丙炔

Second, using DBU as the base for enolization of propargylic esters of unsaturated acids 18e-k, we developed a tandem Ireland-Claisen rearrangement /isomerization reactions. It has been shown that the reaction sequence affords triene molecules 42a-b and 43a-b in moderated to high yields. Interestingly, with allyl hexa-3,5-dienoates 18i-j as the substrate, the rearranged products underwent further aromatization to give uniquely substituted benzyl acids 44a-b.

其次，以含有活泼质子的烯酸炔丙酯18e-k为底物，在DBU为烯醇化碱、TMSCl为硅试剂的条件下，底物18e-h发生了Ireland-Claisen重排/异构化串联反应，得到完全共轭的三烯类化合物42a-b及43a-b；而以己二烯酸炔丙基酯18i-j为底物时，重排/异构化后的产物进一步发生电环化等反应最终得到芳构化产物——取代苯甲酸类化合物44a-b。

Two monomers,bispmpargyl ether of bisphenol-Aand 4,4'-biphenyl dibenzyl azide were synthesized and characterized with FT-IR,1H-NMR and elementary analysis.

合成了两种单体双酚A二炔丙基醚与4，4′-联苯二苄叠氮，研究了一种新的低温聚合体系——双酚A二炔丙基醚与4，4′-联苯二苄叠氮在烘箱中的本体聚合行为。

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。

Dipropargylfluorene was prepared by the reaction of fluorene and propargyl bromide with the catalyst of NaOH/PhCH2N+Me3Cl in 85﹪ yield.

芴与炔丙基溴在NaOH/PhCH2N+Me3Cl催化作用下反应生成85﹪的二炔丙基芴。

Promoted by metal dysprosium, aldehydes and ketones could react smoothly with propargyl bromide to afford the corresponding homopropargylic alcohols in good to excellent yields, and no allenic alcohol s were found.

当用苯基炔丙基溴代替炔丙基溴与醛、酮反应时，主要得到了相应的连二烯醇，而没有发现高快丙醇的存在，由此提出了六元环过渡态的反应机理

Sci.Tech.,Harbin,150080,China） Abstract:Dipropargylfluorene was prepared by the reaction of fluorene and propargyl bromide with the catalyst of NaOH/PhCH2N Me3Cl in 85% yield.

9，9二炔丙基芴的合成和发光性能邱加龙桂太龙许晶王玥摘要：芴与炔丙基溴在NaOH/PhCH2N Me3Cl催化作用下反应天生85%的二炔丙基芴。

The quantitative structure-activity relationships were established based on the 1-octanol/water partition coefficient and an electronic parameters-lowest unoccupied molecular orbit. The result shows that the highest sensitivity is cell density between three end points, and the toxicity of secondary and tertiary propargylic alcohols is correlation to the position of alkynyl and hydrophobicity, respectively.

本次实验结果可发现三个参数中以Final yield的敏感度是最高的，而二级炔丙基醇类之毒性高低是和其炔基接的位置有一定的关联性，三级炔丙基醇类之毒性则与疏水性的高低有关：疏水性越高其毒性越强。

The diblock copolymer of styrene and chloromethyl-4-vinyl-benzene was obtained by means of reverse addition fragmentation chain transfer reaction living free radical polymerization. The chloromethyl groups in PS-bPCVB were transformed into azidomethyl groups, and then into 1,2,3-triazol groups via click chemistry. The diblobk copolymer containing 1,2,3-triazol groups was thus obtained. The results from NMR spectra suggested a complete transformation from chloromethyl groups to triazol groups.

通过RAFT活自由基聚合方法制备聚（苯乙烯-b-对氯亚甲基苯乙烯）二嵌段共聚物，其中的氯亚甲基侧基经叠氮化反应后与丙炔醇进行点击反应，最终获得了含有1，2，3-三氮唑官能团的聚苯乙烯二嵌段共聚物，核磁共振谱表征结果证明，PS-b-PCVB中的氯亚甲基完全转变成了1，2，3-三氮唑基团。

The diblock copolymer of styrene and chloromethyl-4-vinyl-benzene was obtained by means of reverse addition fragmentation chain transfer reaction living free radical polymerization. The chloromethyl groups in PS-b-PCVB were transformed into azidomethyl groups, and then into 1,2,3-triazol groups via click chemistry. The diblobk copolymer containing 1,2,3-triazol groups was thus obtained. The results from NMR spectra suggested a complete transformation from chloromethyl groups to triazol groups.

通过可逆加成－断裂链转移聚合活性自由基聚合方法制备了聚（苯乙烯－b-对氯亚甲基苯乙烯）二嵌段共聚物，其中的氯亚甲基侧基经叠氮化反应后与丙炔醇进行点击反应，最终得到了含有1，2，3-三氮唑官能团的聚苯乙烯二嵌段共聚物，核磁共振谱表征结果证明，PS-b-PCVB中的氯亚甲基完全转变成了1，2，3-三氮唑基团。

After the click reaction of the SCL micelles and azide-terminus PNIPAM homopolymer, the novel PNIPAM-functionalized SCL micelles with pH-responsive cores and outer thermosensitive coronas were prepared, which was investigated act as excellent candidate of nanosized drug delivery vehicles.

另外，还可以使用溴丙炔对ATRP聚合出的PMEO_2MA-b-PDMA-b-PDEA三嵌段的中间PDMA嵌段进行部分季胺化，这样可以利用两端叠氮化的四甘醇来交联由PMEO_2MA-b-PDMA-b-PDEA在不同条件下形成的两种分别以PMEO_2MA或PDEA为核的胶束，从而实现了从同一个聚合物直接在水溶液中得到两种内核不同敏感的壳交联胶束。

By the time of its fall, most of the prisoners were writers who had written against the corruptions of the government.

到它被攻陷的时候，里面多数的犯人是写了反对政府贪污文章的作家。

The most obvious variation to ovum morphological character was that the color was changed from light green to sepiaceous in embryonic development, and all the ovums were almost hatched after 96h.

在胚胎发育过程中卵的形态特征最明显的变化是颜色从淡绿到深褐色，卵在发育96h后卵基本全部孵化。