一类2(1H)-喹喔啉衍生物的电子轰击质谱分析

以邻苯二胺为原料合成表征了一类喹喔啉衍生物;1-烷基-3-甲基-2（1H）-喹喔啉-2-酮（1-alkyl-3-methly-2(1H)-quinoxalin-2-one,简称AMQ,其中alky=H、CH3、Et、n-C3H5、n-C5H11、n-C16H33)。用电子轰击电离质谱（EI-MS）和核磁共振谱图（^1H-NMR)鉴定了AMQ,研究了不同取代基对这类化合物EI-MS谱图的影响,分析得到一些裂解规律。结果表明：所有样品谱图中均有芳香化合物的特征CnHn^ 系列峰m/z78,65,52,39和（或）m/z77、76、64、63、51、50、38、37。对于末取代的样品及低级烷烃取代的样品,谱图中的基峰为分子离子峰,对于取代基中碳数大于等于3的样品。谱图中的基峰不是分子离子峰,分子离子峰强度随着碳数的增加而降低。这些样品一般容易发生骨架重排,丢失一分子CO,生成1-烷基-2-甲基苯并哒唑正离子。此外,还讨论了谱图中其它的一些碎片离子峰。这对于研究和指导喹喔啉衍生物 的合成,探讨它们在药效及结构特征与生理活性的关系等方面具有重要的应用价值和理论意义。     

3-甲基-2(1H)-喹喔啉系列衍生物的电子轰击质谱

用电子轰击质谱（EI－MS）研究了1－烷基－3－甲基－2（1H）－喹喔啉－2－酮（烷基为H,CH3,Et,n-C5H11),1-烷基－3－甲基－6－硝基－2（1H）－喹喔啉－2－酮（烷基为CH3,Et)和1－甲基－3－甲基－6－胺基－2（1H）－喹喔啉－2－酮,结合其结构特征总结出一些裂解规律。讨论了不同取代基对这类化合物熔点的影响,结果表明：在同类喹喔啉化合物中,随着烷基链的增长,样品熔点通常会有所降低,而硝基及胺基的引入会使其熔点升高。     

喹喔啉-三唑衍生物的设计与合成及其抗肿瘤活性

喹喔啉和1,2,3-三唑都是具有广泛生物活性的杂环结构母体。本文基于药物设计的拼合原理,以简单易得的邻苯二胺、苯乙炔及有机叠氮为原料,通过三组分\"两步一锅法\"将喹喔啉和1,2,3-三唑活性亚结构进行拼接,合成了一系列共14个新型喹喔啉-三唑衍生物(3a~3n)。该法操作简单,无需分离中间体,两步总产率52.6%~78.4%。合成的目标化合物结构经~1H NMR、~(13)C NMR和HRMS确证。初步体外抗肿瘤活性测试表明,合成的目标化合物具有一定的抗肿瘤活性。     

含喹喔啉杨梅素衍生物的合成及生物活性

利用活性拼接原理, 将喹喔啉引入到杨梅素结构中, 合成了一系列含喹喔啉基团的杨梅素新型衍生物. 采用浊度法测试了目标化合物的体外抑菌活性, 结果表明, 目标化合物对柑橘溃疡病菌(X. Citri)和水稻白叶枯病菌(X. Oryzae)均表现出较好的抑制活性. 目标化合物对柑橘溃疡病菌的抑制活性(EC₅₀)均优于对照药叶枯唑和噻菌铜(EC₅₀分别为54.85和61.13 μg/mL), 其中化合物4o抑制活性(EC₅₀=11.17 μg/mL)最优; 目标化合物对水稻白叶枯病菌的抑制活性EC₅₀均优于对照药叶枯唑和噻菌铜(EC₅₀分别为148.20和175.47 μg/mL), 其中化合物4f抑制活性(EC₅₀=34.49 μg/mL)最优. 采用半叶枯斑法测试了目标化合物的抗烟草花叶病毒(TMV)活性, 结果表明, 所有目标化合物在浓度为500 mg/L时均有一定的抑制作用.     

一类2(1H)-喹喔啉化合物的裂解机理

用电子轰击质谱（EI-MS）研究了一类喹喔啉化合物;1-烷基-3-甲基-2（1H）-喹喔啉-2-酮（1-alkyl-3-methyl-2(1H)-quinoxalin-2-one,简称AMQ,其中alky1=H,CH3,C2H5,n-C3H7,n-C5H11;结果表明随着烷基链的增长,样品熔点通常会有所降低,结合在电子轰击下所产生的裂解碎片离子,并根据其结构特征为乙基化样品为代表,推导了该类化合物在电子轰击作用下可能发生的裂解机理。     

