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。     

过硫酸铵促进喹喔啉-2(1H)-酮三氟甲基化反应

报道了温和条件下,过硫酸铵促进喹喔啉-2(1H)-酮与CF3SO2Na三氟甲基化制备3-三氟甲基喹喔啉-2(1H)-酮类的反应,开发了一种绿色、高效制备3-三氟甲基喹喔啉-2(1H)-酮衍生物的方法.该方法对不同取代的喹喔啉-2(1H)-酮衍生物具有较好的适用性,均以较高的产率得到相应的目标产物.与已有方法相比,本方法具有底物适用范围广、产率高、实验操作简便等优点,为3-三氟甲基喹喔啉-2(1H)-酮的制备提供了有效的路径.     

可见光催化喹喔啉-2(1H)-酮与醇C(sp~2)-H/O-H交叉脱氢偶联反应（英文）

杂环化合物和醇的C(sp~2)-H/O-H交叉脱氢偶联反应为制备杂环醚类化合物提供了一种原子和步骤经济性的方法.然而,已经报道的交叉脱氢偶联反应大部分需要使用过渡金属催化剂和/或者强氧化剂,不仅产生环境问题还增加分离成本.同时,这些合成方法还存在杂环化合物和醇的C(sp~2)-H/C(sp~3)-H交叉脱氢偶联反应的竞争反应,降低了反应的选择性和收率.喹喔啉-2(1H)-酮是生物活性物质和人工药物的核心骨架结构之一,合成多样性官能化的喹喔啉-2(1H)-酮备受关注.近期多种C-3官能化喹喔啉-2(1H)-酮的合成方法被报道,但是目前没有一例通过无金属无强氧化剂条件下的喹喔啉-2(1H)-酮与醇C(sp~2)-H/O-H交叉脱氢偶联反应合成3-烷氧基喹喔啉-2(1H)-酮的相关工作报道.值得一提的是,利用氧气作为氧化剂的可见光催化反应符合绿色化学的要求,在最近几年中发展迅速.本文报道了一种通过可见光催化的喹喔啉-2(1H)-酮与醇的C(sp~2)-H/O-H交叉脱氢偶联反应合成3-烷氧基喹喔啉-2(1H)-酮化合物的绿色制备方法.首先通过对光催化剂、溶剂等参数的筛选,确定了最佳反应条件为喹喔啉-2(1H)-酮化合物0.3 mmol,醇0.9 mmol,乙腈1.5 m L, Acr~+-Mes Cl O_4~-2mol%,空气作为氧化剂, 3 W蓝光作为光源.在最佳条件下,含有供电子、吸电子取代基的喹喔啉-2(1H)-酮化合物和含有各种取代基的烷基醇都能很好地进行反应,得到36种目标化合物,产率70%～94%.另外,成功完成了克级放大实验和一锅法串联反应.机理研究证明,该反应是喹喔啉-2(1H)-酮化合物在光催化氧化作用下生成自由基正离子,醇作为亲核试剂选择性进攻自由基正离子的C3位,最后得到目标产物.     

可见光下g-C3N4催化诱导C(sp2)-H芳基化喹喔啉-2(1H)-酮

建立了一种有效且简单的可见光诱导的g-C₃N₄催化的喹喔啉-2(1H)-酮的芳基化反应。该反应以乙腈为溶剂,K₂S₂O₈为氧化剂,具有反应条件温和、环境友好和官能团耐受性好等优点。该策略提供了一种简单的操作方法,可以获得各种中等到良好产率的3-苯基喹喔啉-2(1H)-酮化合物,最高产率达77%。     

可见光催化喹喔啉-2(1H)-酮与醇C(sp2)-H/O-H交叉脱氢偶联反应(英文)

杂环化合物和醇的C(sp²)-H/O-H交叉脱氢偶联反应为制备杂环醚类化合物提供了一种原子和步骤经济性的方法.然而,已经报道的交叉脱氢偶联反应大部分需要使用过渡金属催化剂和/或者强氧化剂,不仅产生环境问题还增加分离成本.同时,这些合成方法还存在杂环化合物和醇的C(sp²)-H/C(sp³)-H交叉脱氢偶联反应的竞争反应,降低了反应的选择性和收率.喹喔啉-2(1H)-酮是生物活性物质和人工药物的核心骨架结构之一,合成多样性官能化的喹喔啉-2(1H)-酮备受关注.近期多种C-3官能化喹喔啉-2(1H)-酮的合成方法被报道,但是目前没有一例通过无金属无强氧化剂条件下的喹喔啉-2(1H)-酮与醇C(sp²)-H/O-H交叉脱氢偶联反应合成3-烷氧基喹喔啉-2(1H)-酮的相关工作报道.值得一提的是,利用氧气作为氧化剂的可见光催化反应符合绿色化学的要求,在最近几年中发展迅速.本文报道了一种通过可见光催化的喹喔啉-2(1H)-酮与醇的C(sp²)-H/O-H交叉脱氢偶联反应合成3-烷氧基喹...     

