潘多拉唑中间体2-巯基-5-二氟甲氧基-1-氢-苯并咪唑的合成工艺改进

2-硝基-4-二氟甲氧基苯胺在Raney-Ni催化下被水合肼还原,还原产物不经分离直接用于制备标题化合物,总收率达到94％。方法操作简便,安全可靠,适合于工业化生产。对另外几种取代的邻硝基苯胺进行了相同的还原试验,也取得了理想的结果,这为寻找新的具有生理活性的质子泵抑制剂提供了一条安全、有效的途径。     

取代芳(硫)醚峭基物的水合肼催化还原研究

取代芳(硫)醚氨基化合物是重要的制药中间体,本文采用FeCl3.6H2O/C催化下水合肼还原取代芳(硫)醚硝基物,高收率、高纯度制得取代芳(硫)醚氨基化合物.该工艺具有操作方便、后处理简单等特点,反应过程易操控,对设备要求不高,安全可靠,对环境污染小,更适合于工业化生产.4个实例产物收率为85.0%～95.3%,GC纯...     

虫酰肼的合成

以叔丁基肼盐酸盐为起始原料,与对乙基苯甲酰氯反应合成N-(4-乙基苯甲酰基)-N'-叔丁基肼,反应收率97.9%。其再与3,5-二甲基苯甲酰氯反应合成虫酰肼,纯度大于96%,总收率大于86%。     

聚三唑的后修饰

目的:对合成的聚三唑进行后修饰。方法:先用水合肼还原聚三唑重复单元上的酯基,将酰肼基团引入到聚合物结构中。在碱性条件下酰肼基团与二硫化碳反应。然后再与水合肼发生反应环合。酸化后得到侧基为氨基和巯基取代的1,2,4-三氮唑环修饰的聚三唑。     

虫酰肼的合成

以叔丁基肼盐酸盐为起始原料,与对乙基苯甲酰氯反应合成N-(4-乙基苯甲酰基)-N′-叔丁基肼,反应收率97.9%。其再与3,5-二甲基苯甲酰氯反应合成虫酰肼,纯度大于96%,总收率大于86%。     

镍基复合催化剂催化邻硝基苯胺加氢合成邻苯二胺

采用镍基复合催化剂,分别以水、乙醇为溶剂,邻硝基苯胺氢化合成邻苯二胺。实验结果表明,在水中,温度85-105℃、压力1．5MPa下收率为72％-78％（以邻硝基苯胺计）;在乙醇中,温度45℃、压力0．8～1．5MPa下收率为82％-91％（以邻硝基苯胺计）。以乙醇为溶剂镍基复合催化剂催化加氢法与传统的硫化碱还原或铁粉还原工艺相比,在减少废水和降低成本等方面有较大的优势。     

含吲哚基1,3,4-噻二唑双腙的合成

冰乙酸为催化剂,2,5-二肼基-1,3,4-噻二唑与取代吲哚-3-甲醛在乙醇中缩合反应,得到了4种新型含吲哚基的1,3,4-噻二唑类双腙化合物,其结构经IR,1 H NMR所证实。最佳反应条件为:反应温度90℃,n(2,5-二肼基-1,3,4-噻二唑)∶n(取代吲哚-3-甲醛)=1.0∶2.4,反应时间4h,收率75.5%~81.0%。     

2-（2-噻吩）乙胺合成工艺研究

研究了2-（2-噻吩）乙胺的合成工艺.噻吩甲醛与丙二酸经Knoevenagel-Doebner缩合生成3-（2-噻吩）丙烯酸,收率87%.3-（2-噻吩）丙烯酸与氯化亚砜和氨作用生成3-（2-噻吩）丙烯酰胺,收率91%;铜盐催化下用水合肼还原3-（2-噻吩）丙烯酰胺生成3-（2-噻吩）丙酰胺,收率99%;3-（2-噻吩）丙酰胺经Hoffman降解得2-（2-噻吩）乙胺,收率64%.由核磁共振氢谱、质谱和液谱对产物及中间体的结构和纯度进行了表征.     

