卤烃

The sample can be admitted to the ion source only after it is completely vaporized, otherwise,the result of masurement will be severly distorted by fractional distillation.

用接近于待测样品中所含的卤代烃的杂质样品与纯净六氟化铀可配置出已知卤代烃含量的"杂质标样"。

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 dissertation mainly consists of two parts:1. The Reaction Chemistry of Alkynes under Palladium Catalysis Part 1 studies the reaction α,β-unsaturated carbonyl compounds with alkenylpalladium intermediate generated by nucleopalladation, and discovered 1 the Pd-catalyzed tandem addition reaction of halides, alkynes and α,β-unsaturated carbonyls,2 the four-component tandem addition reaction of halides, alkynes and α,β-unsaturated carbonyls, 3 the tandem intramolecular oxypalladation-conjugate additionreaction of alkynoic acids with α,β-enals. These new reactions provide notonly efficient highly stereoselective methods for the synthesis of γ,δ-unsaturated,polyunsaturated carbonyl compounds and γ-lactonic aldehydes, but also thebasic transformations for a number of C-C bond formation reactions which can be usedto design synthesis of many acyclic, cyclic or polycyclic compounds.

本论文的主要工作分为两个部分：一、钯催化下炔烃的反应化学在本小组前人工作的基础上，我们详细研究了炔烃亲核钯化产生的烯基钯中间体与α，β-不饱和羰基化合物的反应，发现两价钯催化下卤离子-炔烃-α，β-不饱和醛酮的串联加成反应、卤离子-炔烃-α，β-不饱和醛酮的西组分串联加成及炔酸分子内氧钯化-串联Michael型加成反应；由此发展了γ，δ-不饱和醛酮、多不饱和羰基化合物和带有醛酮基侧链的γ-丁内酯衍生物的高立体选择性合成方法，这一过量卤离子存在下的烯基钯对α，β-不饱和羰基化合物共轭加成反应的发现，为大量碳-碳键形成反应的实现提供了基础，使我们能够从这一基本反应出发，设计和开发多种分子内、分子间的碳碳成键反应，以好的立体、区域选择性组建开链、环状及多环类型的化合物。

An oxidative halogenation process involving contacting a reactant hydrocarbon selected from methane, a halogenated C1 hydrocarbon, or a mixture thereof with a source of halogen and, preferably, a source of oxygen in the presence of a rare earth halide or rare earth oxyhalide catalyst, so as to form a halogenated C1 hydrocarbon having a greater number of halogen substituents as compared with the reactant hydrocarbon.

一种氧化卤化方法，包括使一种选自甲烷、卤代C1烃、或其混合物的反应剂烃与卤素源和优选的氧源，在稀土卤化物或稀土卤氧化物催化剂存在下，进行接触，从而形成一种卤代C1烃产物，它较所述反应剂烃具有更多数目的卤素取代基。

Halogenated aromatic compounds with great q〓(the most negative net atomic charges on an atom of the molecule), ENC (electron-nuclear attraction energy of the one-center term for the carbon atoms of the weakest carbon-halogen bond), qc (thenet atomic charges on the carbon atom of the weakest carbon-halogen bond) and E〓 tend to be reductively dehalogenated slow, while halogenated aromatic compounds with high values of △E (the difference of front-line orbital energy), EEC (electron-electron repulsion energy of the one-center term for the carbon atoms of the weakest carbon-halogen bond), Mw, q〓 and α tend to be reductively dehalogenated fast.

卤代芳烃化合物的整个分子的最负的原子净电荷，键序最小的碳卤键中碳原子的单中心项电子-核吸引能，该碳-卤键上碳原子的净电荷和E〓与该卤代芳烃化合物还原脱卤的速率常数负相关；而前线轨道间隙能，键序最小的碳卤键中碳原子的单中心项电子-电子推斥能，Mw，q〓和α与该卤代芳烃化合物还原脱卤的速率常数正相关。

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。

The process includes the following steps: dissolving bromine in halogenated hydrocarbon, dropping the bromine solution into reactant system comprising pentabromo toluene, halogenated hydrocarbon, free radical initiator and hydrogen peroxide at 50-65 deg.c, and heating to 60-78 deg.c for reflux reaction until the reactant system becomes transparent; filtering the resultant to obtain solid product, washing with carbon tetrachloride and water separately and vacuum drying to obtain pentabromo benzyl bromide.

具体步骤为：将五溴甲苯、卤代烃、自由基引发剂和过氧化氢组成的反应体系加入到三颈瓶中，将0.07～0.1mol的溴溶于50ml卤代烃配成溶液，在50-65℃温度下滴加到反应体系中，滴加时间为50-70分钟，然后升温至60-78℃温度下回流反应，至反应体系逐渐变透明，且不再产生气泡时，将所得产物过滤，得到固体产物，分别用CCl 4 和水洗涤，真空干燥，即得到五溴苄基溴；其中，五溴甲苯与溴的摩尔比为1∶0.7-1∶1.0，溴与过氧化氢的摩尔比为1∶1.0-1∶1.4，自由基引发剂加入量为五溴甲苯重量的1-10％，卤代烃的加入量为反应体系体积的40％-100％，所用溶剂可以直接进行下一批反应，不需要更换溶剂或蒸馏提纯。

There is still a black market in CFCs, and halon production has increased in countries such as Brazil, India and Mexico.

现在含氯氟烃还存在着黑市交易。在巴西、印度和墨西哥等国家，卤烃的生产依旧有增无减。言午选译

Generally the catalysts have high activity and good selectivity. At present the coupling reactions of organoborahes with terminal olefins s acid chlorides and aryl halides play an important synthetic approaches in organoborane chemical. The catalysts can be used by many kinds of organometal compounds such as: irons cobalt nickel ruthenium rhodium palladiums titaniums zirconiums tins indium and lithium organic compounds; The achievement has been amazed in preparing of unsaturated or saturated compounds and in synthesizing of natural products bioactive molecules and chiral compounds.

目前，卤代烃与不饱和烃的偶联反应和有机硼试剂与酰卤和卤代烃的偶联反应已成为有机合成的研究热点，此类反应可用铁、钴、镍、钌、铑、钛、锆、锡、铟、锂等多种有机金属化合物来催化，用于形成含饱和或不饱和C-C键的化合物，并已在天然产物、液晶、具有生理活性物质和手性化合物的合成中应用。

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。