微波辐射下的1,4-二甲基咔唑-9-羧酸的快速合成

以ＤＭＦ为溶剂,在微波辐射下由１,４－二甲基咔唑和相应的溴酯快速合成了两种１,４－二甲基咔唑－９－羧酸化合物,在最佳反应条件下,产率分别为８５．２％和８３．１％。     

1,4—二氢Hantzsch吡啶衍生物的合成及其^1H NMR和荧光 …

报道了Ｎ－甲基－４－芳基－２,６－二甲基－３,５－二乙基－１,４－二氢吡啶（２ａ－２ｆ）,４芳基－２,６－二苯基－３,５－二乙酯基－１,４－二氢吡啶（３ａ－３ｆ）及其相应的Ｎ－甲基化合物（４ａ－４ｆ）的合成（芳基ｐ－ＲＣ６Ｈ４－;Ｒ＝ＯＣＨ３,ＣＨ３,Ｈ,Ｃｌ,ＣＮ,ＮＯ２）,化合物４－芳基２,６－二甲基－３,５－二乙酯基－１,４－二氢吡啶（１ａ－１ｆ）可发射较强的荧光,化合物３呈现较弱的荥光,它     

1,4-双氯甲基-2-甲氧基-5-壬氧基苯的均聚和共聚

以对甲氧基苯酚和溴壬烷为原料,经过醚化和双氯甲基化反应得到１,４－双（氯甲基）－２－甲氧基－５－壬氧基苯（ＢＣＭＮＯＮＯＢ）,ＢＣＭＭＯＮＯＢ在强碱作用下通过脱氯化氢得到可溶性的聚（２－甲氧基－５－壬氧基）对苯乙炔（ＰＭＯＮＯＰＶ）;首次采用脱氯化氢消除反应实现了ＢＣＭＭＯＮＯＢ与１,４－双（氯甲基）－２,５－二甲基（ＢＣＭＤＭＢ）共聚。讨论了两种单体结构和縻尔比率及溶剂因素对聚合反应和共聚物溶解     

1—芳基—2—苯基—3—甲基—3—异丙基—2—氧代—1,4,2—二氮磷杂？…

利用取代苯基脲与苯基二氮化膦和３－甲基－２－丁酮进行的类Ｍａｎｎｉｃｈ反应合成了１５种新的１,４,２－二氮磷杂环戊－５－酮类化合物（２ａ－２ｏ）,其结构经＾１Ｈ ＮＭＲ,ＩＲ,ＭＳ和元素分析证实,根据ＮＭＲ谱分析,反应主要生成顺式几何异构体,除草活性测试表明,目标化合物对阔叶杂草具有很好的选择性草活性,并对其结构与除草活性关系进行了讨论。     

固相配位化学反应研究（LXVII）：—固—固相反应合成混配…

室温或近室温条件下，Ｃｏ（ａｃａｃ）２（Ｈ２Ｏ）２与第二配体２，２＇－联吡啶、１，１０－啡罗啉、８－羟基喹啉、水杨醛肟固相反应得到４个混配化合物，经ＸＲＤ、ＩＲ、ＵＶ及元素分析表征了这些产物。     

α芳甲酰基—α肉桂基烯酮—1,4—亚丁二硫缩醛的合成

以乙醇钠为碱,由２－（１,４－亚丁二硫基）亚甲基芳甲酰丙酮与芳醛的缩合反应得到标题化合物,其立体化学经ＨＮＭＲ验证为Ｅ－构型。     

三元混配化合物[Cu(8-Q)_2(phen)]·H_2O及[Cu(NCS)_2(phen)_2]·H_2O的固相合成

用室温固相反应合成了［Ｃｕ（８－Ｑ）２（ｐｈｅｎ）］·Ｈ２Ｏ 及［Ｃｕ（ＮＣＳ）２（ｐｈｅｎ）２］·Ｈ２Ｏ 两个三元混配化合物。室温下［Ｃｕ（Ａｃ）２（Ｈ２Ｏ）］与邻菲?啉固体几乎不发生反应，但加入第二配体８－羟基喹啉及ＫＳＣＮ，反应几乎立即发生。ＸＲＤ、ＩＲ谱及元素分析结果表明：第二配体的加入并不仅仅促进［Ｃｕ（Ａｃ）２（Ｈ２Ｏ）］与第一配体的反应，它同时也参与反应，形成了三元混配化合物。用室温固相反应合成上述两个三元混配化合物尚未见报道     

