蓝光诱导N-苯基甲基丙烯酰胺的烷基化环化合成吲哚酮衍生物的研究

室温条件下,以蓝色LED为光源诱导四(三苯基膦)钯[Pd(PPh_3)_4]催化激活烷基卤代烃生成烷基自由基,与N-苯基甲基丙烯酰胺发生烷基化环化反应来简单高效的合成21个3,3-二取代吲哚酮衍生物。在室温下即可反应,具有较好的底物适用性与官能团包容性,与含有多元环、烯烃、长链烷烃、大位阻的溴代物反应均能以较高的产率得到目标产物,产率为70%～87%,很大程度上提升反应的效率,且可避免底物预官能团化、转化率低、副产物多等问题,是探索制备吲哚酮类化合物和开发新试剂的一种更加绿色高效的方法。通过~1HNMR、~(13)CNMR和HR-MS确证产物的结构,选用2,2,6,6-四甲基哌啶-1-氧(TEMPO)来验证该反应可能经过自由基反应过程。     

原位生成自引发单体合成支化共聚物

以α-溴代异丁酸叔丁酯为引发剂,二乙烯苯为支化单体,苯乙烯为共聚单体,经原子转移自由基聚合原位生成自引发单体合成支化共聚物。用核磁共振法、凝胶渗透色谱法、三角激光散射法分别对聚合过程和聚合物进行了表征。结果表明：由于苯乙烯的引入,反应体系的交联得到了很好的控制,所得聚合物为支化结构。     

对溴碘苯的合成研究

以工业品对溴苯胺为原料,经重氮化、碘代合成了对溴碘苯。考察了酸介质、硫酸质量分数、有机溶剂的加入及碘代温度对收率的影响,得出较佳的合成条件：先将0.02mol对溴苯胺溶解在质量分数为20%的硫酸介质中,与0.021molNaNO2在-10℃下反应生成对溴苯基重氮硫酸盐,然后在溶液中加入氯仿与0.021molKI进行碘代反应,经简单后处理得到对溴碘苯粗产品（其中对溴碘苯HPLC纯度为98.4%）,提纯后总收率达80%,较改进前提高了15%。产物经IR和1HNMR进行了结构表征。改进后的方法大大提高了粗产品的纯度,避免了过柱子带来的麻烦,操作简便安全,过程易于控制,成本较低,更适于对溴碘苯的制备。     

E-β-溴代苏合香烯的研究进展

溴代苏合香烯是卤代烃类香料中的代表性产品,其成分主要为E-β-溴代苏合香烯。综述了E-β-溴代苏合香烯立体选择性合成的研究进展。     

两个ATRP大分子引发剂的合成与表征

以十二醇为引发剂,通过开环聚合反应合成单端羟基的聚己内酯(PCL),将PCL进一步与α-溴丙酰溴反应,合成了原子转移自由基聚合(ATRP)的大分子引发剂-α-溴代丙酸聚己内酯。通过α-溴丙酰溴与聚乙二醇(PEG)的反应合成了另一种ATRP大分子引发剂-α-溴代丙酸聚乙二醇酯。用1H NMR和IR证实了这两种大分子引发剂的结构。     

邻溴苯硼酸的合成研究

以邻溴苯胺为原料通过重氮化,碘代反应合成了邻溴碘苯,收率83%（HPLC纯度99.5%）;然后再与异丙基溴化镁反应生成邻溴苯基溴化镁,再与硼酸三甲酯进行亲核取代、水解生成邻溴苯硼酸,收率59.3%（HPLC纯度99.6%）。     

新型对二苯醌衍生物的合成与晶体结构

主要报道了三苯基硼引发的2-烷基取代苯酚双锂盐的自由基偶联反应,生成了硼取代的对二苯醌化合物。有机硼化合物被认为参加自由基反应,以有机硼化合物作为自由基引发剂,并应用于芳烃化合物。我们发现当三苯基硼与2-烷基取代苯酚的双锂盐反应时,促进2-烷基取代苯酚的自由基偶联,生成了一种新型的对二苯醌衍生物,是一种收率较高的对二苯醌衍生物新型制备方法。产物的结构经元素分析、红外光谱和X-射线单晶衍射确定。     

一种星形大分子引发剂的合成与表征

本文以笼形八聚(二甲基硅烷基)倍半硅氧烷(Q8M8H)?烯丙醇??-溴代异丁酰溴为原料通过氢化硅烷化反应和酯化反应合成了八聚(2-溴-2-甲基异丁基硅氧基)倍半硅氧烷(OBPS)星形大分子引发剂,并通过FTIR、1H-NMR、29Si-NMR和GPC对其结构进行了表征,讨论了溶剂?温度和时间对产物结构和产率的影响?最佳反应条件为:以THF为溶剂,0℃反应3h,室温下反应20h,产率可达85.0%?该化合物可进一步做为原子转移自由基聚合的引发剂制备星形聚合物?     

