新型含膦聚合前体4-溴-3-(二苯基膦酰基)-1-(1,2,2-三氟乙烯氧基)苯的合成

以间氨基苯甲醚为原料,经重氮化、溴化、Pd催化偶联、氧化、1,2-二溴四氟乙烷氟烷基化、Zn粉还原脱卤消除等反应制得合成全氟环丁基芳基醚聚合物的新型含膦聚合前体——4-溴-3-(二苯基膦酰基)-1-(1,2,2-三氟乙烯氧基)苯,其结构经NMR和MS表征。     

含有三氟乙烯基芳基醚侧基的聚丙烯酸酯的合成与表征

研究了聚丙烯酸酯侧基上引入三氟乙烯基芳基醚结构单元的方法. 首先, 合成了含有三氟乙烯基芳基醚侧基的丙烯酸酯单体, 然后通过原子转移自由基聚合实现了该单体的均聚和无规共聚, 得到了含有三氟乙烯基芳基醚侧基的聚丙烯酸酯聚合物, 聚合物的分子量分布较窄. 通过控制共聚投料比, 可以得到具有不同含量三氟乙烯基芳基醚侧基的无规共聚物.     

4-(2,2-二溴代乙烯基)二芳基醚的合成及应用

以酚类化合物和4-溴苯甲醛为原料,通过铜催化的Ullmann类型反应和Corey-Fuchs两步反应,高收率地合成了一组4-(2,2-二溴代乙烯基)二芳基醚(含偕二溴乙烯基的二芳醚)类化合物。实验表明,该类化合物可发生消除反应转化为4-乙炔基二芳基醚,并通过和苄基叠氮之间的铜催化[3+2]环加成反应,进一步制备含三氮唑官能团的二芳基醚类化合物。     

由三氟异丙烯基溴化镁制备羧酸

以三氟丙烯和溴为原料加成制得1,2-二溴三氟丙烷,脱溴化氢得到2-溴三氟丙烯,再在一定条件下合成2-溴三氟丙烯的格氏试剂（三氟异丙烯基溴化镁）,与CO2反应最终生成1-溴-2-三氟甲基丙酸。 用碳酸钠溶液萃取的方法得到0.8 g产品,纯度为99.6%,收率为3.6%。 对产物进行了MS、IR、1H NMR和13C NMR等表征,并分析了主要副产物1,2-二氟丙二烯和2,3-二三氟甲基-1,3-丁二烯及其与未反应的2-溴三氟丙烯间的[2+2]或[2+4]环加成反应产物。 确定以2-溴三氟丙烯为原料经格氏反应制羧酸较好的反应条件为：以THF为溶剂,1,2-二溴乙烷作引发剂,制备格氏试剂温度为30 ℃,CO2与格氏试剂反应温度为0 ℃。     

迭代Suzuki偶联反应合成全氟环丁基芳基醚齐聚物的研究

对迭代Suzuki偶联反应合成全氟环丁基芳基醚齐聚物的方法进行了研究, 并合成了全氟环丁基芳基醚齐聚物. 首先从对溴苯酚出发, 合成了含有一个全氟环丁基芳基醚结构单元的中间体3. 芳基硼酸与中间体3进行Suzuki偶联反应, 得到了含有一个全氟环丁基芳基醚结构单元的硼酸. 重复与中间体3进行Suzuki偶联反应, 从而合成了全氟环丁基芳基醚二聚体和三聚体. 最后通过热环化二聚反应合成了全氟环丁基芳基醚三聚体、五聚体和七聚体.     

镍催化(Z)-1,2-二芳硫基-1,2-二芳基烯烃与格氏试剂偶联反应制备多取代烯烃

以5.0 mol%NiCl_2(dppe)作为催化剂,催化(Z)-1,2-二芳硫基-1,2-二芳基烯烃和格氏试剂偶联反应,高选择性制备了一系列多取代烯烃化合物.有机硫基团经水解、氧化后生成二芳基二硫醚,实现了硫资源的循环利用,符合绿色化学要求.同时,此方法对不同取代的(Z)-1,2-二芳硫基-1,2-二芳基烯烃和格氏试剂均具有较好的适用性,以较高的产率获得相应的目标产物,为多取代烯烃的制备提供了有效的路径.     

氟取代聚芳醚酮低温合成及其结构研究

通过傅克酰基化反应合成4,4'-二(4-氟苯甲酰基)二苯醚、4,4'-二(五氟苯甲酰基)二苯醚、4,4'-二(4-氟苯甲酰基)二苯硫醚以及4,4'-二(五氟苯甲酰基)二苯醚4种长链双卤单体,并进一步制备了含二氮杂萘酮聚芳醚酮聚合物.通过多氟取代双卤单体在含二氮杂萘酮聚芳醚酮聚合物主链中引入氟原子.多氟取代双卤单体具有多...     