[Co(N-(2-Aminoethyl)-1,3-propanediamine)(2-(Aminomethyl)pyridine)Cl][ZnCl4]配合物的合成及一种异构体的晶体结构

用过氧化化物法合成了〔Ｃｏ（２,３－ｔｒｉ）（ａｍｐ）ＣⅠ〕ＺｎＬＩ４（２,３－ｔｒｉ＝Ｎ－（２－ＡｍｉｎｏｅｔｈｙⅠ）－１,３－ｐｒｏｐａｎｅｄｉａｍｉｎｅ;ａｍｐ＝２－（ＡｍｉｎｏｍｅｔｈｙⅠ）ｐｙｒｉｄｉｎｅ）中的四个异构体,解析了其中的一个几何异构体的晶体结构：顺式（２,３－ｔｒｉ中仲胺上的氢相对于ＣＩ）经式异构体（ｍ４）。晶体学参数：单斜晶系,空间群Ｐ２．／ｃ,α＝１２．０２５（３）Ａ＾     

CoTPP电化学催化原溴代环己烷的机理

以电化学循环伏安、现场ＥＳＲ电化学以及现场薄层电化学方法研究了电生Ｃｏ（Ｉ）ＴＰＰ与溴代五己烷的反机制。在ＤＭＦ中，Ｃｏ（Ⅱ）／Ｃｏ（Ⅰ）的氧化还原有明显的催化溴代环己烷还原的特片，反现场有自由基生成，反应产物之一是Ｃｏ－Ｃ键化合物，可以在１．３０Ｖ（ＳＣＥ）－电子还原，当存在ＣＨ２－ＣＨＣＮ时，。生成另一种Ｃｏ－Ｃ键化合物，该化合物在－１．１０Ｖ（ＳＣＥ）处一电子还原，证明溴代环己烷与Ｃｏ（Ｉ）     

环氧溴丙烷作重原子微扰剂环糊精诱导室温燐光法测定7种痕量多环芳烃化合物

１引言环糊精诱导室温燐光法（ＣＤ－ＲＴＰ）测定痕量多环芳烃化合物的研究，我们曾做过大量的工作。在此基础上，本文研究ＴＮａ２ＳＯ３化学除氧技术用于环氧溴丙烷作重原子微扰剂β－ＣＤ－ＲＴＰ法测定痕量菲（Ｐｈｅｎ．），苊（Ａｃｅ．），芴（Ｆｌｕ．），７，８－苯并喹啉（７，８－ＢＱ），７－甲基喹啉（７－ＭｅＱ），α－４嗅代萘（α－ＢｒＮ），β－溴代茶（β－ＢｒＮ）中，均取得了成功。说明化学除氧技术在ＣＤ－ＲＴＰ法中具有普遍的意义。２实验部分２．１仪器和试剂ＬＳ－５０Ｂ型发光分析仪；菲、芴、苊（高效液相色…     

Convergent synthesis of polyhalogenated quinoline C-nucleosides as potential antiviral agents

