烯化

A process for preparing alkylene glycols including reacting an alkylene oxide with water in the presence of a combination of additives and an anion exchange resin, wherein the combination of additives comprises carbon dioxide and an organic or inorganic base provided in an amount sufficient to maintain a pH of the reaction mixture between about 5.0 and 9.0, with the proviso that, when the base is bicarbonate or carbonate, then the anion exchange resin is a trimethyl benzyl ammonium anion exchange resin.

制备亚烷基二醇的方法，包括让烯化氧与水在添加剂组合和阴离子交换树脂存在下进行反应，其中添加剂组合包括二氧化碳和以足以保持反应混合物的pH值在约5.0和9.0之间的量提供的有机或无机碱，前提条件是当碱是碳酸氢盐或碳酸盐时，阴离子交换树脂是三甲基苄基铵阴离子交换树脂。

The method involves exposing the cells to a compound having the formula I in which: w is a nucleic acid x is a non-amino acid or non-peptide nucleic acid binding group y is a spacer having a chain length equivalent to 1-30 carbon-carbon single covalent bonds or is absent R4 is H or halogen or CH2O-R3; and R1, R2 and R3 are the same or different and are either hydrogen, methyl, ethyl, alkyl, alkenyl, hydroxylated alkyl, hydroxylated alkenyl groups or ether containing alkyl, alkenyl, hydroxylated alkyl or hydroxylated alkenyl groups optionally being an acyl group having a carbon chain length equivalent to 3-24 carbon atoms saturated or unsaturated, with the proviso that at least one of R1, R2 or R3 includes a group having a carbon chain of 3-24 carbon atoms saturated or unsaturated, or to a compound having the formula II in which: w is a nucleic acid x is a non-amino acid or non-peptide nucleic acid binding group y is a space having a chain length equivalent to 1-30 carbon-carbon single covalent bonds or is absent, R5 is alkyl, alkenyl, hydroxylated alkyl, hydroxylated alkenyl group or ether containing alkyl, alkenyl, hydroxylated alkyl or hydroxylated alkenyl group optionally being an acyl group having a carbon chain length equivalent to 3-24 carbon atoms saturated or unsaturated, with the proviso that R5 includes a group having a carbon chain of 3-24 carbon atoms saturated or unsaturated.

该方法包括使细胞暴露于具有式的化合物，在式中：w是核酸，x是非氨基酸或者非肽核酸结合基团，y是具有等于1―30个碳―碳单共价键的链长的间隔基或者不存在，R4是H或者卤素或者CH2O－R3；R1、R2和R3是相同的或者不同的并且是氢、甲基、乙基、烷基、链烯基、羟基化烷基、羟基化链烯基或者包含烷基、链烯基、羟基化烷基或羟基化链烯基的醚，任选地是来源于具有等于3―24个碳原子的碳链长的饱和或不饱和脂肪酸的酰基，其条件是R1、R2或者R3的至少一个包括具有3―24个碳原子的饱和或不饱和碳链的基团，或者使细胞暴露于具有式的化合物，在式中：w是核酸，x是非氨基酸或者非肽核酸结合基团，y是具有等于1―30个碳―碳单共价键的链长的间隔基或者不存在，R5是烷基、链烯基、羟基化烷基、羟基化链烯基或者包含烷基、链烯基、羟基化烷基或羟基化链烯基的醚，任选地是具有等于3―24个碳原子的饱和或不饱和碳链的链长的酰基，其条件是R5包括具有3―24个碳原子的饱和或不饱和碳链的基团。

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。

By using this methodology, alkenyl silanes which have useful applications from a synthetic point of view could be easily obtained.

藉由改变起始物硫缩醛的取代基，或是使用不同的格林那试剂，我们能利用此烯化反应得到在有机合成上有许多应用的有机矽化合物。

Firstly, 3-ethylthiobutanal was prepared from crotonaldehyde reacting with ethanehiol in triethylamine with high yield. Secondly, methyl acetoacetate was converted to 6-ethylthiohept-3-en-2-one by three steps via hydrolysis, condensation with 3-ethyltio-butanal and dehydration, then 6-ethylthiohept-3-en-2-one was cycloco ndensed with dimethyl malonate by Michael addition and Claisen condensation, followed by saponification and decarboxylation to give the intermediate of 5-(2-ethylthiopropyl)-cyclohexane-1,3-dione.

首先，以巴豆醛与乙硫醇为原料，在三乙胺的催化作用下高收率制得3-乙硫基丁醛；然后从乙酰乙酸甲酯出发，通过碱水解、与3-乙硫基丁醛缩合、脱水三步反应合成6-乙硫基-3-烯-2-庚酮，接着6-乙硫基-3-烯-2-庚酮与丙二酸二甲酯通过Michael加成和Claisen缩合成环，再通过皂化和脱羧反应生成中间体5-[2-丙基]-1，3-环己二酮；再与丙酸酐反应丙酰化，最后与0-3-氯-2-丙烯基羟胺肟化，得到目标化合物烯草酮。

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 the presence of suitable nickel catalyst and without the chelation effect of special designed dithioacetals, simple aliphatic dithioacetals could react with a series of Grignard reagents to give the corresponding olefinic products.

因此在适当的镍触媒存在下，脂肪族硫缩醛在不需要特别的螯合作用下，即可以与一系列的格林那试剂进行烯化反应。

Thus, the phosphonate moiety is remainedin the products and this methodology can be used in the synthesis of substituted vinylphosphonates.

因此在本烯化反应中保留了膦酸酯基团，可用来合成取代的烯基膦酸酯。

The new olefination methods of alkyl substituted propargylic dithioacetals are described in this thesis.

中文摘要本篇论文围绕在烷基取代炔丙基硫缩醛的新型态烯化反应，可分为两部分进行探讨。

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