An efficient synthesis of 2,2′-arylmethylene bis-(3-hydroxy-5,5-dimethyl-2-cyclohexene-1-one) and 1,8-dioxooctahydroxanthenes using ZnO and ZnO-acetyl chloride

2,2'-Arylmethylene bis(3-hydroxy-5,5-dimethyl-2-cyclohexene-1-one) 4l-s produced from reaction between dimedone with various aldehydes in acetonitrile using ZnO as a catalyst;whereas in the presence of ZnO-acetyl chloride catalysts the reaction is limited to give only 1,8-dioxo-octahydroxanthenes 3a-k in very good yields.

Novel synthesis of 2-butyl-5-chloro-3H-imidazole-4-carbaldehyde:A key intermediate of Losartan

A novel method for synthesis of 2-butyl-5 -chloro-3H-imidazole-4-carbaldehyde 2, a key intermediate of Losartan was reported. The compound 2 was synthesized from starting material dimethyl malonate 6 and n-valeronitrile 8 by six steps with an overall yield of 40%. The key step including the reaction of compound 5 with POCl3/DMF followed by hydrolysis to give compound 2 with the yield of 68%.

Coupling Reaction of 4-Chloro-7-H-Pyrrolo[2,3-d]Pyrimidine with 2,3,5-Tri-O-Acetyl-b-D-Ribofuranosyl Chloride

Coupling reaction of 4-chloro-7-H-pyrrolo[2,3-d]pyrimidine with 2,3,5-tri-O-acetyl -β-D-ribofuranosyl chloride under the basic condition was investigated. An abnormal coupling reaction, in which the heterocyclic base attacked at the carbon of 1,2-O-methylidene moiety instead of anomeric carbon of ribose was observed and the structure of products 5a, 5b were identified by NMR and X-Ray diffraction.

Synthesis,Crystal Structure,and Magnetic Property of One 3D Nickel Coordination Polymer Based on 2-Hydroxy-5-(3',5'-terephthalic acid)Pyridine and 1,4-Bis(1-imdazoly)benzene

One novel nickel coordination polymer, {[Ni（OTP）（bib）1.5（H2O）]·2H2O}n（1, H2 OTP = 2-hydroxy-5-（3＇,5＇-terephthalic acid） pyridine, bib = 1,4-bis（1-imdazoly）benzene）, has been synthesized and characterized by elemental analysis（EA）, IR, powder X-ray diffraction（PXRD）, and thermogravimetric（TG） analyses. The crystal of 1 crystallizes in monoclinic, space group P21/n with a = 12.2860（5）, b = 13.8246（6）, c = 19.0140（8） A, β = 104.3870（1）°, V = 3128.2（2） A3, Z = 4, C32H28N7 Ni O8, Mr = 697.32, Dc = 1.481 g/cm^3, F（000） = 1444 and μ（Mo Kα） = 0.684 mm-1. The final R = 0.0704 and w R = 0.1764 for 5485 observed reflections with I 2σ（I） and R = 0.1087 and wR = 0.2010 for all data. Topology analysis reveals that complex 1 is a 3D 2-fold interpenetrated {4^4·6^6}-nov net based on the 1D [Ni（OTP）]n chain and the 2D [Ni2（bib）3]n sql sheet. And the variable-temperature magnetic susceptibility measurements exhibit weak antiferromagnetic coupling interaction.

Synthesis, Crystal Structure and Antitumor Activity of 4-(tert-butyl)-5-(1H-1,2,4-triazol-1-yl)-N-(2-hydroxy-3,5-diiodinebenzyl)-thiazol-2-amine

The title compound, 4-（tert-butyl）-5-（1 H- 1,2,4-triazol- 1 -yl）-N-（2-hydroxy-3,5-diio- dinebenzyl）thiazol-2-amine, was synthesized via the reduction of 4-（tert-butyl）-5-（1H-l,2,4- triazol-l-yl）-N-benzylidene-thiazol-2-amine with NaBH4, and its crystal structure was determined by single-crystal X-ray diffraction. The compound crystallizes in monoclinic system, space group P21/c with a = 7.91944（19）, b = 10.5250（3）, c = 24.4985（6） A, Z = 4, V = 2041.66（9） A3, Mr = 599.22, Dc = 1,949 Mg/m3, S = 1.120, p = 3.203 mm-1, F（000） = 1152, the final R = 0.0283 and wR = 0.0592 for 3490 observed reflections （I 〉 2σ（I））. X-ray analysis displays that the crystal water takes part in three intermolecular hydrogen bonds of O（2）-H（2A）…O（1）, O（2）-H（2B）…N（I） and N（5）-H（5）…O（2）, and an octatomic ring R^（8） is formed via intramolecular hydrogen bond of O（I）-H（IA）…N（4）. Furthermore, the I…I contacts are involved in stabilizing the overall three-dimensional network structure. The preliminary biological test shows the title compound has good antitumor activity with the IC50 value of 26 μM against the Hela cell line.

