芳基化

In chapter 4 an abnormal reaction that the nitro group of 1-aryl-2-nitroethenescan be easily replaced by the organic moity of FG-RZnI using Ni〓 and tertiaryamine as catalyst was first given. The experimental results show that in the presenceof catalytic amount of Ni〓 and tertiary amines, the reaction of FG-RZnI andl-aryl-2-nitroethenes give the substitution products l-aryl-l-alkene, instead ofMichael addition products.

通过实验发现，在催化量的Ni〓及叔胺催化下， l-硝基-2-芳基乙烯与烷基碘化锌并不进行Michael加成反应，而是发生1-硝基-2-芳基乙烯中硝基被取代的反应，生成了高产率的1-芳基-l-烯烃，由于此反应的原料易得、反应条件温和、产物的产率高，因而是合成l-芳基-1-烯烃的有效方法。

In the arylation reaction, the temperature was meliorated from -40℃ to -15℃, which could be easy controlled with ice-salt bath. Furthermore, the reaction could be carried out reposefully by adding the initiator.

其中在以2，5-二氟溴苯格氏试剂进行芳基化反应时，改进了反应条件，克服了文献使用的低温条件(-40℃)，简便了操作，同时通过加入合适的引发剂，使反应能够平稳进行。

The first synthetic route uses 1,2,4-trimethoxybenzene and chloroacetonitrile in forming 2,4,5-trimethoxy-a-chlor-acetophenone under the anhydrous condition, then the intermediate condensates with papaverine forming the core pyrro[2,l-a]isoquinoline, followed by formation and lactonization to form the lactone ring. The second synthetic route uses prepared aldehyde with prepared ethyl nitroacetate by Knoevenagel condensation to obtain 2-Nitro-3-(2,4,5-tris-methoxy-phenyl)-acrylic acid ethyl ester and 2-Nitro-3-(2,4,5-tris-benzyloxy -phenyl)-acrylic acid ethyl ester etal intermediates. The lamellarin skeleton could arise from condensation of the papaverine and these intermediates by Michael reaction, the ester group is provided for subsequent lactonization. The third synthetic route uses coumarin or indan-l,3-dione derivatives and papaverine to form lamellarin under basic conditions.

第一条路线首先从1，2，4-三甲氧基苯出发与卤乙腈作用合成卤代芳酮中间体，然后与罂粟碱反应合成开链片螺素，最后经乙酰化、去保护、成内酯环得到片螺素；第二条路线由制备的芳醛和制备的硝基乙酸乙酯经缩合得到2-硝基-3-芳基丙烯酸乙酯，然后由该中间体与罂粟碱反应，在完成关环的同时也引入酯基，最后去保护、成内酯环得到片螺素；第三条路线是由香豆素或茚二酮出发，经溴代后的中间体与罂粟碱反应，得到片螺素的基本框架。

By means of molecular designing, a series of sodium branched-alkyl benzene sulfonates weresynthesized through seven process, involving Frieded-Crafts reaction, Grignard reaction, sulfonationand neutralization. Those isomers have similar structure, carbons of same quantity, but the position ofalkylaryl dissimilarity. Liner fat acid, metaxylene and halogenated hydrocarbon of different carbonnumber were used as the starting materials. Optimum processing condition was confirmed consideringinfluence of a series of reaction factors such as feed proportioning, quantity of catalysts, quantitysolvent, reaction time, temperature and pressure. Eight kinds of isomers of sodium hexadecylxylolsulfonates were finally synthesized, and characterized by FT-IR.

本文通过分子设计，以不同碳数直链脂肪酸、间二甲苯以及不同碳数的卤代烷为原料，经酰基化、格氏反应、加氢还原、磺化及中和等反应，合成了结构相似、烷烃链碳数一定、芳基在烷烃链不同位置的烷基芳基磺酸盐同分异构体；并考察了原料配比、催化剂用量、反应时间、反应温度、溶剂用量、反应压力等一系列因素对各反应的影响，进而确定最佳工艺条件，最终合成出十六烷基二甲苯磺酸钠的八种同分异构体，利用 FT-IR 对产物结构进行了分析。

This review on organobismuth chemistry is carried out as the following four aspects:(1) the molecular structure characteristics and synthesis of new organobismuth compounds;(2) as reagents for cross-coupling, oxidation, arylation, and other reactions;(3) as catalysts for organic synthesis;(4) as medicines for the treatment of ulcers, anti-tumor and radio-therapy, etc.

