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。     

氯化消毒副产物2-氯-5-酮-3-烯-己二酰氯的质谱分析

2－氯－4－（二氯甲基）－5－羟基－2（H）－呋喃酮（MX）是饮用水氯化消毒过程中产生的一种具有强致突变性的消毒副产物（DBPs)，在对MX的前驱物模拟氯化过程中，发现在MX峰的附近有一峰，有时干扰MX的测定；作者对该未知峰的质谱图进行了解析，初步推断其结构可能为2－氯－5－酮－3－烯－己二酰氯（2－chloro-5-oxo-3-hexene diacyl chloride,COHC).     

2-甲基-6-二乙胺基乙氧基-3(2H)-哒嗪酮的合成及其电子性质

分别利用两种方法合成2－甲基－6－二乙胺基乙氧基－3（2H）－哒嗪酮，用^1H NMR,IR,UV和MS进行结构表征，利用ab initio HF和密度泛函理论（DFT）B3LYP方法，对反应物、中间物、产物及其同分异构体进行几何结构的优化和总能量计算，系统分析前线分子轨道特征和能级分布规律，结果表明，2－甲基－6－二乙胺基乙氧基－3（2H）－哒嗪酮比其同分异构体哒嗪氮烷基化合物的能量低，前比后稳定，与实验事实相符合。     

蛇龙珠干红葡萄酒香气成分的GC-MS分析

研究宁夏贺兰山东麓地区蛇龙珠(Cabemet Gemischt)干红葡萄酒香气的化学成分,采用溶液萃取法提取蛇龙珠干红葡萄酒中的香气成分;用气相色谱一质谱进行分离测定,结合计算机检索技术对分离化合物进行鉴定,应用TIC峰面积归一法测定各成分的相对含量;分离出32个峰,鉴定出29个香气化学成分,共占其色谱流出组分总量的98．06％;其中相对含量以3-甲基丁醇(47．97％)、丁二酸二乙酯(16．49％)、苯乙醇(10．33％)、2-羟基丙酸乙酯(6．41％)、2-甲基丙醇(3．51％)、二氢化-2[3氢]-呋喃酮(2．07％)、2,3-丁二醇(1．93％)、四氢化2-甲基噻吩(1．68％)、乙酸乙酯(1．21％)、己醇(0．95％)等成分为主。     

烯烃锆氢化反应的研究

本文报道几种烯烃锆氢化-氧化反应。锆氢化试剂(η~5-C_5H_5)2_Zr(CI)H(1)与苯乙烯(2),对-甲基苯乙烯(3),α-甲基苯乙烯(4)以及2,4,4-三甲基戊烯-1(5)反应,生成的烷基锆络合物经叔丁基过氧化氢处理得到醇。从5仅得到2,4,4-三甲基戊醇-1,而从(?)(R,R=＇H或CH_3)除主要得到S-醇外,还得到一定量的α-醇。这是在烯烃的锆氢化反应中未曾发现过的。对芳香族烯烃锆氢化反应的非区域专一性,从空间效应和电子效应两方面作了定性的解释。     

2－甲基－3－芳基－7－（5，5－二甲基－3－酮－1－环己烯－1－基）甲酸酯－4（3H）－喹唑啉酮的合成

以2－氨基对苯二甲酸（1）为起始原料，与乙酸酐缩合生成7－羧基乙酰苯邻 甲内酰胺（2）；2和芳胺缩合产生7－羧基－2－甲基－3－芳基－4（3H）－喹唑啉 酮（3）；3和N，N－双环己基碳双亚胺（DCC）加成得到中间体4，4在4－二甲氨基 吡啶（DMAP）催化下和5，5－二甲基－1，3－环己二酮（5）缩合得到目标产物2－ 甲基－3－芳基－7－（5，5－二甲基－3－酮－1－环己烯－1－基）甲酸酯－4（ 3H）－喹唑啉酮（6）。所得15个新型化合物的结构均经^1H NMR、元素分析确证， 部分化合物经IC／MSD确证。     

