烯丙基

While the adsorptions of 1-propanol and 1-Br-propane at 100℃ give rise to 1-propoxy species, which mainly converted to propanal at higher temperature. IR spectrum arising from the interaction of propene with the catalyst at 100 ℃ shows the IR bands of allyl alcoholate and isopropoxy species. As the temperature was increased to 150℃, the bands ascribable to the adsorbed acetone and acrolein were observed. Based on these results, it is suggested that isopropoxy species is one of the intermediates for SOP to acrolein over MoPO/SiO〓 catalyst.

2原位IR光谱实验结果表明：200℃时丙烷/O〓混合气在催化剂表面吸附后的IR谱与同温度下异丙醇吸附的IR谱相似，均检测到吸附态丙酮物种和丙烯醛物种的IR谱峰；溴代异丙烷和异丙醇在催化剂表面吸附后均转化为异丙氧基，异丙氧基主要转化为丙烯和丙酮，丙烯进一步转化为丙烯醛；溴代正丙烷和正丙醇在催化剂表面吸附后均转化为正丙氧基，正丙氧基主要转化为丙醛；丙烯在催化剂表面吸附后转化为σ-氧烯丙基和异丙氧基，升温后σ-氧烯丙基转化为丙烯醛而异丙氧基转化为丙酮。

While the adsorptions of l-propanol and 1-Br-propane at 100 癈 give rise to 1-propoxy species, which mainly converted to propanal at higher temperature. IR spectrum arising from the interaction of propene with the catalyst at 100 癈 shows the IR bands of allyl alcoholate and isopropoxy species. As the temperature was increased to 150 癈, the bands ascribable to the adsorbed acetone and acrolein were observed. Based on these results, it is suggested that isopropoxy species is one of the intermediates for SOP to acrolein over MoPO/SiO2 catalyst.

原位IR光谱实验结果表明：200℃时丙烷／O_2混合气在催化剂表面吸附后的IR谱与同温度下异丙醇吸附的IR谱相似，均检测到吸附态丙酮物种和丙烯醛物种的IR谱峰；溴代异丙烷和异丙醇在催化剂表面吸附后均转化为异丙氧基，异丙氧基主要转化为丙烯和丙酮，丙烯进一步转化为丙烯醛；溴代正丙烷和正丙醇在催化剂表面吸附后均转化为正丙氧基，正丙氧基主要转化为丙醛；丙烯在催化剂表面吸附后转化为σ-氧烯丙基和异丙氧基，升温后σ-氧烯丙基转化为丙烯醛而异丙氧基转化为丙酮。

Diallyl trisulfide was synthesized with a yield of 76.4% based on sodium thiosulfate, allyl bromide and sodium sulfide. And diallyl tetrasulfide was synthesized by the reaction of sulfur monochloride with ally1 mercaptan with a yield of 81.0%.

以硫代硫酸钠、烯丙基澳和硫化钠为原料，合成了二烯丙基三硫，产率为76.4%；以一氯化硫和烯丙硫醇为原料合成了二烯丙基四硫，产率为81.0%。

The allylation reactions of aldehydes with allyl bromide were carried out in 76%～93% yields with Nd-SnCl2-H2O under ultrasound irradiation at room temperature for 50～60 min.

在Nd-SnCl2-H2O体系中，用烯丙基溴超声诱发下进行了一系列芳香醛的烯丙基反应，室温反应50～60min得76%～93%烯丙基化产物；而不用超声波时同样体系中搅拌3～4h高烯丙基醇产率为30%～86%。

Sodium 2-Acrylarnido-Acetate has been synthesized through the reaction of Aminoacetic acid with acryloyl chlorine, then Copolymer of sodium 2-acrylamido-acetate and dimethyl diallyl ammonium chloride with acrylamide had been prepared by free radical polymerization using (NH4)2S2O8 and NaHSO3 as the free radical initiator in water solution.

本论文首先以氨基乙酸和丙烯酰氯为原料制备丙烯酰胺基乙酸钠单体，然后以丙烯院胺丙烯酰胺基乙酸钠和二甲基二烯丙基氯化铵为单体，(NH4)2S2O8和NaHSO3为自由基引发剂，采用水溶液聚合法合成丙烯酰胺／丙烯既胺基乙酸钠／二甲基二烯丙基氯化铵共聚物。

This work, concentrated on the asymmetric allylation of aldehydes controlled by different chiral auxiliaries prepared from rotational pure tartaric acid, can be divided into three parts.The first part aims to review the developments of chiral drugs and asymmetric synthesis, from which derived the present research topic backgrounds and works.Synthesis and applications of allylation from aldehydes are the second part of the thesis. By optimizing the reaction conditions, such as solvents, temperature, time and chiral auxiliaries like N,N\'-dibenzyl tartamide, N,N\'-p-dimethylphenyl tartamide, N,N\'-o-dimethylphenyl tartamide, N,N\'-o-dichlorophenyl tartamide, N,N\'-a-dinaphyl tartamide, N,N\'-dicyclohexyl tartamide and N,N\'-diphenyl tartamide, ideal experimenttal conditions are obtained according to HPLC monitoring, as well as the auxiliaries\' recoveries experiments. Starting from benzaldehyde and 3-bromopropaldehyde, N,N\'-dibenzyl tartamide is considered the best auxiliary in this reaction.

