Polyimides derived from bismethylolimides. II. Polyamine-imides from bismethylolimides and diamines

Compounds in the N-methylolimide group reacted smoothly with amines in the presence of water to yield the corresponding condensation products. Polycondensations of bismethylolimides, N,N′-bismethylolpyromellitic diimide, and N,N′-bismethylolbenzophenonetetracarboxylic diimide, with amines such as aromatic diamines, piperazine, and n-butylamine, were carried out in DMAc that contained 1% water to produce linear polyamine-imides. The polyamine-imides assumed various colors, from very pale yellow to deep purple, and had inherent viscosities in the 0.07–0.37-dl/g range. Most of these polymers were soluble in polar solvents such as DMAc and DMSO. The thermal stability of the polymers was examined by thermogravimetric analysis; decomposition started at 210–350°C and weight residue at 500°C was 22–85% in air.     

L-Vinylglycine from L-Homoserine.

A simple and practical synthesis of L-vinylglycine starting from L-homoserine is described.     

Steroid compounds from ophiuroids. I. New steroid sulfate from Ophiura sarsi

The sulfate of a steroid polyol has been isolated from the Far Eastern ophiuroidOphiura sarsi, and its structure has been established by chemical and spectral methods as cholest-5-ene-3,4,21-diol 3-(sodium sulfate). No steroid compounds of such structure from ophiuroids have been described previously.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Branch, USSR Academy of Sciences, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 375–379, May–June, 1988.     

Alternating Copolymers from Alkyleneimines. I. Copolymers from Ethyleneimine and Dicarboxylic Anhydrides

Ethyleneimine and dicarboxylic anhydrides were copolymerized to alternating copolymers which possess an ester-amide in the repeating unit. The structure of copolymer was Identified by IR, NMR, and elemental analysis. On taking the structure of copolymer, the nucleophllic reactivity of ethyleneimine, and the electrophilic nature of dicarboxylic anhydride Into consideration, a reaction mechanism was elucidated. It Involves ring opening and a stepwise addition reaction in alternating manner, in that one monomer undergoes ring opening and chain propagation exclusively through the interaction with another monomer that is already present at the polymer chain end. The copolymers obtained from halogen containing dicarboxylic anhydrides are useful as fire-retarding additives for plastics and also as thermosetting resin precursor when anhydrides are partially replaced by maleic anhydride.     

Triterpenoids from Abies sp. IX. Triterpene lactones from Abies sibirica bark

Four lanostane lactones have been isolated from an ethereal extract of Siberian fir bark — abieslactone and its hydroxy and keto analogs, and also (25R)-24,25-dihydroabieslactone, the structure of which was established on the basis of a chemical and spectral correlation with known compounds.Novosibirsk Institute of Organic Chemistry, Siberian Branch, USSR Academy of Sciences. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 220–225, March–April, 1989.     

Isoindoles from phthalimidines. N-arylisoindoles

A convenient method was developed for the preparation of N-arylisoindoles by the reduction of the corresponding phthalimidines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1629–1631, December, 1987.     

beta-Silylcarbenes from isolable diazosilanes.

