An Efficient Approach to 6, 7-Disubstituted-1H-quinoxalin-2-ones

A novel approach to the synthesis of 6, 7-disubstituted-1H-quinoxalin-2-ones is described.The title compounds were regioselectively prepared by starting from substituted phenylamines andchloroacetyl chloride through the efficient sequence of acylation, nitration, reduction, intramolecular alkylation, and oxidation.

Spontaneous Changes of Solid 5,7-di-<i>tert</i>-butylspiro(2,5)octa-4,7-diene-6-one in Storage Conditions at Room Temperature

On an example of spontaneous changes 5,7-di-tert-butylspiro (2,5) octa-4,7-diene-6-one at room temperature, a new example of condensations in a solid station is opened. The single crystal of 2-(3’, 5'-di-tert-butyl-4'-hydroxy-phenyl)-ethyloxy-p-cresole is produced as result of a structure transformation 5,7-di-tert-butylspiro (2,5) octa-4,7-diene-6-one in a solid phase at room temperature except a single crystal at transformation 5,7-di-tert-butylspiro (2,5) octa-4,7-diene-6-one a new substance is formed too. Spectrums 1Н and 13С NMR differ from similar spectrums of initial compound and the single crystal. New substance represents an admixture of isomeric compounds, capable reversible to be transformed in initial 5,7-di-tert-butylspiro(2,5) octa-4,7-diene-6-one and 2-(3’, 5'-di-tert-butyl-4'-hydroxyphenyl)-ethyloxy-p-cresole.

A Facile Synthesis of 9,10-Dimethoxybenzo[6,7]- ox-epino[3,4-<i>b</i>]quinolin-13(6<i>H</i>)-one and Its Derivatives

A concise and efficient method for the synthesis of novel 9,10-imethoxybenzo[6,7]oxepino[3,4-b]quinolin13(6H)-one and its derivatives 7a-p has been developed via the intramolecular Friedel-Crafts acylation reactions of 6,7-dimethoxy-2-(phenoxymethyl)quinoline-3-carboxylic acids 6a-p with polyphosphoric acid (PPA) as catalyst and solvent under mild conditions. The key intermediates 6a-p were prepared through the in situ formation of ethyl 6,7-dimethoxy-2-(phenoxymethyl)quinoline-3-carboxylates 5a-p followed by hydrolysis with aqueous ethanolic sodium hydroxide solution. The novel synthetic method has the advantages of good yields, easy work-up, and environmentally friendly character, which may provide a novel highly efficient process for making quinoline and related azaheterocycle libraries.

Design,synthesis characterization and in vitro biological activity of a series of 3-aryl-6-(bromoarylmethyl)-7H-thiazolo[3,2-b]-1,2,4-triazin-7-one derivatives as the novel acetylcholinesterase inhibitors

Bromination is used as a strategy to improve biological activity in medicinal chemistry.In order to study on the structure-activity relationships of the novel acetylcholinesterase inhibitors with 7H-thiazolo[3,2-b]-1,2,4-triazin-7-one scaffold,based on our previous work and molecular modeling,a series of novel 3-aryl-6-（bromoarylrnethyl）-7H-thiazolo[3,2-b]-1,2,4-triazin-7-one derivatives were designed by molecular docking,synthesized and characterized by mass spectra,infrared spectra,proton NMR and elemental analyses.The study of AChE inhibitory activity was carried out using the Ellman colorimetric assay with huperzine-A as the positive control.Most of all target compounds exhibited more than 45%inhibition at 10μmol/L.The preliminary structureactivity relationship was the bromine atoms and the hydroxyl group at the phenyl ring at the C6 position of the parent nucleus played significant roles in the AChE inhibitory activity of the target compounds.

A novel and convenient synthesis of thiazolo[3,2-a]pyrimidin-7-ones and pyrido[1,2-a]pyrimidin-2-ones using Vilsmeier reagent

A novel route for the synthesis of thiazolo[3,2-a]pyrimidin-7-ones and pyrido[1,2-a]pyrimidin-2,ones from acetylated 2- aminothiazoles and 2-aminopyridines under Vilsmeier conditions has been developed. The plausible mechanism has also been proposed.

Synthesis and bioassay of all four stereoisomers of (2E,4E)-4,6,10,12-tetramethyl-2,4-tridecadien-7-one, the assignment of the absolute configuration of the sex pheromone of Matsucoccus matsumurae Japanese pine bast scale

A facile enantioselective synthesis of all four stereoisomers of (2E,4E)-4,6,10,12-tetramethyl-2,4-tridecadien-7-one (1) is described. The stereochemistry at 6-C and 10-C of 1 was constructed by using optically active citronellal as starting material and by the asymmetric crotylic metal reaction. In the bioassay and field tests, only la, i.e. (6R,10R)-1 was active. The other three isomers 1b (6S,10R), 1c (6R,10S) and 1d (6S,10S) were inactive. Therefore, the naturally occurring pheromone was assigned as (6K,10R)-1.

