Synthesis and Crystal Structure of 5-Diazo-4-ethoxycarbonyl-3-methylthio Pyrazol

The crystal of the title compound, 5-diazo-4-ethoxycarbonyl-3-methylthio pyrazole, has been prepared and determined by X-ray diffraction. The crystal belongs to the monoclinic system, space group C2/c with a = 29.174(8), b = 4.7592(12), c = 15.956(4) ? b = 117.632(4), C7H8N4O2S, Mr = 212.23, V = 1962.7(9) ?, Z = 8, Dx = 1.436 g/cm3, S = 1.000, m(MoKa) = 0.31 mm-1, T = 298(2) K, F(000) = 880, R = 0.0658 and wR = 0.1741 for 1091 independent reflections with I ≥ 2s(I). The crystal of the title compound is formed with p-p interactions through electrostatic attractions. Moreover, no HSO4- exists in the crystal structure. Therefore, only diazo pyrazole was obtained rather than either diazonium salt of the corresponding pyrazole or diazoaminopyrazole when 5-amino-4-ethoxycarbonyl-3-methylthio pyrazole was diazotized with sodium nitrite, catalyzed by sulfuric acid at 0 ℃.

Cu(Ⅱ) and Ni(Ⅱ) Complexes with 5,5'-Bis(2-acylphenyl)diazo-dipyrromethane:Syntheses,Structures and Properties

The reactions of 5,5＇-bis（2-acylphenyl）diazo-dipyrromethane （H2L） with CuSO4 and NiCl2 resulted in the formation of corresponding mononuclear coordination complexes 2 （CuL） and 3 （NIL）. The crystal of complex 2 is of monoclinic system, space group P21 with a = 10.040（5）, b = 11.900（5）, c = 11.170（5） A, β = 93.057（8）°, V = 1332.8（2） A3, Z = 2, C29H28N602Cu, Mr = 556.11, Dc = 1.386 g/cm, F（000） = 578 and/z（MoKa） = 0.857 mm^-1. The crystal of complex 3 belongs to the monoclinic system, space group P21/n with a = 12.0445（6）, b = 17.2101（8）, c = 16.3304（6） A, β = 128.407（2）°, V = 2654.6（2） A3, Z = 4, C29H28N6O2Ni, Mr= 551.28, Dc= 1.380 g/cm, F（000） = 1152 and μ（MoKa） = 0.770 mm^-1. In both complexes, the metal ions are in square-planar geometry by coordinating to two azo N atoms and two deprotonated pyrrole N atoms. Intramolecular Cu…O=C in complex 2 and intermolecular Ni…O=C in complex 3 were found. The UV-Vis spectra and thermal stability of complexes 2 and 3 were also studied.

Crystal Structure and Thermal Decomposition Kinetics of 3-Nitro-4-diazo-5-oxygenpyrazole

A novel compound 3-nitro-4-diazo-5-oxypyrazole was synthesized by the nitration of 4-amino-3,5-dinitropyrazole using nitrification agents of fuming nitric acid and trifluoroacetic anhydride. The compound was purified by column chromatography and characterized by IR, NMR, MS and elemental analysis. Two different single crystals obtained by culturing with ethyl acetate as a solvent were measured by X-ray single-crystal diffractometer. The molecular weight of C3HN5O3 is 155.09 and the two crystals belong to monoclinic system, space groups P21/n and P21/c. For 1： a = 5.5007（2）, b = 9.0691（4）, c = 11.4158（4） A, β = 92.710°, V = 568.85 A3, Z = 4, Dc = 1.811 g/cm3, μ = 0.162 mm-1, F（000） = 312 and the final deviation factor is 0.0213. Crystals 1 and 2 have similar unit cell parameters, except that a = 10.1828（12）, b = 5.5925（6）, c = 10.5574（10） A and β = 108.330（4）° in crystal 2. The thermal behavior of the compound was studied by TG-DSC and melting endothermic peak and decomposition exothermic peak are at 425.7 and 534.5 K in DSC curve. The activation energy and pre-exponential factor of the exothermic decomposition reaction of the title compound obtained by Kissinger method and Flynn-Wall-Ozawa method are 50.38 k J/mol, 4.59 × 1022 s^（-1） and 55.89 k J/mol.

