新型含2—苯基—1，2，3—三唑基的1，5—苯并硫氮杂Zhuo及其β—内酰胺衍生物的合成

α，β－不饱和酮（1a-1e）与邻氨基苯硫酚反应，得到含2－苯基－1,2,3-三唑基的1，5－苯并硫氮杂Zhuo(2a-2e），然后以其为原料与烯酮“现场”进行[2 2]环加成，合成出一系列含2－苯基－1，2，3－三唑基的β－内酰胺并合的1，5－苯并硫氮杂Zhuo衍生物（3a-3j），产物经^1H NMR,IR，元素分析及MS加以确证。     

新型氮杂蒽醌衍生物的设计、合成及抗肿瘤活性

以氮杂蒽醌为母核结构，通过引入卤素和氨基侧链，设计并合成了4种新型的氮杂蒽醌衍生物（AQ-1~4）。其中，以异喹啉为起始原料，依次经氧化，脱水和傅克环酰化反应，制得6,9-取代苯并[g]异喹啉-5,10-蒽醌卤代衍生物（AQ-1和AQ-2）; AQ-F与胺类化合物发生芳环亲核取代反应，合成了6,9-二取代苯并[g]异喹啉-5,10-蒽醌衍生物（AQ-3和AQ-4），其结构经¹H NMR, ¹³C NMR和HR-MS（ESI）表征。采用CCK-8法研究了AQ-1~4对人肺癌细胞（A549），人乳腺癌细胞（MCF 7）和人宫颈癌细胞（Hela）的体外抗肿瘤活性。结果表明：AQ-4的抑制活性最好，IC₅₀分别为14.84 μmol·L^-1, 10.36 μmol·L^-1和10.55 μmol·L^-1。     

含（1—芳乙酰胺基—2—叔胺基）乙烷结构的六氢—1H—1，4—二氮Zhuo类新化合物的合成（Ⅰ）

合成了N,N′－二苄基－2－甲氧羰基－六氢－1H－1,4－二氮Zhuo（3）。3经还原、氯取代、胺取代、胺脱苄、单酰化及酰化反应后得到了10个带有（1－久乙酰胺基－2－叔氨基）乙烷结构的六氢－1H－1,4－二氮Zhuo类目标化合物（9a-9i和10）。     

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。     

3-(1-氢多氟烯基)-1-氧代-2，4，1-苯并噁嗪与双亲核试剂反应合成含氟杂环化合物

本文研究了3-(1-氢多氟烯基)-1-氧代-2，4，1-苯并噁嗪1与几种双亲核试剂的反应。化合物1与乙二胺反应生成7-氟烷基-1，4-二氮杂卓[1，2-d]喹唑啉-11-酮；在吡啶溶剂中与盐酸羟胺反应得到了2-氟烷基异噁唑[3,2-b]并喹唑啉-9-酮；与邻苯二胺反应得到2-氟烷基苯并咪唑类化合物。     

5-羟基-3,4-二氢异喹啉-1-酮的合成

以异喹啉为起始原料,经成盐、磺化得异喹啉-5-磺酸(3),3与熔融的氢氧化钠和氢氧化钾反应得1,5-二羟基异喹啉(4),以5%Pd-C为催化剂还原4得5-羟基-3,4-二氢异喹啉-1-酮(1),总收率47.6%。1的结构经1H NMR和MS确证。     

微波作用下1，5－苯并硫氮杂Zhuo－α－氨基－β－内酰胺衍生物的合成及晶体结构

甘氨酸N－端保护试剂邻苯二甲酰亚胺乙酰氯、1，5－苯并硫氮杂Zhuo在三乙 胺的存在下，用微波辐射合成了5个1，5－苯并硫氮杂Zhuo-α－氨基－β－内酰胺 衍生物，反应在6min内完成，产率较为满意。X射线衍射分析确定了产物的立体结 构，结果表明，微波辐射下的反应为立体 专一性反应，β－内酰胺环上的两个取 代基位于环的同侧为顺式。     