2,3－二甲基－4－甲氧甲酰－2－环己烯醇的合成

2;3－二甲基－4－甲氧甲酰－2－环己烯醇的合成;二甲基甲氧甲酰环己烯醇;甲基甲氧甲酰环己烯酮;二甲基甲氧甲酰环己烯酮;氢化钠;氢化三叔丁氧基铝锂     

2，3—二氰基—2，3—二（p—X苯基）丁二酸二乙酯的分子构型和取代基电子效应对613 NMR谱的影响

测定了meso-和dl-2,3－二氰基－2，3－二（p-X苯基）丁二酸二乙酯（X＝OCH3，CH3，H，Cl,NO2)的^13C NMR谱。结果表明，，中心碳－碳键两端相连基团的各碳原子的化学位移值相同，与dl-异构体相比，所有相应meso-异构体的乙氧羰基^13C NMR吸附峰均处于高场，苯环对位取代基的Hammett基团常数σ与氰基碳原子和乙氧羰基中的羰基碳及次甲基碳的化学位移间线性相关，而且meso-异构体比dl-异构体有更好的线性关系。     

2-溴甲基-3-(二溴甲基)喹喔啉的合成研究

以2，3－二（溴甲基）喹喔啉为原料，以N－溴琥珀酰亚胺为溴化试剂合成了2－溴甲基－3－（二溴甲基）喹喔啉（1），1是Diels-Alder环加成反应中形成含杂原子环的C60衍生物的一种重要中间体。通过IR，^1H NMR,^13C NMR,DEPT谱和MS对其进行了结构表征。     

微波辐射下2-氨基苯并[h]喹唑啉衍生物的合成

2-芳亚甲基-3，4-二氢-2H-1（2H）-萘酮和碳酸胍在以乙二醇为溶剂、微波辐 射下反应，生成一系列新的2-氨基-4-芳基-5，6-二氢化苯并[h]喹啉衍生物，产物 的结构通过单晶X射线衍射分析确证。     

Factors affecting the selectivity of the oxidation of methyl p-toluate by cobalt(III)

The anaerobic oxidation of methyl p-toluate by cobalt(III) in acetic acid was investigated. Observed products were 4-carbomethoxybenzaldehyde (2), 4-carbomethoxybenzoic acid (3), 4-carbomethoxybenzyl acetate (1), 4,4'-dicarbomethoxybibenzyl (6), methyl 2,4-dimethylbenzoate (8), and methyl 3,4-dimethylbenzoate (9). Deuterium isotope labeling showed that 2 was not formed from 1, but appeared to be formed directly from methyl p-toluate via 4-carbomethoxybenzyl alcohol (5). The ratio of (2 + 3) to 1 was 0.5 with [py3Co3O(OAc)5OH[PF6] and 1.0 with cobaltic acetate. Cobaltic acetate was generated in situ by the reaction of cobaltous acetate and peracetic acid. When the oxidation was carried out in the presence of chromium (0.05 equiv based on cobalt), the ratio increased dramatically and no 6 was observed. Other transition metals such as vanadium, molybdenum, and manganese had a similar effect, but were not as effective as chromium. Chromium was observed to form a mixed-metal cluster complex with cobalt. Treatment of an acetic acid solution of cobaltous acetate and methyl isonicotinate with K2CrO4 produced a solid tentatively identified as [(MIN)3Co2CrO(OAc)6][CrO4H] (MIN = methyl isonicotinate). The selectivity for the oxidation of methyl p-toluate exhibited by the mixed-metal cluster complex was similar to that observed by the addition of chromium to oxidations using [py3Co3O(OAc)5OH[PF6].     

Separation of nine compounds from Salvia plebeia R.Br. using two‐step high‐speed counter‐current chromatography with different elution modes

Nine compounds were successfully separated from Salvia plebeia R.Br. using two‐step high‐speed counter‐current chromatography with three elution modes. Elution–extrusion counter‐current chromatography was applied in the first step, while classical counter‐current chromatography and recycling counter‐current chromatography were used in the second step. Three solvent systems, n‐hexane/ethyl acetate/ethanol/water (4:6.5:3:7, v/v), methyl tert‐butyl ether/ethyl acetate/n‐butanol/methanol/water (6:4:1:2:8, v/v) and n‐hexane/ethyl acetate/methanol/water (5:5.5:5:5, v/v) were screened and optimized for the two‐step separation. The separation yielded nine compounds, including caffeic acid ( 1 ), 6‐hydroxyluteuolin‐7‐glucoside ( 2 ), 5,7,3′,4′‐tetrahydroxy‐6‐methoxyflavanone‐7‐glucoside ( 3 ), nepitrin ( 4 ), rosmarinic acid ( 5 ), homoplantaginin ( 6 ), nepetin ( 7 ), hispidulin ( 8 ), and 5,6,7,4′‐tertrahydroxyflavone ( 9 ). To the best of our knowledge, 5,7,3′,4′‐tetrahydroxy‐6‐methoxyflavanone‐7‐glucoside and 5,6,7,4′‐tertrahydroxyflavone have been separated from Salvia plebeia R.Br. for the first time. The purities and structures of these compounds were identified by high‐performance liquid chromatography, electrospray ionization mass spectrometry, ¹H and ¹³C NMR spectroscopy. This study demonstrates that high‐speed counter‐current chromatography is a useful and flexible tool for the separation of components from a complex sample.     

