4-二甲氨基吡啶催化的1,3-二酮与3-丁炔-2-酮的苯环化反应

在4-二甲氨基吡啶(DMAP)催化下, 1,3-二酮与3-丁炔-2-酮可以区域选择性地合成四取代的苯, 该方法具有反应条件温和和操作简单等优点, 产物的结构通过IR, 1H NMR, 13C NMR, HRMS确证.     

用二茂锆配合物一锅法合成1,1’-二取代联烯

二氯二茂锆(Cp_2ZrCl_2)与乙基溴化镁(EtMgBr)反应生成二乙基二茂锆(Cp_2ZrEt_2),再与1,4-二烷氧基-2-丁炔反应形成锆杂环戊烯,经过烷氧基在锆原子上的消除直接得到1,1′-二取代联烯(端联烯)。或者Cp_2ZrCl_2与正丁基锂(n-BuLi)反应生成二丁基二茂锆(Cp_2ZrBu_2),再与α-烯烃反应形成锆杂环戊烷,然后与1,4-二烷氧基-2-丁炔反应形成锆杂环戊烯,经过烷氧基在锆原子上的消除得到端联烯。上述反应合成端联烯的收率都比较高,这为构造端联烯衍生物提供了一种简单实用的方法。     

单分散PPE齐聚物的合成及其荧光性质

合成了PPE的齐聚物{1,4-二[3,5-二（3-甲基-3-羟基-1-丁炔基）苯炔基]苯）（4）,通过^1H—NMR对其结构进行表征,并对其荧光性质做了研究。研究结果表明引入四个2-甲基-2-羟基-丁炔基作为取代基团后,溶解性提高。取代基的引入导致齐聚物4旋转阻力增大,溶液荧光有明显的精细结构。而4具有较好的荧光单色性,因而是一种潜在的新型荧光发射材料。     

基于4,6-二甲基-2-巯基嘧啶结构的联烯衍生物的合成及抗菌活性研究

以4,6-二甲基-2-巯基嘧啶、3-溴丙炔和取代苯甲醛为原料,经过亲核取代和加成反应,以42～78%的分离收率得到了11个4-((4,6-二甲基嘧啶-2-基)硫代)-1-(取代苯基)-2-丁炔基乙酸酯衍生物3(a-k)。在金属镍的催化下,4-((4,6-二甲基嘧啶-2-基)硫代)-1-(取代苯基)-2-丁炔基乙酸酯衍生物(3)与三甲基铝发生S_N2’取代反应合成了11个含有4,6-二甲基-2-巯基嘧啶结构的联烯衍生物4(a-k)。探讨了各种反应条件对目标产物收率的影响,并且对这些条件进行了优化。结果表明,在60℃,四氢呋喃作溶剂,碳酸钾作碱,用2mol%NiCl_2/4mol%PPh_3催化三甲基铝试剂与4-((4,6-二甲基嘧啶-2-基)硫代)-1-(取代苯基)-2-丁炔基乙酸酯衍生物(3)进行S_N2’取代反应,可以顺利地以22～63%的分离收率得到含有4,6-二甲基-2-硫基嘧啶结构的联烯衍生物。所有目标化合物均经~1H(~(13)C)NMR,IR,HRMS分析对其结构进行确证。该类化合物的合成方法具有操作简单和反应条件温和的优点。经体外活性测试表明有5个化合物对大肠杆菌有一定的抑制作用,其最小抑制浓度可达4 ug·mL~(-1)。     

