Al2O3催化克脑文格尔缩合反应

在Ａｌ２Ｏ３催化下活泼亚甲基化合物和羰基化合物进行克脑文格尔缩合反应，在温和的反应条件下得到较高收率的产物，将超声波辐射应用于该缩合反应使反应速度明量提高。     

FeCl3催化乙酰丙酮的炔丙基化反应

FeCl3,催化炔丙醇与乙酰丙酮在1,2-二氯乙烷中发生亲电加成反应得炔丙基化产物--3-炔丙基-2,4-戊二酮,其结构经1H NMR,13C NMR,IR和MS表征.于90℃反应8 h,产率80.9%-94.2%.     

FeCl3催化羰基化合物与芳烃的还原Friedel-Crafts烷基化反应

在二甲基氯硅烷作用下, FeCl3能催化羰基化合物(醛、酮)与芳烃及噻酚的还原Friedel-Crafts烷基化反应, 在温和的条件下一步实现羰基化合物的还原和C—C键的构造.     

3C化学位移与某些杂环化合物的取代反应

~（１３）Ｃ化学位移与某些杂环化合物的取代反应丁金昌（温州师范学院化学系３２５００３）近年来，杂环化合物在有机化学领域中发展很快，已越来越引起人们的重视。在杂环化合物的合成中，除了需合成一些杂环母核外，更多的是需要合成环上带有取代基的化合物，这些环上?..     

镧系金属用于有机反应的研究──NdCl_3／萘锂体系与羰基化合物的反应

由萘锂还原无水ＮｄＣｌ_３制得的活性金属Ｎｄ＊在与羰基化合物的反应中显示出较高的反应活性。该反应经水解可生成相应的醇、片呐醇和烯烃，其还原状态不仅与羰基化合物的性质有关，还取决于Ｎｄ＊：ＲＣＯＲ′的摩尔比以及反应温度和反应时间。本文还较详细地研究了Ｎｄ＊：二苯酮的反应，不同的Ｎｄ＊：二苯酮摩尔比以及外加配体或改变溶剂都将改变该反应的选择性。对该反应的机理亦进行了探讨。     

三水合稀土氯化物RECl3·3H2O的热化学研究

本文报道了一套化学反应绝热式热量计的设计和建立,用(HOCH_2)_3CNH_2与0.1mol·dm~3HCl的反应焓检验标定了热量计装置,测得ΔH_(208.15)=-245.41J·g~(-1),sdm=±0.24,与IUPAC的推荐值-245.76±0.26J·g~(-1)十分吻合,证明热量计和操作手续是可靠的。用这样的热量计测定了十一种三水合稀土氯化物RECl_3·3H_2O(RE=La,Ce,Nd,Sm,Eu,Gd,Tb,Dy,Er,Yb,Y)298.15K时在水中的积分溶解热(终浓度-0.01541mol·kg~(-1))。计算了这些水合物的标准生成焓和脱水焓。     

FeCl3催化作用下醇的氯代反应研究

氯代反应是将含氧基团化合物转化为氯代化合物的一种重要的反应方法。一般使用HCl,SOCl2/HMPT,PCl3,PPh3/CCl4,Vilsmeier-Haack试剂,Viehe盐等作为氯代试剂对醇类化合物的羟基进行氯代反应[1-5]。然而,在反应中因为氯化氢的产生,使该反应方法发生一些副反应,影响产物提纯和收率     

杂多酸化合物的酸催化反应

杂多酸化合物(Heteropoly Compounds下称HPC)是无机M—O簇型催化剂,由高对称中心的MO_x单元聚合组成(M=V,Mo,W,Nb,Ta等)的一类多核配合物。HPC既有酸     

阳极氰化反应的研究进展

本文综述了近30年来阳极氰化反应在有机电合成中的应用,主要回顾了阳极氰化胺、阳极氰化杂环化合物和阳极氰化芳香化合物的研究.此外,还报道了乳化技术在阳极氰化反应中的应用.     

FeCl3催化羰基化合物的还原卤代反应

在甲基二氯硅烷作用下, FeCl₃能催化羰基化合物(醛、酮)的还原氯代反应, 得到相应的氯代产物; 在甲基二氯硅烷、PBr₃或NaI作用下, FeCl₃可以催化羰基化合物(醛、酮)的还原溴代或碘代反应, 分别以良好的收率得到相应的溴代烷或碘代烷.     

