glutamate)

To enhance its solubility in common solvents poly(γ-methyl-L -glutamate) (PMG) was transesterificated with ethylene chlorohydrin, ethylene cyanohydrin, and β,β,β-trichloroethanol, respectively. The aminolyses of the resulting polymers proceeded easily in pendant ester groups to give the corresponding amides in reasonable yields without main chain fission. By these procedures the incorporation of functional groups such as azide, amino acid, and thiol into PMG is successfully performed.     

Syntheses and reduction of polymers with alloxan structures

The polymer(Poly A) which contains alloxan moiety was prepared by the oxidation of the copolymer of allyl barbituric acid and vinyl acetate with chromium trioxide. The photoreduction of Poly A by ultraviolet (UV) irradiation was used to isolate the polymer(Poly A·) in which the alloxan radical was present. The properties of this polymer(Poly A·) thus obtained were investigated. Poly A was also reduced by chemical agents to obtain the polymer(Poly D) which had a dialuric acid structure.     

Cationic polymerization of 1-phenyl-4-ethyl-2,6,7-trioxabicyclo[2.2.2]octane

Cationic polymerization of bicyclo ortho ester, 1-phenyl-4-ethyl-2,6,7-trioxabicyclo[2.2.2]octane, was carried out with Lewis acids and cation sources to obtain the polyether containing ester group in the side chain. It was found that boron trifluoride etherate was the most active initiator in the Lewis acids. Magnesium perchlorate and triphenylcarbenium tetrafluoroborate, which have lower nucleophilic counter ions, initiated effectively the polymerization of bicyclo ortho ester.     

Preparation and Stereochemistry of Dioxatetraazaperhydroanthracenes and -perylenes from the Reaction of 2-Hydrazinoethanols with Aldehydes and Glutaraldehyde

Hydrazinoethanols 1 were reacted with aldehydes 2 and 6 and glutaraldehyde (14) in aqueous solution to give dioxatetraazaperhydroanthracenes 3, 7, 12, and 13 and -perylenes 15 in yields of 19-88 and 42-72%, respectively. Compounds 3, 7, 12, and 15 were deduced by (13)C-NMR spectra to have two C(2) symmetry axes, while compound 12 was shown to have a symmetry axis by X-ray crystallography. The most favorable stereoisomers were consistent with predictions obtained by the semiempirical molecular orbital method AM1. The structure of compound 15 was confirmed by X-ray crystallography.     

Reduction of quinones by alloxantin or alloxan-derived radical

Quinones can be reduced apparently by water mediated by alloxantin (AT) or alloxan radical(A·) produced photochemically from alloxan monohydrate (A-hydrate).     

Heterocyclization of 2,4-disubstituted thiosemicarbazides with haloketones

2,4-Disubstituted thiosemicarbazides were allowed to react with α-bromoacetophenone to give the anticipated 2,3-dihydro-6H-1,3,4-thiadiazines, whereas with β-propiophenone and γ-butyrophenone to afford the unexpected 2,3-dihydro-1,3,4-thiadiazole. The reaction mechanism was also discussed.     

A new route to 1,2,4- triazoles and 1,3,4- thiadiazoles from 1-acylbithiourea

The intramolecular cyclization of 1- acylbithiourea 1 gave 1,2,4-triazole 2 and 1,3,4-thiadiazole 3 . The reaction of 1 with p-toluenesulfonyl chloride in the presence of trithylamine afforded 3 . Treatment of 1 with methyl iodide in the absence of any base yielded 2-methylthio-1,3,4-thiadiazole 10 and 2-imino- 1,3,4-thiadiazoline 12 .     

Pyrolysis of sulfoxide. III. Conversion of 2-(phenylsulfinyl)enoate to 2,4-dienoate and synthesis of pellitorine

2,4-Dienoate was prepared by pyrolysis of 2-(phenylsulfinyl)enoate. N-Isobutyl-E,E-2,4-decadieneamide (pellitorine) was synthesized from decanoic acid in a satisfactory yield.