带手性酰胺醇侧链的1，5－二氮环辛烷的合成

用手性α－氨基醇和氯乙酰氯作用得到的手性酰胺醇（2a－2f）和1，5－二氮 环辛烷反应，合成了带手性侧臂的1，5－二氮环辛烷衍生物N，N’-二[（S）／（ R）－N－（1－羟甲基羟基）－乙酰胺－2]－1，5－二氮环辛烷（1a－1f）。     

2－乙基－1－（α－呋喃基）－1－戊烯－4－炔－3醇的合成

２－乙基－１－（α－呋喃基）－１－戊烯－４－炔－３醇的合成肖蓉，孙悦（成都科技大学化学系６１００６５）涂君俐（中国科学院成都有机化学研究所，６１００４１）蚊香和电热片是拟除虫菊醋类药剂，也是家庭卫生用药的代表性剂型。如果能开发出挥发性高，在非加热条件...     

2－甲基－3－芳基－7－（5，5－二甲基－3－酮－1－环己烯－1－基）甲酸酯－4（3H）－喹唑啉酮的合成

以2－氨基对苯二甲酸（1）为起始原料，与乙酸酐缩合生成7－羧基乙酰苯邻 甲内酰胺（2）；2和芳胺缩合产生7－羧基－2－甲基－3－芳基－4（3H）－喹唑啉 酮（3）；3和N，N－双环己基碳双亚胺（DCC）加成得到中间体4，4在4－二甲氨基 吡啶（DMAP）催化下和5，5－二甲基－1，3－环己二酮（5）缩合得到目标产物2－ 甲基－3－芳基－7－（5，5－二甲基－3－酮－1－环己烯－1－基）甲酸酯－4（ 3H）－喹唑啉酮（6）。所得15个新型化合物的结构均经^1H NMR、元素分析确证， 部分化合物经IC／MSD确证。     

x－甲基丙烯酸2，3－环氧丙基酯与α－甲基丙烯酸甲酯嵌段共聚物的合成与鉴定

α－甲基丙烯酸２，３－环氧丙基酯与■－甲基丙烯酸甲酯嵌段共聚物的合成与鉴定张洪敏侯元雪程■（北京化工大学高分子系北京１０００２９）关键词■－甲基丙烯酸２，３－环氧丙基酯，甲基丙烯酸甲酯，嵌段共聚物■－甲基丙烯酸２，３－环氧丙基酯（ＥＰＭＡ）含有两个可...     

α－甲基丙烯酸2，3－环氧丙基酯的选择性阴离子聚合

通过对α－甲基丙烯酸２，３－环氧丙基酯双键的选择性阴离子聚合的研究发现：在较低温度下（＜－４０℃），聚合中的副反应主要发生在引发阶段，以引发剂与单体中环氧基的副反应为主；当温度较高时（＞－２０℃），则易出现交联现象而难以进行双键的选择性聚合。ＧＰＣ、１ＨＮＭＲ及ＦＴＩＲ鉴定表明，在较低温度下用１，１′二苯基己基锂作引发剂可合成每个重复单元上均定量带有的环氧基的单分散（　＜１．１０）官能性聚合物，该聚合物易溶于多种溶剂。     

手性氨基醇（R）－2－氨基－1，1－二苯基－3－（2－萘基）－1－丙醇：制备及其对前手性酮硼烷还原的对映选择性催化作用

用丙二酸酯法合成了Ｎ－乙酰基－３－（２－萘基）－ＤＬ－α－丙氨酸乙酯３．３经酶法拆分，得光学活性的Ｄ－３，后者经盐酸水解、酯化后再与苯基溴化镁作用，制得标题化合物６。在０．５ｍｍｏｌ６存在下，用过量硼烷对一系列前手性酮还原，得到了相应的光学活性二级醇。对映体过量（ｅ．ｅ值）５７．０～１００％。     

