三溴化三乙基苄铵对于苯偶姻的氧化反应

作者前曾报道,三溴化三乙基苄铵(PhCH_2Et_3NBr_3~-,TEBABr_3,1)和三碘化三乙基苄铵(TEBAL_3)能作为有效的溴代和碘代试剂而与芳胺反应,以高产率生成多溴代和多碘代芳胺。在进一步对TEBABr_3在有机合成     

四异丙氧基钛对苯偶姻体系的氧化反应

Ti(OPr^i)4作为氧化剂直接氧化有机物尚属首例, ti(OPr^i)4很容易将苯偶姻氧化生成苯偶酰。室温下, 以THF作溶剂, 反应仅需10min。同样, Ti(OPr^i)4也能将氯、甲基和甲氧基取代的苯偶姻以及糠偶姻(Furoin)氧化生成相应的二酮。实验结果表明:Ti(OPr^i)4与苯偶姻体系的反应, 条件温和, 产率很高, 是一条实用、而有效的由苯偶姻制备苯偶酰的途径。     

偶苯酰双缩吡啶酰腙的合成及其结构表征

合成了Schiff碱化合物偶苯酰双缩吡啶酰腙;利用元素分析、红外光谱、紫外光谱和X射线单晶衍射等手段对其结构进行了表征.结果表明,标题化合物属于单斜晶系,P21/n空间群;晶胞参数为:a=0.8481(2)nm,b=0.5934(1)nm,c=2.1912(3)nm,β=94.331(3)°,V=1.0996(3)nm3,Z=2,Dc=1.355g/cm3,μ=0.090mm?1,F(000)=468,R1=0.0381,wR2=0.0628.分子内氢键N-H…N作用有利于稳定化合物的分子结构,而晶体堆积过程中通过分子间π-π作用和C-H…π作用形成三维超分子结构.     

盐酸三甲胺三氧化铬／硅胶载体试剂的制备及其对苯偶姻体系的氧化

报道了盐酸三甲胺三氧化锆／硅胶载体试剂的制备方法及其对苯偶姻的氧化反应。该试剂制备简单，用于地苯偶姻的氧化，高收率地得到相应的苯偶酰在化合物，并且反应条件温和，产物易分离。     

四异而氧基钛对苯偶姻体系的氧化反应

在水溶液中,很多试剂,如浓硝酸,Cu~(++)/Py,Bi_2O_3/H~+,Fe(CN)_6~(3-)/OH~-等可将苯偶姻(Benzoin)氧化生成苯偶酰(Benzil),而在有机介质且中性条件下反应的例子不多。Ho曾报道,Ph_3P·Br_2在无水乙腈中能氧化苯偶姻制得苯偶酰,产率75～98％。Swern还使用过Me_2SO/(COCl)_2/CH_2Cl_2,产率64～95％。     

N-苯磺酰脯氨酰腈的合成

酰基腈是一类重要的有机合成、医药中间体 .自 1 832年 Wohler和 L iebig首次合成苯甲酰腈以来 ,人们对芳环、芳杂环系列化合物的合成作了大量研究 [1 ] .氨基酸类 N-苯磺酰脯氨酰腈合成 ,迄今未见文献报道 .该类化合物可用于合成α-酮酸等具有生理活性的物质 .本文报道该化合物的合成 ,并对反应机理作了探讨 .反应式如下 :　　试剂均为分析纯 .仪器为 PE- 1 730型傅立叶变换红外分光光度仪 ;GC- MS- EI,70 e V,HP5 989A型质谱仪 ;Carl- Erba 1 1 0 6 R/ 5 0型元素分析仪 .称取一定量的 KCN与 Cu CN于四口瓶中 ,加 80 m L无水乙腈…     

一锅法合成N-呋喃酮基磺酰腙类化合物

以3,4-二卤-2(5H)-呋喃酮、磺酰肼和羰基化合物为起始原料,利用一锅法策略同时构建一个C—N键和一个C=N键,以良好收率合成一系列N-2(5H)-呋喃酮基磺酰腙类化合物.这种无需金属催化的转化在室温下就可实现,且具有好的底物适用性和选择性,即使对于Csp2—C1型的3,4-二氯-2(5H)-呋喃酮类底物,这种绿色...     