Synthesis and in vitro Anti-hepatitis B Virus Activity of Some Ethyl 5-Hydroxy-4-substituted Aminomethyl-2-sulfinylmethyl-1H-indole-3-carboxylates

A novel series of ethyl 5-hydroxy-4-substituted aminomethyl-2-sulfinylmethyl-lH-indole-3-carboxylates 8a--8j and 11e--11f was synthesized and evaluated in HepG2.2.15 cells for their anti-hepatitits B virus（HBV） activity and cytotoxicity. Among them, six compounds showed more potent inhibitory activity than lamivudine. Compound 8e exhibited the most significant anti-HBV activity with an IC50 value of 1.62 μmol/L, which was 33-times more potent than the reference drug lamivudine（IC50=54.78μmol/L）.

Determination of Trace Manganese (Ⅱ) by Its Catalytic De-colourizing Reaction On the Aerial Oxidation of 1.5-his (2-hydroxy-5-chlorophenyl)-3-cyanoformazan and Its Kinetic Reaction Mechanism

A kinetie method is described for the determination of trace amounts of mangancsc (Ⅱ)based on its catalylic effect on the aerial oxidation of 1.5-bis (2-hydroxy-5-chlorophenyl)-3-cyanofrmazan. The reaction is followed spectrophotometrically by measurin the rate of change in absorbance at 580nm. The calibration curve (rate constant vs. manganese concentration) is linearin the range of 10~200ng in 25ml solutions. Kinetic parameters of the reaction are reported. Thereare few Interferences.

Synthesis and Crystal Structure of [2-Hydroxy-5-(4-hydroxy-3-phenyliminomethyl-benzyl)-benzylidene]-phenyl-amine

The title compound [2-hydroxy-5-（4-hydroxy-3-phenyliminomethyl-benzyl）-benzylidene]-phenyl-amine （C27H22N2O2, Mr = 406.47） was synthesized by 5,5′-methylene-bissalicylal- dehyde with aminobenezene, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group C2/c with a = 4.4026（6）, b = 1.501（13）, c = 0.95818（12） nm, β = 90.868（2）°, V= 4.2813（9） nm^3, Z= 8, Dc= 1.292 g/cm^3,μ = 0.010, F（000） = 1744, R = 0.0576 and wR = 0.1450 for 3766 observed reflections with I 〉 2σ（I）. X-ray analysis reveals that the molecule has a pair of intramolecular OH…N hydrogen bonds.

Auxiliary Ligands Mediated One- and Two-dimensional Cd(Ⅱ) Coordination Polymers Incorporating Methyl-3- hydroxy-5-carboxy-2-Thiophenecarboxylate Ligand

Two N-donor ligands mediated Cd（Ⅱ） coordination polymers, namely,[Cd（L）（dmpz）2]n （1） and {[Cd（L）（atr）05（H20）]（H2O）}n （2） （H2L = methyl-3-hydroxy-5-carboxy-2-thiophenecarboxylate, dmpz = 3,5-dimethylpyrazole, and atr= 4-amino-l,2,4-triazole）, havebeen produced. Their structures were characterized by single-crystal X-ray diffraction analysis,elemental analyses and infrared spectra. Compound 1 possesses a one-dimensional （1D） chainstructure and is finally extended into a three-dimensional （3D） supramolecular architecturethough hydrogen bonding interactions. Compound 2 features a two-dimensional （2D） networkwith 4-connected sql topology based on dinuclear Cd（Ⅱ） clusters as nodes, which is alsoassembled into a 3D supramolecular architecture through hydrogen bonding interactions.Furthermore, compounds 1 and 2 exhibit high thermal stabilities and intense fluorescent emissionin the solid, and can be explored as potential luminescent materials.

