N─苯基邻苯二甲酰亚胺和N─对甲苯基邻苯二甲酰亚胺的晶体和分子结构

报道一种新类型的有机电子晶体Ｎ－苯基邻苯二甲酰亚胺（１）（Ｃ＿（１４）Ｈ＿９ＮＯ＿２）和Ｎ－对甲苯基邻苯二甲酰亚胺（２）（Ｃ＿（１５）Ｈ＿（１１）ＮＯ＿２）的晶体和分子结构，（１）属正交晶系，空间群为Ｐｃａｂ，ａ＝７．６４９（４），ｂ＝１１．６５９（２），ｃ＝２３．７３９（３）Ａ，Ｖ＝２１１７．０Ａ￣３，Ｚ＝８，Ｄ＿ｃ＝１．４０１ｇ／ｃｍ￣３，Ｍ＿ｒ＝２２３．２３，μ＝０．８８５ｃｍ￣（－１），最终偏离因子Ｒ＝０．０５３，Ｒ＿ω＝０．０４８；（２）属正交晶系，空间群为Ｐｎａ２＿１，ａ＝７．６２４（２），ｂ＝１１．２３７（１），ｃ＝１３．８５６（２）Ａ，Ｖ＝１１８７．０　Ａ３，Ｚ＝４，Ｄ＿ｃ＝１．３２８ｇ／ｃｍ￣３，Ｍｒ＝２３７．２６，μ＝２．７６４ｃｍ－１，最终偏离因子Ｒ＝０．０３６，Ｒ＿ω＝０．０３２。晶体结构测定结果表明，邻苯二甲酰亚胺的内酰亚胺碳、氮、氧原子与其苯并环共平面。化合物（２）中的甲基碳原子与取代基苯环共平面，苯并酰亚胺平面与取代苯环平面间的夹角分别为５８．４°（化合物１）和５６．２°（化合物２）。     

N─苯基邻苯二甲酰亚胺和N─对甲苯基邻苯二甲酰亚胺的晶体和分子结构

报道一种新类型的有机电子晶体Ｎ－苯基邻苯二甲酰亚胺（１）（Ｃ＿（１４）Ｈ＿９ＮＯ＿２）和Ｎ－对甲苯基邻苯二甲酰亚胺（２）（Ｃ＿（１５）Ｈ＿（１１）ＮＯ＿２）的晶体和分子结构，（１）属正交晶系，空间群为Ｐｃａｂ，ａ＝７．６４９（４），ｂ＝１１．６５９（２），ｃ＝２３．７３９（３）Ａ，Ｖ＝２１１７．０Ａ￣３，Ｚ＝８，Ｄ＿ｃ＝１．４０１ｇ／ｃｍ￣３，Ｍ＿ｒ＝２２３．２３，μ＝０．８８５ｃｍ￣（－１），最终偏离因子Ｒ＝０．０５３，Ｒ＿ω＝０．０４８；（２）属正交晶系，空间群为Ｐｎａ２＿１，ａ＝７．６２４（２），ｂ＝１１．２３７（１），ｃ＝１３．８５６（２）Ａ，Ｖ＝１１８７．０　Ａ３，Ｚ＝４，Ｄ＿ｃ＝１．３２８ｇ／ｃｍ￣３，Ｍｒ＝２３７．２６，μ＝２．７６４ｃｍ－１，最终偏离因子Ｒ＝０．０３６，Ｒ＿ω＝０．０３２。晶体结构测定结果表明，邻苯二甲酰亚胺的内酰亚胺碳、氮、氧原子与其苯并环共平面。化合物（２）中的甲基碳原子与取代基苯环共平面，苯并酰亚胺平面与取代苯环平面间的夹角分别为５８．４°（化合物１）和５６．２°（化合物２）。     

N-苄氧基邻苯二甲酰亚胺的合成

以N－羟基邻苯二甲酰亚胺、氯化苄和乙酸钠或三乙胺为原料,通过控制反应温度和反应时间高产率地制备了N－苄氧基邻苯二甲酰亚胺。     

氟双相催化合成N-异丙基邻苯二甲酰亚胺

用苯-二-[4-(十三氟正辛基)苯基]膦和二-(十三氟正辛基)重氮二羧酸酯作氟双相催化剂,在THF中由邻苯二甲酰亚胺和异丙醇合成N-异丙基邻苯二甲酰亚胺。反应条件为:邻苯二甲酰亚胺0.14 mmol,n(胺)∶n(醇)=1.0∶1.5,n(胺)∶n(催化剂)=1.0∶1.5,室温反应3.0 h,产率83.4%,纯度99.5%(GC分析)。     