二苯基羟乙酮的合成

本文研究了维生素B1（VB1）催化下二苯羟乙酮的合成，找出了最佳反应条件，提高了产物的收率且重现性好。     

钯催化氧化/水解2-炔基芳基叠氮一锅法合成2-苯甲酰胺基苯甲酸

描述了通过钯催化2-炔基芳基叠氮一锅法氧化/水解制备2-苯甲酰胺基苯甲酸的合成方法.在温和的反应条件下,反应以良好至极好的产率完成.     

CrO3.CH3NH2.HCl／Al2O3的制备及其对苯偶姻体系的氧化反应

ＣｒＯ３·ＣＨ３ＮＨ２·ＨＣｌ／Ａｌ２Ｏ３的制备及其对苯偶姻体系的氧化反应张贵生＊石启增陈密峰蔡昆（河南师范大学化学系新乡４５３００２）关键词ＣｒＯ３·ＣＨ３ＮＨ２·ＨＣｌ／Ａｌ２Ｏ３，苯偶姻，苯偶酰，氧化１９９６－０８－１８收稿，１９９６－１１－０...     

Fe2O3/Al2O3催化氧化苯偶姻制备苯偶酰

考察了几种常用载体负载金属氧化物催化分子氧氧化苯偶姻制备苯偶酰的性能 ，发现氧化铁、三氧化二铝催化活性较高，稳定性较好。以吡啶为溶剂，用483K下 活化的含铁14．8％的氧化铁／三氧化二铝作催化剂，当其用量为苯偶姻用量20％ （质量分数），253K下反应1h,苯偶酰平均产率98．1％。用IR，MS，和^1H NMR光 谱对其结构进行了表征。     

微波辐射下苯偶姻的干法氧化反应

研究了微波辐射下干法氧化苯偶姻生成苯偶酰的反应。结果表明，硅胶和酸性氧化铝是本反应的良好载体，空气是良好的氧化剂。在较短时间内(8～15min)即可获得很高的产率(92%～98%)，为一种有效的苯偶姻氧化反应新方法。     

Direct Electrochemical Synthesis and Crystal Structure of a New Mononuclear Copper(Ⅱ) Complex: [(bipy)_2Cu(PhCOO)]ClO_4·(benzil) (benzil = 1,2-Diphenyl-ethane-1,2-dione)

A new mononuclear copper(Ⅱ) complex [(bipy)2Cu(PhCOO)]ClO4·(benzil) (bipy = 2,2′-bipyridine, benzil = 1,2-diphenyl-ethane-1,2-dione) was synthesized by direct electrochemical oxidation of Cu electrode in an acetonitrile solution with benzoic acid, 2,2′-bipyridine and benzoin. As soon as the current flowed in the cell, benzoin was oxidized to benzil quickly. The crystal structure was determined by X-ray diffraction. It belongs to monoclinic system, space group P21/c with a = 14.860(2), b = 20.784(3), c = 11.9150(17) , β = 101.401(3)°, V = 3607.3(9) 3, Z = 4, Mr = 806.69, Dc = 1.485 g/cm3, F(000) = 1660, μ = 0.742 mm-1, R = 0.0788 and wR = 0.1519 for 6254 observed reflections (I > 2σ(I)). The complex contains a mononuclear [(bipy)2Cu(PhCOO)]+ cation, a solvate benzil molecule and a ClO4- anion which locates around the cation outside acting as the counter ion. The Cu(Ⅱ) ion is coordinated by two 2,2′-bipyridines and one benzoato ligand to form a distorted square-pyramid.     