5-碘-2-甲基苯并咪唑的合成和工艺改进

文中阐述了由邻硝基苯胺经过卤化、还原和闭环三步合成5-碘-2-甲基苯并咪唑的新的反应工艺,并对工艺进行了优化。考察了碘化中I2和氧化剂H2O2的用量,还原阶段中催化剂Raney Ni的使用量、反应中压力的影响,以及闭环阶段催化剂醋酸的用量、反应时间、反应温度对反应收率的影响。通过研究,获得了最优工艺条件,在优化条件下总收率达到75.1%。     

α-(对硝基苯氧基)十四酸酰肼的合成

报道了α-(对硝基苯氧基)十四酸酰肼的合成方法。以十四酸为原料经α-(对硝基苯氧基)十四酸乙酯中间体,用水合肼肼解得到α-(对硝基苯氧基)十四酸酰肼。用乙腈-氯仿混合溶剂重结晶获得纯品,收率67.9%。通过元素分析、红外光谱及核磁共振谱确定了该化合物的结构。     

Synthesis of 3,6-diaryl-1,4,5-thiadiazepines from substituted 2-thiocyano acetophenone and investigation of reaction mechanism

In this work, we have studied the reaction of substituted 2-thiocyanoacetophenone and hydrazine hydrate as a novel and simple pathway for the preparation of the substituted 1,4,5-thiodiazepine ring system. The mechanism of this reaction revealed that in the initial step condensation of hydrazine with carbonyl groups of substituted 2-thiocyanoacetophenons 2a–2f gives the corresponding substituted aromatic dithiocyano azide intermediates which in turn undergo cyclization to1,4,5-thiadiazepines in the presence of hydrazine. This cyclization is a novel method for the preparation of sulfide bond from the reaction of hydrazine and a dithiocyano intermediate. An account of the reaction mechanism is given.     

芳硝基物水合肼催化氢转移还原研究

采用自制廉价催化剂、水合肼为清洁还原剂研究了不同结构芳硝基物的水合肼催化氢转移还原反应,发现取代基的性质及位置对水合肼还原反应均有影响,苯环上吸电子基的存在有利于硝基还原;水合肼还原法不还原蒽醌结构中的醌式羰基。在水合肼用量接近理论量的前提下,N-甲基-4-硝基苯胺、N-甲基-N-(4'-硝基苄基)-4-甲基苯磺酰胺、4,4'-二硝基二苯砜的水合肼还原产品收率分别达到99%、97%、92%。实验中以高效液相色谱对还原反应过程进行跟踪分析,分别采用大气压离子化质谱(APCI-MS)、核磁共振谱及红外光谱对还原产物的结构进行了表征。     

水杨醛缩肼基二硫代甲酸苄酯类Schiff碱配体的合成

由水合肼、CS2与取代的溴化苄在低温条件下反应,合成肼基二硫代甲酸苄酯类化合物,再在无水乙醇体系中及高温回流条件下与取代的水杨醛进行反应,合成了一系列标题化合物,其结构经质谱、紫外光谱、红外光谱、元素分析及1H核磁共振等进行表征.     

Synthesis of pyrazolo[4′,3′:5,6]pyrido[1,2-a]benzimidazole derivatives and study of their fluorescence properties

Synthesis of pyrazolo[4′,3′ :-5,6′pyrido]1,2-a benzimidazoles was achieved by the condensation of 1-chloro-2-formyl-3-methyl pyrido[1,2-a]benzimidazole-4-carbonitrile and 1-chloro-3-methyl pyrido[1,2-a]benzimidazole-2,4-dicarbonitrile with hydrazine hydrate and phenyl hydrazine. The fluorescence properties of the resulting compounds were studied. Some of the compounds when applied on polyester fibres as fluorescent brighteners gave excellent results.     