α-溴代对苄基苯基烷基酮合成研究

α-溴代芳基烷基酮类化合物是一类重要的有机合成中间体,广泛应用于医药中间体和精细化学品等领域。本文以芳基烷基酮为原料,经苄醚化后,与溴代试剂在溶剂中反应,得到α-溴代芳基烷基酮类化合物。     

碘代化合物存在下光引发的可逆-休眠自由基聚合研究进展

碘代化合物存在下光引发的可逆-休眠自由基聚合（reversible deactivation radical polymerization, RDRP）具有体系组成简单、适用光源波长范围宽等优点,近年来受到广泛关注。本文主要介绍了最近几年碘代化合物存在下光引发的可逆-休眠自由基聚合的研究进展,以及该聚合方法与其他研究方向的交叉应用。具体包括：光引发的碘转移聚合、光引发的可逆络合聚合以及这些聚合方法在其它研究方向的应用。概述了聚合机理、聚合适用的光源,以及上述聚合方法作为工具实现聚合物“刷”的制备和诱导自组装（polymerization-induced self-Assembly,PISA）,实现了不同聚合物形貌的设计。     

Polymerisation du chlorure de vinyle par les systèmes Ti(OR)y Cl4–y–AlRxCl3–x en milieu CCl4

Vinyl chloride polymerizations by Ti(OR)_yCl_4–y–AlR_xCl_3–x systems, using carbon tetrachloride as solvent, obey a radical mechanism. Free radicals are generated from alkyl aluminum by way of decomposition of an organometallic compound of tetravalent titanium; the latter is formed either by direct reaction between aluminum and titanium compounds, or after reoxidation by CCl₄ of a compound of trivalent titanium. The organometallic compound so obtained contains organic groups more complex than the alkyl group initially bond to aluminum.     

固有碳酸盐和硅酸盐对太姥油页岩热解产物的影响

通过逐级酸洗脱除新疆太姥油页岩中的碳酸盐和硅酸盐矿物,采用铝甑炉对油页岩原样和脱矿样进行热解,分析油气产物的组成性质,基于产物产率和性质考察了固有矿物质对油页岩热解的影响。结果表明,碳酸盐能促进热解生油,且使页岩油中含氮、氧化合物含量增大,硅酸盐则抑制热解生油,并抑制含氧化合物的生成,二者均使页岩油的H/C降低。硅酸盐可促进烷基自由基与氢自由基的结合,使页岩油中烷烃含量升高、烯烃含量降低,且使H₂产率减小,并能催化长链脂肪烃的裂解,使页岩油中长链烃含量降低、短链烃含量升高,且使烃类气体产率增大,而碳酸盐则抑制自由基的结合和长链脂肪烃的裂解。     

矿井水回用处理中卤代烃生成及其去除

分析了中国煤矿井水消毒处理后出水中卤代烃含量高的原因，论述了煮沸曝气、吸附、化学氧化及超声空化效应去除水中卤代烃的过程。提出了超声联合Ｏ３氧化去除矿井水中卤代烃母体是克服投氯消毒产生卤代烃的有效办法。     

用脂肪烃溶液型磷酸酯稀土催化剂合成高顺式聚异戊二烯

在三(2-乙基己基)磷酸酯钕的己烷溶剂中加入少量二氯二甲基硅烷,对其在己烷溶剂中形成的低聚物解缔合,制备出溶液型磷酸酯钕。以溶液型磷酸酯钕Nd(P_(204))_3(简称Nd)/烷基铝(简称Al)/氯化合物(简称Cl)催化体系催化异戊二烯聚合,考察了不同烷基铝、氯源种类、Al/Nd、Cl/Nd及聚合温度对异戊二烯聚合的影响。结果表明,用Nd/Al(i-Bu)_3/Al(i-Bu)_2Cl催化体系制备的聚合物相比于Nd/Al(i-Bu)_2H/Al(i-Bu)_2Cl体系具有更高的分子量,两种催化体系均可制得具有高顺式-1,4-结构含量、窄分子量分布的聚异戊二烯。     