水溶剂中芳醛与5，5－二甲基－1，3－环己二酮的反应

芳醛1与5，5－二甲基－1，3－环己二酮（2）在氯化三乙基苄基铵（TEBA）催 化下在水中生成2，2'－芳业甲基双（3－羟基－5，5－二甲基－2－环己烯－1－酮 ）（3），若在体系中有对甲苯磺酸存在时则生成3，3，6，6－四甲基－9－芳基－ 1，8－二氧代八氢化氧杂蒽（4）或3，3－二甲基－9－（3－羟基－5，5－二甲基 －2－环己烯－1－酮－2－基）－1－氧代四氢代氧杂蒽（6）而不是生成3，产率接 近定量。     

苯甲酸（1H－1，2，4－三唑－1－基）－3，3－二甲基－2－丁酮酯衍生物的合成

用冠醚作催化剂，通过苯甲酸盐同１－溴代－１－（１Ｈ－１，２，４－三唑－１－基）－３．３－二甲基丁酮－２－反应，合成了一系列苯甲酸（１Ｈ－１，２，４－三唑－１－基）－３，３－二甲基－２－丁酮酯类新化合物，并对合成方法进行了探讨。通过ＩＲ、￣１ＨＮＭＲ及元素分析，确定了化合物的结构。     

双－（3－烷基／芳基）－7H－1，2，4－三唑并[3,4-b]-1,3,4-噻二嗪类化合物的合成及波谱性质

利用1，4－二溴丁二酮（1）分别与3－烷基／芳基－4－氨基－5－巯基－1， 2，4－三唑（2a-2n）反应，合成了14种新的双－（3－烷基／芳基）－7H－1，2， 4－三唑并[3,4-b]－1，3，3-噻二嗪类化合物（3a-3n），并利用EA、IR，~1H NMR和MS确定了其结构。     

二氯菊酸2－甲基－3－（2－呋喃基）－2－丙烯酯的合成

报导了一种新拟除虫菊酯的设计和合成。标题化合物是由二氯菊酰氯与新自制的２－甲基－３－（２－呋喃基）－２－丙烯－１－醇酯化合成。     

2-[2-(4,6-二甲基)-嘧啶基]-4-苯基-1,2,4-噁二唑烷-3,5-二酮的合成

异氰酸苯醇和N-[2-(4,6-二甲基)-嘧啶基]-羟胺(5)反应生成1-[2-(4,6-二甲基)-嘧啶基]-1-羟基-3-苯基脲(6)。化合物(6)在三乙胺存在下和氯甲酸乙醇反应生成2-[2-(4,6-二甲基)-嘧啶基]-4-苯基-1,2,4-噁二唑烷-3,5-二酮(1)。     

Molecular and Crystal Structure of 1- ( 2- chloro) - Benzoyl - 3- (4- methylphenyl ) Thiourea

1　INTRODUCTIONBenzoylphenyltioureas having a generalformula( ) were reported to have in secticidalactivity〔1〕,which isclosely related to theirstructures,particularly tothedi hedralangle between the- CONH- plane and phenylring〔2〕.Surprisingly there islittle reported in the literature,only three related structures stored in CSD〔3〕 until1 998.In thispaper,we reportthe crystalstructure ofthe title compound.R CONHCSNHR2　EXPERIMENTAL2 .1　Synthesis　　The synthesisofthetitl…     

[Z]-2-(芳基锡基)-1-(9-芴醇)乙烯的合成、结构与性质

用三苯基氢化锡,三对甲苯基氢化锡作为锡氢化试剂与9-乙炔基-9-芴醇进行反应,合成了2个有机锡化合物:[Z]-2-(三苯基锡基)-1-(9-芴醇)乙烯(1)和[Z]-2-(三对甲苯基锡基)-1-(9-芴醇)乙烯(2)。化合物1和2分别与ICl,Br~2,I~2反应,得到6个有机锡一卤化物,6个有机锡二卤化物和2个有机锡混合卤化物(3-16)。有机锡一碘化物7,13和有机锡二碘化物8,14与KOH乙醇溶液反应,分别得到相应的有机锡氢氧化物17,18和有机锡氧化物19,20。有机锡二碘化物8,14分别与含氮双齿配体1,10-邻菲罗啉(Phen),2,2'-联吡啶(Bipy),8-羟基喹啉(Oxin)反应,得到6个相应的配合物21-26。26个新化合物通过元素分析,锡含量测定,IR,^1HNMR测定对其结构进行了表征。同时测定了化合物2的晶体结构,晶体属单斜晶系,空间群P2~1/c。化合物2是以Sn原子为中心扭曲的四面体构型。     