2,5,6-Trichloro-1-(beta-d-ribofuranosyl)benzimidazole (TCRB) and 2-bromo-5,6-dichloro-1-(beta-d-ribofuranosyl)benzimidazole (BDCRB) are benzimidazole nucleosides that exhibit strong and selective anti-HCMV activity. We proposed to synthesize 2-halo-6,7-dichloro-4-(beta-d-ribofuranosyl)quinolines as 6 + 6 bicyclic analogues of TCRB. The synthesis used Wittig reactions in two key steps. The first Wittig reaction coupled a fully functionalized benzene with a ribofuranose derivative to provide (Z)-6-O-(tert-butyldimethylsilyl)-1-(4,5-dichloro-2-nitrophenyl)-1,2-dideoxy-3,4-O-isopropylidene-d-allo-1-enitol (5) as the basic skeleton for the target compounds. The following electrophile-mediated intramolecular cyclization of the cis-alkene (5) was found to afford (1S,2S)-2,5-anhydro-1-bromo-6-O-(tert-butyldimethylsilyl)-1-deoxy-1-(4,5-dichloro-2-nitrophenyl)-3,4-O-isopropylidene-d-allitol (8) as the major product. This alpha-stereoselectivity was contrary to the literature precedence. A double-bond isomerization was established to be the cause of the unexpected stereochemistry. The bromo group of 8 was displaced by a hydroxyl group. Oxidation of the hydroxy group and the reduction of a phenylnitro group provided (2S)-1-(2-amino-4,5-dichlorophenyl)-2,5-anhydro-6-O-(tert-butyldimethylsilyl)-3,4-O-isopropylidene-d-allose (11), which was subjected to the second Wittig reaction with a phosphacumulene to construct 4-[5-O-(tert-butyldimethylsilyl)-2,3-O-isopropylidene-alpha-d-ribofuranosyl]-6,7-dichloroquinolin-2-one (13). Halogenation followed by deprotection of 13 and led to the synthesis of 4-(alpha-d-ribofuranosyl)-2,6,7-trichloroquinoline (17) as the major product. The 2-aminophenone alpha-nucleoside (11) was successfully anomerized to the beta-anomer (19), which led to the synthesis of the targeted 2-chloro- and 2-bromo-6,7-dichloro-4-(beta-d-ribofuranosyl)quinolines (18and 21, respectively).     

Thermolysis of 1-(1-aryl-1-bromomethyl)cyclopropyl bromides: a reinvestigation

Two compounds, the (Z)- and (E)-isomers of 2,4-dibromo-1-p-tolyl-1-butene 2a and 3a, respectively, were isolated in 65% total yield when 1-(1-bromo-1-p-tolylmethyl)cyclopropyl bromide (1a) was heated at 150 degrees C for 1 h. 1,1-Dibromo-2-p-tolylcyclobutane (4a), previously reported to be the only product in this reaction, was not detected. The phenyl analogue of 1a reacted similarly and gave the (Z)- and (E)-isomers of 2,4-dibromo-1-phenyl-1-butene 2b and 3b, respectively, in 60% yield. A rationale for the reaction is presented.     

Regio - and stereospecific halogenation of 7alogenoalkenes in liquid hydrogen fluoride

The products of bromo and chlorofluorination of E and Z-1,2-dichloroethylenes, 1, 3-dichloro-1-propenes, 1, 1-dichloro- ethylene and 1, 3-dichloro-2-fluoro-1-propene by N-bromosuccinimide and hexachloromelamine in anhydrous hydrogen fluoride have been studied. It was found that the reaction was in all cases 100% regio and 93–100% trans-stereospecific with the exception of E-1, 2-dichloro-ethylene, its trans-stereospecificity being 85%.Threo and erithro-1-bromo-1, 2-dichloro-2-fluoroethanes, 2-bromo-1, 3-dichloro-1-fluoropropanes and 1, 2, 3-trichloro-1-fluoro-propanes as well 1, 1, 2-trichloro-2-fluoroethane, 1-bromo-2, 2-dichloro-2-fluoroethane, 1, 2, 2-trichloro-2 fluoroethane, 1-bromo-1, 3-dichloro-2, 2-difluoropropane, and 1, 1, 3-trichloro-2,2-difluoropropane were obtained in 50–70% yield.The bromination of E and Z-1, 3-dichloro-1-propenes with molecular bromine in carbon tetrachloride in the dark is non-stereospecific and gives a mixture of erithro and threo-1, 2-dibromo-1, 3-dichloropropanes in the ratio about 1:1. However, the bromination reaction in anhydrous hydrogen fluoride solution proceeds with a high degree of stereospecificity (94–95%) and gives threo-1, 2-dibromo-1, 3-dichloropropane from Z and erithro-1, 2-dibromo-1, 3-dichloropropane from E-1, 3-dichloro-1-propene.The data obtained are considered in terms of an electrophilic mechanism of halogenoalkene halogenation in anhydrous hydrogen fluoride and a free-radical mechanism in carbon tetrachloride.     