2-取代-3,4-二氢-1-异喹啉酮的合成及其血管舒张活性

以3-羟基-4,5-亚甲二氧基苯甲酸甲酯或5-羟基-1,3-苯二甲酸二甲酯为原料,经烯丙基醚化、Claisen重排、氧化、与伯胺反应(生成Schiff碱)、还原、分子内酯的酰化合成了4种新的2-取代-3,4-二氢-1-异喹啉酮(1a～1d),其结构经1HNMR和MS表征。离体动脉环张力实验证明1在浓度为1×10-4mol.L-1时具有明显舒张血管的作用。     

Bischler-Napieralski反应合成那可丁及其衍生物的立体化学

对通过Bischler-Napieralski反应制备的那可丁及其衍生物的立体选择性进行了研究. 以N-β-(3-甲氧基-4,5-亚甲二氧基苯基)乙基-6 ,7 -二甲氧基苯并呋喃酮-3-酰胺(1)和N-β-(3,4-亚甲二氧基苯基)乙基-6 ,7 -二甲氧基苯并呋喃酮-3-酰胺(2)为原料, 经Bischler-Napieralski反应和硼氢化钠还原制得五对苯酞类四氢异喹啉类化合物对映体3, 4a, 4b, 5a, 5b, 其中3和5a经氮甲基化反应得到外消旋的那可丁(α-narcotine)和白毛莨碱(b-hydrastine). 该法制得的苯酞类四氢异喹啉类化合物具有一定的立体选择性, 产物构型以赤式对映体为主, 中间产物二氢异喹啉环8位取代基的空间位阻将导致硼氢化钠还原时产生立体选择性.     

3－环戊氧基雌甾－1，3，5（10），16－四烯并[17,16-b]喹啉及其衍生物的合成

以雌酚酮1为原料，与溴代环戊烷作用经Williamson反应合成雌酚醚2，再与邻 氨基苯甲醛发生Friedlaender缩合反应，合成3－环戊氧基雌甾－1，3，5（10）， 16－四烯并[17,16-b]喹啉（3）及其它的衍生物4，其结构经IR，UV，^1H NMR,MS 和元素分析进行结构测定和表征。     

Behaviour of 2-subst1tuted 6,8-dibromo-3,1-benzoxazin-4-ones towards o-phenylenediamine and anthranilic acid ; a case of unusual cleavage of 6,8-d1bromo-2-methyl-3,1-benzoxazin-4-one

6,8-Dibromo-2-methyl-3,l-benzoxazin-4-one (1) reacts with o-phenylenediamine to give a mixture of 3,5-dibromoanthranilic acid (2), 2-methylbenzimidazole (3) and 3-(o-aminophenyl)-6,8-dibromo-2-methylquinazolin-4-one (4). However, when the reaction was conducted in ethanol or in the absence of solvent at elevated temperature, a mixture of (2) & (3) was obtained. A similar cleavage of (1) took place when it was allowed to react with anthranilic acid yielding a mixture of (2) and N-acetylanthranilic acid (6). The reaction of o-phenylenediamine with 6,8-dibromo-2-phenyl-3,1-benzoxazin-4-one (7) proceeded normally to give 3-(o-aminophenyl)6,8-dibromo-2-phenylquinazolin-4-one (8) or 2-benzoyl-amino-3, 5-dibromo-N-(o-aminophenyl)benzamide (9), depending upon the reaction conditions.     