(S)-2-氨基-1,1-二苯基-1-丙醇的合成和外消旋Droxidopa前体的拆分

(S)-2-氨基-1,1-二苯基-1-丙醇是一种合成多种手性助剂的重要中间体,也用于外消旋屈昔多巴前体化合物的拆分。从价廉易得的L-丙氨酸出发,通过四步反应制得,总收率55.6%L-丙氨酸经甲酯化,苄氧羰基保护制得的L-2-苄羰基氨基丙酸甲酯与苯基溴化镁反应制得(S)-2-苄氧羰基氨基-1,1-二苯基-1-丙醇。是在5%Pd/C催化加氢下脱除苄氧羰基得到标题化合物。该制备方法涉及的中间体及目标化合物易于纯化,总收率高且重现性好。我们用制得的氨基醇能成功地拆分外消旋苏式屈昔多巴前体化合物3-3,4-二苄氧苯基)-N-苄氧羰基丙氨酸。     

5-[5-(3-吡啶)-2H-四唑亚甲基]-2-芳酰氨基-1,3,4-噻二唑的合成

本文首先用5-(3-吡啶)-2H-四唑乙酰基酰肼与芳酰基异硫氰酸盐反应制备成化合物1-[5-(3-吡啶)-2H-四唑乙酰基]-4-芳酰氨基硫脲化合物1a～j, 然后用冰醋酸回流处理1a～j得到一系列化合物5-[5-(3-吡啶)-2H-四唑亚甲基]-2-芳酰氨基-1,3,4-噻二唑2a～j . 化合物1a～b在强碱介质中首先发生降解, 然后进行环化反应 .     

1-(2-Quinoxalyl)-, 1-[3,5-Di(trifluoromethyl)phenyl]-, 1-(2-Carboxyphenyl)-, and 1-Ethoxycarbonyl-4-oxo-4,5,6,7-tetrahydroindazoles

The corresponding 1-(2-quinoxalyl)-, 1-[3,5-di(trifluoromethyl)phenyl]-, and 1-ethoxycarbonyl-3-methyl-4-oxo-4,5,6,7-tetrahydroindazoles have been obtained from reactions of 2-acetyl-1,3-cyclohexanedione, its 5,5-dimethyl and 5-(2-furyl) derivatives, with 2-hydrazinoquinoxaline, 3,5-di(trifluoromethyl)phenylhydrazine, and ethoxycarbonylhydrazine. On interaction with ethoxycarbonylhydrazine the intermediate 2-[1-(-ethoxycarbonyl)hydrazino]ethylidene-1,3-cyclohexanediones were also isolated. From the potassium salt of 2-formyldimedone and 2-carboxyphenylhydrazine hydrochloride, 2-(2-carboxyphenyl)hydrazinomethylene-5,5-dimethyl-1,3-cyclohexanedione was obtained, the cyclization of which in ethanol in the presence of HCl led to 1-(2-carboxyphenyl)- and 1-(2-ethoxycarbonylphenyl)-6,6-dimethyl-4-oxo-4,5,6,7-tetrahydroindazole.     

Study on the Crystal Structure of RS-1-(2-methoxyphenyl)-4-〔3-(1-naphthyloxy)-2-hydroxypropyl〕-piperazine

ＩＮＴＲＯＤＵＣＴＩＯＮＮａｆｔｏｐｉｄｉｌ，ＲＳ １ （２ ｍｅｔｈｏｘｙｐｈｅｎｙｌ） ４ 〔３ （１ ｎａｐｈｔｈｙｌｏｘｙ） ２ ｈｙｄｒｏｘｙｐｒｏｐｙｌ〕 ｐｉｐｅｒａｚｉｎｅ，ｉｓａｎｏｖｅｌａｎｔｉｈｙｐｅｒｔｅｎｓｉｖｅｄｒｕｇｃｕ...     

