卤代醇

The deoxygenation and reduction of some organic substrates with samarium diiodide were investigated.

本文研究了二碘化钐对一些有机化合物的脱氧反应，以及它在醇存在下对α-卤代酮、偶氮苯和苯醌的还原反应。

It has been demonstrated that the methods are successfully used for QSRR studies of quinazoline derivatives, alkypyridine, haloid alkane, ketone, alcohol, sulfur alcohol compounds.

本文成功地用该方法对喹唑啉类、烷基吡啶化合物、卤代烃、醇、羰基化合物和硫醇化合物的结构保留关系进行了探讨。

Master the Keto-Enol tautomerism; reactions of enols:α-H substitution reactions;α-halogenation of aldehydes and ketones;α-bromination of carboxylic acids; acidity ofα-H atoms: enolate ion formation; reactivity of enolate ions; alkylation of enolate ions; mechanism of carbonyl condensation reactions;condensations of aldehydes and ketones: the Aldol reaction; dehydration of Aldol products; the Claisen condensation reaction; the Michael addition.

熟练掌握酮式－烯醇式互变异构；烯醇的反应：α-H的活性；醛酮的α卤代反应；羧酸的α-溴代反应；α-H的酸性：烯醇负离子的形成；烯醇负离子的反应；烯醇负离子的烃基化；羰基化合物的缩合反应机理；醛酮的缩合反应－Aldol缩合；Aldol缩合产物的脱水反应； Cleisen 酯缩合反应；麦克尔加成反应。

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。

This paperindicated that it was good for condensation reaction when benzene-ring bearingelectron-attaching groups. It also showed that and the 6-hydroxyl group could bereacted with acyl halide, haloid ether and halo alkene, but not with halo alkane. It wasnot only the first time to find that the reaction product of D-mannitol and aromaticaldehyde is tri-condensation derivatives, but also the first time to obtain thep-phthaldehyde-sorbitol derivatives containing eight hydroxyl groups.

研究发现：苯环上有吸电子基团时对缩合反应有利；多元醇缩醛衍生物6-羟基除与酰氯反应外，也能和卤代酸酯、溴代烯反应，但不与卤代烷反应；首次发现D-甘露醇与醛反应主要得到三缩合物；首次合成了含有8个羟基的对苯二甲醛和山梨醇的缩合物。

The way to prepare iodomethane using methanol, potassium iodine and acid as regents has the disadvantages such as many side reactions and low yield, while the synthesize route from dimethyl sulfate and potassium iodine has the advantages of high yield and simple separation.

醇与氢卤酸作用是制备卤代烃的常用方法，以甲醇为试剂，以碘化钾与酸作用生成氢碘酸制备碘甲烷的方法存在副反应多、收率不高的特点；而以硫酸二甲酯及碘化钾为试剂的合成路线具有操作容易、收率高、纯化简单的优点。

Accordingly a further feature of the invention is a combined process wherein a dialkyl phenylethylmalonate is made from an alkyl phenylacetate and a dialkyl carbonate by a process comprising adding to a quantity of sodium which is covered with a hydrocarbon solvent boiling above 100°C, at least a chemically equivalent proportion of a lower aliphatic alcohol, subsequently adding an approximately equivalent proportion of a dialkyl carbonate and of an alkyl phenylacetate, heating the mixture to induce reaction and continuously distilling out the alcohol formed from the reaction zone and finally causing the sodio diethyl phenylmalonate so obtained to interact with an ethylating agent, such as ethyl halide, diethyl sulphate of ethyl p-toluene-sulphonate.

因此，本发明的另一个应用是一个组合工艺过程：二烷基苯基乙基丙二酸酯由烷基乙酸苯酯和二烷基碳酸酯得到，具体工艺过程是：向覆盖有沸点超过一百摄氏度的团庆化合物溶剂的金属钠中添加至少化学平衡的低级脂肪族醇，然后加入大约相同当量的二烷基碳酸酯和烷基乙酸苯酯，加热混合物引导反应进行，持续蒸馏把形成的醇类从反应区域移出，最后使获得的二乙基苯基丙二酸酯和乙基化试剂如卤代乙烷，二乙基硫酸酯形成乙基p-甲苯磺酸酯。

The conversion of alcohols to alkyl halides was investigated using acidic ionic liquid X as halogenating agent, acidic catalyst as well as medium.

2以酸性离子液体X兼作卤代试剂、反应介质和酸性催化剂，研究了醇转化为卤代烃的反应。

The conversion of alcohols to alkyl halides was investigated using acidic ionic liquid X as halogenating agent, acidic catalyst as well as medium. The reactions of primary alcohols gave very satisfactory conversions and selectivities except for the substrates with lower boiling point,such as n-octanol and benzyl alcohol. They obtained the corresponding halides with almost quantitative yields(95%-100%).The secondary alcohols also gave the corresponding halides with excellent conversions, however, the by-products of dehydration were detected.

伯醇除某些低沸点底物外，都以高转化率(最高达100％)和高选择性(最高达100％)转化为相应的氯代烃、溴代烃和碘代烃，例如正辛醇、苯甲醇，在X中进行卤代反应得到令人满意的结果，无论氯代、溴代还是碘代得到卤代产物的收率一般都很好华东师范大学化学系01级博士学位论文(95十100%)，极少有重排产物及脱水产物被检测出来。

Hence, for the whole process, the reaction consumed equivalent of halogen acid and alcohol to produce halide and water.

反应实际消耗的是等当量的氢卤酸和醇生成卤代烃和水，是制备伯卤代烃非常有效和清洁的方法。

I didn't watch TV last night, because it .

昨晚我没有看电视，因为电视机坏了。

Since this year, in a lot of villages of Beijing, TV of elevator liquid crystal was removed.

今年以来，在北京的很多小区里，电梯液晶电视被撤了下来。