Synthesis of p-Alkylcalixarenes by Friedel-Crafts Alkylation

Calix[n]arenes 1 - 3 (n = 4, 6 and 8) were alkylated with alkyl chlorides in the presence of anhydrous aluminium chloride in chloroform by Friedel-Crafts reaction to give p-alkylcalix[n]arenes 5 - 7 (n = 4, 6 and 8) in good to excellent yields.     

A New and Facile Synthesis of Novel Pyrazolothienopyrimidines and Imidazopyrazolothienopyrimidines

4‐Amino‐3‐methyl‐1‐phenyl‐1H‐thieno[2,3‐c]pyrazole‐5‐carboxamide ( 5 ), which was synthesized by an innovative method, was used as a versatile precursor for synthesizing pyrazolothienopyrimidines and imidazopyrazolothienopyrimidines compounds. Reaction of amino thienopyrazole carboxamide 5 with triethyl orthoformate afforded thienopyrazolopyrimidine 6 . Chlorination of the latter compound, using phosphorus oxychloride afforded the chloro pyrazolothienopyrimidine 7 , which underwent nucleophilic substitution reactions with various primary and secondary amines to give the alkyl (aryl) amino pyrimidine compounds 8a–d . On the other hand, the reaction of chloropyrimidine 7 with thiourea afforded the pyrimidine thione compound 9 , which was alkylated with α‐halogentaed compounds to afford the S‐alkylated derivatives 10a–c . Also, chloroacetylation of the amino carboxamide 5 using chloroacetyl chloride yielded the chloromethyl pyrazolothienopyrimidine 12 , which underwent nucleophilic substitu‐ tion reactions with various primary and secondary amines to afford the alkyl (aryl) aminomethyl compounds 13a–f . The latter Compounds underwent Mannich reaction to give imidazopyrimidothieno‐ pyrazoles 14a–c . The newly synthesized compounds and their derivatives were fully characterized by elemental and spectral analysis.     

Phase transfer catalysis in N-alkylations of the pharmaceutical intermediates 5H-dibenz[b,f]azepine and 5H-10,11-dihydrodibenz[b,f]azepine

The two title compounds were alkylated under very mild phase-transfer-catalysis conditions. Differences in reactivities of the two heterocyclic nucleophiles, and in the reactivities of various alkyl halides are discussed.     

Condensation of thiourea with uracyl derivatives containing ketone and ketoester fragments,alkylation and macrocyclization of the condensation products

By condensation of thiourea with 6-methyluracyl derivatives containing ketone and ketoester fragmenst in the alkyl chains attached to the nitrogen atoms of the pyrimidine ring the products containing 6-methyl- or 3,6-dimethyluracyl fragment and one or two 6-methyl-4-oxo-2-thio-1,2,3,4-tetrahydropyrimidin-5-yl fragments were synthesized. These compounds can be alkylated with alkyl bromides.     

Synthesis of Some Thienotetrahydroquinoline Derivatives

2‐Thioxo‐1,2,5,6,7,8‐hexahydroquinoline‐3‐carbonitrile ( 2 ) was easily S‐alkylated to produce alkyl mercapto derivatives 3a‐g . The latter compounds were cyclized to afford thienotetrahydroquinolines 4a‐g . Several pyrimidothienotetrahydroquinolines 5a‐d , and 6a‐d were obtained from the condensation of compounds 4c‐f with different reagents. o‐Aminocarbohydrazide derivative 11 was reacted with aromatic aldehydes, acetylacetone, nitrous acid and CS₂ to afford compounds 12–15 . Compound 24 was coupled with aryldiazonium chloride to afford arylazo derivatives 25 . Also it condensed with aromatic aldehydes to give arylidene derivatives 26 . The latter compounds were reacted with malononitrile to give pyrano derivative 27 .     

Structure and mesomorphism of neodymium(III) alkanoates

The structural and thermal behavior of all members of the homologous series of neodymium(III) alkanoates, ranging from neodymium(III) butyrate to neodymium(III) eicosanoate are described. Neodymium(III) butyrate monohydrate, Nd(C3H7COO)3.H2O crystallizes in space group P1 (No. 2), Z = 2. The lattice parameters are a = 9.824(2) A, b = 11.974(2) A, c = 14.633(2) A, alpha = 86.21(2) degrees, beta = 75.92(2) degrees, gamma = 77.97(2) degrees. The crystal structure consists of ionic layers of neodymium ions, separated by bilayers of butyrate anions. In the ionic layers, the neodymium ions are connected by bridging tridentate carboxylate groups to zigzag chains, whereas the chains are connected among themselves by bridging bidentate carboxylate groups. The two crystallographically different neodymium ions are both having coordination number 9, with a geometry close to a monocapped square antiprism. The structure of the higher homologues can be derived from the structure of neodymium butyrate by extending the alkyl chains. These compounds have a lamellar bilayer structure with planes of neodymium(III) ions coordinated to the carboxylate groups and with the alkyl chains in an all-trans conformation. All homologous compounds from neodymium(III) pentanoate to neodymium(III) pentadecanoate display a thermotropic mesophase, which was identified by high-temperature X-ray diffraction as a smectic A phase. For the series from neodymium(III) pentanoate to neodymium(III) undecanoate an additional high viscosity mesophase is present between the crystalline state and the smectic A mesophase.     

