烯烃基

The reaction of α-hydroxyketone with Michael acceptor nitroalkene.was studied. After many experiments, we then found that in the presence of Zn2 and cinchonine, the α-hydroxyketone could successfully react with nitroalkene. Under our optimized condition, we gained the 95% yield of product with the ratio of syn : anti of 3:1 and 72% ee value for syn-product.

有机碱作用下α－羟基酮对硝基烯烃的加成反应研究研究了α－羟基酮类化合物与Michael受体硝基烯烃类化合物的反应，通过分析和实验发现在Zn2和辛可宁的作用下α－羟基苯乙酮能够与硝基烯烃化合物顺利反应，在优化的条件下以95%产率和3：1的Dr主要得到顺式产物，其中顺式产物的ee值最高为72%。

The thermolysis of the isomerized products derived from norbornadiene-coordinated carbonyl iron complexes gave two sorts of the thermolytic products based on different substituents on the olefin ligands. One is the corresponding diiron dimer complex, and the other is the complex in which the C-C bond of the cycloolefin ligand is broken.

以降冰片二烯三羰基铁络合物衍生出来铁卡宾络合物的异构化产物的热解，随着烯烃配体上取代基的不同，而分别得到了络合物发生二聚和烯烃配体发生碳碳键断裂的两类热解产物。

In chapter 4 an abnormal reaction that the nitro group of 1-aryl-2-nitroethenescan be easily replaced by the organic moity of FG-RZnI using Ni〓 and tertiaryamine as catalyst was first given. The experimental results show that in the presenceof catalytic amount of Ni〓 and tertiary amines, the reaction of FG-RZnI andl-aryl-2-nitroethenes give the substitution products l-aryl-l-alkene, instead ofMichael addition products.

通过实验发现，在催化量的Ni〓及叔胺催化下， l-硝基-2-芳基乙烯与烷基碘化锌并不进行Michael加成反应，而是发生1-硝基-2-芳基乙烯中硝基被取代的反应，生成了高产率的1-芳基-l-烯烃，由于此反应的原料易得、反应条件温和、产物的产率高，因而是合成l-芳基-1-烯烃的有效方法。

The invention provides a method for homopolymerizing conjugated dialkene or co-polymerizing conjugated dialkene and monovinyl aromatic hydrocarbon. The method comprises the following steps: the conjugated dialkene is homopolymerized or the conjugated dialkene and the monvinyl aromatic hydrocarbon are co-polymerized randomly. The method is characterized in that at least one alkali metal alkoxide compound expressed by the formula is used as a structure regulator; in the formula, R is linear chain or branched chain alkylidene radical having 1 to 10 carbon atoms; M is alkali metal selected from Li, Na, K, Rb and Cs.

本发明提供了一种使共轭二烯烃均聚或者使共轭二烯烃与单乙烯基芳烃共聚的方法，包括在阴离子聚合条件下使共轭二烯烃进行均聚或者使共轭二烯烃与单乙烯基芳烃进行无规共聚，其特征在于采用至少一种式所示的碱金属醇盐化合物作为结构调节剂，其中R为具有1-10碳原子的直链或支链亚烷基；以及M为选自Li、Na、K、Rb和Cs的碱金属。

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。

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。

These compounds were identified as follows:chrysophanol (FP-1),physcion(FP-2),eriosematin(FP-3),scoparone(FP-4),lupeol(FP-5),betulinic acid(FP-6),3\',4\'-Dihydroxy-trans-cinamic acid octacosyl ester(FP-7),β-sitosterol (FP-8),flemiphilippinone A(FP-9),monopalmitin(FP-10),emodin(FP-11),islandicin (FP-12),salicylic acid(FP-13),p-methoxyphenylpropionic acid(FP-14),trideca-1, 3-diene(FP-15),lupinifolin(FP-16),flemichin D(FP-17),flemiphilippinin A(FP-18), auriculasin(FP-19),erythrinin B(FP-20),6-C-prenylluteolin(FP-21), 8-(1,1-dimethylallyl) genistein(FP-22),flemiphilippinin E(FP-23),flemiphilippinin F (FP-24),5,7,3\',4\'-tetrahydroxy-6,8-diprenylisoflavone(FP-25),flemiphilippinin D (FP-26),dorsmaninsⅠ(FP-27),osajin(FP-28),6,8-diprenyleriodictyol(FP-29), lupinalbin A(FP-30),genistein(FP-31),3\'-O-methylorobol(FP-32),orobol(FP-33), 5,7,2\',3\',4\'-pentahrdroxyflavone(FP-34),the mixture of biochanin A and prunetin (FP-35 and 36),genistin(FP-37),sophororicoside(FP-38),3\'-O-methylorobol-7-glucoside(FP-39),the mixture of sissotrin and prunetin 4\'-O-β-D-glucoside(FP-40 and 41),adenosine(FP-42) and luteoloside(FP-43,mixture).

