阴离子碳菁染料的合成与聚集动力学研究

自从1938年,Scheibe^[1]发现了菁染料聚集体中的能量传递现象,人们对菁染料的聚集行为展开了大量的研究^[2,3].由于菁染料聚集体对乳剂具有特殊的增感作用,人们主要研究聚集体在乳剂中的增感机理^[4,5]以及菁染料聚集的溶剂效应与浓度效应^[6]等,而对于菁染料聚集的动力学行为研究较少.     

2-氨基-4-氯-5-甲基苯磺酸的合成研究

2 氨基 4 氯 5 甲基苯磺酸是合成染料和颜料的重要中间体 ,主要用于合成Ｃ .Ｉ.颜料红等[1] 。目前该产品的合成是以对硝基甲苯为原料 ,经氯化、还原、磺化而成[2 ] 。磺化过程需在压力容器中进行 ,存在成本高 ,溶剂及副产物二氯苯、多氯联苯有毒等问题[3,4] 。为此采用无毒、价廉的汽油和石油醚作为混合溶剂 ,常压下合成 2 氨基 4 氯 5 甲基苯磺酸是本工作的目的。1　实验部分1 .1　主要仪器和药品Ｘ4熔点测定仪 ,日本 2 6 0 5 0型红外光谱仪 ,日本ＬＣ 6Ａ高效液相色谱仪 ,ＪＥＯＬＦＸ 90Ｑ型核磁共振光谱仪 ,美国ＰＥ 2 4 0 0自动元…     

水相中磺化杯[6]芳烃催化醇的胺基化反应研究

研究了水相中磺化杯[6]芳烃在酸性条件下催化合成含C—N键类化合物的反应,高效的合成了一系列产物,其结构经1H NMR,13C NMR表征.并探究了时间、温度对反应的影响和催化剂的循环使用情况.研究表明水溶性的磺化杯[6]芳烃具有很好的相转移催化性能和多次重复使用性.     

卤化银乳剂颗粒上不对称菁染料J-聚体荧光的研究

光谱增感机理的研究是感光科学中的一个重要课题Gilman^[1]和Kuhn等^[2]曾经提出光谱增感的电子转移和能量传递理论。随着现代谱学手段的出现,为人们了解光谱增感的初始过程提供了条件。近年来,电子转移的机理已被广泛接受,并用来解释与光谱增感有关的各种现象。但在ns~ps范围内的光谱增感动力学方面的研究还不多见。Dahne认为光谱增感不仅决定于染料与卤化银的能级关系,而且是由动力学控制的^[3],激发态染料向卤化银导带注人电子的电子转移过程与辐射及其他无辐射去活过程是竞争的^[4]我们通过对两种不对称的苯并咪哇唾碳著染料在AgBrI乳剂颗粒上吸附形成的J一聚体的荧光性质的研究,以求深人了解光谱增感的电子转移机理及其动力学过程,无疑是有重要意义的。     

对枯基酚合成工艺

α甲基苯乙烯是异丙苯法合成苯酚、丙酮的副产物,以它为原料生产用途广泛的精细化工原料———对枯基酚是α甲基苯乙烯综合利用的一个重要途径．国外从８０年代初开始对枯基酚的合成工艺进行研究［１］．其主要方法是在强酸,大孔阳离子交换树脂,酸性白土等酸性催化...     

三氮吲哚利嗪对氯化银乳剂光谱增感性能的影响

三氮吲哚利嗪(TAI)是一种常用的银盐感光材料的稳定剂,许多研究表明TAI在化学增感或光谱增感乳剂中具有超增感作用^[1,2],另有报道,它与光谱增感染料两者之间的添加次序对增感效果有很大的影响^[1,6,7].     

Pd(OH)2纳米粒子的制备、结构表征及其在HBIW催化氢解中的应用

2,4,6,8,10,12－六硝基－2,4,6,8,10,12－六氮杂异伍兹烷（HNIW）作为目前威力最大的单质炸药,日益受到各国国防和航空工业的重视^[1,2]。HNIW的合成,大体上分为缩合、催化氢解和硝化三步。在原料2,4,6,8,10,12－六氯杂异伍兹烷（HNIW）作为目前威力 最大的单质炸药,日前受到各国国防和航空工业的重视^[1,2]。HNIW的合成,大体上分为缩合、催化氢解和硝化三步。在原料2,4,6,8,10,12－六苄基－2,4,6,8,10,12-氮杂异伍兹烷（HBIW,化合物1）催化氢解中,催化剂Pd(OH)2/C因制备和回收工艺繁锁而成本较高,是造成HNIW生产成本居高不下的主要原因^[3]。改进催化氢解的催化剂,对HNIW的工业化生产具有重要意义。很多催化剂的催化效率随催化剂颗粒减小到纳米量级而显著提高[4,5],Pd(OH)2纳米粒子催化活性可望超过Pd(OH2)/C催化剂,用于催化氢解中。本文用共沸蒸馏法对自制的水合Pd(OH)2进行脱水处理,首次制得了Pd(OH)2纳米粒子。采用高分辨率透射电镜、激光动态光散射、紫外－可见吸收研究了Pd(OH)2纳米粒子的微观结构,并比较了Pd(OH)2纳米粒子和Pd(OH)2/C在化合物1催化氢解中的活性。     

新型2-烯丙氧基-4-辛氧基苯甲酸对丙基联苯酯的合成及其液晶性能

分别以2,4-二羟基苯甲酸和对苯基苯酚为原料,设计并合成了两种新型液晶中间体2-烯丙氧基-4-辛氧基苯甲酸(5)和4-(4-丙基苯基)苯酚(10);5和10在4-吡咯基吡啶催化下经脱水酯化合成了一个新型的液晶化合物——2-烯丙氧基-4-辛氧基苯甲酸对丙基联苯酯(11),收率81.2％,其结构经1H NMR,13C NMR和元素分析表征.用碘量法测定了11的烯键含量,并用DSC和POM研究了11的液晶性能.结果表明,11为单向向列型液晶化合物,液晶区间55.8℃～12.1℃.     

方酸菁染料的合成

方酸菁染料业经证明具有光谱增感作用,但迄今未见其作为照相材料应用的报道.1973年法国Siegfried等将其用于巨脉冲红宝石激光的无源切换;最近Morel等又研究了它们在太阳能电池中的应用.作者合成了八个方酸菁染料,并对它们的照相性能和光电转换特性作了初步研究;发现其中的个别化合物不但具有良好的光谱增感作用,而且与照相工业中常用的染料“1833”相比,衰退也比较慢;部分化合物还表现出相当高的光电转换效率. 作者曾报道方酸的合成.本文介绍另一种方法,即以醋酸钠-醋酸环化1,1,3-三氯-2,     

反相液相色谱法测定双酚A和苯酚

双酚A[4,4′-双(4-羟苯基)丙烷]是生产环氧树脂、聚碳酸酯、巨砜和改性酚醛树脂等高聚物的重要原料,此外,还大量用来制造涂料、粘合剂、橡胶防老化剂和农药杀菌剂等。 合成双酚A的主要原料是苯酚,因此,来反应的苯酚单体就成了双酚A产品中的主要杂质,为了随时掌握苯酚的转化率、监控产品质量,需要建立一种快速、灵敏、简便、准确地测     

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%.     

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.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

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.     

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.     

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.     

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.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.