Highly trans-1,4 selective (co-)polymerization of butadiene and isoprene with quinolyl anilido rare earth metal bis(alkyl) precursors

The N-R-quinolinyl-8-amino ligands HL(1-3) (R = 2,6-(i)Pr(2)C(6)H(3) (HL(1)), 2,6-Et(2)C(6)H(3) (HL(2)), 2,6-Me(2)C(6)H(3) (HL(3))) have been prepared, which reacted readily with one equiv. of rare earth metal tris(alkyl)s to afford the corresponding bis(alkyl) complexes L(1)Y(CH(2)SiMe(3))(2)(THF) (1) and L(1-3)Lu(CH(2)SiMe(3))(2)(THF) (2-4) via alkane elimination. Contrastingly, treatment of the in situ generated neodymium tri(alkyl)s with HL(1) afforded a mono(alkyl) neodymium complex (5). Complexes 1, 2 and 5 in combination with aluminium alkyls and organoborates established homogenous ternary systems that exhibited versatile catalytic activities and trans-1,4 selectivities for the polymerization of butadiene, depending on the types of aluminium alkyl, organoborate and rare earth metal used. Furthermore, the trans-1,4 selective copolymerization of butadiene and isoprene was achieved by using the ternary system of 1/AlMe(3)/[Ph(3)C][B(C(6)F(5))(4)]. Both the kinetics of copolymerization and the thermal behavior of the copolymers were investigated.     

乙烯线性齐聚的研究 X．烷氧基锆的催化性能

乙烯线性齐聚的研究Ｘ．烷氧基锆的催化性能何仁，于净，卫锋（大连理工大学化工学院，大连１１６０１２）关键词乙烯，齐聚，直链ａ－烯烃，锆络合物，叔膦乙烯线性齐聚是合成直链低碳ａ一烯径最先进的方法．直链低碳ａ一烯烃是重要的共聚单体和合成许多精细化学品的原料...     

A Convenient Synthesis of 3-Behzyl, 3-Benzyl-4-Substituted Coumarins and Their Benzo Derivatives

It is reported in the literature that alkylation of simple (unsubstituted) phosphorane with alkyl halide in ethyl acetate leads to equimolar mixture of alkylated phosphorane and salt of the unsubstituted phosphorane. Here we report exclusive formation of alkylated phosphorane from its salt from benzyl bromide in chloroform. This alkylated phosphorane (2) on reaction with 2-hydroxy carbony1 compounds (1a-1) provide E-ethyl Oc-benzyl cinnamates in high yields which on thermal cyclisation gave 3-benzylf 3-benzyl-4-substituted and benzocoumarins. Thus this method can be used conveniently to synthesise above compounds in good yields.     

25,26-Dialkoxycalix[4]arenes. Part 2: 1-Alkoxy-3-benzoyloxy route

Benzoylation of calix[4]arene monoalkyl ethers with benzoyl chloride yielded the corresponding 3-benzoates and/or 2,3-dibenzoates in different reaction conditions. A simple recrystallization process was able to isolate the 3-benzoates in good yield. In the presence of NaH as reaction base, the 1-alkoxy-3-benzoyloxycalixarenes were alkylated with active alkyl halides at proximal position and yielded the corresponding 1,2-dialkoxy derivatives. Basic hydrolysis of compounds afforded the expected 25,26-dialkoxycalix[4]arenes. For the less active alkyl halides, alkylation of 1-alkoxy-3-benzoyloxycalix[4]arenes afforded both the 1,2-dialkoxy derivatives and the benzoyl-migrated 1,3-dialkoxy derivatives. Only the highly symmetrical 1,3-diethoxy-2-benzoyloxycalix[4]arene was able to be isolated upon the deliberate recrystallization process. After basic hydrolysis of the dialkylated crude products, 25,26-dialkoxycalix[4]arenes were chromatographic separated.