氢氧化铯催化二硫醚、二碲醚与端炔反应研究

氢氧化铯催化下, 以商业THF作溶剂, 在氮气氛中二芳基二硫醚与端炔室温反应, 立体选择地生成(Z)-1,2-二芳硫基烯. 在空气氛中反应, 得到(Z)-1,2-二芳硫基烯与炔硫醚的混合物. 二芳基二碲醚与端炔反应, 不论在氮气氛中或空气氛中, 都只产生炔碲醚. 但是在氮气氛中炔碲醚的收率仅为空气氛中反应的50%, 对上述反应机理进行了讨论.     

磺酸基在侧链萘环上的磺化聚芳醚质子交换膜的制备与性能研究

以β-萘甲醛和2,6-二甲基苯酚为原料,合成出一种新型双酚单体.以此双酚单体和二氟单体(4,4'-二氟二苯甲酮或4,4'-二氟二苯砜)为基础,通过亲核取代反应,制备出两种高分子量聚芳醚.用氯磺酸对聚合物进行磺化,得到了2种磺酸基在侧链萘环上的磺化聚芳醚.该磺化聚芳醚能溶于N,N-二甲基乙酰胺(DMAc)、N,N-二甲基甲酰胺(DMF)、二甲基亚砜(DMSO)等常见的有机溶剂,通过溶液浇注的方法制备出光滑、柔韧的膜.用红外光谱(FTIR),核磁共振谱(1H-NMR)表征了聚合物结构.用示差扫描量热仪(DSC),热重分析仪(TGA)研究了聚合物的耐热性能.结果表明,这些侧链磺化的质子交换膜具有高的电导率(4.2×10-2S/cm)、高的机械强度、低的溶胀率和较好的氧化稳定性.     

阴离子协助镍催化碳氟键官能团化反应机理研究

由于碳-氟键的化学惰性,其高效催化转化一直是有机化学中的难题之一.本文运用密度泛函理论(DFT)计算,研究了镍催化碳-氟/碳-氢键交叉偶联反应构建2-芳基噁唑衍生物的机理.计算结果表明,体系中氟负离子能够稳定零价镍金属催化剂,得到氟负离子配位的阴离子镍活性催化物种.在氟负离子协助下碳-氟键对阴离子镍氧化加成得到二价芳基镍物种,是催化循环的速控步骤.在碳氢键切断过程中,Br?nsted碱直接进攻去质子,得到二芳基镍中间体,最终通过还原消除得到交叉偶联产物.在这一过程中,阴离子镍活性催化物种的稳定性明显高于通常推测的中性镍催化物种,这一模型为理解惰性碳-氟键活化反应机理提供了新的思路.     

Halofluorination of 1,2-difluoro-1,2-di(p-tolyl)ethene, 1,2,3,4-tetrafluoro-1,4-di(p-tolyl) butadiene and its nonfluorinated parent compounds

The reactions of (E)-1,2-difluoro-1,2-di (p-tolyl) ethene (1) with N-bromo- or N-chlorosuccinimide gave mainly the expected halofluorination products 1-bromo-1,2-di(p-tolyl)-1,2,2-trifluoroethane (2) or 1-chloro-1,2-di(p-tolyl)-1,2,2-trifluoroethane (4), respectively. As a side reaction halogenation of the double bond has been obtained. With (E,E)-1,4-di(p-tolyl)-1,2,3,4-tetrafluorobuta-1,3-diene (6) under the same conditions the products of 1,2- and 1,4-addition or its consecutive hydrolysis products were isolated. (E)-Stilbene (19) on bromofluorination gave solely erythro-1-bromo-2-fluoro-1,2-diphenylethane (20), while with 1,4-diphenylbuta-1,3-diene (17) mainly higher molecular weight products were formed.     

Synthesis of 2-bromo-1-aryl-1H-indenes via a Ag(I) promoted domino 2π-electrocyclic ring-opening/4π-electrocyclization reaction of 1,2-diaryl substituted gem-dibromocyclopropanes

2-Bromo-1-aryl substituted indenes can be synthesized from 1,2-diaryl substituted gem-dibromocyclopropanes via a domino reaction sequence. The cascade reaction involves silver(I) promoted ionization and 2π-disrotatory electrocyclic ring-opening, followed by a 4π-conrotatory electrocyclic ring closing reaction of the allylic carbocation intermediate. Reaction conditions utilize silver tetrafluoroborate (AgBF₄) in dichloroethane at 65 °C. Selectivity effects for the electrocyclization were also studied. The 2-bromoindenes can be further functionalized using cross-coupling reactions, such as the Suzuki–Miyaura protocol. The alkene π-bond of the indenes can also be isomerized to give the thermodynamically more stable 2-bromo-3-aryl-1H-indene isomers using triethylamine in dichloromethane at room temperature.     

