Photoinduced depolymerization of poly(olefin sulfone)s possessing photobase generator side‐chains: Effect of spacer‐chain length

Photoinduced depolymerization of poly(olefin sulfone)s possessing photobase generators in the side‐chain was investigated. Irradiation with UV light generated base on the side‐chains and induced depolymerization based on proton abstraction on the main‐chain. The effect of the length of the spacer chain, which connects the photobase‐generating moiety to the polymer main chain on the photoinduced depolymerization, also was investigated. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3873–3880     

Facile S-alkyl thiocarbamate synthesis by a novel DBU-assisted carbonylation of amines with carbon monoxide and sulfur

A novel DBU-assisted carbonylation of amines with carbon monoxide and sulfur has been developed for the synthesis of S-alkyl thiocarbamates. In the presence of DBU (1,8-diazabicyclo[5.4.0]undec-7-ene), S-alkyl thiocarbamates are synthesized in excellent yields from amines, carbon monoxide, sulfur, and alkyl halides under mild conditions (1 atm, 20°C). In the absence of DBU, however, no formation of S-alkyl thiocarbamate is observed. The present DBU-assisted carbonylation can also be applied to new synthetic methods for benthiocarb and orthobencarb (herbicides) and carbamoyl chlorides.     

Molecular mechanics (MM3) calculations on lithium amide compounds

The MM3 force field has been extended to deal with the lithium amide molecules that are widely used as efficient catalysts for stereoselective asymmetric synthesis. The MM3 force field parameters have been determined on the basis of the ab initio MP2/6-31G* and/or DFT (B3LYP/6-31G*, B3-PW91/6-31G*) geometry optimization calculations. To evaluate the electronic interactions specific to the lithium amides derived from the diamine molecules properly, the Lewis bonding potential term for the interaction between the lithium atom and the nonbonded adjacent electronegative atom such as nitrogen was introduced into the MM3 force field. The bond dipoles were evaluated correctly from the electronic charges on the atoms calculated by fitting to the electrostatic potential at points selected. The MM3 results on the molecular structures, conformational energies, and vibrational spectra show good agreement with those from the quantum mechanical calculations.     

Stereoselective synthesis of trans olefins by the reaction of Wittig reagents with selenium. Formation of selenocarbonyl compounds.

Wittig reagents were successfully changed to symmetrical olefins when treated with elemental selenium. The reaction proceeds through a selenocarbonyl intermediate, which existence was confirmed by Diels-Alder reaction.     

Biopolymer-Polysiloxane Double Network Aerogels

A new series of transparent aerogels of biopolymer-polysiloxane double networks is reported. Biopolymer aerogels have attracted much attention from green and sustainable aspects but suffered from strong hydrophilicity and difficulty to make homogeneous structures in nanoscale; these drawbacks are overcome by compositing with a polysiloxane network. Alginate-polymethylsilsesquioxane aerogel has high optical transparency, water repellency, comparable superinsulation property and improved bending flexibility compared to pure polymethylsilsesquioxane aerogel. The nanoscale homogeneity is realized by separating the crosslinking steps for two networks in a sequential protocol: condensation of siloxane bonds and metal-crosslinking of biopolymer. The crosslinking order, biopolymer-first or siloxane-first, and universality/limitation of biopolymer-crosslinker pairs are discussed to construct fundamental chemistry of double network systems for their further application potentials.     

Studies on glycolipids. III. Glyceroglycolipids from an axenically cultured cyanobacterium, Phormidium tenue.

Seven new monogalactosyl diacylglycerols (1-7) and six new digalactosyl diacylglycerols (11-16) were isolated from an axenically cultured cyanobacterium, P. tenue. Their structures were elucidated on the basis of physicochemical evidence and the results of enzymatic hydrolysis using a lipase (from Rhizopus arrhizus). Comparison of antialgal activity for P. tenue between monogalactosyl diacylglycerols (1-8) and digalactosyl diacylglycerols (11-19) revealed that the former showed more potent activity than the latter.     

Studies on cardiac ingredients of plants. VII: Chemical transformation of proscillaridin by means of the Diels-Alder reaction and biological activities of its derivatives.

The Diels-Alder reactions of a cardiac glycoside, proscillaridin (1), with some dienophiles were investigated. The reaction of 1 with alkenes such as methyl vinyl ketone and methyl acrylate afforded 3-oxo-2-oxabicyclo[2.2.2]oct-7-enes (2-5) and para-substituted benzene derivatives (6 and 7), while 1 reacted with alkynes (3-butyn-2-one, methyl propiolate) to yield para- or meta-substituted benzene derivatives (6-9). The biological activities of the resulting derivatives were evaluated by the use of isolated guinea-pig papillary muscle preparations and Na+,K(+)-adenosine triphosphatase (ATPase) preparation from dog kidney. Among the proscillaridin derivatives, compounds 4 and 7 moderately inhibited Na+,K(+)-ATPase activity. Furthermore, the concentration range of 7 over which its positive inotropic effect on guinea-pig papillary muscle preparations, increased from 5% to 95% of maximum was broader than that of 1, i.e., concentration dependency was maintained over a greater range of concentration.     

Approaches to dioxin analysis by HRGC-HRMS and hybrid HRGC-MS-MS

A hybrid mass spectrometer with an EBQQ configuration was used to investigate two approaches to trace dioxin analysis: high resolution gas chromatography – high resolution mass spectrometry (HRGC-HRMS) and high resolution gas chromatography – mass spectrometry – mass spectrometry (HRGC-MS-MS). It is shown that selected ion monitoring (SIM) HRGC-HRMS exhibits better selectivity for dioxins separated on a cyanopropyl column than is otherwise obtained under medium resolution mass spectrometry (3,000 resolution), while optimization of conditions for HRGC-MS-MS allowed the observation of 350 femtograms of the highly toxic 2,3,7,8-TCDF at a S/N ratio of 5:1. Both methods were applied to environmental samples with good results.     

Oxidation of 7,8‐diaminotheophylline with lead tetraacetate and reaction of the oxidation product, 6‐cyanoimino‐5‐diazo‐1,3‐dimethylpyrimidine‐2,4‐dione with alcohols or amines

Oxidation of 7,8‐diaminotheophylline (1) with lead tetraacetate in refluxing toluene gave a mixture of 3‐amino‐5,7‐dimethylpyrimido[4,5‐e][1,2,4]triazine‐6,8‐dione ( 2 ) and 6‐cyanoimino‐5‐diazo‐1,3‐dimethylpyrimidine‐2,4‐dione ( 4 ). The latter was transformed to 2 by the reaction with 1‐propanethiol in quantitative yield. The reaction of 4 with methanol, ethanol and 1‐propanol in the presence of rhodium ( II ) acetate gave 5‐alkoxy‐6‐(2‐alkyl‐3‐isoureido)‐1,3‐dimethylpyrimidine‐2,4‐diones ( 7a‐c ). A similar reaction of 4 with alkylamines such as n‐propylamine, n‐butylamine, isobutylamine and n‐hexylamine gave a mixture of 7‐alkyl‐8‐aminotheophyllines ( 8a‐d ) and (5‐alkylamino‐1,3‐dimethyl‐2,4‐dioxopyrimidin‐6‐yl)cyanamides ( 9a‐d ).