Pyridazine Derivatives and Related Compounds,Part 1. Some Reactions with 4-Cyano-5,6-Diphenyl-2,3-Dihydropyridazine-3-One

4-Cyano-5,6-diphenyl-2,3-dihydropyridazine-3-onc 1 reacts with phosphorous oxychloride to give 70% of the corresponding 3-chloro derivative 2. Treating 2 with anthranilic acid in butanol, 4-cyano-2,3-diphenyl-10H-pyridazino[6,1-b]quinoxaline-10-one, 3 was obtained. Compound 1 reacts with phosphorous pentasulphide to give 3-mercapto derivative 4, which was converted by acrylonitrile to S-(2-cyanoethyl)pyridazine derivative 5. Compound 4 reacts with ethyl bromoacetate and with phenacyl bromide gave the corresponding thieno[2,3-c] pyridazine derivatives 8, 9, Alkylation of 1 with ethyl chloroacetate afforded 3-0-carbethoxymethyl derivative 10. Compound 10 reacts with amines (aniline, hydrazine) to give the corresponding amide and acid hydrazide 13, 12 respectively. Hydrolysis of 10 with sodium hydroxide gave the corresponding acid derivative 11. Treating 1 with methyl iodide, 3-0-methyl derivative 14 was obtained, which was converted by ammonium acetate/acetic acid to 3-amino-4-cyano-5,6-diphenyl pyridazine 15. Compound 1 reacts with methyl magnesium iodide gave 4-acetyl derivative 16, which was reacted with hydrazine, phenyl hydrazine and with hydroxylamine to give the substituted I H pyrazolo [3,4-c] pyridazine 17 a,b and isoxazolo [5,4-c] pyridazine 18 derivatives respectively.     

Reaction of adamantan-2-amine and (adamantan-1-yl)methylamine with methyl 2-(4-allyl-2-methoxyphenoxy)acetate

A reaction of methyl 2-(4-allyl-2-methoxyphenoxy)acetate with adamantan-2-amine and (adamantan-1-yl)methylamine in butanol leads, together with the target amides, to the formation of butyl ester of the corresponding acid, which is resistant to aminolysis.     

Suppressive effect of the SOS-inducing activity of chemical mutagen by citric acid esters from Prunus mume Sieb. Et Zucc. using the Salmonella typhimurium TA1535/pSK1002 umu test

A methanol extract from Prunus mume Sieb. Et Zucc. showed a suppressive effect of the SOS-inducing activity on the mutagen 3-amino-1,4-dimethyl-SH-pyrido[4,3-b]indole(Trp-P-1) in the Salmonella typhimurium TA1535/pSK1002 umu test. The methanol extract was re-extracted with hexane, dichloromethane, ethyl acetate, butanol and water. The dichloromethane and ethyl acetate fractions showed suppressive effect. Suppressive compounds were isolated by silica gel column chromatography and identified as trimethyl citrate (1) and dimethyl citrate (2) by GC-MS, IR and 1H and 13C-NMR spectroscopy. Compounds 1 and 2 suppressed 51 and 39% of the SOS-inducing activity at a concentration of 2.0 micromol/mL.     