4’-氯-2-（1H-1，2，4-三唑-1-基）苯乙酮的合成

以无水氯化铝为催化剂,氯苯和氯乙酰氯为原料,氯化铝与氯乙酰氯的物质的量之比为1．3：1,在45℃条件下反应3-4h,生成2-氯-1-（4-氯苯基）乙酮,产率可达87％;然后再以2-氯-1-（4-氯苯基）乙酮和1,2,4-三唑为原料,用摩尔数为1,2,4-三氮唑3％的四丁基溴化铵为相转移催化剂,45℃下反应4～5h,可得到68％的4’-氯-2-（1H-1,2,4-三唑-1-基）苯乙酮。     

Über die Darstellung isomerenfreier verzweigter Carbonsäuren

Preparation of Branched Carboxylic Acids Free from Isomers A method for the preparation of branched saturated and unsaturated carboxylic acids, free from isomers, from tertiary γ-lactones by means of alkyl aluminium chlorides is reported. Saturated branched carboxylic acids were obtained in high yields by the reaction with ethyl aluminium chloride, whereas the reaction with diethyl aluminium chloride yielded the unsaturated acids. Splitting of lactones with mixtures of both the ethyl aluminium chlorides gave mixtures of saturated and unsaturated acids. The structure of the unsaturated carboxylic acid was determined by hydrogenation, ozonolysis, iodine value and gas chromatography.     

A kinetic study of the decomposition of benzoyl peroxide assisted by Lewis acids

Summary The rates of decomposition of benzoyl peroxide have been studied in solvent alone and in presence of three Lewis acids, viz., boron trifluoride etherate, aluminum chloride and antimony pentachloride at the temperature range of 10–90°C. The rates have also been studied in presence of acetonitrile (to mimic the action of a complexing monomer) and an efficient radical trap such as m-dinitrobenzene. Benzoyl peroxide undergo rapid decompositions at room temperatures or below in presence of Lewis acids such as aluminum chloride and antimony pentachloride via a polar mechanism to yield >96% phenylbenzoate and one mole of carbon dioxide. Kinetics do not indicate the presence of trappable free radicals. The implication of these results to the initiation of alternating copolymerizations of donor with acceptor monomers is discussed.     

Thermal alkylation of aromatic nucleus with aryl benzyl ethers

The introduction of the benzyl group into the aromatic nucleus is brought about by heating benzyl-α- and β-naphthyl ethers with the aromatic compounds, such as, naphthalene, 2-methylnaphthalene and isoquinoline. It has been concluded that the reaction depends initially on homolytic fission of the alkyl aryl ether into aryloxy and alkyl free radicals which are able to react with the aromatic nucleus. The homolytic mechanism of the alkylation studied and the isomer distribution in the alkylation products separated are discussed on bases of theories of free valency and atom localisation energy of aromatic compounds.     

Computational Design of Radical Recognition Assay with the Possible Application of Cyclopropyl Vinyl Sulfides as Tunable Sensors

The processes involving the capture of free radicals were explored by performing DFT molecular dynamics simulations and modeling of reaction energy profiles. We describe the idea of a radical recognition assay, where not only the presence of a radical but also the nature/reactivity of a radical may be assessed. The idea is to utilize a set of radical-sensitive molecules as tunable sensors, followed by insight into the studied radical species based on the observed reactivity/selectivity. We utilize this approach for selective recognition of common radicals—alkyl, phenyl, and iodine. By matching quantum chemical calculations with experimental data, we show that components of a system react differently with the studied radicals. Possible radical generation processes were studied involving model reactions under UV light and metal-catalyzed conditions.     

Kinetics of isomerization and doping of poly(t-butyl-acetylene)

Summary The kinetics of doping with I₂and isomerization of poly(t-butylacetylene) has been studied. A first-order reaction in polymer and iodine was observed during the doping process, as was found for unsubstituted polyacetylene. However, for the isomerization process, a reaction order of 0.5 in iodine and no simple order in poly(t-butylacetylene) were determined. These results can be explained using a free radical mechanism where the free radicals catalyze the isomerization. In contrast to unsubstituted polyacetylene, the isomerization and doping processes are not related; isomerization occurs first, within about 30 min, and it is followed by doping at much later times.