Organophosphorus Chemistry 34 1 . The Reaction of Alkyl Phosphites and Hexamethylphosphorus Triamide with 1-Phenyl-3-methyl-4-ylidene-5-pyrazolones

1-Phenyl-3-methyl-4-ylidene-5-pyrazolones ( 1a-c ) produce the respective 1:1 phosphonate adducts ( 4a-i ) upon reaction with the appropriate dialkyl phosphites ( 2a-c ). The reaction of 1a-c with trialkyl phosphites ( 3a-c ) proceeds only in presence of water, also to give phosphonates 4a-c almost exclusively. Hexamethylphosphorus triamide ( 3d ) was successfully utilized to introduce the bis(dimethylamino)-phosphoryl function in the f , g -unsaturated carbonyl moiety in 1a-c , producing phosphoramidates 15a-c . Possible reaction mechanisms were discussed. Compatible elemental and spectroscopic results were recorded for the new products.     

2-烷硫基-4-芳基亚甲基-5-氢-1-苯氨基-1H-咪唑啉-5-酮的合成与杀菌活性

应用CS2与烯基膦亚胺1的氮杂Wittig反应,得到的异硫氰酸酯2再与苯肼作用得到氨基硫脲3,而后用3与卤代烷在K2CO3的作用下反应直接得到2-烷硫基-4-芳基亚甲基-5-氢-1-苯氨基-1H-咪唑啉-5-酮衍生物4.探讨了反应的条件以及合成的新型杂环化合物的生物活性,结果表明部分化合物表现出较好的杀菌活性.如4e在50 mg/L浓度时,对黄瓜灰霉菌的抑制率为87%.     

Reactions of perfluorinated 1-ethyltetrahydronaphthalene, 1-ethylindan, and 1,1-diethylindan with pentafluorobenzene in antimony pentafluoride

The reaction of perfluoro(1-ethyltetrahydronaphthalene) with pentafluorobenzene in SbF₅, followed by treatment of the reaction mixture with water, afforded a mixture of 1-hydroxyperfluoro(1-phenyl-4-ethyletetrahydronaphthalene) and perfluoro(5-phenyl-8-ethyl-2,6,7,8-tetrahydronaphthalen-2-one). From perfluoro(1,1-diethylindan), 1-hydroxyperfluoro(1,1-diethyl-3-phenylindan) was obtained. Perfluoro(1-ethylindan) reacted with an equimolar amount of pentafluorobenzene in SbF₅ to give (after hydrolysis) 1-hydroxyperfluoro-(3-ethyl-1-phenylindan), 1-hydroxyperfluoro(3-ethyl-1,3-diphenylindan), and perfluoro(1-ethyl-1-phenylindan), while in the reaction with excess pentafluorobenzene, followed by treatment with anhydrous hydrogen fluoride, perfluoro(1-ethyl-3-phenylindan) and perfluoro(1-ethyl-1,3-diphenylindan) were formed.     

Synthesis of 1-phosphaadamantane

The annelation reaction between 1,2,3,6-tetrahydro-1-phenyl-4-(1-pyrrolidinyl)phosphorin 1-oxide (4) and ethyl 2-bromomethyl-3-bromopropanoate (5) yielded a mixture of two stereoisomers of the 3-phosphabicyclo[3.3.1]nonane derivative 6. The keto function of 6 was reductively removed to furnish 8 which with LiAlH₄ was reduced to 9. Treatment of 9 with trichlorosilane gave the 1-phenylphosphoniaadamantane 11. The phenyl group of 11 was cleaved with sodium to give the title compound 1, or with NaOH to give the oxide 12 of 1. With benzyl bromide, 1 was quaternized to 13.     

Eine neue Synthese von (±)-Dihydrorecifeiolid

A New Synthesis of (±)-Dihydrorecifeiolide Ethyl 1-(2′-formylethyl)-2-oxocyclooctane-1-carboxylate ( 2 ) prepared by Michael reaction of ethyl 2-oxocyclooctane-1-carboxylate ( 1 ) was regioselectively methylated at the aldehyde group with (CH₃)₂Ti[OCH(CH₃)₂]₂ to give 3 (Scheme 1). The alcohol 3 was treated with Bu₄NF to give the deethoxycarbonylated product 4 which by distillation gave the bicyclic enol ether 5 . Oxidation (m-chloroperbenzoic acid) of 5 and reduction of the resulting oxolacton 6 yielded the title compound (±)-dihydrorecifeiolide ( 7 ) in an overall yield of nearly 50 %. Methylation of the aldehyde 2 with MeLi gave the ring-enlarged lacton 9 in poor yield (13 %). The deethoxycarbonylation reaction 3 → 4 was studied in more detail (Scheme 3).     