可见光诱导玫瑰红催化喹喔啉-2(1H)-酮的C3-H烷基化反应

建立了一种简单、实用的光诱导一锅法高选择性N-甲基喹喔啉酮类化合物和苯乙酮类化合物合成一系列3-烷基化喹唑啉-2(1H)-酮类化合物的方法。该方法在室温条件下,以玫瑰红作为光催化剂,在18 W 460nm的蓝色LED下照射8 h,通过直接C3-H活化的方案,较好收率获得一系列相应的3-烷基化喹喔啉-2(1H)-酮类化合物,最高产率可达到76%。反应体系具有经济实用性和底物适用范围广的特点,为3-烷基化喹喔啉-2(1H)-酮类化合物类化合物的合成提供了一种简便经济的方法。     

可见光诱导下喹喔啉-2(1H)-酮与重氮盐的直接C—H 3-芳基化反应（英文）

发展了一种简单、实用可见光诱导喹喔啉-2(1H)-酮与重氮盐的直接C—H 3-芳基化反应.该反应采用便宜Eosin Y为催化剂,可以在室温、空气下高效完成3-芳基喹喔啉-2(1H)-酮的构建.该方法不需要任何金属试剂、碱、酸和强氧化剂,为3-芳基喹喔啉-2(1H)-酮提供一个价格便宜、操作简便的合成方法.     

十一种2,3-二取代喹喔啉-1,4-二氧化物抗菌剂的合成与谱学研究

采用直接氧化法和Beirut反应合成了十一种抗菌剂2,3-二取代喹喔啉-1。4-二氧化物.给出了完整的UV,IR,NMR数据和有关谱学特性.EPR研究表明这些N-氧化物在溶液光解过程中生成稳定的顺磁物.从含有2,3-环丁亚基喹喔啉-1,4-氧化物(2g)的氯仿溶液光解体系记录的EPR谱得到9.69G(1N)、3.59G(2H),1.25G(2H)和0.76G(1H)等超精细分裂值,指认为1-羟基-2,3-环丁亚甲基喹喔啉-4-氧基(4).指出喹喔啉-1,4-氧化物与对萘醌化合物有结构、物性的类似性.     

光/电化学合成在喹喔啉-2(1H)-酮C—H键官能化中的应用

喹喔啉-2(1H)-酮是一类重要的含氮杂环化合物,具有很强的生物活性与化学特性,在合成化学、功能材料及药物工业等方面具有重要应用.近年来,通过C—H官能化构建3-官能化的喹喔啉-2(1H)-酮引起了很多学者的关注,并取得了重要进展.其中,基于绿色化学导向的光催化及电化学合成正成为喹喔啉-2(1H)-酮的C—H官能化的强有力工具.鉴于光电化学在合成化学中的巨大影响,总结了可见光催化与电化学合成实现喹喔啉-2(1H)-酮3位C—H官能化的研究现状,希望能促进绿色合成策略在含氮杂环官能化中的进一步发展.     

无催化条件下三组分一锅法合成呋喃并吡啶并喹喔啉衍生物

以芳醛、6-氨基喹喔啉和季酮酸为原料,三组分一步构建了11-芳基-8,11-二氢化呋喃并[3',4':5,6]吡啶并[3,2-f]喹喔啉-10(7H)-酮衍生物,并通过X单晶衍射分析确证了11-(4-硝基苯基)-8,11-二氢化呋喃并[3',4':5,6]吡啶并[3,2-f]喹喔啉-10(7H)-酮(4g)的结构.该方法操作简单,无需催化剂和分离中间体,为分子内同时含呋喃、吡啶和喹喔啉稠合四环杂环提供了很好的合成方法.     

