Synthesis of arylidene derivatives of N-unsubstituted pyrrolin-2-ones

5-Alkyl(aryl)-3-arylidene-3H-pyrrolin-2-ones were synthesized by ammonolysis of their O-heteroanalogs or by the reactions of 5-alkyl(aryl)-3H-pyrrolin-2-ones with aromatic aldehydes. The structures of the compounds obtained were confirmed by ¹H NMR spectra.     

Synthesis,characterization, and blends of high temperature poly(arylether sulfone)s

The preparation of poly(4-oxy-1,4-phenylenesulfonyl-4,4′-biphenylene-4-sulfonylphenylene) (PBP) has been accomplished by the base mediated, polycondensation reaction between two biphenyl containing monomers. The bisphenol, 4,4′-bis[(4-hydroxyphenyl) sulfonyl]biphenyl (HSB), was reacted with 4,4′-bis[(4-chlorophenyl)sulfonyl]-biphenyl (CSB) in tetramethylene sulfone solvent. The highest mechanical properties and glass transition temperature was observed for polymer PBP with a reduced viscosity around 1.0 dL/g. Consequently, the current synthesis route provides polymer with higher properties than other historical preparative routes. Blends of PBP with a different poly(ether sulfone) were miscible based on the observance of a single glass transition temperature. The T_gs of the polymer blends exhibited an unusual positive deviation from the weighted linear averages of the components.     

L-脯氨酸催化下甲基酮和1-芳基-2,2,2-三氟乙酮的不对称Aldol反应

Direct asymmetric aldol addition of methyl ketones to 2,2,2-trifluoro-1-phenylethanone and its ring-substituted derivatives was achieved using L-proline as a chiral promoter. Various optically active β-trifluoromethyl-β-hydroxy ketones were obtained in almost quantitative yields with moderate enantioselectivities up to 64 % ee.     

Crystal engineering of photochromic diarylethene single crystals

Photochromic performance of diarylethene single crystals was controlled by crystal engineering using non-covalent aromatic-aromatic interactions as the directional intermolecular force. A diarylethene derivative with two pentafluorophenyl groups, 1,2-bis(2-methyl-5-pentafluorophenyl-3-thienyl)perfluorocyclopentene (1a), formed stoichiometric co-crystals with benzene (Bz) and naphthalene (Np) by aryl-perfluoroaryl interactions. Face-to-face pi-stacking interactions between the pentafluorophenyl groups of 1a and the aromatic molecules are responsible for 2:1 and 1:1 stoichiometric compositions in 1a/Bz and 1a/Np co-crystals, respectively. The diarylethene underwent thermally stable and photoreversible photochromic reactions in a homo-crystal of 1a and co-crystals 1a/Bz and 1a/Np. The absorption spectra of the photogenerated closed-ring isomers varied depending on the conformation of the diarylethene molecules packed in the crystals. The diarylethene 1a also formed 1:1 stoichiometric co-crystals with different kinds of diarylethenes, 1,2-bis(2-ethyl-5-phenyl-3-thienyl)perfluorocyclopentene (2a) and 1,2-bis[2-methyl-5-(1-naphthyl)-3-thienyl]perfluorocyclopentene (3a). Both co-crystals 1a/2a and 1a/3a showed photochromism. Although 1a, 2a, and 3a underwent efficient photocyclization reactions in their homo-crystals, highly selective photocyclization reactions of 2a or 3a were observed in the co-crystals. The selective reactions were confirmed by HPLC and X-ray crystallography. Excited energy transfers from 1a to 2a and from 1a to 3a are considered to occur and cause the selective reactions.     

A Convenient Procedure for N-Amination of 4-OXO-1,4-Dihydroquinolines

A high yielding N-amination of quinolones at low temperature via the use of O-mesitylenesulfonylhydroxylamine is reported.     

1,4-双(二苯基膦)丁烷交联的季膦化聚芳醚酮阴离子交换膜

以1,4-双(二苯基膦)丁烷为交联剂,以具有四甲基联苯结构的聚芳醚酮为基体材料,分别制备了刚性三苯基膦和柔性三丁基膦修饰的阴离子交联膜材料.交联剂在交联结构形成的过程中转变成季膦盐,在提高膜材料机械稳定性的同时保持离子交换功能基团的含量.研究了2种阴离子交换膜的尺寸稳定性、电导率、机械性能及耐碱稳定性等.研究结果表明,当交联度为20%时,三苯基膦与三丁基膦修饰的阴离子交换膜的拉伸强度分别由未交联时的27和18 MPa提高到45和30 MPa;交联的膜材料在60℃的3 mol/L KOH溶液中浸泡120 h后,三苯基膦修饰的阴离子交换膜的电导率保留率为81%,三丁基膦修饰的阴离子交换膜的电导率保留率为69%,膜的耐碱稳定性均较未交联时有明显提高.交联度相同时,三苯基膦修饰的阴离子交换膜表现出更高的拉伸强度和更好的耐碱稳定性.     

Recent progress and current applications of Sonogashira coupling reaction in water

The use of aqueous media in palladium‐catalyzed reactions has become popular because water‐based synthetic processes are inherently safer as well as being inexpensive. Moreover, it does not require dry solvents, and the products may easily be isolated by extraction, which greatly facilitates the operation. Thus the use of water in palladium‐catalyzed reactions represents one of the most economically and environmentally viable options for many organic transformations. In this review, recent developments of Sonogashira reaction in water or aqueous media will be disclosed. Copyright © 2013 John Wiley & Sons, Ltd.     

Suzuki–Miyaura coupling reactions of aryl chlorides catalyzed by a new nickel(II) σ‐aryl complex

A new nickel(II) σ‐aryl complex, trans‐chloro(9‐phenanthrenyl)bis(triphenylphosphine)nickel(II), was used as a precatalyst for the Suzuki–Miyaura coupling reactions of aryl chlorides. The catalytic conditions were optimized by investigating the cross‐coupling of p‐chloroanisole with phenylboronic acid. The results show that this complex is efficient for both electron‐rich and electron‐deficient aryl chlorides, though it gives better yields for activated arylboronic acids than deactivated ones. All isolated cross‐coupled biaryl products have been characterized by ¹H and ¹³C NMR, and their spectral data are consistent with those reported. Side products from the coupling of arylboronic acid with the precatalyst complex have also been isolated and characterized, which is helpful for understanding the coupling mechanism. Copyright © 2013 John Wiley & Sons, Ltd.