Photogeneration and reactivity of 1,n-diphenyl-1,n-azabiradicals

The 1,5-diphenyl-1,5-azapentanediyl biradical Ia was generated by photolysis of 1,2-diphenylazacyclopentane (pyrrolidine 1a). Among the reaction pathways followed by Ia, C-N bond reformation with ring closure was found to be the predominating process, as determined by separate irradiation of either of the pure enantiomers of 1a. Disproportionation was a minor process and took place only via H abstraction by the C5 benzylic radical. Another minor pathway was C5-aryl coupling, with formation of 5-phenyl-2,3,4,5-tetrahydro-1H-benzo[b]azepine (4a), which is equivalent to photo-Claisen rearrangement of 1a. Likewise, the 1,4-diphenyl-1,4-azabutanediyl biradical Ib was generated by photolysis of 1,2-diphenylazacyclobutane (azetidine 1b). This species underwent predominating C2-C3 cleavage, as indicated by the extensive styrene formation. Although N1-C4 bond reformation also took place, this is not the major pathway occurring from Ib. Besides, C4-aryl coupling to give 4-phenyl-1,2,3,4-tetrahydroquinoline (4b) was also observed. All the possible reaction pathways were theoretically studied at the UB3LYP/6-31G computational level; the results were found to be in good agreement with the experimental observations.     

1-(2'-苯基-1', 2', 3'-三唑-4'-甲酰基)-4-芳基氨基硫脲及其 环化产物的合 成

以2-苯基-1,2,3-三唑-4-甲酰肼为原料合成了几种新的1-(2'-苯基-1',2',3'-三唑-4'-甲酰基)-4-芳基氨基硫脲,在不同条件下环化,制得一系列新的1,3,4-噻二唑、1,3,4-恶二唑和1,2,4-均三唑衍生物。化合物的结构经元素分析、IR、^1HNMR和MS确证,并对其波谱性质进行了讨论。     

3-位苯并含氮杂环取代的焦脱镁叶绿酸-a甲酯的合成

以焦脱镁叶绿酸-a甲酯(MPP-a)(1)为起始原料，在二氯甲烷中与醋酸锌共回流得锌配合物2，在四氯钯锂催化下，通过与苯基氯化汞的偶联反应生成3b-苯基焦脱镁叶绿酸-a甲酯(3)．分别选用四氧化锇、高钌酸四丙基铵(TPAP)和N-甲基吗啉N-氧化物将环外烯键氧化成邻二酮(4)．在酸性条件下，4与邻苯二胺的缩合形成了3-位喹喔啉取代的焦脱镁叶绿酸-a甲酯(5)．用四氧化锇和高碘酸钠将1的3-位碳碳双键氧化，则生成焦脱镁叶绿酸-d甲酯(6)．所得卟吩醛与环己二酮和萘胺进行一锅法反应，得到3-位苯并吖啶取代的焦脱镁叶绿酸-a甲酯(7)．所合成的新卟吩化合物均经UV，IR，^1H NMR及元素分析证明其结构．     

The reaction of α-haloketones with N-alkyl benzothiazolium salts

Phenacyl chloride ( 1a ) reacts with the 3-methylbenzothiazolium quaternary salt ( 2 ) to give 4-methyl-2-benzoyl-4H-1,4-benzothiazine ( 4a ). A mechanism is discussed. Secondary α-haloketones give benzothiazolines. Merocyanine dyes are formed by the reaction of 2 with carbanions. It is shown that 2 functions as a hydride ion abstractor in the formation of merocyanine dyes.