醚溶液中烯烃硼氢化反应机理的理论模拟

在B₃LYP/6-31G^*水平上以二甲醚(Me₂O)模拟四氢呋喃(THF)对烯烃在THF溶液中硼氢化反应的机理进行了研究.计算结果发现,烯烃通过类似SN₂的交换过程从醚与BH₃构成的配合物获得BH₃结合成π配合物中间体,这一交换是整个硼氢化反应的决速步骤.     

Ab Initio Studies on MCH2(OH) and CH3OM(M=H, -, Li, Na)

IntroductionThe greatsynthetic utility of organolithium reagents has been extended by the introduc-tion ofα-lithium-etherreagents[1— 4] .Those reagentsareeasily prepared,and they can be usedas anionic resources to synthesize a large variety of compounds stereo-selectively[5— 8] .Fur-thermore,such reagents can react with nucleophiles like RLi,only a typical reaction of car-benoid[9,1 0 ] .Though the ambidentnature isof greatinterest,only a little work has been doneon model molecule Li CH2 …     

冠醚液晶混合物及其离子传输研究

本文研究了不同熔点的单臂脂环冠醚液晶的二元混合物，获得了不同摩尔比的熔点和清亮点曲线并以摩尔比为１：２的混合物进行了复合膜的离子传输研究。     

Heat-resistant, pyridine-based polyamides containing ether and ester units with improved solubility

<正>A diamine containing ether and ester units,as basic monomer for the preparation of polyamides,was prepared via three consecutive reactions.Nucleophilic substitution reaction of 1,4-dihydroxy benzene with 4-nitrobenzoyl chloride produced 4-hydroxyphenyl 4-nitrobenzoate(HPNB).Reduction of nitro groups to amino groups using Fe and HC1 resulted in preparation of 4-hydroxyphenyl 4-aminobenzoate(HPAB).The diamine was synthesized through nucleophilic substitution reaction of HPAB with 2,6-dichloropyridine The precursors and diamine were fully characterized by common methods,and the diamine was polycondensed with different diacid chlorides in the presence of an acid scavenger to prepare new polyamides.The polyamides were characterized,and their physical properties including thermal stability and behavior, inherent viscosity and solubility were studied.     

Optimized structures and vibration frequencies of the ether–water complex: a DFT and FTIR study

The infrared spectrum of ether was studied using Fourier transform infrared spectroscopy in conjunction with the density functional theory (DFT). The optimized structures and vibrational frequencies of the ether·(H₂O) _n (n = 1–3) complexes were obtained at B3LYP/6-31G(d) theory levels. Compared to those of free-form ether, the C–O stretching vibrational frequencies of the ether–water complexes are found to shift to red by up to 39 cm^?1 with an increase in the C–O length of 0.016 Å. Meanwhile, the frequency of the O–H stretching modes of water in the complexes appears significantly redshifted to a varying degree. The DFT calculations suggest that these shifts are caused by the hydrogen bonding between ether and water.     

某些芳氧基嘧啶醚类化合物的合成及除草活性

设计并合成了１９余种以嘧啶衍生物为中心,分别含有三氯水杨酸甲酯及１,２,４－三唑并嘧啶的醚类新化合物。利用＾１Ｈ ＮＭＲ谱及元素分析确定了产物结构。除草活性测定结果表明,所合成的化合物均表现出一定的活性,个别化合物对阔叶杂草活性较好。     

金红石型纳米TiO_2浆料改性氯醚树脂防腐涂层研究

用金红石型纳米TiO2对氯醚树脂防腐涂料改性,电化学阻抗考察该纳米TiO2对漆膜防腐性能的影响.结果表明,添加金红石型纳米TiO2不能明显改善氯醚树脂漆膜的附着力、柔韧性和耐冲击性能,但能提高漆膜耐紫外线老化,以及漆膜的光泽度,此外适当的添加量还能提高漆膜的防腐性能.     

以1,4-二氯甲氧基丁烷为氯甲基化试剂合成线型氯甲基化聚苯乙烯

采用自制的氯甲基化试剂——1,4-二氯甲氧基丁烷(BCMB),使用Lewis酸催化剂,在均相反应体系中高效地实现了聚苯乙烯的氯甲基化.研究了反应机理,考察了各种因素对氯甲基化反应的影响规律,优化了反应条件,通过红外光谱法与Volhard分析法表征了产物的化学结构与组成.实验结果表明,反应机理可能由苯环亲电取代与伴随着醚键断裂的亲核取代两类反应构成,氯甲基化试剂用量、催化剂的酸性与用量、溶剂的性质与用量及反应温度等因素对反应都有显著的影响,其一,会影响聚苯乙烯的氯甲基化程度,其二,会导致或避免大分子链之间通过Friedel-Crafts反应而发生交联.以四氯化碳为溶剂、以SnCl4为催化剂并在较低温度(18℃)下进行反应,可制得氯甲基化程度达80%且完全线型化的氯甲基化聚苯乙烯.