Synthesis and cationic polymerization of oxyranyl-functionalized triphenylamine

Synthesis and cationic polymerization of N-{4-[(oxiranylmethoxy)methyl]phenyl}-N,N-diphenylamine is reported. Diaryliodonium salts and iron-arene complex were used as photoinitiators. Iodonium salts have appeared to be much more effective photoinitiators for polymerization of the monomer than iron-arene complex. The effect of the temperature on the rate of photopolymerization of the monomer with iron-arene complex has been studied.     

Scope and limitations of montmorillonite K 10 catalysed opening of epoxide rings by amines

Montmorillonite K 10 efficiently catalyses the opening of epoxide rings by amines in high yields with excellent regio- and diastereo-selectivities under solvent-free conditions at room temperature affording an improved process for synthesis of 2-amino alcohols. Reaction of cyclohexene oxide with aryl/alkyl amines leads to the formation of trans-2-aryl/alkylaminocyclohexanols. For unsymmetrical epoxides, the regioselectivity is controlled by the electronic and steric factors associated with the epoxide and the amine. Selective nucleophilic attack at the benzylic carbon of styrene oxide takes place with aromatic amines, whereas, aliphatic amines exhibit preferential nucleophilic attack at the terminal carbon. Aniline reacts selectively at the less hindered carbon of other unsymmetrical epoxides. The difference in the internal strain energy of the epoxide ring in cycloalkene oxides and alkene oxides led to selective nucleophilic opening of cyclohexene oxide by aniline in the presence of styrene oxide. Due to the chelation effect, selective activation of the epoxide ring in 3-phenoxy propylene oxide takes place in the presence of styrene oxide leading to preferential cleavage of the epoxide ring in 3-phenoxy propylene oxide by aniline.     

Influence of temperature and nature of photoinitiator on the formation kinetics of an interpenetrating network photocured from an epoxide/methacrylate system

This paper deals with the synthesis of an interpenetrating network made of dimethacrylate and dicycloepoxide oligomers by photopolymerization. More particularly, the influence of several parameters (among which the photoinitiator nature and the reaction temperature) on the polymerization kinetics of each oligomer was studied. Two complementary analysis techniques were then used : the photocalorimetry and the RTIR spectroscopy. The study proceeded in several steps. Firstly, photopolymerization of each monomer was studied. Then, the same study was carried out on mixture of both monomers under conditions in such way than only one network is formed. It was shown that the second compound played the role of plasticizer on the network formed by the first monomer. Finally, the dimethacrylate/dicycloepoxide mixture was studied in the presence of both radical and cationic photoinitiators to synthesize an interpenetrating network (IPN). At 30 °C, ultimate products show a very incomplete epoxide conversion whereas the yield in methacrylic double bonds reaches 70%. On the other hand, epoxy functions react a little more than methacrylic double bonds at 90 °C. It was also shown that the presence of a radical photoinitiator is not necessary, and even slightly unfavourable, since the cationic photoinitiator is able to initiate both radical and cationic polymerization mechanisms.     

A mild and efficient synthesis of β-amino alcohols from epoxides using a mesoporous aluminosilicate catalyst

Mesoporous aluminosilicates catalyze efficiently the ring-opening reactions of a range of epoxides with aromatic amines to produce β-substituted alcohols in high yields under mild reaction conditions.     

环氧─聚氨酯阴极电泳涂料的研制

以聚酰胺改性的环氧树脂为主链，聚醚封端的异氰酸酯为交联剂，选择适当的催化剂和助溶剂，制备出了脱封温度较低，成膜时间较短，性能稳定的水溶性环氧一聚氨酯阴极电泳涂料。本文考察了反应温度，投料顺序，催化剂浓度对反应速度的影响；对影响电泳涂料性能和漆膜性能的因素进行了讨论。     

Hydrazones Possessing a Phenyl-1,2,3,4-tetrahydroquinoline Moiety as Hole Transporting Materials

Summary.  Hydrazones containing 1-phenyl-1,2,3,4-tetrahydroquinoline units were synthesized starting from diphenylamine. These compounds were found to constitute novel hole transporting materials and were characterized by the time of flight method. The hole drift mobility in these compounds exceeds 10⁻⁶ cm² V⁻¹ s⁻¹ at an electric field of 10⁶ V cm⁻¹.     

分子筛催化下环氧氯丙烷开环反应的溶剂效应

环氧化合物与羧酸的开环加成酯化是有机化学中一类重要反应,开环形成的羧酸β-羟基酯有着十分广泛的用途。这类反应的进行通常需要高活性的催化剂,我们曾将Fe(Ⅲ)改性的ZSM-5分子筛应用于羧酸β-羟基酯的合成。本文用Fe-ZSM-5分子筛为催化剂,以环氧氯丙烷与丙酸反应作为模型,研究了取代苯为溶剂时对反应速率的影响,发现反应的速率     

Total synthesis of (+)-blastmycinone and formal synthesis of (+)-antimycin A3b

The formal synthesis of (+)-antimycin A_3b and the total synthesis of (+)-blastmycinone were achieved using, as a key step, a method developed by us for the synthesis of 2-methyl-1,3-diols via Ti(III)-mediated diastereo- and regioselective opening of trisubstituted 2,3-epoxy alcohols, to carry out the stereoselective construction of the hydroxy-acid segment. An interesting intramolecular radical translocation took place during the epoxide opening process transforming its vicinal PMB-ether in situ, into an ‘1,2-O-(p-methoxy)benzylidene’ ring.     

Studies on radical cyclization of 2,3-epoxy alcohols containing a β-(alkoxy)acrylate moiety using Cp2TiCl

Radical-mediated opening of chiral 2,3-epoxy alcohols, containing suitably positioned β-(alkoxy)acrylate moieties, using Cp₂TiCl triggered intramolecular cyclization to give tetrahydrofuran and tetrahydropyran moieties.     

Synthesis of β-hydroxy sulfones via opening of hydrophilic epoxides with zinc sulfinates in aqueous media

Reaction of hydrophilic epoxides (ethylene oxide and propylene oxide) with readily accessible zinc sulfinates in aqueous solution under essentially neutral conditions afforded β-hydroxy sulfones in good yields. This method avoids the need for organic solvents and produces ZnO as the only major reaction byproduct. 2-(Methylsulfonyl)ethanol, a common reagent for the protection of various functional groups, was obtained by this methodology from ethylene oxide in 78% yield. Reaction of various simple zinc alkane- and benzenesulfinates with propylene oxide proceeded regioselectively in 63-67% yield. The corresponding opening of these epoxides with zinc 1,3-butadiene-1-sulfinate afforded 1-butadienyl β-hydroxyalkyl sulfones in 30% yield. Mechanistic studies revealed that the yields of these products were limited by their consumption in competing intra- and intermolecular Michael addition processes.