本文介绍了醛的不对称烯丙基化反应，以光学纯酒石酸为原料，研究了不同构型手性配体在醛的烯丙基化反应中的立体选择性，全文共分三部分十个章节：第一部分对当前手性药物和手性技术进行了概述，并由此展开了本文的研究背景和任务；第二部分为有机合成部分，对醛的不对称烯丙基化反应进行了深入探讨，以苯甲醛为原料对反应条件进行优化，在优化的反应条件下对制备的七种可回收手性酰胺配体(N-苄基酒石酸二酰胺、N-对甲苯基酒石酸二酰胺、N-邻甲苯基酒石酸二酰胺、N-邻氯苯基酒石酸二酰胺、N-a-萘基酒石酸二酰胺、N-环己基酒石酸二酰胺和N-苯基酒石酸二酰胺)进行筛选，优化配体回收实验条件，最终确定出N-苄基酒石酸二酰胺在苯甲醛的不对称烯丙基化反应中具有较大优越性，结晶回收的手性配体光学纯度保持不变。

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。

In this Ph. D. dissertation, reverse microemulsion method was fully used infabricating and modifying polyacrylamide with functional and high-relative moleculeweight. The copolymerization of 2-acrylamide-2-methylpxopanesulfonic acid, fluorescent monomer 4-methoxy-N-(2-N\', N\'-dimethylamino ethyl)naphthalimide alkyl chloride quaternary ammonium salt, fluorescentmonomer 4-(N\'-methyl-1-piperazinylallyl)-N-butyl-naphthalimide chloride quaternaryammonium salt, Cationic monomer dimethylethylammonium bromide and hydrophobical monomer octadecylacrylate with acrylamide and properties of the copolymers werestudied. The interaction between five polymers and Al_2O_3(012) crystal surface have beensimulated by Materials Studio 3.0 program package, binding energies and non-bondinteraction energies and deformation energies have also been acquired.

本文以制备具有较高相对分子质量和功能型PAM为研究目的，将反相微乳液法运用到其制备及改性的有关环节，通过反相微乳液聚合工艺，将几种改性功能单体2-丙烯酰胺基-2-甲基-丙磺酸、荧光单体2-(4-甲氧基-1，8-萘二甲酰亚胺基)-乙基二甲基烯丙基氯化铵、荧光单体4-(N'-甲基-1-哌嗪基)-N-丁基-1，8-萘烯丙氯季铵盐、阳离子单体丙烯酰氧乙基-二甲基-乙基溴化铵和疏水单体丙烯酸十八酯与AM共聚，制备AMPS改性PAM、荧光示踪型PAM、阳离子单体DMB改性PAM和OA改性PAM等四类不同功能单体改性PAM，并研究其应用性能。

The results of in situ DRIFTS on propylene oxidation show that the allyl species originated from α-H abstraction of propylene were located at the wavenumbers of 1454 cm~(-1) and 1427 cm~(-1). The rate-determining step is the abstraction of an α-H abstraction from a lattice oxygen linked to a bismuth ion to form a π-allyl intermediate coordinated to a molybdenum ion. The metal-oxo group then attacks the allyl intermediate forming a σ-bonded oxygen-allyl species, which is in a rapid equilibrium with the π- bonded species. The σ-bonded species then transforms to acrolein by further abstraction of α-H. Such species as formate, carboxylate, carbonate transform to deep oxidation products. The acetone was derived from propylene by an enolic species at lower temperatures.

丙烯氧化反应体系的原位漫反射红外光谱研究结果表明，由丙烯脱氢生成的烯丙基中间物种吸收峰在1454cm~(-1)和1427cm~(-1)处；基于此提出了较完整的丙烯氧化反应网络：丙烯选择氧化生成丙烯醛主要经历丙烯脱除甲基上的一个H，生成烯丙基物种，该物种嵌氧生成σ-O络合物，脱氢得到丙烯醛前驱体，脱附生成丙烯醛；完全氧化产物是由催化剂表面上生成甲酸盐、羧酸盐、碳酸盐等形式的中间物种转化而成；较低反应温度下丙烯氧化生成丙酮，通过烯醇式中间物种氧化生成丙酮前驱体得到。

Laba garlic, the formation of green pigment and red onion with a certain degree of similarity, diallyl sulfide and propylene oxide exists at the same time, Green took place, there is Propylene oxide sulfide, there is no oxidation of allyl sulfur objects when changes occur red.

腊八蒜绿色素的形成与洋葱红变具有一定的相似性，烯丙基与丙烯基硫氧化物同时存在时，就发生绿变，存在丙烯基硫氧化物，不存在烯丙基硫氧化物时，就发生红变。

We have no common name for a mime of Sophron or Xenarchus and a Socratic Conversation; and we should still be without one even if the imitation in the two instances were in trimeters or elegiacs or some other kind of verse--though it is the way with people to tack on 'poet' to the name of a metre, and talk of elegiac-poets and epic-poets, thinking that they call them poets not by reason of the imitative nature of their work, but indiscriminately by reason of the metre they write in.

索夫农 、森那库斯和苏格拉底式的对话采用的模仿没有一个公共的名称；三音步诗、挽歌体或其他类型的诗的模仿也没有——人们把&诗人&这一名词和格律名称结合到一起，称之为挽歌体诗人或者史诗诗人，他们被称为诗人，似乎只是因为遵守格律写作，而非他们作品的模仿本质。

The relationship between communicative competence and grammar teaching should be that of the ends and the means.

交际能力和语法的关系应该是目标与途径的关系。