芳基化

To improve the cyano reactivity, cyano-terminated PPENs were prepared by the end-capping reaction of PPEN-OL with CBN; benzonitrile terminated polys were also prepared by the polycondensation of excess 4,4'-oxydianiline with 1,2-dihydro-2-(4-carboxyphenyl)-4-[4-(4-carboxyphenoxyl)phenyl]-phthalazinone, followed by end-capping with CBA. The polymers synthesized exhibited good solubility in NMP, DMAc and DMF, and were crosslinked to afford phenyl-s-triazine-containing polymers under the similar conditions.

为提高氰基活性，以对氯苯腈为原料，对PPEN-OL进行封端，设计合成了含氰端基的聚芳醚腈；以含二氮杂萘酮联苯结构二酸单体与4，4'-二氨基二苯醚为原料，经Yamazaki膦酰化缩聚，并用对氰基苯甲酸进行封端，合成了含氰端基的聚芳醚酰胺。

Water,Hydrogenated Polyisobutene,Cyclohexasiloxane,Glycerin,Alcohol Denat,Cetearyl Alcohol,PEG-20,Petrolatum,C13-14 Isoparaffin,Zea Mays Oil,Tocopheryl Acetate,Hydroxypropyl Tetrahydropyrantriol,Hydrolyzed Soy Protein,CI 14700/Red 4,Phenoxyethanol,Adenosine,PEG-100 Stearate,Ethylparaben,Triethanolamine,Polyacrylamide,Malus Domestica Stem Cell Culture,CI 19140/Yellow 5,Dimethyl Isosorbide,Dimethicone,Dimethiconol,Limonene,Xanthan Gum,Pentaerythrityl Tetra-Di-T-Butyl Hydroxyhydrocinnamate,Linalool,2-Oleamido-1,3-Octadecanediol,Capryloyl Salicylic Acid,Acrylates/C10-30 Alkyl Acrylate Crosspolymer,Passiflora Edulis Seed Oil,Disodium EDTA,Castanea Sativa Seed Extract,Butyrospermum Parkii· Cetyl Alcohol,Butylene Glycol,Octyldodecanol,Cetearyl Glucoside,Methylparaben,Citronellol,Prunus Armeniaca Kernel Oil,Laureth-7,Coumarin,Oryza Sativa Bran Oil,Glyceryl Stearate,Fragrance

水，甘油，氢化聚异丁烯，液体石蜡/矿油，丁二醇，环己硅氧烷，鲸蜡醇，甘油硬脂酸酯，棕榈油，玉米胚芽油，PEG-100硬脂酸酯，白蜂蜡/蜂蜡，肉豆蔻醇肉豆蔻酸酯，石蜡，香精，腺苷，苧烯，山梨醇，CI 14700，CI 19140，稻糠油，杏仁油，EDTA二钠，羟丙基四氢吡喃三醇，苯氧乙醇，聚乙二醇-14M，异十六烷，氢氧化钠，辛基十二醇，季戊四醇四（双-t-丁基羟基氢化肉桂酸）酯，山梨坦三硬脂酸酯，水解大豆蛋白，卡波姆，鸡蛋果籽油，苹果果实提取物，欧洲栗籽提取物，异山梨醇酐二甲醚，聚山梨醇酯-80，辛酰水杨酸，2-油酰胺基-1，3-十八烷二醇，氯苯甘醚，麦芽糖醇，香豆素，黄原胶，微晶蜡，丙烯酰胺/丙烯酰基二甲基牛磺酸钠共聚物，丙二醇，芳樟醇，香茅醇，玉米油，羟苯丙酯，羟苯甲酯

The influence of each condition on the reaction speed and yield was studied, and the optimal conditions were: the ratio of the amount of substance of aromatic amine and heptafluoro-isopropyl iodine was 1:1.1~1.5, the amount of substance of sodium dithionite, sodium bicarbonate, aniline compounds were respectively 1.1~1.3, the amount of substance of phase transfer catalyst TBAB and aniline compounds was 0.05~0.1, the concentration of aniline compound was 0.5~1.0 mol/L, reaction temperature was 10~20 ℃, and the solvent was aether.

最佳结果为：芳胺与七氟异丙基碘的物质的量比1：1.1~1.5，连二亚硫酸钠、碳酸氢钠与苯胺的物质的量分别为1.1~1.3，相转移催化剂四丁基溴化铵与苯胺的物质的量比在0.05~0.1，溶剂总用量使苯胺浓度在0.5~1.0 mol/L；反应温度10~20℃；溶剂采用乙醚。取代基供电子性越强，反应时间越短，产率越高；氨基的对位优先反应，氨基的邻位较难发生反应；且七氟异丙基总是优先取代在芳环电子云密度较高的位置上。

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。

In order to find biologically active urea compounds,seven new N-[5-(3-pyridyl)-1,3,4-thiadiazol-2-yl]-N'- urea derivatives were synthesized by the reaction of 2-amino-5-(3-pyridyl)-1,3,4-thiadiazole with aroylazides,which were prepared starting from carboxylic acids,ethyl chloroformate and sodium azide by one-pot procedure.