野鸦椿的植物化学成分研究

从野鸦椿 (EuscaphisjaponecaKantiz)枝叶的甲醇提取物分离得到 6个化合物 ,通过波谱分析鉴定为 5 ,7 dihydroxy 2 methyl benzopyran 4 one(Ⅰ ) ,3,4 ,5 trihydroxy benzoicacidmethylester(Ⅱ ) ,3,7 dihydroxy 5 octanolide(Ⅲ ) ,methyl 5 ,7 dihydroxy 2 (Z) octenoate(Ⅳ ) ,7 hydroxy 2 octen 5 olide(Ⅴ )和vomifoliol(Ⅵ )。

苏木心材中一个新黄酮类化合物

目的:从苏木Caesalpinia sappan中寻找新的活性成分。方法:用溶剂萃取及硅胶正相色谱进行活性成分的分离纯化,根据理化性质、光谱数据进行结构鉴定。结果:从苏木95%乙醇提取物中分离得到了9个化合物:3,8-dihydroxy-4,10-dimethoxy-7-oxo-[2]benzopyrano[4,3-b][1]benzopyran-7-(5H)-one(1),3-deoxysappanchal-cone(2),sappanchalcone(3),3-deoxysappanone B(4),鼠李素(rhamnetin,5),原苏木素C(protosappanin C,6),3,7-di-hydroxy-chroman-4-one(7),己二酸二甲酯(8),胡萝卜苷(daucosterin,9)。结论:化合物1为新化合物,化合物7,8为首次从该植物中分离得到。药理筛选结果表明,化合物3对多种癌细胞株具有一定的抑制活性。

冰糖草化学成分的分离与鉴定

目的研究冰糖草(Scoparia dulcis L.)全草乙醇提取物的正丁醇萃取部位的化学成分。方法运用硅胶、Sephadex LH-20和半制备HPLC等各种方法进行分离纯化,根据理化性质和波谱数据等鉴定化合物结构。结果分离得到16个化合物,分别鉴定为(2S)-7-methoxy-2H-1,4-benzoxazin-3(4H)-one 2-O-β-glucopyranoside(1)、(2R)-7-methoxy-2H-1,4-benzoxazin-3(4H)-one 2-O-β-glucopyranoside(2)、对羟基苯甲酸甲酯(3)、对羟基苯甲醛(4)、2-唑啉酮(5)、对羟基苯乙酮(6)、薏苡素(7)、苯甲酸(8)、对羟基肉桂酸甲酯(9)、黑麦草内酯(10)、异黑麦草内酯(11)、橙酰胺乙酸酯(12)、apigenin 7-O-rutinoside(13)、hispidulin-7-O-rutinoside(14)、isoschaftoside(15)和schaftoside(16)。结论化合物1为新化合物,化合物13~16为首次从冰糖草中分离得到。

Catalyst Free One-Pot Synthesis of Chromeno Quinolines and Their Antibacterial Activity

An efficient greener one pot synthesis of dimethyl-dihydro-7H-chromeno[3, 2-h]quinolin-8(9H)-one derivatives has been synthesized through cyclization of aromatic aldehyde, dimidone and 8-hydroxy-quinoline through one-pot condensation method is described. The synthesized compounds are screened for further biological activities against Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, Bacillus subtilis, Bacillus using cut plate method and disc diffusion method.

An efficient synthesis of novel pyridothieno-fused thiazolo[3,2-α]pyrimidinones via Pictet–Spengler reaction

An efficient method for the synthesis of novel pyrido[3＇＇,2＇＇：4＇,5＇]thieno[3＇,2＇：2,3]pyrido [4,5：d][1,3]thiazolo[3,2-a]pyrimidine-4-one derivatives（5） has been developed using a Pictet–Spengler reaction between 2-（3-aminothieno[2,3-b]pyridin-2-yl）thiazolo[3,2-a] pyrimidin-5-one（3）, which could be obtained from the condensation of 7-（chloromethyl）-5H-thiazolo[3,2-a]pyrimidin-5-one（1） with3-cyanopyridine-2-thione（2） via Thorpe–Ziegler isomerization, and aromatic aldehydes under NH2SO3 H as catalysis in good yields.