本文回顾了近10多年来有机铋化学的研究状况，主要从以下4个方面进行综述：(1)新型有机铋化合物的合成途径与结构特征；(2)有机铋化合物作为交联偶合、氧化、芳基化和其它反应的试剂；(3)作为催化剂；(4)作为生物医药用于溃疡、肿瘤和放射治疗等。

Using classical diazotisation of anilines, 5-(4-aminophenyl)-10,15,20-triphenyl-porphyrin was converted to a series of meso-tetraarylporphyrins with different substituents, including 5-(4-hydroxylphenyl)-10,15,20-triphenylporphyrin (80%), 5-(4-chlorophenyl)-10,15,20-triphenylporphyrin (74%), 5-(4-iodinphenyl)-10,15,20-triphenylporphyrin (76%), 5-(4-hydrazinephenyl)-10,15,20-triphenylporphyrin (67%) and 5-(4-bisphenyl)-10,15,20-triphenylporphyrin (32%). Therefore an efficient way of synthesizing unsymmetrically substituted TAPs was developed.

利用芳胺的重氮化及重氮盐反应，研究了5-(4-氨基苯基)-10，15，20-三苯基卟啉上氨基官能团的转化反应，以较高产率合成了5-(4-羟基苯基)-10，15，20-三苯基卟啉(80%)、5-(4-氯苯基)-10，15，20-三苯基卟啉(74%)、5-(4-碘基苯基)-10，15，20-三苯基卟啉(76%)、5-(4-肼基苯基)-10，15，20-三苯基卟啉(67%)和5-(4-联苯基)-10，15，20-三苯基卟啉(32%)等一系列含单个para-取代基的meso-四芳基卟啉，为合成不对称取代的芳基卟啉提供一条有效途径。

A new convenient synthesis of a series of 1-aryl-2-propanones using aromatic amines as precursors, via diazo reaction and improved Meerwein arylation reaction under mild conditions, was achieved. In addition, 1-[3,5-bisphenyl]-2-propanone is a new compound among the synthesized compounds. This approach is an efficient synthetic method for the aryl-propanones with the different substituting groups.

以芳香胺为原料，经重氮化和改进的Meerwein芳基取代反应，合成了一系列的1-芳基－2-丙酮，其中1-（3，5-二三氟甲基苯基）2-丙酮是一个新化合物改进后的方法简化了合成步骤，提高了收率，可方便地用于在苯环上具有不同取代基的芳基丙酮的合成。

Under these conditions several aryl iodides bearing a wide range of functional groups were converted into the corresponding aryl azides in good yields.

在重新优化后的条件下，大部分不活泼芳基溴化物可以与叠氮化钠发生交叉偶联反应得到良好收率的芳基叠氮化合物，但是有拉电子基团取代的芳基溴化物与叠氮化钠的偶联反应则难以进行。

Under these conditions several aryl iodides bearing awide range of functional groups were converted into the corresponding aryl azides in good yields.

在重新优化后的条件下，大部分不活泼芳基溴化物可以与叠氮化钠发生交叉偶联反应得到良好收率的芳基叠氮化储蓄型投资银条合物，但是有拉电子基团取代的芳基溴化物与叠氮化钠的偶联反应则难以进行。

The recent research progress of oxidation carbonylation of amines/β-amino alcohols, alkoxycarbonylation of epoxides, carbonylative Suzuki coupling, carbonylative Sonogashira, and double carbonylation of aryl iodides has been presented, focusing on the carbonylation reactions studied by us in the past few years, with 81 references.

综述了胺／氨基醇类化合物氧化羰化、环氧化合物氢酯基化、碘代芳烃的羰化Suzuki偶联、羰化Sonogashira以及双羰基化等重要羰基化反应的研究状况，特别是结合本课题组近年来在该领域中的工作，并对羰基化反应的发展及应用前景进行了展望。

Breath, muscle contraction of the buttocks; arch body, as far as possible to hold his head, right leg straight towards the ceiling (peg-leg knee in order to avoid muscle tension).

呼气，收缩臀部肌肉；拱起身体，尽量抬起头来，右腿伸直朝向天花板（膝微屈，以避免肌肉紧张）。

The cost of moving grain food products was unchanged from May, but year over year are up 8%.

粮食产品的运输费用与5月份相比没有变化，但却比去年同期高8％。