可见光诱导下喹喔啉酮与吡咯衍生物的氧化偶联（英文）

发展了一种区域选择性的喹喔啉酮3-位氧化偶联富电子吡咯衍生物的方法.以Mes-Acr-Me⁺ClO₄^-(3 mol%)为光敏剂,空气氧为氧化剂,高收率得到喹喔酮与吡咯衍生物的氧化偶联产物.该方法底物的官能团适用范围广,反应高效绿色,可快速构建基于喹喔啉酮-吡咯衍生物的药物分子库.相同测试条件下的Stern-Volmer荧光淬灭实验表明缺电子芳烃1-甲基喹喔啉酮对光敏剂的淬灭速率常数K_q=1.2×10⁹ L·mol^-1·s^-1,而富电子芳烃1-甲基吡咯/1-甲基吲哚的淬灭常数约为1.06～1.07×10¹⁰ L·mol^-1·s^-1,后者的荧光淬灭速率几乎是前者的10倍.     

SBA-15/NiCl2催化超声合成喹喔啉衍生物

以苯偶姻和邻苯二胺为原料,SBA/NiCl2为催化剂,在超声条件下合成了喹喔啉衍生物,其结构经1H NMR和IR确证。考察催化剂类型、原料摩尔比和催化剂的用量对产率的影响。在最佳条件(苯偶姻和邻苯二胺物质的量比为1.0/1.0,催化剂用量为苯偶姻的10 mmol%,于70℃超声反应5 min)下,产率可达94.7%。     

铜催化一锅法合成吡咯[1,2-a]喹喔啉衍生物

建立了一种简单实用、经济高效的以邻碘苯胺、吡咯甲醛为起始原料,廉价的CuI为催化剂,价廉、易获得的2,2-联吡啶为配体,110℃条件下一锅法合成吡咯[1,2-a]喹喔啉类衍生物的催化体系,得到中等到优良产率.本方法具有催化剂廉价易得、操作简便、合成效率高的优点.     

喹喔啉—2,3—二甲酰胺与3d过渡金属配合物的合成及性质研究

首次合成了喹喔啉－２，３－二甲酰胺（Ｑｘｄａ）与３ｄ过渡金属的三种固体配合物：Ｍ（Ｑｘｄａ）２ｃｌ２（Ｍ＝Ｃｏ（Ｉ），Ｎｉ（Ｉ），Ｃｕ（Ⅱ）。通过元素分析，摩尔电导，红外光谱，电子光谱，磁化率，热分析等手段对配合物的组成和性质进行了研究。     

基于侧链不对称喹喔啉聚合物的高效非富勒烯太阳电池

喹喔啉衍生物由于合成简单,易功能化,成本较低等特点在众多领域都有广泛应用。其自身具有平面刚性结构,也是构建光电聚合物的重要单体。基于喹喔啉单元的有机分子化学结构和电子结构可修饰性强,通过骨架、侧链和取代基等修饰,易于调控分子的能级和吸光光谱,因此,当使用喹喔啉体系的共轭给体与球形富勒烯受体(如PCBM)及弱结晶性非富勒烯受体(如ITIC)均可表现出优异的光伏性能。在本工作中,基于结晶性较强的非富勒烯受体(o-IDTBR),我们首次制备出侧链不对称喹喔啉(简称：不对称喹喔啉)基聚合物(TPQ-1)与之匹配。相比于侧链对称性喹喔啉(简称：对称喹喔啉)(HFQx-T)与o-IDTBR组合,“弱结晶给体-强结晶受体”组合能表现出更佳均匀的相分离尺度,从而获得更高的短路电流及能量转换效率。TPQ-1与o-IDTBR共混后器件效率为8.6%,加入15%的TB7-Th后,器件效率达到9.6%。     

Novel Transient Species of DNA Bases From Laser Photolysis

The laser photochemistry and photosensitization of DNA bases were carried out by using a nanosecond kinetic spectroscopy. A novel triplet state of thymine and its OH adduct were observed in N_2 and N_2O saturated aqueous solution respectively. The transient absorption spectra of triplet cytosine, cytidine and deoxycytidine monophosphoric acid were observed for the first time. Triplet guanosine was confirmed and its pK, value, 8.7, was obtained. Kinetic studies of the growth-decay of the above transient species were performed and their reaction mechanisms were elucidated in detail.     