Chemical components of Hyssopus seravshanicus: antioxidant activity,activations of melanogenesis and tyrosinase,and quantitative determination by UPLC-DAD

Hyssopus seravshanicus (Dubj.) Pazij has been used as traditional herb and food due to its wide biological properties. Seventeen known compounds were isolated from the ethyl acetate fraction. Their structures were identified by spectroscopic data and comparison with published data. Among them, 14 ones were identified from H. seravshanicus for the first time. DPPH and ABTS radical scavenging activities for crude ethanol extract (CEE), ethyl acetate fraction (EAF), butanol fraction (BF) and compounds 1, 3, 8, 10, 11 and 13 were performed. CEE, compounds 1, 3, 11 and 13 exhibited potent antioxidant activities. Compound 1 was found to increase the melanin content and tyrosinase activity of B16 melanoma cells. Moreover, the quantitative estimation of compound 1 in the ethyl acetate fraction was carried out by UPLC-DAD and the method was validated. This is the first report on the isolation and bioactivity research on the non-valotile components of H. seravshanicus.     

卤代-2-(3-甲基-5-取代-4H-1,2,4-三唑-4-基)-苯甲酸的合成

杂环化合物的结构变化繁多 ,具有广泛的生物活性 .已受到化学研究者的广泛关注 .在含氮杂环化合物中 ,三唑类化合物的研究引人注目 ,如已商品化的杀菌剂三唑酮[1] ;植物生长调节剂多效唑[2 ] ;杀虫剂唑蚜威 [3] 以及除草剂唑草胺 ( CH- 90 0 ) [4 ] 等 .为了寻找新型高生物活性三唑化合物或其先导化合物 ,我们以邻氨基苯甲酸为起始原料 ,经过卤化得到卤代邻氨基苯甲酸 ( 1 ) ;1和乙酸酐缩合得到卤代 - 3-甲基 - 1 H- 2 ,4-苯并嗪 - 1 -酮 ( 2 ) ;2与取代酰肼 ( 3)缩合得到一类新型的卤代 - 2 - ( 3-甲基 - 5 -取代 - 4H-1 ,2 ,4-三唑 - …     

Two new phenolic compounds and some biological activities of Scorzonera pygmaea Sibth. & Sm. subaerial parts

Abstract

Phytochemical composition of ethyl acetate fraction and total phenolic content, in vitro antioxidant, anti-inflammatory, antimicrobial activities of petroleum ether, chloroform, ethyl acetate and n-butanol fractions of the ethanol extract obtained from the subaerial parts of Scorzonera pygmaea Sibth. & Sm. (Asteraceae) were investigated. Nine compounds; scorzopygmaecoside (1), scorzonerol (2), cudrabibenzyl A (3), thunberginol C (4), scorzocreticoside I (5) and II (6), chlorogenic acid (7), chlorogenic acid methyl ester (8), 3,5-di-O-caffeoylquinic acid (9) were isolated and identified using spectroscopic methods. All substances were isolated for the first time from this species. Compounds 1 and 2 are new. The fractions showed high antioxidant capacity correlated with their phenolic content and no significant antimicrobial activity against tested bacteria and fungi. COX inhibition test was used to evaluate the anti-inflammatory activity and all the fractions showed low inhibition in comparison with indomethacin.     

Synthesis,structural characterization and cytotoxic activity of organotin derivatives of indomethacin

The synthesis, characterization and cytotoxic properties in vitro of tri‐n‐butyltin 1‐(4‐chlorobenzoyl)‐5‐methoxy‐2‐methyl‐1H‐indole‐3‐acetate ( 1 ), tri‐phenyltin 1‐(4‐chlorobenzoyl)‐5‐methoxy‐2‐methyl‐1H‐indole‐3‐acetate ( 2 ), tetra‐n‐butyltin[bis‐1‐(4‐chlorobenzoyl)‐5‐methoxy‐2‐methyl‐1H‐indole‐3‐acetato]distannoxane ( 3 ) and di‐n‐butyltin bis‐1‐(4‐chlorobenzoyl)‐5‐methoxy‐2‐methyl‐1H‐indole‐3‐acetate ( 4 ) are described. These compounds have been characterized by ¹H, ¹³C and ¹¹⁹Sn NMR spectroscopy in solution and ¹¹⁹Sn NMR in the solid state, infrared spectroscopy, elemental analysis and X‐ray diffraction for compound 1 . The growth inhibition effects of compounds 1–4 against the lung adenocarcinoma cell line SK‐LU‐1 as well as the cervical cancer cell line HeLa were determined. Compounds 1 and 2 exhibit cytotoxic activity, whereas compounds 3 and 4 are inactive. Copyright © 2008 John Wiley & Sons, Ltd.