为了寻找高生物活性的脲类化合物，通过2-氨基-5-(3-吡啶基)-1，3，4-噻二唑与酰基叠氮化物反应，设计合成了7个新的N-[5-(3-吡啶基)-1，3，4-噻二唑-2-基]-N'-取代苯基脲，其中芳酰基叠氮化物是以芳酸、氯甲酸乙酯、叠氮化钠为起始原料采用&一锅法&所制得。

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。

It was found that the thermodynamically unfavourable isomerization of quadracyclane to norbornadiene could be accomplished in the presence of toluene or durene as a co-sensitizer.

首次发现在甲苯、杜苯等芳烃共敏化下，可以使原来不能进行的、热力学不利的四环烷→降冰片二烯异构化得以进行，并根据CIDNP结果提出这是由于生成了敏化剂/底物/芳烃三元基激络合物使反应的势能面改变造成的并促进单线态的系间窜跃。

The p-tert-butyl calix arene (n=4,6,8) were synthesized by p-tert-butyl phenol, formaldehyde aqueous solution as raw materials. Six kinds of calixarene oligomeric surfactants were prepared by etherification of the calix arene with 1,3-propane sultone and 1,4-butane sultone.

以对叔丁基苯酚、甲醛为主要原料合成杯芳烃母体对叔丁基杯芳烃(n=4，6，8)；以1，3-丙烷磺内酯、1，4-丁烷磺内酯为醚化试剂，经Williamson醚化反应，合成出6种杯芳烃基低聚表面活性剂。

The experimental results show that the distributions of content and toxicity equivalent quantity of PAHs in raw coal are similar to coal gasification but this compositions and contents are different. The rise of coal rank leads to the decrease of the content and TEQ of PAHs in raw coal and the increase of TEQ during coal gasification, while the content of PAHs emission from coal gasification increases first and then decreases with the increase of coal rank. The total PAHs contents generated in coal gasification of some sorts of coals are higher than in raw coal. The types of PAHs formed in coal gasification include undecomposed PAHs in raw coal, pyrosysthensis PAHs, and radical polymerization PAHs at high temperature.

试验结果表明：煤气化前后多环芳烃质量分数和毒性当量质量分数的分布特徵相似，但多环芳烃的组成和质量分数不同；煤化程度增加，原煤多环芳烃质量分数和毒性当量质量分数减小，煤气化多环芳烃质量分数先增后减，毒性当量质量分数与煤化程度呈线性关系；部分煤种气化多环芳烃的质量分数高於原煤多环芳烃质量分数，且煤气化多环芳烃的种类分为原煤未分解的多环芳烃、热解合成的多环芳烃、自由基高温缩合生成的多环芳烃。

Monophenyltin trichloride reacts withdicarbonyl dicyclopentadienyl titanium immediately at room temperature, but no ti-tanium-tin complex produced, and the products were diphenyltin dichloride〓 and tin or stannous Chloride. When diaryltin dihalides were used, only the chlorides and bromides reacted with 〓form the complexes containing titaninm-tin bond,〓. but the corresponding iodide complex was not found. This reaction is Sensitive totemperature,when the temperature is belw 10℃,the reaction hardly takes place,but as the temperature is above 25℃,more 〓 will be found and the reactionbecome more complex.

Ph-SnC〓室温下即可与Cp〓迅速反应，但不生成含钛一锡链的化合物，而是生成Ph〓和Sn或Sn〓二芳基二卤化锡化物中，只有氯化物和溴化物才能和〓反应生成含钛〓锡键的化合物〓相应的碘化物则不行，而且反应对温度比较敏感，低于10℃，反应几乎不能进行，而高于25〓，则会生成更多的〓，在回流条件下得不到含钛〓锡键的化合物，只能得到分解产物，〓和Sn或〓。

However, as the name（read－only memory）implies, CD disks cannot be written onorchanged in any way.

然而，正如其名字所指出的那样，CD盘不能写，也不能用任何方式改变其内容。

Galvanizes steel pallet is mainly export which suits standard packing of European Union, the North America. galvanizes steel pallet is suitable to heavy rack. Pallet surface can design plate type, corrugated and the gap form, satisfies the different requirements.

镀锌钢托盘多用于出口，替代木托盘，免薰蒸，符合欧盟、北美各国对出口货物包装材料的法令要求；喷涂钢托盘适用于重载上货架之用，托盘表面根据需要制作成平板状、波纹状及间隔形式，满足不同的使用要求。