Cu(Ⅰ)与2-甲基-3-丁炔-2-醇中性膦配合物的电化学合成

甲基丁炔醇;铜配合物;Cu(Ⅰ)与2-甲基-3-丁炔-2-醇中性膦配合物的电化学合成     

1,4-二乙氧基苯的合成研究

以甲醇或乙醇为溶剂,在氢氧化钾存在下对苯二酚与溴乙烷于60℃反应3h,可以直接合成1,4－二乙氧基苯,收率大于80％。     

取代喹喔啉-1,4-二氧化物合成方法的改进

苯并呋咱-1-氧化物(1)分别与1,3-二酮、β-酮酯(2a～c)在氢氧化钾(钠)的醇溶液中反应,合成了取代喹喔啉-1,4-二氧化物(3a～c),产率较高。将本方法与在有机胺中合成这些化合物的Beirut反应作了比较,并且讨论了溶剂和反应温度对产物的影响。     

1,4-丁炔二醇与4,4′-二乙炔联苯共聚物的合成及表征研究

本文用(Ph_3P)_2PdCl_2为催化剂,合成了1,4-丁炔二醇(BD)与4,4-二乙炔联苯(DEBP)共聚物。对用不同比例的两种单体得到的共聚物测定了比重(d_4~(25)、溶胀度(θ_D)、最良溶剂及相邻两交联点之间的平均分子量(M_c)。实验表明,在两种单体摩尔比中,DEBP用量越多,共聚物中泡状微孔越多,颜色越淡,溶胀度和比重越小,交联度越大;DEBP/BD(摩尔比)大于1/5时,共聚物的最良溶剂为苯,溶度参数为9.15卡~(0.5)·cm~(-1.5),是1/10时,其最良溶剂为乙醇,溶度参数是12.7卡~0.5·cm~(-1.5)。对共聚物还做了红外光谱表征。     

9,9-二甲基-2-(N-联苯基)氨基芴的合成

以芴为原料,苄基三甲基三溴化铵为溴化试剂,室温下在甲醇和二氯甲烷中溴化得到2-溴芴,然后以四氢呋喃为溶剂,在叔丁醇钾作用下与碘甲烷反应合成9,9-二甲基-2-溴芴,最后与4-联苯胺通过Buchwald-Hartwig偶联反应合成目标化合物9,9-二甲基-2-(N-联苯基)氨基芴,总收率为56.0%～62.4%。通过1HNMR、13CNMR、MS、IR和元素分析确证了其结构。     

低价钛引起的(3-氧代-1,3-二芳基)丙基丙二腈的还原环化反应

报道了低价钛试剂(TiCl-Zn体系)与(3-氧代-1,3-二芳基)丙基丙二腈的反应.研究发现,低价钛可引起(3-氧代-1,3-二芳基)丙基丙二腈的成环反应,生成2-氰基-3,5-二芳基-1-氨基环戊烯、反式和顺式2-氨基-3-氰基-1,4-二芳基-2-环戊烯-1-醇3种产物,并用X射线衍射法确定了后两种异构体的构型.     

A chemical study of 2-butyne-1,4-diol

Commercial grade 2-butyne-1,4-diol has been used in electroplating for several years. In laboratory experiments, its presence in the electrolyte increases the current efficiency of zinc electro-winning. Its chemical behaviour in solution is not well known. The present paper indicates that the brownish technical grade 2-butyne-1,4-diol contains the monomer, the dimer and some trimer. Pure monomeric 2-butyne-1,4-diol is a white solid obtained by evaporation of the technical grade product. The monomer is slowly transformed into dimer and possibly into a trimer when dissolved in water. Various analytical techniques were used in the study of this system. Factor analysis with column cross-validation was applied to chromatographic data to help in the resolution of the system.     

Procedures for recovery of crystalline 2-butyne-1,4-diol from industrial aqueous solutions and for its purification

Four procedures for recovery of crystalline 2-butyne-1,4-diol from aqueous solutions and for its purification were examined. Samples of crystalline 2-butyne-1,4-diol containing 98.5 to 99.9 wt % target product were obtained.     

Electrolytic reduction of 2-butyne-1,4-diol as a route to trans-2-butene-1,4-diol

The effect of the cathode material on the electrochemical transformations of 2-butyne-1,4-diol at atmospheric pressure was studied by chromatographic analysis. The optimal parameters of the selective synthesis of trans-2-butene-1,4-diol were determined.     