5-(2-Hydroxylphenyl)diazo-dipyrromethane:Synthesis,Structure and Fluoride Ion Detection

A new azopyrrole compound, 1, has been synthesized and characterized. The crystal of 1 is of monoclinic system, space group P21/c with a = 8.7167（9）, b = 17.5929（19）, c = 12.8096（15） ？, β = 97.565（2）o, V = 1947.3（4） ^3, Z = 4, C（20）H（26）N4O2, Mr = 354.45, Dc = 1.209 g/cm^3, F（000） = 760 and μ（Mo Kα） = 0.080 mm^-1. In the crystal, 1 binds one methanol molecule through N–H…O, O–H…O and O–H…π interactions. UV-Vis titration and 1H NMR titration studies reveal that compound 1 can selectively detect fluoride ion in the DMSO solution.

小议重氮片(Diazo)

重氮片因其感光片的暗区呈棕色或棕黄色．所以称之为偶氮棕片或棕偶片或棕片．也有人称之为黄菲林。

Theoretical Study on Vibrational Spectra, Detonation Properties and Pyrolysis Mechanism for Cyclic 2-Diazo-4,6-dinitrophenol

在 DFT-B3LYP/6-311+G * 基于完整的优化分子的几何结构 * 水平，在那里存在为周期的 2-diazo-4,6-dinitrophenol 的 intramolecular 氢契约相互作用。分配红外线的光谱被获得并且过去常计算热力学的性质。结果证明在标题混合物的计算红外系列有四个主要典型区域。爆炸速度和压力被使用方程形成基于计算密度和压缩阶段加热的 Kamlet-Jacobs 也评估。热稳定性和 2-diazo-4,6-dinitrophenol 的热分解机制被在 B3LYP/6-311+G * 计算契约分离精力调查 * 水平。

Synthesis of 9,10-Phenanthrenes via Rh(III)-Catalyzed[4+2]Annulation of 2-Biphenylboronic Acids with Diazo Compounds

A Rh(III)-catalyzed,transmetalation triggered C—H activation/annulation of 2-biphenylboronic acids with diazo compounds fromβ-keto esters or 1,3-dicarboxylates has been developed,leading to the synthesis of two kinds of 9,10-phenanthrenes.Notably,a rhodacyle was synthesized by treating the rhodium catalyst with stoichiometric amounts of 2-biphenylboronic acids and pyridine,which was further verified to be active for the catalytic system.The reactions proceeded under redox-neutral and air-tolerant conditions to produce a series of all-carbon six-membered rings with high efficiency.

A Copper-Catalyzed[5+1]Cycloaddition of Terminal Alkynes with Diazo Esters through a Tandem 1,5-H-Shift Cyclization

A copper-catalyzed[5+1]cycloaddition reaction of terminal alkynes with diazo esters for the rapid construction of protected naphthalen-1(2H)-one derivatives in moderate to good yields has been disclosed along with good functional group compatibility and a broad substrate scope.The mechanistic investigations reveal that this tandem cyclization process proceeds through a Cu(I)-catalyzed coupling of terminal alkyne with diazoacetate,a 1,5-H shift process and a thermally induced pericyclic reaction via an allene intermediate.The synthetic utility and the further transformations of the obtained cycloadduct to naphthalenone,naphthol and dihydronaphthol have been also presented in this paper.

Facile synthesis of ( β -chlorodifluoroethyl)phosphonates via chlorination reaction of difluoroalkyl diazo derivatives with HCl

An efficient chlorination reaction of in situ generated(β-diazo-α,α-difluoroethyl)phosphonates has been achieved with hydrochloric acid as a chlorine source under mild and operationally convenient conditions.The reaction does not need any catalyst and tolerates a wide scope of substrates,which affords the(β-chlorodifluoroethyl)phosphonate products in good to excellent yields.This reaction represents the first example of the halogenation of difluoroalkyl diazo compounds,and also provides an easy way for the synthesis of difluoromethylenephosphonate-containing compounds.

Phosphine-Relayed Aldehyde-Olefination and Aza-Wittig Reaction with 2,2,2-Trifluorodiazoethane

Phosphine-relayed olefination and aza-Wittig reactions of readily available aldehydes with 2,2,2-trifluorodiazoethane （CF3CHN2） have been realized. This protocol enables the facile construction of a series of trifluoromethylated alkenes and hydrazones in good to high yield under mild conditions.