BHEN缩聚反应研究

通过NDC与EG酯交换反应合成中间体2,6-萘二甲酸乙二醇酯(BHEN), 采用正交实验设计方法, 研究了BHEN缩聚反应合成PEN的影响因素, 筛选出醋酸锌为反应催化剂位阻酚1010为抗氧剂; 并确定了其反应温度为295 ℃; 每摩尔BHEN用催化剂的量为4×10^-4 mol, 反应时间为180 min; 每摩尔BHEN用抗氧剂的量为1×10-⁵ mol.     

Evidence for intermolecular interaction between sulfonium and sulfide sulfur atoms and its application to synthesis of cyclic bis(disulfide) dimer

On the basis of the remote Pummerer reaction of p-bis(alkylthio)-aromatic S-oxides, the intermolecular interaction between the sulfonium and sulfide sulfur atoms is described. (1) In marked contrast to the Pummerer reaction of 1b-d(3) with (CF(3)CO)(2)O (J. Org. Chem. 1999, 64, 3190-3195), the reaction of 3,3',5,5'-tetramesityl-4-(trideuteriomethylsulfinyl)-4'-(methylthio)biphenyl (1a-d(3)) as a sterically hindered analogue of 1b gave only 2a-d(2). (2) Both reactions of the two unsymmetrical regioisomers of 1-(ethylthio)-4-(methylthio)benzene S-oxide (5a and 5b) with (CF(3)CO)(2)O afforded a mixture of the mono-Pummerer products 6a and 6b, the bis-Pummerer product 7, and the bis-sulfide 8 in a similar ratio. The quenching at the initial stage of both reactions produced 5a, 5b, 8, and the bis-sulfoxide 10 in a similar ratio. These results indicate the equilibrium in the intermolecular interaction between the sulfur atoms. (3) The reaction of the p-bis(benzylthio)-aromatic S-oxide 16 with (CF(3)SO(2))(2)O gave the cyclic bis(disulfide) dimer 17 for the diphenyl sulfide and diphenylmethane spacers or the cyclic tetrakis(disulfide) tetramer 19 for the benzene and biphenyl spacers via the debenzylation of an intermolecular dithia dication. The cyclic bis(dithia dication) dimer A resulting from the intermolecular interaction between the sulfonium and sulfide sulfur atoms is proposed as an intermediate throughout the present reactions.     

Peculiarities of inclusion complex formation in the 1,4-benzodiazepine-benzene system

5-Phenyl-1-methyl-7-bromo-3-hydroxy-1,2-dihydro-3H-1,4-benzodiazepin-2-one and its 5-(o-chloro)-phenyl analog form 2:1 (host:guest) inclusion compounds with benzene. The crystal structures of the compounds were studied by the single-crystal XRD method and were interpreted as host (H) (benzodiazepine) — guest (G) (benzene solvent molecule) complexes. The studied structures, revealing H-H and H-G interactions as both typical hydrogen bonds and π-π, C-H?π weak interactions, may serve as models for ligand-receptor binding.     

Reaction of Styrene with Chlorine Dioxide

Reaction of styrene with chlorine dioxide under various conditions selectively produces 1-phenyl- 2-chloroethanone, with 1-phenyl-2-chloroethanol, 2-hydroxy-1-phenylethanone, (1,2-dichloroethyl)benzene, (2-chloro-1-phenyl)ethene, and (1,2,2-trichloroethyl)benzene isolated as reaction byproducts.

     

两种新型丁二炔衍生物的合成

以3,5-二溴-1-｛3-（十二烷氧基）-2-［（十二烷氧基）甲基］丙氧基｝苯和2-甲基-3-丁炔-2-醇为原料,经选择性Sonogashira偶联反应,Sonogashira偶联反应和去硅保护基反应制得中间体--3-乙炔基-5-（3-甲基-3-羟基)-丁炔基-1-（3-十二烷氧基）-2-｛［（十二烷氧基）甲基］丙氧基｝苯（6）; 6经改良的Glaser偶联反应(CuI为催化剂,Et₃N为溶剂)合成了一个新型的丁二炔衍生物（1）。 6与2,2′-［（2,5-二碘-1,4-亚苯基）双（氧基）］双（四氢-2H-吡喃）经Sonogashira偶联,脱 THP保护基和改良的Glaser偶联反应合成了一个新型的丁二炔衍生物（2）。中间体,1和2的结构经¹H NMR, ¹³C NMR和MALDI-TOF-MS表征。     

