2-(p-取代苯乙烯基)-3,3-二甲基-3 H-吲哚盐的合成及性能研究

2,3,3-三甲基-3 H-吲哚氢溴酸盐分别与五种取代苯甲醛在乙醇介质中反应,可得到五种新的2-(p-取代苯乙烯基)-3,3-二甲基-3H-吲哚氢溴酸盐(R=H(3a);Br(3b);MeO(3c);HO(3d);Me_2N(3e)]。研究了化合物3a-e的紫外光谱和Hammett常数的定量关系。以位移增量△λ_p,对△σ(△σ=σ_p-σ_m)作图可得到一条直线,说明它们紫外光谱的取代基效应遵守Hammett方程,即随着取代基给电子能力的增强,吸收带向红移。五个化合物以3e的光谱增感性能最好。     

2-(P-取代基苯乙烯基)-3,3-二甲基-3 H-吲哚盐的合成及性能研究

2,3,3-三甲基-3H-吲哚氢溴酸盐分别与五种取代苯甲醛在乙醇介质中反应,可得 到五种新的2-(P-取代苯乙烯基)-3,3-二甲基-3H-吲哚氢溴酸盐(R=H(3a);Br(3b);MeO(3c);HO(3d);Me~2N(3e)].研究了化合物3a-e的紫外光谱和Hammett常数的定量关系.以位移增量△λ~p对△σ(△σ=α~p-σ~m)作图可得到一条直线,说明它们紫外光谱的取代基效应遵守Hammett方程,即随着取代基给电子能力的增强,吸收带向红移.五个化合物以3e的光谱增感性能最好.     

取代基对1,4-双[β-(4-取代苯基)乙烯基]苯化合物红外光谱的影响

取代基对红外光谱特征频率的影响曾有报导,但对1,4-双[β-(取代苯基)乙烯基]苯类化合物还未曾研究。我们测试了它们的红外光谱,发现取代基常数σ_p、σ_p~o及σ_p~ 与反式烯键上碳—氢键的面外变角振动频率δ=C-H(面外)之间存在一定线性关系。     

吲哚碳菁染料的合成及光谱特征

在吡啶中, 吲哚啉碘盐与原乙酸三乙酯缩合合成了一些新的吲哚碳菁染料.根据紫外-可见光谱, 荧光光谱讨论了它们的取代基和光谱特征的关系.     

有机胂化合物的研究 Ⅳ.溴化α-噻吩甲酰基代甲基三苯鉮的合成及其与芳胺的反应

本文报道了溴化α-噻吩甲酰基代甲基三苯鉮的合成及其与取代苯胺,α(β)-萘胺的反应,并合成了一系列2-(α-噻吩基)吲哚和苯骈吲哚化合物。经元素分析、红外光谱和核磁共振谱及吲哚环的显色反应,确证了产物的结构。     

1-苯基-3-(3'-吲哚基)-5-取代苯基-2-吡唑啉的合成及1H NMR和MS中的取代基效应

J-(3'-吲哚基)-3-取代苯基-2-丙烯-1-酮与茉肼反应,合成了10种新的1-苯基-3-(3'-吲哚基)-5-取代苯基-2-吡唑啉衍生物,其结构通过各种波谱证实.讨论了此系列化合物¹HNMR和Ms中的取代基效应,得出取代基常数σ或σ⁺与质子化学位移,碎片相对丰度之间存在着良好的线性关系.     

自支撑柔性聚(5-吲哚硼酸)膜的电化学合成及表征

在三氟化硼乙醚/乙腈的混合体系中,5-吲哚硼酸的电化学氧化可以获得导电率为9×10-4 S·cm-1的自支撑柔性聚(5-吲哚硼酸)膜.5-吲哚硼酸在80％的三氟化硼乙醚亿腈溶液中的起始氧化电位约为0.80V红外光谱确定了5-吲哚硼酸的聚合位点在C2和C3位上.紫外可见光谱测试结果表明聚(5-吲哚硼酸)的能隙约为2.48...     

吲哚取代10H—吡啶并[1,2—a]吲哚盐的合成

通过2,3,3-三甲基-3H-吲哚高氯酸盐与吲哚取代查耳酮或芳基乙烯基酮在异戊醇介质中反应,合成了15种新的10H-吡啶并[1,2-a]吲哚高氯酸盐,其结构用各种波谱确定,从结构上进一步推理提出了反应历程,并讨论了~1H NMR谱中取代基对吡啶环质子化学位移的影响。     

Ⅱ.芳香胺类中新型σ~-值的应用

本文成功地将取代苯胺的偶极短与其取代基常数σ相互关联起来,并发现在一定的条件下取代苯胺的熔点与后者也有良好的直线相互关系.证明了将本文所得σ~-值用之于苯胺在红外吸收光谱中的直线相互关系较旧有的最适合的σ值在相关系数上有改进,并将这些直线关系中的一部分推广到近红外区;成功地将取代苯胺在紫外吸收光谱中有相反的电子效应的取代基对其共轭光谱带的影响用本文所得?值归并在同一直线相互关系上,且其相关系数胜过用其他各种类似的取代基常数;再则共主光谱带与其相应克分子折射率也有良好直线相互关系.无须选用特殊的σ值和仅直接采用本文的σ~-值即能适用于取代苯胺在核磁共振谱中有关其氨基氢的化学位移的直线相互关系中,且其相关系数较旧有值有改进.为了尝试以σ~-与σ_(I.R.)~-相结合俾适合应用于芳香亲核取代反应的直线自由能关系中,已将现有数据逐一运算,并发现其实用价值与Miller所采用的数值不相上下.     

固体酸Amberlyst 15催化合成3-吲哚取代的苯酞类化合物

室温下, 以吲哚和邻甲酰苯甲酸为原料, 通过Amberlyst 15 (15 wt%)催化的傅-克反应, 高产率合成得到一系列3-吲哚取代的苯酞类化合物. 并通过1H NMR, 13C NMR, 红外光谱, 高分辨质谱确证了产物的结构.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.