四(5-氟尿嘧啶-1-基乙酰氧基苯基）卟啉及其锌配合物的合成

以二环己基碳二亚胺为脱水剂,meso-四(对羟基苯基)卟啉与5-氟尿嘧啶-1-基乙酸反应,合成了一种新型meso-四[4-(5-氟尿嘧啶-1-基乙酰氧基)苯基]卟啉化合物(A),产率12.7%;将其与乙酸锌反应得到其锌配合物(B),产率30.8%。 通过1H NMR、IR、MS、UV-Vis及元素分析确证了卟啉化合物A及其锌配合物B的结构。     

Green approach for the synthesis of 3‐methyl‐1‐phenyl‐4‐((2‐phenyl‐1H‐indol 3‐yl)methylene)‐1H‐pyrazole‐5(4H)‐ones and their DNA Cleavage,antioxidant, and antimicrobial activities

3‐Methyl‐1‐phenyl‐4‐((2‐phenyl‐1H‐indol‐3‐yl)methylene)‐1H‐pyrazol‐5(4H)‐ones (5a‐i) was prepared by the condensation reaction of different 3‐formyl‐2‐phenylindole derivatives (2a‐i) and 3‐methyl‐1‐phenyl‐2‐pyrazoline‐5‐one in quantitative yield by applying various green synthetic methods as grinding, microwave irradiation using different catalysts under solvent‐free mild reaction conditions with high product yields. The structures of the synthesized compounds were characterized on the basis of elemental analysis, infrared, ¹HNMR, ¹³C NMR, and mass spectral data. The synthesized compounds were screened for free radical scavenging, antimicrobial, and DNA cleavage activities. Most of the tested compounds belonging to the 3‐methyl‐1‐phenyl‐4‐((2‐phenyl‐1H‐indol‐3‐yl)methylene)‐1H‐pyrazol‐5(4H)‐ones series exhibited promising activities.     

Synthesis and Properties of Chiral Pyrazolidines Derived from (+)‐Pulegone

Several enantiomerically pure N(2)‐substituted octahydroindazoles were prepared as bicyclic pyrazolidine derivatives of (+)‐pulegone. Condensation of pulegone with hydrazine delivered a hexahydroindazole intermediate, which underwent N(2)‐substitution with various electrophiles (alkyl halides, acyl chlorides, phenyl isocyanate). The resulting N(2)‐substituted hexahydroindazoles could be reduced with LiBEt₃H in THF to the target compounds. In addition, a N(2)‐thiobenzoyl and some N(2)‐carbamoyl derivatives as well as a N(1)‐substituted octahydroindazole were synthesized. The compounds showed medium activity as iminium ion catalysts promoting quantitatively the Michael addition of nitroethane to cinnamaldehyde in up to 82 % ee for the resulting syn‐diastereoisomer and 78 % ee for the anti‐diastereoisomer. Unexpectedly, the N(2)‐acyloctahydroindazoles were readily oxidized under aerobic conditions. Moreover, it was shown that an oxidation of methyl phenyl sulfide to the corresponding sulfoxide is promoted by an N(2)‐acyloctahydroindazole in deuterochloroform as solvent. It is proposed that the oxidation of N(2)‐acyloctahydroindazoles proceeds by in situ generation of hydrogen peroxide, which in turn can act as an oxidant.     

The carbonylation of phenyl bromide and its derivatives under visible light irradiation

The carbonylation of phenyl bromide catalyzed by Co（OAc）₂ has been investigated with PhCOPh as a sensitizer under visible light in the presence of basic additive.With strong base CH₃ONa,PhCOOCH₃ is produced in 70%yield with 100%selectivity,the similar results are also obtained with a stronger base（CH₃）₃CONa.However,with another strong base NaOH,the yield of the ester is only 40%.On the other hand,with weak base NaOAc or（n-C₄H₉）₃N,phenyl bromide cannot be carbonylated.The results of carbonylation of the six substituted phenyl bromides suggest that the activities of o,m,p-BrC₆H₄CH₃ are similar to phenyl bromide, while the activities of o,m,p-BrC₆H₄Cl are higher with the high yields（≥93%） of the corresponding chloro-esters.In addition,the relative position of bromine and chlorine or methyl on phenyl ring has little effect on the activity of the carbonylation.     

无溶剂无催化剂微波促进下 1-苯基-3-甲基-5-吡唑啉酮与芳醛的反应研究

无溶剂无催化剂条件下,微波促进1-苯基-3-甲基-5-吡唑啉酮与芳醛的缩合反应选择不同辐射功率将分别得到4-芳亚甲基-3-甲基-1-苯基-5-吡唑啉酮和4,4′-芳亚甲基-双(1-苯基-3-甲基-5-吡唑啉酮),产率良好.产物结构经1H NMR,13CNMR和IR进行了表征.     

