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环二烯烃

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Part 2. Annulation reaction of 3, 4-dichlorocoumarin (1) and 3, 4-dichloromaleimide (8) by a new general annulation strategy developed in this group with 2-phenylbenzofuran (15), 3-phenylbenzofuran (16), 2, 5-diphenyloxazole (17), 2, 5-diphenylthiazole (18), 2-methyl-4-phenylthiazole (19) and 2, 3-dimethoxy-1, 3-butadiene (40) were investigated.

二。在本课题组前一阶段提出的从二氯代环烯酮与1,1-二芳基乙烯的光化反应以及光化反应中得到的环丁烷产物的连续电环化反应对3,4-二氯马来酰亚胺以及3,4-二氯香豆素进行增环反应的工作基础上,研究了3,4-二氯香豆素(1)和3,4-二氯马来酰亚胺(8)与5个α-苯基取代的环烯烃2-苯基苯并呋喃(15),3-苯基苯并呋喃(16),2,5-二苯基噁唑(17),2,5-二苯基噻唑(18),2-甲基-4-苯基噻唑(19),以及一个丁二烯——2,3-二甲氧基丁二烯(40)进行的芳香族增环反应。

In part one, the reactions of some active fluorine-containing compounds such as 2, 2-dihydropolyfluoroalkanoic acids and ethyl 2-hydropolyfluoroalkenoates were studied and various fluorine-containing heterocyclic compounds were synthesized. Using 2, 2-dihydropolyfluoroalkanoic acids as the starting material, 4-fluoroalkyl quinolin-2-ols, 2- [ -1-hydropolyfluoro-1-alkenyl] -4H-3, 1-benzoxazin-4-ones, 1-aryl -4, 9-dihydro-3-fluoro-alkyl-1H-pyrazo [3, 4-b] quinolin-4-ones, 5-fluoroalkyl-12H-quin olino [2, 1-b] quinazolin-12-ones, 4-fluoroalkyl-1, 3-dihydro-1, 5-benzodiazepin-2-ones and 4-fluoroalkyl-2H-pyrido [1, 2-a] pyrimidin-2-ones were synthesized through its condensation reaction with anilines, anthranilic acid, N'-aryl-o-aminobenzamides, o-nitro aniline, o-amino pyridine and their derivatives and the subsequent transformations. 5-Fluoroalkyl isoxazolidines, 3-fluoro-3-fluoroalkylisoxazolidino [4, 3-c] quinolin-4-ones, 3-fluoroalkylisoxazolino [4, 3-c] quinolin-4-ones and 2-aryl-3per fluoroacylindoles were synthesized by inter-and intramolecular 1, 3-dipolar cycloaddition of fluorine-containing olefins and nitrones.

第二部分,我们研究了α,α-二氟苄基卤类化合物的亚磺化脱卤反应、产物的转化及全氟烷基亚磺酸盐与芳环化合物的全氟烷基化反应,发现全氟苄基碘或溴及α,α一二氟苄基溴在保险粉等亚磺化脱卤试剂引发下可生成相应的亚磺酸盐;全氟苄基亚磺酸盐与氯气或溴反应可生成全氟苄基磺酰氯或磺酰溴;在烯烃存在下,全氟苄基碘则与烯烃发生加成反应,生成相应的1:1加成产物;在三价醋酸锰的作用下,部分芳香化合物如茴香醚,二甲氧基苯,吡啶,喹啉等可以和过量的全氟烷基亚磺酸盐发生双全氟烷基化反应,反应表现出一定的区域选择性,产率良好。

Results:The experiments showed that 59 components were identified,accounting for 72.91 percent of the total essential oil.The essential oil was mainly composed of dehydrocostuslactone、costunolide、cedrenol、α-elemene、1,3-cyclooctadiene、eudesmol、α-selinene、β-caryophyllene、-longifolene、3,4-octadiene,7-methyl-etc.Among them Lactones like Dehydrocostuslactone and costunolide are essential components.

结果:GC-MS法分析鉴定了木香挥发油中59个成分,其主要成分为去氢木香内酯、木香烃内酯、雪松烯醇、α-榄香烯、环辛二烯、桉叶醇、α-芹子烯、丁子香烯、长松叶烯、7-甲基-3,4辛二烯等,占挥发油总量的72.91%;首次发现木香挥发油及去氢木香内酯、木香烃内酯具有抑制ADP诱导的血小板聚集活性。

Photoinduced Electron Transfer [2+2] Cycloaddition Reactions ofBenzannelated Isoquinolin-1-ones with Electron Deficient Alkenes Photoinduced [2+2] cycloaddition reactions of 11H-benzoxazolo[3,2-b]isoquinolin-11-one 8 and 11H-benzothiazolo[3,2-b]isoquinolin-11-one 13 with electron deficient alkenessuch as acrylonitrile, methyl acrylate, dimethyl fumarate and dimethyl maleate afforded a group of polycyclic isoquinoline derivatives bearing cyclobutane moieties ingood to excellent yields and resulted in the Schenck isomerization of the alkenes.