Approach to synthesis of novel chiral 3-chloro-2(5H)- furanone and its application in asymmetric reactions

The synthetic method of the novel chiral synthon, 5-/-menthyloxy-3-chloro-2-(5H)-furanone 5a and its application in asymmetric reactions were investigated. 5a is easily obtained in highly optical purity, and acts as a stable acceptor of Michael addition with oxygen nucleophiles in tandem double Michael addition / internal nucieophilic substitution to offer the spiro-cyclopropane derivative containing four stereogenic centers 8, which it is difficult to obtain by routine methods. The synthetic methods for 5a and 8 are reported in detail and the new compounds are identified on the basis of their analytical data and spectroscopic data, such as UV, IR, H NMR,13 C NMR, MS and elementary analysis. The absolute configuration of the interesting spiro-cyclopropanes, spiro [1-chloro-4-(/-menthyloxy)-5-oxo-6-oxa-biscyclo[3.1.0]hexane-2,3i(4’-/-menthyloxy-5’-/-menthyloxy- butyrolactone)] 8 was established by X-ray crystallography. This result can provide important synthetic strategy in synthesis of some complex

A highly enantioselective synthesis of 5- (ι-menthyloxy) -4-substituted-3-chloro-2(5H) -furanones

In this paper, stereocontrolled tandem Michael addition-elimination reaction of the novel chiral source, S-(ι-menthyloxy)-3,4-dichloro-2(5H)-furanone, with various thiols and amines has been investigated. A series of new enantiomerically pure compounds, 5-(ι-menthyloxy)-4-substituted-3-cnloro-2(5H)-furanones, were obtained in good yields with d. e.(?)98% under mild conditions.

Studies on the Chemical Components of Clematis chinensis

Two novel compounds, clemaphenol A and dihydro-4-hydroxy-5-hyroxymethyl-2(3H)-fura-none were isolated together with eight known compounds, isoferulic acid, b-sitosterol, daucosterol, 5-hy-droxymethyl-2-furancarboxaldehyde, 5-hydroxy-4-oxo-pentanoic acid, palmitic acid, linoleic acid and anemonin from the root of Clematis chinensis Osbeck.

A New Hemiterpene Derivative from Prinsepia utilis

A new hemiterpenoid, （＋）-（2R,3S）-2-chloro-3-hydroxy-3-methyl-T-buty-rolactone was isolatexi from the leaves of Prinsepia utilis Royle. Its structure was clucidatexi by spectroscopic methods and X-ray crystallographic analysis.

A New Halogenated Biindole and A New Apo-carotenone from Green Alga Chaetomorpha basiretorsa Setchell

A new halogenated biindole and a new apo-carotenone have been isolated from the ethanolic extract of the green alga Chaetomorpha basiretorsa Sethcell. On the basis of chemical and spectroscopic methods including 2D NMR technique, their structures have been elucidated as 4,4′-dichloro-5,5′-dibromo-7,7′-dimethoxy-2,2′-bi-1H-indole and 1′S*,4′R*-8-(4′-hydroxy-2′,6′,6′- trimethylcyclohex-2-enyl)-6-methyloct-3E,5E,7E-trien-2-one, respectively.

A New Chromone Derivative from Stellera chamaejasme L

A new chromone derivative, 3-[1- (2, 4, 6-trihydroxyphenyl) 3-di-(4-hydroxyphenyl) 1-propanone-2-yl] 5,7-dihydroxy-8-di(4-hydroxyphenyl)methyl-4H-1-benzopyran-4-one, named as isomohsenone was isolated from the roots of Stellera chamaejasme L. together with known chamaechromone. Its structure was determined by the analysis of MS and NMR data, especially 2D NMR spectra.

A New Bisxanthone from Hypericum japonicum Thunb.ex Murray

A new bisxanthone, named bijaponicaxanthone C, was isolated from the whole plant of Hypericum japonicum. The structure was elucidated as 6-[1’’,5’’,6’’-trihydroxy-2’’’-(β-hydroxy-β- methylethyl)-2’’’,3’’’-dihydrofuran(5’’’,4’’’,3’’,4’’)xanthone-3’’’-oxyl]-1,3,5-trihydroxy-4-isoprenylxant- hone (1) on the basis of the spectral and chemical evidences.