2,2-二(3-氨基-4-羟基)苯基丙烷的合成与结构表征

分别在Pd/C、FeOOH和FeCl3·6H2O/C三种不同催化剂存在下,由水合肼还原2,2 二(4 羟基 3 硝基)苯基丙烷(1)合成了2,2 二(3 氨基 4 羟基)苯基丙烷,筛选出成本低、收率高的理想催化剂为FeCl3·6H2O/C。当物料配比n(水合肼):n(1)=5:1,反应起始温度为70℃,反应时间为80min时,收率为93 0%。产物经重结晶纯化后,由元素分析、红外光谱、核磁共振谱和质谱对其结构进行了表征,确证了产物的结构。     

Reactions of fatty acid chlorides: II. Synthesis of monohydrazides or dihydrazides by acylation of hydrazine hydrate with saturated fatty acid chlorides

The acylation of hydrazine hydrate with a series of saturated fatty acid chlorides containing from eight to 18 carbon atoms was studied under a variety of conditions in order to obtain the desirable fatty acid monohydrazides. Optimum yields were obtained (ranging from 31.5% to 75% as the series ascended from C-8 to C-18) for the even-numbered monohydrazide members through the use of a large excess of hydrazine hydrate in several organic solvents. Diethyl ether was found to be suitable if the acid chloride is dissolved in it and added slowly to a cold mixture of hydrazine hydrate in ether. The Schotten-Baumann technique was found suitable for the preparation of the symmetrically substituted fatty acid dihydrazides in better than 82% yields when one mole of hydrazine hydrate was acylated with two of acid chlorides. Physical and chemical properties of both series of fatty nitrogen derivatives are briefly treated. Stearic monohydrazide was condensed with acetonylacetone to give a substituted pyrrole. An unsymmetrical dihydrazide was prepared by the acylation of myristic monohydrazide with lauroyl chloride. Stearic dimethylhydrazide was prepared by the acylation of dimethylhydrazine with stearoyl chloride. Two quaternizations of this product were carried out. Part I. JAOCS31, 151 ({dy1954}). Presented at the AOCS Meeting, New York, October 1960.     

水中CuO-Al_2O_3催化水合肼还原芳香族硝基化合物

以NaOH溶液快速沉淀CuC l2和A lC l3的混合溶液制备了催化剂CuO-A l2O3,当n(CuO)∶n(A l2O3)=1∶2时所得催化剂性能最好。在水中,以邻硝基甲苯为底物,考察了几种因素对反应的影响。较优的反应条件为:4.11 g(30 mmol)邻硝基甲苯,3.53 g(60 mmol)水合肼,0.45 g CuO-A l2O3,80℃反应50 m in。在此条件下邻甲基苯胺的收率达到98%。在同样的条件下,CuO-A l2O3催化水合肼,几种还原芳香族硝基化合物得到相应的芳胺,收率90%~99%。     

水合肼催化还原对硝基苯乙酸的研究

研究了以水合肼为还原剂，FeCl3.6H2O/C为催化剂，对硝基苯乙酸还原为对氨基苯乙酸的反应。对反应条件的探讨表明，水合肼浓度为70％，pH值为5，回流8h，产率可达89％。     

Evolution of copper nanowires through coalescing of copper nanoparticles induced by aliphatic amines and their electrical conductivities in polyester films

Copper nanowires were synthesized by the wet chemical reduction method using copper sulfate as the copper precursor, aliphatic amines (methylamine, ethanediamine, 1,2-propanediamine) as the inducing reagents, and hydrazine hydrate as the reductant through the aging and reduction processes. The high-resolution transmission electron microscopy (HRTEM) images reveal that the copper nanowires were synthesized by coalescing extremely small-sized copper nanoparticles with the particle sizes of 1–6 nm in copper complex micelles. A longer aging time period favored the coalescing of the copper nanoparticles to form thinner copper nanowires in the following reduction process. The coalescing extent of copper nanoparticles in copper nanowires was highly enhanced by ethanediamine and 1,2-propanediamine as compared with that by methylamine. The copper nanowire-filled polyester films had higher electrical conductivity than the copper nanoparticle-filled ones.