这些化合物分别为大黄酚(FP-1)、大黄素甲醚(FP-2)、eriosematin(FP-3)、滨蒿内酯(FP-4)、羽扇豆醇(FP-5)、白桦酸(FP-6)、咖啡酸二十八烷酯(FP-7)、β-谷甾醇(FP-8)、蔓性千斤拔酮A(FP-9)、单棕榈酸甘油酯(FP-10)、大黄素(FP-11)、islandicin(FP-12)、水杨酸(FP-13)、对甲氧基苯丙酸(FP-14)、十三烷-1，4-二烯烃(FP-15)、lupinifolin(FP-16)、千斤拔素D(FP-17)、蔓性千斤拔素A(FP-18)、auriculasin(FP-19)、erythrinin B(FP-20)、6-C-异戊烯基木犀草素(FP-21)、8-(1，1-二甲烯丙基)-染料木黄酮(FP-22)、蔓性千斤拔素E(FP-23)、蔓性千斤拔素F(FP-24)、5，7，3′，4′-四羟基-6，8-双异戊烯基异黄酮(FP-25)、蔓性千斤拔素D(FP-26)、dorsmaninsⅠ(FP-27)、osajin(FP-28)、6，8-双异戊烯基圣草素(FP-29)、lupinalbin A(FP-30)、染料木黄酮(FP-31)、3\'-O-甲基香豌豆苷元(FP-32)、奥洛醇(FP-33)、5，7，2′，3′，4′-五羟基黄酮(FP-34)、鹰嘴豆素甲和樱黄素的混合物(FP-35和FP-36)、染料木苷(FP-37)、槐属苷(FP-38)、7-葡萄糖基-3\'-O-甲基香豌豆苷(FP-39)、印度黄檀苷和樱黄素4′-O-β-D-葡萄糖苷的混合物(FP-40和FP-41)、腺嘌呤核苷(FP-42)和木犀草苷(FP-43，混合物)。

The results of AD reactions are as follows:(1) When the AD reaction of eight olefins was performed at 0.5mo1% OsO〓 and 2mol% ligand 8 in PEG/NMO system, the diols were obtained in 78～90% yields and 78～96% ees (except for trans-5-decene and ally naphthyl ether).

催化结果如下：(1)在PEG/NMO体系中，将配体8用于八种烯烃的AD反应，配体、OsO〓和底物的摩尔比为0.02/0.005/1时，化学产率为78～90％，除反式-5-癸烯和萘基烯丙基醚较低外，其它六种烯烃的相应二醇产物的ee值为78～96％。

Molybdophopsphoric Acid Catalysis in the Oxidative Cleavage of Olefins by the Hydrogen Peroxide Oxidative cleavage of the double bond could be catalyzed by H_3PMo_(12)O_(40) using H_2O_2 as oxidant, various trisubstituted olefins were oxidized to aldehydes or ketones in high yields. The system was not satisfied for electron-deficient olefins such as trans-(2-nitrovinyl) benzol or chalcone. The reaction of aliphatic olefins did not occur under the same conditions.

二、磷钼酸催化过氧化氢对烯烃的氧化断裂反应用过氧化氢(30％)作为氧化剂，磷钼酸可以催化氧化碳碳双键的断裂反应，三取代的烯烃被氧化生成醛或酮，产率较高；此体系对于缺电子烯烃如查尔酮，不饱和硝基化合物的断裂反应效果较差，脂肪族烯烃在此体系下的氧化并不发生。

This PhD thesis mainly summarizes the original results on studies of aromatic amide-derived phosphines,including the precatalyst system consisting of Aphos and Pd_2 and the applications for promoting room temperature Suzuki cross-coupling of aryl chlorides and aryl/vinyl bromides,respectively,with aryl/vinyl boronic acids,and alkyl boranes.

本博士学位论文主要总结了对芳基酰胺衍生的膦配体的研究，以及该类型配体与Pd_2组成的催化剂在室温下催化氯代芳烃、溴代芳烃、溴代烯烃分别同芳基硼酸、烯基硼酸及烷基硼试剂进行的Suzuki偶联反应中的表现。

For a big chunk of credit-card losses; the number of filings (and thus charge-off rates) would be rising again, whether

年美国个人破产法的一个改动使得破产登记急速下降，而后引起了信用卡大规模的亏损。

Eph. 4:23 And that you be renewed in the spirit of your mind

弗四23 而在你们心思的灵里得以更新