微波辐射法合成4-氨基邻苯二甲酰亚胺

以4-硝基邻苯二甲酰亚胺为原料,通过微波辐射合成了4-氨基邻苯二甲酰亚胺。结果表明:选择铁粉作为催化剂,乙酸乙酯为萃取剂,在4-硝基邻苯二甲酰亚胺/氯化铵/铁粉的摩尔比为1.0∶1.0∶3.5,微波辐射时间100 s,微波辐射功率480 W的条件下,4-氨基邻苯二甲酰亚胺的收率最高,达到93.4%。     

N-羟基邻苯二甲酰亚胺及其类似物催化下的分子氧氧化反应

本文综述了近年来N-羟基邻苯二甲酰亚胺（NHPI）及其类似物催化下分子氧氧化的各种反应,并对它们的催化机理作了简要介绍。NHPI与过渡金属离子组成的催化体系能高效的催化乙烷氧化为乙酸、环烷烃氧化为二元羧酸、甲苯氧化为苯甲酸、烯烃氧化为环氧化物、炔烃氧化为炔酮、酰胺氧化为酰亚胺;NHPI单独使用能催化金刚烷发生氧化羰基化反应、催化氧化醇制取过氧化氢;NHPI与有机助催化剂如：偶氮二异丁腈、溴化季铵盐、蒽醌、醇等也能催化分子氧氧化反应。     

N-羟基邻苯二甲酰亚胺引发的聚乙烯熔融接枝反应

研究了N-羟基邻苯二甲酰亚胺(NOP)用于引发4种卤胺类前驱单体包括甲基丙烯酰胺(MA)、N-叔丁基丙烯酰胺(N-t-BuA)、马来酰亚胺(MI)和N,N-二烯丙基三聚氰胺(NDAM)与线性低密度聚乙烯(LLDPE)的熔融接枝聚合反应,并将其与工业上普遍应用的有机过氧化物(过氧化二异丙苯,DCP)引发法作对比。在接枝效率方面,NOP的引发效率与单体的分子结构和投料量密切相关。这4种单体中,N-t-BuA的接枝效率最高,与DCP法的差异在2.5%~16.0%之间;MI的接枝效率最低,比DCP法低55%。在副反应控制方面,实时扭矩、凝胶含量和熔融指数测试证实NOP引发体系中聚乙烯交联副反应程度明显低于DCP,接枝反应更加可控。     

N-羟基邻苯二甲酰亚胺(NHPI)用于有机氧化反应的研究进展

综述了N-羟基邻苯二甲酰亚胺(NHPI)及其类似物作为电化学氧化基质和催化剂用在有机氧化反应中的研究进展。对它们的合成,在催化体系中的作用和催化氧化反应机理作了重点评述。     

Ring opening reactions of quinoline substituted epoxides

6-Oxiranyl- and 3-oxiranyl-2-phenylquinoline-4-carboxylic acid diisopropylamides react with secondary amines and lithium amides to give (aminohydroxyethyl)quinolines but with opposite regioselectivities. Upon epoxidation of 3-formylquinoline 2 a 5:1 mixture of atropisomers is formed. This ratio is maintained upon epoxide ring-opening with amines in ethanol at reflux, but with lithium amides at room temperature a 1.3:1 ratio of isomers is obtained.     

Task specific ionic liquid as solvent,catalyst and reagent for regioselective ring opening of epoxides in water

Task specific ionic liquid as a novel and environmental eco-friendly green catalyst has been synthesized and used in the ring opening of epoxides under green conditions. This ionic liquids as solvent, catalyst and reagent afforded the corresponding thiocyanohydrins and azidohydrines with good regioselectivity and very short reaction times. The desired thiocyanohydrins and azidohydrines in 83–93% isolated yields.     

ZrCl4 as a new and efficient catalyst for the opening of epoxide rings by amines

Zirconium(IV) chloride catalyses the nucleophilic opening of epoxide rings by amines leading to the efficient synthesis of β-amino alcohols. The reaction works well with aromatic and aliphatic amines in short times at room temperature in the absence of solvent. Exclusive trans stereoselectivity is observed for cyclic epoxides. Aromatic amines exhibit excellent regioselectivity for preferential nucleophilic attack at the sterically less hindered position during the reaction with unsymmetrical epoxides. However, in case of styrene oxide, selective formation of the benzylic amine was observed during the reactions with aromatic amines.     