Photochemical reactions of acyl iodides with aryl halides

Photochemical reactions of acyl iodides RC(O)I (R = Me, Ph) with aryl halides, fluoro-, chloro-, and bromobenzenes, 1,4-dibromobenzene, 2- and 3-bromotoluenes, and 4-bromo-1,2-dimethylbenzene, were studied. Acetyl iodide reacted with chloro- and bromobenzenes and 1,4-dibromobenzene according to the exchange pattern to give iodobenzene and 1,4-diiodobenzene, respectively. No halogen exchange was observed in the reactions of acetyl iodide with fluorobenzene and hexafluorobenzene. Benzoyl iodide failed to react with chloro- and brombenzene under UV irradiation but underwent polycondensation with formation of black nonfusible oligomers which were found to possess paramagnetic and semiconducting properties. Ultraviolet irradiation of a mixture of MeCOI with 2- or 3-bromotoluene, as well as with 4-bromo-1,2-dimethylbenzene, also led to the formation of polymeric products as a result of polycondensation of aryl iodides formed initially via replacement of bromine by iodine. Irradiation of benzoyl iodide in 2- or 3-bromotoluene involved recombination of benzoyl radicals to give benzil as the only product.     

Stereoselective synthesis of optically active disilanes and selective functionalization by the cleavage of silicon-naphthyl bonds with bromine

Optically active disilanes with one chiral silicon center, (R)-1,2-dimethyl-1-(naphth-1-yl)-1,2,2-triphenyldisilane and (R)-1,2,2-trimethyl-2-(4-methoxynaphth-1-yl)-1-(naphth-1-yl)-1-phenyldisilane, were obtained by the reaction of (S)-methyl(naphth-1-yl)phenylchlorosilane (> 99% ee) with methyldiphenylsilyllithium or by the reaction of methyldiphenylchlorosilane with optically active (S)-methyl(naphth-1-yl)phenylsilyllithium and by the reaction of (S)-methyl(naphth-1-yl)phenylchlorosilane (> 99% ee) with dimethyl(4-methoxynaphth-1-yl)silyllithium. Under the optimized conditions, the reactions proceeded with almost complete inversion for the cholorosilanes and retention for the silyl anions. Optically active disilanes with two chiral centers, (1R,2R)-1,2-dimethyl-1,2-di(naphth-1-yl)-1,2-diphenyldisilane and (1S,2S)-1,2-di(4-methoxynaphth-1-yl)-1,2-dimethyl-1,2-diphenyldisilane, were obtained in high optical purity by the reactions of corresponding optically active halogenosilanes (Cl or F) with optically active silyllithiums. The silicon-silicon bond and the silicon-naphthyl bond of (R)-1,1,2-trimethyl-1,2-di(naphth-1-yl)-2-phenyldisilane and (1R,2R)-1,2-dimethyl-1,2-di(naphth-1-yl)-1,2-diphenyldisilane were cleaved without selectivity on bromination. The silicon-(4-methoxynaphth-1-yl) bond of (R)-1,2,2-trimethyl-2-(4-methoxynaphth-1-yl)-1-(naphth-1-yl)-1-phenyldisilane was regiospecifically cleaved, followed by the stereoselective cleavage of the remaining chiral silicon-naphthyl bond (94% inversion). Although the silicon-(4-methoxynaphth-1-yl) bonds of (1S,2S)-1,2-di(4-methoxynaphth-1-yl)-1,2-dimethyl-1,2-diphenyldisilane (> 99% ee) were regioselectively cleaved without silicon-silicon bond scission, remarkable racemization could not be avoided during the one-pot reaction.     

磷酸特地唑胺的合成新方法

以(5R)-3-(4-溴-3-氟苯基)-5-羟甲基噁唑烷-2-酮为起始原料,在[PdCl₂(dppf)]·CH₂Cl₂催化下与联硼酸频那醇酯反应得到硼化物,继而与5-溴-2-(2-甲基-2H-四唑-5-基)吡啶进行Suzuki反应得到特地唑胺,收率82.9%。 分别考察了催化体系对硼化反应和Suzuki反应的影响,确定了较佳的反应条件。 特地唑胺与二苄基N,N-二异丙基亚磷酰胺反应得到二苄基保护的磷酸特地唑胺,随后经Pd/C脱苄得到磷酸特地唑胺,总收率66.2%。