Preparation and Study of Some Copolyesters

Terephthalate unsaturated copolyesters with ethylene glycol and 2-butene-1,4-diol, with ethylene glycol and 2-butyne-1,4-diol, with ethylene glycol and diethylene glycol, and with 2-butyne-1,4-diol were synthesized by trans-esterification reactions. Proton nuclear magnetic resonance spectroscopy was used to elucidate the structures of the copolyesters. The intrinsic viscosities of the copolyesters were measured in o-chlorophenol at 30°C. The number-average molecular weights of these copolyesters were determined by using a vapor pressure osmometer. The thermal behaviors of the copolyesters were studied by differential thermal analysis and are discussed in terms of structural differences.     

Potentialities of the Voltammetry of 2-Butyne-1,4-diol at Mechanically Renewed Solid Electrodes

The electrochemical behavior of 2-butyne-1,4-diol was studied at solid platinum, gold, silver, cobalt, nickel, copper, and graphite electrodes. The working surfaces of the electrodes were renewed by cutting a thin 0.5-µm layer in the test solution immediately before recording every voltammogram. 2-Butyne-1,4-diol was oxidized in alkaline solutions at graphite, nickel, silver, and copper electrodes at positive potentials; the voltammograms obtained at these electrodes were suitable for analytical purposes. The dependence of the anodic current of 2-butyne-1,4-diol on its concentration was linear in the range from 0.03 to 0.3 g/L.__________Translated from Zhurnal Analiticheskoi Khimii, Vol. 60, No. 5, 2005, pp. 499–503.Original Russian Text Copyright © 2005 by Skvortsova, Aleksandrova, Kiryushov.     

Catalytic hydrogenation of 2-butyne-1,4-diol to 2-butene-1,4-diol at atmospheric pressure in the liquid phase

Selective hydrogenation of 2-butyne-1,4-diol to 2-butene-1,4-diol on suspended palladium and Raney nickel catalysts at atmospheric pressure was studied. The optimal parameters of this reaction were determined. Samples containing 90% 2-butene-1,4-diol were prepared.     

Reductive cleavage of C-OH bonds in allyl position-formation of gaseous products in the course of the cathodic reduction of some simple unsaturated alcohols

The problem of the reductive cleavage of C?OH bonds in allyl position has been considered starting from the literature data concerning the behaviour of allyl alcohol. The formation of hydrocarbons has been shown in the case of the electroreduction of crotyl alcohol, 2-butene-1,4-diol, propargyl alcohol, 2-butyne-1,4-diol and 1-butyne-3-ol. The composition of the gaseous products was analyzed, current efficiency values with respect to the hydrocarbon formation were calculated. Schemes for the reduction path were given.     

Raman-spectrum investigation of 2-butyne-1,4-diol 2-butyne-1,4-diol diacetate,and 1,4-dichloro-2-butyne

Summary 2-Butyne-1,4-diol, 2-butyne-1,4-diol diacetate, and 1,4-dichloro-2-butyne exist in cisoid and transoid forms because of the operation of factors hindering free rotation of individual groups of atoms in these molecules around the corresponding single bonds.     

Analysis of products from hydrogenation of 2-butyne-1,4-diol

Conclusions A qualitative and quantitative method has been developed for analysis of a mixture of butane-1,4-diol, cis-2-butene-1,4-diol, trans-2-butene-1,4-diol, and 2-butyne-1,4-diol in the form of their diacetates by gas chromatography.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 942–944, April, 1970.     

Liquid-phase catalytic hydrogenation of 2-butyne-1,4-diol to 1,4-butanediol at atmospheric pressure on suspended catalysts

The optimum parameters of hydrogenation of 2-butyne-1,4-diol to 1,4-butanediol on the suspended palladium and Ni-Raney catalysts at atmospheric pressure were found. In selected conditions a yield up to 90% of 1,4-butanediol was reached.