Photoinduced self-substitution of haloquinones

A series of novel oligo(halobenzoquinoid) compounds have been obtained from the photoinduced self-substitution of 2,5-dibromo-1,4-benzoquinone (1a), 2,6-dibromo-1,4-benzoquinone (1b), 2-chloro-1,4-benzoquinone (1c), 2-bromo-5-chloro-1,4-benzoquinone (1d), 2,3,5,6-tetrachloro-1,4-benzoquinone (1e) and 1,4-benzoquinone (1f) in the presence of N,N-dimethyl-t-butylamine (2) in acetonitrile. Dimers, trimers and/or pentamers of these haloquinones were found to be the major products.     

Halogenation of Imidazo[4,5-<Emphasis Type="Italic">b</Emphasis>]pyridin-2-one Derivatives

Chlorination and bromination of 2,3-dihydro-1H-imidazo[4,5-b]pyridin-2-one and its N-methyl-substituted derivatives in acetic acid at 90–95°C leads to formation of the corresponding 5,6-dichloro(dibromo)-2,3-dihydro-1H-imidazo[4,5-b]pyridin-2-ones. Iodination of the same substrates with ICl under analogous conditions yields 6-iodo derivatives. Chlorination of 6-iodo-1,3-dimethyl-2,3-dihydro-1H-imidazo[4,5-b]pyridin-2-one is accompanied by replacement of the iodine atom by chlorine with formation of 5,6-dichloro-1,3-dimethyl-2,3-dihydro-1H-imidazo[4,5-b]pyridin-2-one. Bromination of 6-bromo- and 6-chloro-2,3-dihydro-1H-imidazo[4,5-b]pyridin-2-ones gives 5,6-dibromo- and 5-bromo-6-chloro-2,3-dihydro-1H-imidazo[4,5-b]pyridin-2-ones, respectively.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 4, 2005, pp. 586–589.Original Russian Text Copyright © 2005 by Yutilov, Lopatinskaya, Smolyar, Gres’ko.     

Reactivity of some 3-substituted derivatives of 2,6-dihalogenopyridines towards potassium amide in liquid ammonia [a]

Reactions of 2,6-dichloro-3-phenyl-, 2,6-dibromo-3-phenyl-, 2,6-dichloro-3-dimethylamino- and 2,6-dibromo-3-dimethylaminopyridine with potassium amide in liquid ammonia were investigated. Whereas 2,6-dichloro-3-phenylpyridine yields 4-amino-2-benzylpyrimidine, from 2,6-dibromo-3-phenylpyridine as a product of a novel ring fission 2-amino-l-cyano-l-phenyl-but-l-en-3-yne was isolated, together with 4-amino-6-bromo-3-phenylpyridine and 2,6-diamino-3-phenylpyridine. It was shown that neither 2-amino-6-bromo-3-phenyl- nor 6-amino-2-bromo-3-phenylpyridine are intermediates in the formation of the 2,6-diamino derivative, as these bromo compounds are transformed in the basic medium into 1,3-dicyano-l-phenylpropene. From both 2,6-di-chloro-3-dimethylamino- and 2,6-dibromo-3-dimethylaminopyridine mixtures are obtained from which only 2-amino-l-cyano-l-dimethylamino-but-l-en-3-yne and 4-amino-6-halogeno-3-dimethylaminopyridine were isolated. Mechanisms for the reactions studied are proposed, i.e. a S_N(ANRORC) mechanism for the aminodebromination of 2,6-dibromo-3-phenylpyridine into the corresponding 2,6-diamino compound.     

