New π-electron donors: Ethanediylidene-2,2′-bis(1,3-diselenole) and ethanediylidene-2-(1,3-dithiole)-2′-(1,3-diselenole)

This communication describes synthesis and electrochemical properties of new type of π-donors containing 1,3-diselenole ring, ethanediylidene-2,2′-bis(1,3-diselenole)(1a) and ethanediylidene-2-(1,3-dithiole)-2′-(1,3-diselenole)(2a). The conductivities of the charge-transfer complexes of these donors with tetracyanoquinodimethane (TCNQ) are also demonstrated.     

Formyl and formylvinyl derivatives of 2-methylenebenzo-1,3-dithiole

2,5-Dimethyl- and 2-ethyl-5-methyl-1,3-benzodithiolium perchlorates react with dimethylformamide and N-phenyl-N-methylaminoacrolein to give monoiminium salts, the hydrolysis of which yields the corresponding aldehydes. The trans-transoid structure ofβ-formylvinyl-substituted 2-methylenebenzo-1,3-dithioles was established by a comparison of the experimental and calculated dipole moments, absorption maxima, and intensities of the electron transitions and also by analysis of the PMR spectra.     

The preparation of derivatives of 2,2′-(2,6-naphthalenediylidene)bis(1,3-dithiole) (nbdt): New donors for organic metals

Routes from 2,6-bis(bromomethyl)naphthalene to compounds (3) and (4) are described. A complex between (4) and iodine has been obtained.     

Monomers and polymers with silicon-containing functional groups

The novel monomer, p-vinylphenoxy(trimethyl)silane, has been prepared and copolymerized with styrene. The hydrolysis of the copolymer in dioxan has been examined briefly. Monomers of the type p-CH₂CHC₆H₄SiMe₂R (RH, OMe, OEt, OPr, CH₂Cl and NMc₂) have been prepared, polymerized and the resulting polymers cross-linked by hydrolysis.     

Functional polymers. XXVII: 2[2-hydroxy-4-acryloxy(methacryloxy)phenyl]2H-benzotriazole: Monomers,polymers, and copolymers

2(2,4-Dihydroxyphenyl)2H-benzotriazole has been prepared in about 50% yield by condensation ofo-nitrobenzenediazonium chloride with resorcinol followed by reductive cyclization of the initially obtained azo compound with zinc and sodium hydroxide. The condensation of the diazonium salt had to be carried out under carefully controlled conditions and in acidic medium, otherwise bis-condensation occurred which, after reductive cyclization, yielded 2(2,4-dihydroxyphenyl)1,3-2H-dibenzotriazole. 2(2,4-Dihydroxyphenyl)2H-benzotriazole was allowed to react with acryloyl or methacryloyl chloride. Monoacylation in the 4-position occurred by interfacial acylation technique and 2[2-hydroxy-4-acryloxy (or 4-methacryloxy)]2H-benzotriazole was obtained in over 60% yield. The two monomers were homopolymerized and copolymerized with styrene, methyl methacrylate, andn-butyl acrylate to polymers of high molecular weight. Incorporation of 2[2-hydroxy-4-acryloxy (or 4-methacryloxy)]2H-benzotriazole into the copolymer was from 1 to 10 mol% of the comonomer mixture. The ultraviolet spectra of monomers, homo- and copolymers were also determined.This paper is dedicated to Professor Dr.Karl Schlögl on the occasion of his 60th birthday with our warmest wishes.     

2-(3,5-Diaryl-Δ4-1,3,4-thiadiazolin-2-yliden)-1,3-dithiole eine neue klasse elektronenreicher olefine

The dithiolium perchlorates 3a and b were smoothly converted into the phosphonium perchlorates 4a and b by reaction with tributylphosphin. Their deprotonation with butyllithium generates the methylen-phosphoranes 7 (not isolates), from which the electron-rich olefines 9a-d are obtained by successive treatment with the Δ⁴-1,3,4-thiadiazolium perchlorates 5d and e such as triethylamine. The olefine synthesis can be performed too by the reverse way, that is by the reaction of the phosphonium salts 6a-c with the dithiolium salts 3a and b under authentic conditions. In this way the electron-rich olefines 9e-h are obtained.     