3苯并增环异喹啉-1-酮与缺电子烯烃的光诱导电子转移[2+2]环加成反应 11H-苯并恶唑[3,2-b]异喹啉-11-酮8和11H-苯并噻唑[3,2-b]异喹啉-11-酮13与缺电子烯烃如丙烯腈,丙烯酸甲酯,富马酸二甲酯及马来酸二甲酯的光诱导[2+2]环加成反应以高产率给出一系列含有环丁烷结构单元的多环异喹啉衍生物并导致烯烃的Schenck异构化作用。

The chapter two was focused on the samarium diiodide promoted organic reactions and their applications in organic synthesis, firstly, a new synthesis of highly substituted cyclopentadienes from a,β-alkynone promoted by samarium diiodide was investigated and the highly substituted cyclopentadienes were prepared in moderate to good yields under mild conditions. Secondly, the Michael addition and Michael-aldol tandem reaction of diorganyl diselenides or diorganyl disulfides with α,β-alkynones mediated by samarium diiodide were studied and a series of alkenylsulfides and alkenylselenides were prepared in good yields. Then the highly regioselecfive nucleophilic addition of the allylsamarium bromide to α,β-alkynones were explored. We found that the allylsamarium bromide reacts with α,β-alkynones to afford regiospecificly 1. 2-nucleophilic addition products in good yields under mild condition. At last we studied the coupling reaction of aryl halides promoted by NiCl〓/PPh〓/Sm〓.

第二章 研究了二碘化钐、金属钐促进的有机反应:1、二碘化钐促进下α,β-炔基酮的偶联环化反应,提供了一种制备多取代环戊二烯的新方法;2、二碘化钐促进下的二硫醚、二硒醚与α,β-炔基酮的Michael加成反应,为高产率地制备多取代的烯基硫或烯基硒化合物提供了方便可靠的新方法;3、二碘化钐促进下的二硫醚、二硒醚与α,β-炔基酮和醛、酮的Michael—aldol串联反应,提供了一种一锅法高产率地制备多取代的含硫的烯丙基醇或含硒的烯丙基醇类化合物的方便可靠的原子经济性的新方法;4、烯丙基溴化钐与α,β-炔基酮的高度区域选择性的1,2-亲核加成反应;5、NiCl〓/PPh〓/Sm〓促进的卤代芳烃的偶联反应-一种从各种卤代芳烃制备联苯类化合物的有效方法。

And then is the 2 to 4 ring PAH, in which the content of naphthyl- and phenanthryl- substance is more than 70%.

轻质馏分脂肪烃主要为环烯烃和二烯烃等烯烃,烷烃中以环烷烃居多;中质以上馏分的脂肪烃主要由C_(13)~C_(32)的正构烷烃组成。

The application markets of three kinds of isoolefines(isoprene, cyclopentadiene ,piperylene) from the cracking C5 fractions and their downstream derivatives were reviewed.

着重评述了裂解C5馏分资源中3种异构烯烃(异戊二烯、环戊二烯和间戊二烯)及其下游衍生物的应用市场,并剖析了我国裂解C5资源的利用现状及应用前景。

The more the types of unstable constituents,such as unsaturated hydrocarbons,especially conjugated dienes,arene s and so on,and the higher the unstable constituent contents in diesel fuel,the more easily the oxygen absorption reaction takes place.

柴油中含有某些不饱和烃,特别是共轭二烯烃、环烷、芳香烃类等不安定组分的种类越多及含量越高,就越容易发生吸氧氧化反应,安定性能或质量下降越明显。

In order to decrease copolymerization loss of isoprene during thermal dimerization of cyclopentadiene in C5-fraction,the effect of three inhibitors,diethylhydroxylamine,p-tert-butylcatechol and o-nitrophenol,on dienes' polymerization in the process was investigated by experiment with sealed glasstube.

为减少C5馏分环戊二烯热二聚过程中异戊二烯的聚合损失,采用封管实验方法考察了添加阻聚剂二乙基羟胺、对叔丁基邻苯二酚、邻硝基苯酚对热二聚过程中各二烯烃组分聚合程度的影响。

Herein the latest developments of olefin aqueous polymerization which are mainly promoted by late- transition metal catalysts are reviewed including ethylene,α-olefins, cyclo-olefins and dienes polymerization, along with ROMP of cyclo-olefins and CO/olefins copolymerization.

本文综述了后过渡金属催化剂水相催化烯烃配位聚合的一些新进展,内容包括烯、α-烯烃、环烯烃、二烯烃的聚合反应和环烯烃的开环聚合反应以及CO/烯烃的共聚反应等方面。

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