Dechlorination of beta-methylallyl chloride by electrogenerated [Co(I)(bipyridine)3]+: an electrochemical study in the presence of cationic surfactants

We have investigated the electrocatalytic dehalogenation of beta-methylallyl chloride (beta-mAC), widely used in the polymer industry, using [Co(I)(bpy)3]+ (where bpy=2,2'-bipyridine) electrochemically generated in situ from [Co(II)(bpy)3]2+ at a glassy carbon electrode in the presence of three different cationic surfactants in aqueous solution. Cetyltrimethylammonium bromide (CTAB), tetradecyltrimethylammonium bromide (TDTAB), and cetylbenzyldimethylammonium chloride (CBDAC) were employed in the present investigation. The [Co(II)(bpy)3]2+-cationic surfactant systems show excellent electrocatalytic activity toward dehalogenation of beta-mAC. The dependence of the catalytic current, the corresponding potential, and the current function on the potential scan rate has been analyzed to assess the nature of the catalytic reaction. The second-order rate constant, kchem, for the reaction between the beta-mAC substrate and the electrogenerated-micelle stabilized-Co(I) complex has been calculated by a cyclic voltammetry technique. The reduction products after 3 h of bulk electrolysis have been identified by GC/MS to be one nonchloro compound (2-methyl-1,5-hexadiene (IV)) and two chloro compounds (1-chloro-2,5-dimethyl-2,5-hexadiene (V) and spiro[1.2]cylopropyl-6-chloro-5-methyl-hex-4-ene (VI)). Based on the electrochemical results and the mass spectral data, a reaction scheme involving all the reduction products has been proposed. Finally, a good correlation between the catalytic efficiency and the structural features of the surfactant molecules is demonstrated. The present study emphasizes the need for further optimization work to achieve maximum yield of nonchloro compound (IV) to employ the present [Co(II)(bpy)3]2+-cationic surfactant systems with a high catalytic efficiency as promising for possible applications.     

Chlorimine formation and deamination of the model nucleobase 1-methylcytosine

Treatment of the model nucleobase 1-methylcytosine with chlorine in aqueous solution gives, depending on the reaction conditions, 5-chloro-1-methylcytosine ( 3 ) or its hemiprotonated form 2 , 5,5-dichloro-6-hyd-roxy-5,6-dihydro-4-chlorimino-1-methylpyrimidin-2-one ( 5 ), and 5,5-dichloro-6-hydroxy-5,6-dihydro-1-methyl-uracil ( 4 ). While substitution of H5 of 1-methylcytosine by chlorine giving 2 and 3 , and subsequent addition of hypochlorous acid to the 5,6-double bond is not unexpected, chlorination of the exocyclic amino group 5 and deamination to give 4 is novel. The X-ray structures of 4 and 5 are reported.     

Bromo derivatives of 1-(4-hydroxyphenyl)dihydrouracil and 1-(4-hydroxyphenyl)-5- or -6-metehyldihydrouracils

Bromination of 1-(4-hydroxyphenyl)dihydrouracil and its 6-methyl derivative with bromine in refluxing acetic acid gave 1-(3,5-dibromo-4-hydroxyphenyl)-5-bromo-, 1-(3,5-dibromo-4-hydroxyphenyl)-5-bromo-, and 1-(3,5-dibromo-4-hydroxyphenyl)-5-bromo-6-methyldihydrouracils and 1-(3,5-dibromo-4-hydroxyphenyl)-5-methyluracil. 5-Bromo- and 5,5-dibromodihydrouracils were dehydrobrominated, and the same compounds undergo decomposition to 3,5-dibromo-4-hydroxyphenylurea upon alkaline hydrolysis.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1251–1254, September, 1982.     

Synthesis of isothiocoumarin derivatives

A method was developed for the synthesis of 1-oxo-1H-isothiochromenes from 2-benzofuran-1(3H)-one (phthalide). 3-Bromo-6-chloro- and 3,6-dibromo-2-benzofuran-1(3H)-ones were prepared by the bromination of 6-chloro- and 6-bromo-2-benzofuran-1(3H)-ones and were converted by hydrolysis into 5-chloro- or 5-bromo-2-formylbenzoic acids. The condensation of these acids with rhodanine followed by recyclization gave 7-chloro- and 7-bromo-1-oxo-1H-isothiochromene-3-carboxylic acids.