A Dinuclear Cd(Ⅱ)Cluster-based Coordination Polymer:Synthesis,Structure and Luminescence Property

One two-dimensional coordination polymer with a formula of {[Cd（L）（imidazole）（H2O）]（H2O）}n（1） was obtained by the synthetic reactions in aqueous solution using a newly synthesized H2L（H2L = methyl-3-hydroxy-5-carboxy-2-thiophenecarboxylate） ligand.Compound1 crystallizes in monoclinic system,space group C2/c with a = 18.3176（11）,b = 8.5366（9）,c =8.4152（5）A,β = 101.789（6）°,V = 2797.1（3）A^3,Dc = 1.979 g/cm^3,C（10）H（12）N2O7SCd,Mr = 416.68 F（000） = 1648,μ = 1.745 mm^-1,F（000） = 1648,the final R = 0.0323 and wR = 0.0604 for 2604 observed reflections with I 〉 2s（I）.Structure analyses reveal that the compound is constructed by dinuclear Cd（Ⅱ） clusters bridged by two hydroxyl oxygens of L^2-anions,which features a two-dimensional network with 4-connected sql topology.Furthermore,the compound exhibits high thermal stability and intense fluorescent emission,and could be explored for potentia luminescent materials.

Mild and Efficient Synthesis of 1-（6-Chloroquinoxalin-2-yl）-2- [4-（trifluoromethyl）-2,6-dinitrophenyl] Hydrazine Derivatives by Microwave Irradiation

Some 1-（6-chloroquinoxalin-2-yl）-2-[4-（trifluoromethyl）-2,6-dinitrophenyl] hydrazine derivatives have been synthesized via both conventional and microwave assisted organic synthesis（MAOS） methods. The MAOS method is more effective on synthesizing these compounds than the conventional method in regard to the higher chemical yields of products（76%-98%） and the shorter reaction time（1-15 min）.

铁皮石斛醋酸乙酯部位化学成分研究

目的进一步研究铁皮石斛Dendrobium officinale活性醋酸乙酯部位的化学成分。方法运用大孔树脂、MCI、硅胶、凝胶(Sephadex LH-20)、ODS等柱色谱、制备薄层色谱及制备高效液相色谱法等分离技术,进行化合物的分离纯化,根据^(1)H-NMR、^(13)C-NMR、MS等波谱数据和理化性质鉴定化合物的结构。结果从铁皮石斛乙醇提取物的醋酸乙酯部位分离得到了34个化合物,分别鉴定为moscatin(1)、黑麦草内酯(2)、柚皮素(3)、橙皮苷(4)、甘草素(5)、2-(4-hydroxy-3-methoxyphenyl)-3-(2-hydroxy-5-methoxyphenyl)-3-oxo-l-propanol(6)、异甘草素(7)、(E)-4-hydroxycinnamic acid(8)、(Z)-4-hydroxycinnamic acid(9)、coniferyl p-coumarate(10)、sinapyl p-coumarate(11)、tinosporaic acid A(12)、N-trans-coumaroyltyramine(13)、N-trans-feruloyltyramine(14)、丁香脂素(15)、pinoresinol(16)、梣皮树脂醇(17)、lirioresionol(18)、2(5H)-Furanone 5-hydroxy-3,4-dimethyl-5-pentyl(19)、丁香酸(20)、十六烷酸(21)、对羟基苯甲酸(22)、对羟基苯甲醛(23)、阿魏酸(24)、二氢松柏醇(25)、十七烷(26)、4-羟基-3,5-二甲氧基反式肉桂醛(27)、dihydro-p-cinnamic acid(28)、(+)-(4S)-(2E)-4-羟基-2-壬烯酸(29)、1,3-benzenediol(30)、对羟基苯酚(31)、水杨酸(32)、对羟基苯乙酮(33)和香草醛(34)。结论化合物2首次从石斛属植物中分离得到,化合物3~7均为首次从铁皮石斛中分离得到。

Two pairs of unusual scalemic enantiomers from Isatis indigotica leaves

Two pairs of unusual scalemic enantiomers with a dimethoxyphenyl）ethyl]-2-methoxyindolin-3-one, novel carbon skeleton of 2-[1′-（4＂-hydroxy-3＂,5＂- named isatidifoliumindolinones A-D （1-4）, were isolated from an aqueous extract of lsatis indigotica leaves （da qing ye）. Their structures including absolute configurations were determined by spectroscopic data analysis combined with comparison of their experimental CD and calculated ECD spectra. Validity of the ECD spectra calculation to assign the absolute configurations is discussed. Plausible biosynthetic pathways of 1-4 are proposed. Stereochemistry-dependent activity against LPS-induced NO production in BY2 cells was observed, and among the stereoisomers compound 4 is most active.