Photophysical Properties and Photoinduced Electron Transfer between [60] Fullerene-Containing Cyclic Sulphoxide [C_(60)-C_6H_8SO] and Tetrathiafulvalene (TTF) by Laser Flash Photolysis

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Laser flash photolysis generation and kinetic studies of corrole-manganese(V)-oxo intermediates

Corrole-manganese(V)-oxo intermediates were produced by laser flash photolysis of the corresponding corrole-manganese(IV) chlorate complexes, and the kinetics of their decay reactions in CH2Cl2 and their reactions with organic reductants were studied. The corrole ligands studied were 5,10,15-tris(pentafluorophenyl)corrole (H3TPFC), 5,10,15-triphenylcorrole (H3TPC), and 5,15-bis(pentafluorophenyl)-10-(p-methoxyphenyl)corrole (H3BPFMC). In self-decay reactions and in reactions with substrates, the order of reactivity of (Cor)Mn(V)(O) was TPC > BPFMC > TPFC, which is inverted from that expected based on the electron-demand of the ligands. The rates of reactions of (Cor)Mn(V)(O) were dependent on the concentration of the oxidant and other manganese species, with increasing concentrations of various manganese species resulting in decreasing rates of reactions, and the apparent rate constant for reaction of (TPFC)Mn(V)(O) with triphenylamine was found to display fractional order with respect to the manganese-oxo species. The kinetic results are consistent in part with a reaction model involving disproportionation of (Cor)Mn(V)(O) to give (Cor)Mn(IV) and (Cor)Mn(VI)(O) species, the latter of which is the active oxidant. Alternatively, the results are consistent with oxidation by (Cor)Mn(V)(O) which is reversibly sequestered in non-reactive complexes by various manganese species.     

Femtosecond-Picosecond Laser Photolysis Studies on Photoinduced Electron Transfer Phenomena in Solutions

Results of our femtosecond-picosecond laser photolysis studies on photoinduced electron transfer phenomena in solutions including exciplex dynamics and its solvent dependences, energy gap dependences of photoinduced charge separation and charge recombination of various geminate ion pairs, mechanisms of chemical reactions via exciplexes and ion pairs, dynamics of photoinduced election transfer in hydrogen bonding complexes, dynamics and mechanisms of photoinduced electron transfer in fixed distance donor acceptor dyads and photosynthetic reaction center models, and mechanisms of electron ejection from solute fluorescent state in polar solutions are summarized and discussed.     

Temperature-dependent Kinetics on Laser Induced Photolysis of Aqueous CS2-HONO Solutions

Considerable quantities of wastewater effluents containing CS2are produced by industries engaged in the manufacture of artificial leather,viscose,and other synthetic fibers.In addition,CS2also naturally occurs in the condensation of water vapor and its precipitation from the atmosphere in the form of rain,snow or hail.The oxidation of CS2is the subject of a number of studies1-4.Nitrous acid is another pollutant which has been the subject of intensive investigation in recent years.The review…     

Laser flash photolysis and pulse radiolysis study on chemical activity of VP-16 and podophyllotoxin

Time-resolved laser flash photolysis and pulse radiolysis have been used to study the chemical activity of podophyllotoxin(PPT) and etoposide(VP-16). The mechanism of photoioniza-tion of etoposide and podophyllotoxin has been confirmed and illustrated. It is demonstrated that VP-16 and PPT in aqueous solution can be photoionized at 248 nm to give hydrated electron and neutral radical resulting from rapid deprotonation of radical cation of VP-16 and PPT. The quantum yield for the photoionization of VP-16 and PPT with single-photo is 0.21 and 0.61, respectively. In addition, they can react with hydrated electron, hydrogen radical and hydroxyl radical. This will give chemists some advice on synthesizing new derivatives of podophyllotoxin in cancer treatment.     

Laser Flash Photolysis of Phthalocyanines in Solution and Microemulsion

Triplet state formation (Φ_isc) and properties (ε_T-T, τ_T) of phthalocyanine (HPC) and zinc phthalocyanine (ZnPC) have been characterized in homogeneous solutions (1-chloronaphthalene, 1-propanol) and in microemulsion by investigating the variation of the transient optical density as a function of the intensity of the exciting laser. Experimental results follow the theoretically predicted dependence only for very low intensities of the exciting pulse. At higher intensities, a more complicated scheme of primary reactions has to be taken into account, implicating qualitative restrictions in the application of saturation experiments. The observed transients at high-intensity excitation are interpreted as being perturbed by aggregational phenomena.     

Modulation of Spectrokinetic Properties of o‐Quinonoid Reactive Intermediates by Electronic Factors: Time‐Resolved Laser Flash and Steady‐State Photolysis Investigations of Photochromic 6‐ and 7‐Arylchromenes

A variety of differently substituted 6‐ and 7‐arylchromenes such as that depicted undergo photoinduced C? O bond cleavage to yield colored o‐quinonoid intermediates. A combined analysis of μs–ms (laser flash) and real‐time kinetic data show that the o‐quinonoid intermediates decay faster when the C2‐aryl and C6‐/C7‐aryl rings contain electron‐donating and electron‐accepting groups, respectively. Similarly, the decay occurs slowly for the reversed scenario, while intermediate decay rates are observed when both substituents are electron donating.