Silver-Catalyzed Three-Component Coupling of Carbon Dioxide, Amines and α-Diazoesters

A silver-catalyzed three-component coupling reaction of carbon dioxide, amines and α-diazoesters has been developed for the first time. The novel reaction provides an efficient and practical methodology for the synthesis of a wide range of new α-carbamoyloxy esters, which are difficult to prepare by existing methods. The advantages of the method include the use of readily available starting materials, simple catalytic system, good atom economy and high functional group tolerance.

In Situ Generation of Oxazole Ylide and Interception with Sulfonamide： Construction of Amidines Using Two Diazo Molecules

A novel generation of oxazole vlide and interception with sulfonamide have been well developed to construct fully substituted amidines. This copper-catalyzed four-component reaction incorporates two diazo molecules to target amidines and shows broad substrate scope, excellent functional groups tolerance and good to excellent yields.

Dual Incorporation of Trifluoromethyl and Cyano Groups into Pyrazole Pharmcophores via Silver-Catalyzed Cycloaddition Reaction of Trifluorodiazoethane

The dual incorporation of two important functional groups—trifluoromethyl and cyano moieties into one heterocyclic core in a single-step reaction represents an appealing but largely unaddressed synthetic challenge.Here we demonstrate that a silver-catalyzed[3+2]cycloaddition reaction of dicyanoalkenes with trifluorodiazoethane(CF_(3)CHN2)could render a facile construction of a unique category of pyrazoles that are simultaneously adorned by trifluoromethyl and cyano groups.Changing the location pattern of the cyano group in starting dicyanoalkene material allows regiodivergent access to two series of previously elusive trifluoromethyl cyanopyrazoles with an exquisite level of regiocontrol.Thus,this method could be applied in the preparation of cyano-analogues of CF_(3)-containing drugs(Celecoxib)and agrochemicals(Penthiopyrad and Fluazolate).Notably,several cyano-analogues of Celecoxib demonstrate enhanced inhibitory activity towards cyclooxygenase-2(COX-2),thereby laying a good foundation for developing new lead-based antiinflammatory agents.

SYNTHESES AND PROPERTIES OF 3-METHOXY-DIPHENYLAMINE-4-DIAZONIUM SALTS AND THEIR DIAZO RESINS

This note reports for the first time the preliminary results concerning the syntheses of 3-methoxy-dephenylamine-4-diazonium salts (M DADS)and the structures and properties of diazo resins produced by them and 4,4′-di-(methoxymethyl)-diphenylether (DMMDE).

基于α-苯基重氮酯的卡宾型染料的合成及其对氨纶的染色性能

为提升分散染料染色氨纶的色牢度,在偶氮染料结构中引入α-苯基重氮酯结构,合成3支新型卡宾型染料,用该类染料对氨纶进行染色,并测试了上染率、色深、固色率和色牢度等性能参数。结果表明:3支卡宾型染料通过高温处理即可牢固结合在纤维上,在无外界环境干扰情况下,染色氨纶最高固色率可达80.7%~96.3%;优化的水相染色法工艺条件为在95℃染色45 min,再在130℃固色30 min,在该条件下,所得染色氨纶的固色率能达到50.6%~80.7%,耐皂洗、耐摩擦和耐升华色牢度可达4级及以上,颜色迁移率为6.2%~8.9%。采用卡宾型染料对氨纶进行的反应性染色研究结果为完善氨纶的高色牢度染色技术提供了有益参考。

Palladium（o）-Catalyzed Si-Si Bond Insertion by the Terminal Nitrogen of Diazo Compoundst

The palladium（o）-catalyzed nitrogen insertion into cyclic Si-Si bonds has been realized by using N-tosylhydrazones/diazo compounds as the nitrogen source. The palladium（Ⅱ） nitrene formation and subsequent migratory insertion process are proposed as the key steps for this reaction.

人名反应在化学制药工艺学中的教学探索——重氮化反应

人名反应是经典的反应,化学制药工艺学中要应用到较多的人名反应。本文以重氮化反应为专题从五方面给学生进行讲解,有利于学生对反应的深入理解和熟练运用,达到更好的教学效果。