UPLC-Q/TOF法同时定性定量分析滇芹药材中主要化学成分

目的建立UPLC-Q/TOF法同时定性、定量分析滇芹中主要化学成分。方法采用超高效液相色谱串联飞行时间质谱法进行分析,色谱柱为Agilent Poroshell 120 Hilic,流动相为乙腈-0.1%甲酸水溶液,梯度洗脱,体积流量0.3 m L/min;定性、定量采用Q-TOF正负离子全扫描+IDA(信息关联采集)模式。结果利用已建立的筛查数据库将满足质量误差小于5×10-6、同位素分布正确且含有二级碎片的离子作为分析目标化合物,结合软件Formula Finder、Mass Calculators等功能、在线数据库(Human Metabolome Database、Pub Chem、Chemical Book等)及二级碎片裂解规律,共鉴定出23个化合物,滇芹首次发现4个化合物。确定阿魏酸为定量分析指标性成分,其定量、定性离子分别为178和149;阿魏酸检测质量浓度线性范围为1.14~1 140 ng/m L(r=1.000),检测限、定量限分别为0.87、2.91 ng/m L,精密度、稳定性、重复性试验的RSD<2%,加样回收率为98.13%~101.25%(RSD=1.37%,n=5)。结论该方法灵敏度高、重现性好,分析快速、准确、可靠,可用于同时定性、定量检测滇芹药材中主要化学成分;云南滇芹中阿魏酸含量要高于西藏滇芹。

新鲜烟叶中的1个新二萜类成分

目的研究烟草Nicotiana tabacum叶中的西松烷二萜类化学成分。方法采用柱色谱技术对烟草的95%乙醇提取物进行分离纯化,采用波谱技术结合化学方法进行结构鉴定。结果从烟草提取物中分离得到了5个西松烷二萜类成分,分别鉴定为(1R,3E,7E,10S,11E)-3,7,11-cem-bratriene-10,15-diols(1)、(1S,2E,4S,6R,7E,10E,12S)-2,7,10-cembratriene-4,6,11-triol(2)、(1S,2E,4R,6R,7E,10E,12S)-2,7,10-cembratriene-4,6,11-triol(3)、(1S,2E,4S,6R,7E)-4,6,11-trihydroxy-1-isopropyl-4,8-dimethylpentadeca-2,7-dien-12-one(4)、(1S,2E,4R,6R,7E,11S,12S)-11,12-epoxy-2,7-cembradiene-4,6-diol(5)。结论化合物1为1个新化合物,命名为烟叶二萜B;化合物4首次在植物中发现,为1个新的天然产物。

一测多评法测定毛郁金中5种成分

目的建立毛郁金药材中不同成分同时测定的一测多评法。方法以毛郁金中莪术二酮为指标,建立莪术二醇、ocathydro-1,4-dihydroxy-1,4-dimethyl-7-(propan-2-ylidene)azulen-5(1H)-one、原莪术醇和姜黄素的相对校正因子,在考察相对校正因子的重现性后,进一步采用外标法对一测多评法所计算出的成分含量进行验证。结果 10批毛郁金药材中,各成分采用相对因子计算的含量与采用外标法计算的结果无显著差异。结论以莪术二酮为参照物,采用一测多评测定和计算其他4种成分含量的方法是可行的,结果较为准确。

二妙丸HPLC指纹图谱及UPLC-LTQ-Orbitrap成分分析

目的建立二妙丸的HPLC指纹图谱质量评价方法,并对二妙丸中的化学成分进行UPLC-LTQ-Orbitrap定性分析。方法指纹图谱采用HPLC法,色谱柱为Shiseido C18柱(250 mm×4.6 mm,5μm),乙腈-0.1%甲酸水溶液为流动相进行梯度洗脱,体积流量为1.0 m L/min,检测波长为330 nm,以黄柏、苍术混合对照药材生成的色谱图为标准对照图谱,采用"中国药典委员会相似度评价软件(2012A)"对样品进行相似度评价;采用UPLC-LTQ-Orbitrap技术对二妙丸中化学成分进行定性分析,色谱柱为Thermo Scientific Syncronis C18柱(100 mm×2.1 mm,1.9μm),乙腈-0.1%甲酸水溶液梯度洗脱,经DAD检测器后采用LTQ-Orbitrap Elite质谱正离子模式采集,各成分的一级全扫描离子在离子阱内进行CID多级质谱、FT检测高分辨质谱数据分析。结果所建立的指纹图谱有10个共有色谱峰,20批样品的相似度在0.869~0.992。通过对照品指认、文献比对以及高分辨质谱数据解析,鉴定了21个化学成分,分别为neo-chlorogenic acid、木兰箭毒碱、竹叶椒碱、木兰花碱、3-O-feruloylquinic acid、蝙蝠葛碱、demethyleneberberine、oxyberberine、非洲防己碱、药根碱、小檗红碱、巴马汀、小檗碱、丁香酸、咖啡酸、(E)-4-(3-hydroxyprop-1-en1yl)-2-methoxyphenol、白术内酯II、acetosyringone、白术内酯I、selina-4(14),7(11)-dien-8-one、苍术素。结论建立的二妙丸HPLC指纹图谱专属性强,重现性好,结合液质联用技术的定性分析,可全面评价二妙丸的内在质量。