1-(3-吡唑基)薁-3-甲酸甲酯类衍生物的合成

室温下,1-乙酰基薁-3-甲酸甲酯与N,N-二甲酰胺缩甲醛缩合后再与肼或苯肼反应,合成了6个新的1-(3-吡唑基)薁类衍生物,其结构经1HNMR,MS和元素分析表征。并对反应机理进行了探讨。     

New 7‐phosphanorbornenes derived from 2‐methyl‐1‐phenyl‐ and 1‐cyclohexyl‐3‐ methyl‐2,5‐dihydro‐1H‐phosphole 1‐oxides

Novel 7‐phosphanorbornene derivatives, such as 4, 5, 10 , and 11 were synthesized utilizing 1‐phenyl‐2‐methyl‐2,5‐dihydro‐1H‐phosphole oxide ( 1 ) and 1‐cyclohexyl‐3‐methyl‐2,5‐dihydro‐1H‐phosphole oxide ( 7 ) as the starting materials. Products 4 and 10 were prepared by trapping the corresponding phosphole oxide intermediates ( 3 and 9 , respectively) by N‐phenylmaleimide, while 5 and 11 were obtained by the dimerization of 3 and 9 , respectively. The trapping reaction was studied in details; on one hand, bromo‐2,3‐dihydro‐1H‐phosphole oxides ( 6‐1 and 6‐2 ) were pointed out as the intermediates, on the other hand, the trapping reaction was optimized. Bri‐ dged P‐heterocycles 4, 5, 10 , and 11 were tested in the fragmentation‐related phosphorylation of methanol. Hydrogenation of phosphanorbornenes 4 and 5 led to the corresponding phosphanorbornanes ( 12 and 14 , respectively) and to a reductive type of retro cycloaddition. © 2005 Wiley Periodicals, Inc. Heteroatom Chem 16:320–326, 2005; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20097     

Clay‐supported 2‐phenyl‐1H‐imidazole derivatives for heterogeneous catalysis of Henry reaction

Six derivatives ( 1 , 2 , 3 , 4 , 5 , 6 ) of 2‐phenyl‐1H‐imidazole were tested as catalysts of Henry reaction. Three new ( 4 , 5 , 6 ) 2‐phenyl‐1H‐imidazole derivatives, differently substituted (thio)ureas, were synthesized and determined by ¹H NMR and IR spectroscopy and elemental analysis. Two types of catalysis, homogeneous and heterogeneous, were examined and compared. Clay minerals Ca‐MMT and Cu‐MMT were used as solid supports for heterogeneous catalysis. The best results were obtained using compound 2 under conditions of heterogeneous method D from the point of view of yield and reaction time. J. Heterocyclic Chem., (2011)     

新型含吡唑环的N-甲氧基氨基甲酸甲酯类化合物的设计、合成及生物活性

以苯(吡啶)乙/丙酮类化合物为原料, 经酯化、环化和缩合三步制得新型含吡唑环的N-甲氧基氨基甲酸甲酯类化合物3a~3r, 化合物及其中间体的化学结构经红外光谱、核磁共振谱及元素分析确认. 生物活性结果表明, 化合物3在400 mg/L下分别对水稻稻瘟病、黄瓜霜霉病和小麦白粉病具有很好的防治效果. 对水稻稻瘟病, R₁为甲基或甲氧基取代的苯基时活性最好; 对于黄瓜霜霉病和小麦白粉病, R₁为苯基或甲基取代苯基的化合物杀菌活性优于其它化合物, R₂为甲基的化合物杀菌活性优于R₂为氢的化合物.     

氯化铜催化三组分“一锅法”合成新型N1-取代3,4-二氢嘧啶酮衍生物

以二水合氯化铜为催化剂,通过等摩尔芳香醛、乙酰乙酸甲(乙)酯和N-取代脲的Biginelli缩合反应,"一锅法"合成了19个N1-取代的3,4-二氢嘧啶酮衍生物,其中11个为新化合物,其结构经~1H NMR,~(13)C NMR和MS表征。考察了催化剂用量和反应温度对产物收率的影响。结果表明最优反应条件为:催化剂用量为0.3mmol,反应温度为90℃。并对催化机理进行了探讨。