Ring opening of epoxides with alcohols using Fe(Cp)2BF4 as catalyst

Fe(Cp)₂BF₄ is an efficient catalyst for the alcoholysis of aromatic, aliphatic, and cyclic epoxides giving excellent yields of the corresponding β-alkoxy alcohols under ambient conditions. The methanolysis of styrene oxide using Fe(Cp)₂BF₄ as a catalyst (5 mol %) gave excellent yield of 2-methoxy-2-phenylethanol with complete regio-selectivity. The ring opening of cyclic epoxides gave 77–97% yields of trans-β-methoxy alcohols, in 0.5–6 h. The use of 1,2-epoxyhexane and 1,2-epoxydodecane as substrates gave both regioisomers in excellent yields. The first order rate of reaction with respect to catalyst was observed for the kinetics of ring opening of 1,2-epoxyhexane with methanol.     

A magnetic nanoparticle‐catalyzed regioselective ring opening of epoxides by aromatic amines

Sulfonic acid‐functionalized silica‐coated magnetic Fe₃O₄ nanoparticles were synthesized and applied as a green catalyst for an efficient and environmentally friendly ring opening of epoxides with aromatic amines in good to excellent yields with high chemoselectivity. Clean aminolysis of various aliphatic and aromatic epoxides in ethanol generates β‐hydroxyamines under mild reaction conditions. The synthesized acidic magnetic nanoparticles were recovered using a simple external magnet and successfully reused for five runs without any appreciable loss of catalytic activity. Copyright © 2016 John Wiley & Sons, Ltd.     

Graphene oxide as an acid catalyst for the room temperature ring opening of epoxides

The minute amount of hydrogen sulfate groups introduced into the graphene oxide (GO) obtained by Hummers oxidation of graphite renders this material as a highly efficient, recyclable acid catalyst for the ring opening of epoxides with methanol and other primary alcohols as nucleophile and solvent.     

Regio- and stereoselective ring opening of vinyl epoxides with MgBr2

The regio- and stereoselective ring opening of vinyl epoxides has been achieved by the use of Lewis acid, MgBr₂, affording bromohydrins in excellent yield, which are readily transformed to azidoalcohol, a key intermediate of several classes of pyrrolizidine and indolizidine alkaloids. The scope and limitations of the reaction are discussed.     

Lithium chloride as catalyst for the ring-opening polymerization of lactide in the presence of hydroxyl-containing compounds

Lithium chloride was found to be an effective and biocompatible catalyst for the ring-opening polymerization of lactide in the presence of hydroxyl-containing compounds. Ethylene glycol (EG) and methyl α-D -glucopyranoside (MGlc) were used as multifunctional initiators. The polymerization was carried out at 128°C in bulk with 1% (w/w) of LiCl. Polylactide (PLA) of different molecular weights was obtained with varied molar ratios of monomer/initiator ([M]₀/[I]₀). The LiCl-catalyzed ring-opening polymerization was applied to the synthesis of a number of amphiphilic PLA copolymers when poly(ethylene glycol) (PEG), hydroxyethyl cellulose (HEC), and hydroxypropyl cellulose (HPC) were used as macroinitiators. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3486–3491, 1999     

环氧化合物羰基化反应研究新进展

通过催化的方法在有机化合物分子中引入羰基和其它基团而成为含氧化合物的羰基化反应,具有"原子经济性"反应的高选择性和对环境的友好性,可充分利用资源和保护环境,符合绿色化学发展趋势等优点,备受学术界及工业界青睐.综述了近年来羰基钴金属化合物催化的环氧化合物和一氧化碳羰基化反应研究的新进展,涉及的反应类型主要包括羰基化扩环、羰基化开环共聚以及羰基化开环,讨论了不同类型反应的相关机理,并展望了该领域的研究前景.     

Demonstration of a phosphazirconocene as a catalyst for the ring opening of epoxides with TMSCl

[reaction: see text] In this study, it was demonstrated for the first time that a phosphazirconocene catalyzes the ring opening of epoxides with TMSCl. This reactivity leads to a facile preparation of chlorohydrins. The late transition metal Fe analogue was found to catalyze the reaction at rates and stereoselectivity comparable to those of the Zr complex.