Ultrasound-enhanced Green Synthesis of 5,5-Diphenylhydantoin Derivatives Using Symmetrical or Unsymmetrical Benzils

A rapid, highly efficient and mild green synthesis of 5,5‐diphenylhydantoin derivatives was achieved from the reaction of symmetrical or unsymmetrical benzil derivatives with urea in the presence of ethanolic KOH under ultrasound irradiation. This simple method affords 5,5‐diphenylhydantoin derivatives at room temperature in short reaction time with high yield and purity. This study aimed to overcome the limitations and drawbacks of the reported methods such as tedious work‐up, low yield and long reaction time.     

Simple and Efficient One-Pot Synthesis of Nitriles from Amides and Oximes Using in Situ–Generated Burgess-Type Reagent

The dehydration of aldoximes and amides, and oxidation of benzoin are accomplished in one-pot using in situ–generated Burgess-type reagent.

Benzil Photoperoxidations in Polymer Films and Crosslinking by the Resultant Benzoyl Peroxides in Polystyrene and Other Polymers

Benzil (BZ) can be converted almost quantitatively to benzoyl peroxide (BP) in aerated polymer films upon irradiation at >400 nm (i.e., the long-wavelength edge of the n→π* absorption band of BZ, where BP does not absorb). Here, we summarize results for the photoperoxidation of BZ structures with molecular oxygen, principally in glassy polymer matrices. Some of the polymers are doped directly with BZ or its derivatives, and others, contain covalently attached BZ pendant groups from which BP groups are derived. While the decomposition of low-molecular-weight BP doped into polymer films (such as those of polystyrene (PS)) results in a net decrease in polymer molecular weight, thermal decomposition of pendant BP groups is an efficient method for chain crosslinking. Crosslinking of PS films doped with a molecule containing two covalently linked BZ or BP groups proceeds in a similar fashion. Free radicals from the covalently attached BP allow grafting of new monomers, as well. Additionally, the use of radiation filtered through masks has been used to create patterns of polymers on solid surfaces. Crosslinking of photodegradable poly(phenyl vinyl ketone) with BP structures obtained by photoperoxidation of BZ structures for the preparation of photodegradable polymer networks is described as well. In sum, the use of BZ and BP and their derivatives offers simple and convenient routes for modifying polymer chains and, especially, for crosslinking them. Specific applications of each use and process are provided. Although applications with PS are featured here, the methodologies described are amenable to a wide variety of other polymers.     

反相高效液相色谱法结合计时波长切换紫外检测法测定苯妥英及其中间体的含量

以盐酸酸化的二甲亚砜为溶剂,铁盐催化空气氧化安息香制备苯偶酰,再由苯偶酰与尿素缩合制备苯妥英。在此合成过程中需对反应液中安息香的浓度、中间产物苯偶酰的含量以及最终产物苯妥英的浓度进行检测。试验提出了采用反相高效液相色谱法结合计时波长切换紫外检测法对上述各化合物进行测定。将所需测定的样品溶于乙腈中,所得溶液经0.45μm滤膜过滤。取滤液(进样量为20μL)通过kromasil 100-5C18色谱柱(200mm×4.6mm,5μm),以体积比为80∶20的乙腈-水溶液作为流动相进行等度洗脱,洗脱液按预设程序进行计时紫外检测。在0~3.0min和波长218nm处检测苯妥英;在3.0~4.0 min和波长247nm处检测安息香;在4.0~6.0min和波长260nm处检测苯偶酰。3种化合物标准曲线的线性范围均为0.1~100mg·L^-1,并测得其检出限(3S/N)依次为0.010,0.003 0,0.007 0mg·L^-1。在实际样品基础上加入3个浓度水平的混合标准溶液进行回收试验,测得3种化合物的回收率为95.4%~105%;测定值的相对标准偏差(n=6)为1.8%~4.2%。