Manganese dioxide oxidation of the hydrazone derivative of tert-butyldimethylsilyl acetophenone gave 2-tert-butyldimethylsilyl-1-phenyldiazoethane (17) an isolable diazocompound. Thermal and Rh(II)-catalyzed decomposition of diazosilane 17 in cyclohexane led to 1-tert-butyldimethylsilyl-1-phenylethylene (19) as the major product. The formation of alkene 19 presumably involves (tert-butyldimethylsilyl)methylphenylcarbene (21), which undergoes preferential 1,2-silyl migration as opposed to 1,2-hydrogen migration. Thermal decomposition of 17 in cyclohexane under oxygen gave substantial amounts of tert-butyldimethylsilyl acetophenone, presumably by reaction of the intermediate carbene with oxygen. Thermal decomposition of 17 in methanol led to alkene 19 and 2-tert-butyldimethylsilyl-1-methoxy-1-phenylethane (22) as major products, along with a significant amount of trans-1-tert-butyldimethylsilyl-2-phenylethylene (20). Kinetic studies indicate that these products are not derived from acid-catalyzed decomposition of the diazocompound 17. Formation of the methyl ether product 22 suggests the involvement of a beta-silyl carbocation intermediate, and solvent isotope effect studies indicate that this cation is at least partially derived from protonation of diazocompound 17 by neutral methanol. Photochemical decomposition of 17 in methanol produced the alkene 19 (97%) along with a small amount (2.4%) of the methyl ether 22. Capture of a photochemically generated carbene 21 by methanol is the proposed origin of this minor product. Geometry optimization of trimethylsilylmethylphenylcarbene (8) and carbene 21 at the HF/6-31G computational level led to a conformation consistent with a hyperconjugative interaction between the vacant p-orbital of these carbenes and the adjacent C-Si bond. Carbenes 8 and 21 are not energy minima at the B3LYP/6-31G level, where they rearrange to alkenes without barrier via silyl migration. These theoretical findings contrast with the proposed trapping of carbene 21 by methanol and oxygen.     

Saponins from Amaranthus hypochondriacus.

Four triterpenoid saponins were isolated from Amaranthus hypochondriacus which are grain crops in the Nepal, Mexico and South America. Their structures were elucidated based on spectral evidence to be: (1) 3-O-alpha-L-rhamnopyranosyl(1----3)-beta-D-glucuronopyranosyl-2 beta,3 beta-dihydroxyolean-12-en-28-oic acid 28-O-beta-D-glucopyranosyl ester. (2) 3-O-alpha-L-rhamnopyranosyl(1----3)-beta-D-glucuronopyranosyl-2 beta,3 beta- dihydroxyolean-12-en-23-al-28-oic acid 28-O-beta-D-glucopyranosyl ester; (3) 3-O-alpha-L-rhamnopyranosyl(1----3)-beta-D-glucuronopyranosyl-2 beta, 3 beta-dihydroxy-30-norolean-12,20(29)-dien-28-oic acid 28-O-beta-D-glucopyranosyl ester. (4) 3-O-alpha-L-rhamnopyranosyl (1----3)-beta-D-glucuronopyranosyl-2 beta, 3 beta-dihydroxy-30-norolean-12, 20(29)-dien-23-al-28-oic acid 28-O-beta-D-glucopyranosyl ester.     

Polyimides derived from bismethylolimides. I. Polyamide–imides from bismethylolimides and dinitriles

New polyamide–imides were synthesized from bismethylolimides and dinitriles. The bismethylolimides, N,N′-bismethylolpyromellitdiimide and N,N′-bismethylolbenzophenonete-tracarboxylic diimide, were prepared by the hydroxymethylation of the corresponding diimides with formaldehyde. The polymerization reaction was carried out in either concentrated sulfuric acid or poly(phosphoric acid), and the former was found to be superior to the latter. The polyamide–imides had inherent viscosities in the 0.08–0.41 dl/g range. Most of these polymers were soluble in m-cresol and dichloroacetic acid. The thermal stability of the polymers was examined by thermogravimetric analysis, and they were found to start to decompose at 275–350°C in air.     

Biopolymers from marine invertebrates. XII. A novel cytolytic factor from a hermit crab, Clibanarius longitarsus.

Bioactive polymers were sought in marine arthropoda and a novel cytolytic factor was found in a hermit crab, Clibanarius longitarsus. The partially purified factor showed activity in fractions corresponding to a molecular weight of about 10 kilodaltons on a Sephadex G-75 column. This cytolytic factor was halfmaximally active for tumor cells at 0.13-0.66 micrograms/ml and for normal cells at 1.9-82 micrograms/ml. Tumor lysis by the factor was time dependent and was complete within 12 h. This bioactive polymer was labile on heating, at low and high pH.