1-(1-Phthalazinyl)- and 1-(4methoxyphenyl)-6,6dimethyl-4oxo-4,5,6,7-tetrahydroindazole

2-(1-Phthalazinylhydrazino)methylene-(IIIa) or 2-(1-phthalazinylhydrazino)ethylidene-5,5-dimethyl-1,3-cyclohexanediones (IIIb) were prepared from 1-hydrazinophthalazine and 2 formyl- or 2-acetyldimedone. Cyclization of IIIb in the presence ofp- TsOH gave 1-(1-phthalazinyl)3, 6, 6-trimethyl-4-oxo-4, 5, 6, 7-tetrahydroindazole. Reaction of 4-methoxyphenylhydrazine with 2 formyl- and 2-acetyidimedone gave the corresponding 1-(4methoxyphenyl)-4-oxo-4, 5, 6, 7-tetrahydroindazole. In the case of 2 -formyldimedone the intermediate 2-(4methoxyphenylhydrazinomethylene)-5, 5-dimethyl-1,3-cyclohexanedione was isolated.Riga Technological University, Riga LV-1658. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 708–710, May, 1996. Original article submitted December 31, 1995.     

A theoretical study on 1-(thiophen-2-yl-methyl)-2-(thiophen-2-yl)-1H-benzimidazole

The molecular geometry and vibrational frequencies of 1-(thiophen-2-yl-methyl)-2-(thiophen-2-yl)-1H-benzimidazole (C(16)H(12)N(2)S(2)) in the ground state has been calculated using the Hartree-Fock (HF) and density functional method (B3LYP) with 6-31G(d) basis set. The optimized geometric bond lengths and bond angles obtained by using HF and DFT (B3LYP) show the best agreement with the experimental data. Comparison of the observed fundamental vibrational frequencies of 1-(thiophen-2-yl-methyl)-2-(thiophen-2-yl)-1H-benzimidazole (C(16)H(12)N(2)S(2)) and calculated results by density functional B3LYP and Hartree-Fock methods indicate that B3LYP is superior to the scaled Hartree-Fock approach for molecular vibrational problems.     

Synthesis and calcium antagonistic activity of (+)-(R)- and (-)-(S)-3-acetyl-2-[5-methoxy-2-[4-[N-methyl-N-(3,4,5- trimethoxyphenethyl)amino]butoxy]phenyl]benzothiazoline hydrochloride

SA2572 ((+)-1), 3-acetyl-2-[5-methoxy-2-[4-[N-methyl-N-(3,4,5-trimethoxyphenethyl) amino] butoxy]phenyl]-benzothiazoline hydrochloride is a newly synthesized Ca2+ antagonist having a inhibitory effect on the fast Na+ inward channel. In order to clarify the absolute configurations and the pharmacological properties of both enantiomers, compounds ((+)-1 and (-)-1) were synthesized. The configurations of these compounds were assigned on the basis of an X-ray crystallographic analysis of synthetic precursor (5). The in vitro Ca2+ channel blocking activities of (+)-1 and (-)-1 were evaluated in terms of the inhibitory activities on depolarization-induced contraction of guinea pig taenia cecum and rabbit aorta. The in vivo efficacy of the enantiomers was evaluated with their hypotensive effects in spontaneously hypertensive rats. Compound (-)-1 showed more potent Ca2+ antagonistic activities on guinea pig taenia cecum and rabbit aorta and the hypotensive effect than those activities of (+)-1. In the electrophysiological study of Langendorff perfused rabbit hearts, compound (+)-1 showed more potent inhibitory effect on the fast Na+ inward channel than that of compound (-)-1, and an approximately equal potent inhibitory effect on the slow Ca2+ inward channel as compared with compound (-)-1. Stereoselectivity of the pharmacological activity was found.