Monomers and polymers from plant oils via click chemistry reactions

As a consequence of the depleting of fossil reserves and environmental issues, today, plant oils and fatty acids derived therefrom have a respectable status within the polymer chemistry community. However, maximizing the benefits of these renewable feedstocks requires the utilization of sustainable and efficient chemical transformations. The emergence of click chemistry concept and especially the renaissance of thiol‐ene addition reaction have had an impact on the way to make plant oil‐derived polymers. This highlight discusses the applicability and success of thiol‐ene addition and other click reactions in the transformation of oleochemicals into monomers and polymers. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013     

Synthesis and Crystal Structure of 2-Morpholinylthioformyl-2-phenyl-4-morpholinyl-5-phenyl-1,3-dithiole

1　ＩＮＴＲＯＤＵＣＴＩＯＮα Ｔｈｉｏｃａｒｂｏｎｙｌｔｈｉｏｆｏｒｍａｍｉｄｅｓｗｅｒｅｓｙｎｔｈｅｓｉｚｅｄｉｎ 1 980 [1～ 2 ],ｈｏｗｅｖｅｒ,ｔｈｅｒｅｗａｓｎｏｒｅｐｏｒｔｏｎｔｈｅｉｒｐｒｏｐｅｒｔｉｅｓａｎｄｒｅａｃｔｉｏｎａｃｔｉｖｉｔｉｅｓ[3].Ｗｅｒｅｐｏｒｔｅｄｔｈｅｒｅａｃｔｉｏｎｏｆα ｔｈｉｏｃａｒｂｏｎｙｌｔｈｉｏｆｏｒｍａｍｉｄｅｓｐｒｅｖｉｏｕｓｌｙ[4 ].Ｈｅｒｅ ,ｗｅｒｅｐｏｒｔｔｈｅｓｙｎｔｈｅｓｉｓｏｆ 2 ｍｏｒｐｈｏｌｉｎｙｌｔｈｉｏｆｏｒｍｙｌ 2 ｐｈｅｎｙ…     

铁基配合物在催化1,3-二烯单体均相配位-插入聚合中的应用

开发环境友好的催化剂非常迫切。铁元素含量丰富且无毒的双重特性与这种趋势完全一致。在过去的几十年中,基于结构明确的铁络合物的催化反应研究增长非常迅速。在Gibson和Brookhart聚合乙烯的开创性工作之后,越来越多研究者使用铁基催化体系进行1,3-二烯的配位-插入聚合反应。1,3-二烯的聚合具有广泛的工业应用范围。本文通过研究近年来开发的催化体系来更新该领域的研究进展。就活性和选择性(相关时)及其局限性而言,特别着重强调其配合物的结构和催化性能间的关系。     

Magnetomesogens: Bis(1,3-di(4'-decoxyphenyl)propane-1,3-dionato)oxovanadium (IV)

β-Diketonate complexes of oxovanadium (IV) have been synthesized and their mesomorphic behaviour investigated. The title complex exhibits a short range monotropic columnar discotic phase, identified by its optical texture and by miscibility studies. The optical texture of the phase is retained on cooling to the crystal. As a consequence of the unpaired electron on vanadium the complexes are paramagnetic.     

Selenium heterocycles. XXXI. Reaction of ethyl propiolate with 5-phenyl-2-thioxo-1,3-thiaselenole and 4-phenyl-2-thioxo-1,3-dithiole

Reaction of ethyl propiolate with 4-phenyl-2-thioxo-1,3-dithiole afforded 4-carbethoxy-2-thioxo-1,3-dithiole in high yield. Reaction of ethyl propiolate with 5-phenyl-2-thioxo-1,3-thiaselenole gave 4-carbethoxy-2-thioxo-1,3-thiaselenone (IX), 4-carbethoxy-2-selenoxo-1,3-dithiole (X) and 5-carbethoxy-2-thioxo-1,3-thiaselenole (XI). A possible mechanism for the formation of these compounds is given.     

Regioselective synthesis of 1,3-thiazines by sequential 4-oxothiazolidine to 1,2-dithiole to 1,3-thiazine transformations: role of intramolecular non-bonded S?O interactions

A new synthetic approach to 2,3-dihydro-4H-1,3-thiazine derivatives based upon reductive rearrangement of 1,2-dithiole-3-ylidene thiones has been developed. In turn, the 1,2-dithiole derivatives were prepared by an efficient ring-opening-closing process of 2-alkylidene-4-oxothiazolidines, induced in the presence of Lawesson's reagent by intramolecular non-bonded 1,5-type S?O interactions in the 4-oxothiazolidine precursors.     

Peroxy-Containing Monomers as Coating Components Based on 1,1,2-Trichlorobuta-1,3-diene

Russian Journal of Applied Chemistry - The copolymerization of 1,1,2-trichlorobuta-1,3-diene with peroxide-containing acrylates and methacrylates in bulk at different temperatures, process time and...