几种β-二酮化合物及其互变异构体的光谱

合成了 6种β-二酮化合物 :1 ,3-二 (4 -硝基苯基 ) -1 ,3-丙二酮 ,1 -(4 -硝基苯基 ) -3-(3-硝基苯基 ) -1 ,3-丙二酮 ,1 ,3-二 (3-硝基苯基 ) -1 ,3-丙二酮 ,1 ,3-二 (4 -氨基苯基 ) -1 ,3-丙二酮 ,1 -(4 -氨基苯基 ) -3-(3-氨基苯基 ) -1 ,3-丙二酮和 1 ,3-二 (3-氨基苯基 ) -1 ,3-丙二酮 .采用多种光谱法对其结构进行了鉴定 .测量了不同溶剂中β-二酮化合物的酮式含量 ,给出了酮式 -烯醇式异构化平衡常数和烯醇式异构体的存在比例     

Synthesis of β-（ 1→6）-Branched （ 1→3）-Glucononaoside with Alter-nate β- and α-Bonds in the Backbone

Lauryl glycoside of β-D-Glcp-(1→3)-[β-D-Glcp-(1→6)-]α-D-Glcp-(1→3)-β-D-Glcp-(1→3)-[β-D-Glcp-(1→6)-]α-D-Glcp-(1→3)-β-D-Glcp-(1→3)-[β-D-Glcp-(1→6)-]β-D-Glcp was synthesized through 3 3 3 strategy. 3-O-Allyl-2,4,6-tri-O-benzoyl-β-D-glucopyranosyl-(1→3)- -[2, 3, 4, 6-tetra-O-benzoyl-β-D-glucopyranosyl-(1→6)-] 1,2-O-isopropylidene-α-D-glucofuranose was used as the key intermediate which was converted to the corresponding trisaccharide donor and acceptor readily.     

Synthesis of Analogues of the Antitumor （1→6）-Branched （1→3）-Glucohexaose

β-D-Glcp-(1→）3-[β-D-Glcp-(1→6)-]α-D-Manp-(1→3)-β-D-Glcp-(1→3)-[β-D-Glcp(1→6)-]D-Glcp(18)and β-D-Glcp(1→3)-[β-D-Glcp(1→6)-]α-D-Manp-(1→3)-β-D-Glcp(1→3)-[β-D-Glcp(1→6)-]β-D-Glcp-D-(1→3)-Glcp-1→OM3(29)were synthesized as the analogues of the immunomodulator β-D-Glcp-(1→3)-[β-D-Glcp(1→6)-]α-D-Glcp(1→3)-β-D-Glcp(1→63)-[β-D-Glcp(1→6)-]D-Glcp through coupling of trisaccharide donors 9 with trisaccharide acceptor 16 and tetrasaccharide acceptor 27 followed by deprotection,respectively.     

2003年催化学报第24卷作者索引

AAFANASIEVP .(1 ) 32安保正一(1 1 ) 84 5安立敦 (3) 2 0 3(9) 6 91安太成 (5 ) 338安增建 (1 ) 1安振涛 (1 1 ) 839B白长敏 (1 ) 5 7(8) 5 6 5白华萍 (1 0 ) 795白吉玲 (4 ) 2 4 1白杰 (1 ) 73(1 1 ) 80 5白亮 (4 ) 2 99(5 ) 343白琰 (3) 1 81包淑娟 (1 2 ) 90 9包信和 (2 ) 1 2 3(3) 2 0 3(4 ) 2 84(5 ) 32 3(6 ) 4 33鲍骏 (1 1 ) 82 6毕颖丽 (2 ) 1 1 5卞国柱 (3) 1 87(1 1 ) 82 6C蔡国辉 (1 1 ) 86 7蔡天锡 (1 ) 1(6 ) 4 71(7) 5 4 9蔡铁军 (1 2 ) 95 1蔡伟民 (3) 1 75蔡晔 (8) 5 79蔡英灵 (7) 5 1 3操小栋 (6 ) 4 0 3曹崇江 (6 …     

Oleanane-triterpene Saponins from Clinopodium urticifolium

Four new oleanane triterpene saponins were isolated and purified from the whole plant of Clinopodium urticifolium. They were 3β, 16β, 23, 28-tetrahydroxyoleana-9 (11), 12(13)-diene-3-yl-[β-D-glucopyranosyl-(1→2)]-[β-D-glucopyranosyl-(1→3)]- β-D-fucopyranoside 1; 3β, 16β,21β, 23, 28-pentahydroxyoleana-9(11), 12(13)-diene-3-yl-[β-D-glucopyranosyl-(1→2)]-[ β-D-glucopyranosyl-(1→3)]- β-D-fucopyranoside 2; 3β, 16β, 23, 28-tetrahydroxyoleana-9(11), 12(13)-diene-3-yl-[β-D-glucopyranosyl-(1→β)- β-D-glucopyranosyl-(1→3)]-[β-D-glucopyranosyl-(1→2)]-β-D-fucopyranoside 3; 3β, 16β, 23, 28-tetrahydroxyoleana-9(11), 12(13)-diene-3-yl-[β-D-gluco-pyranosyl-(1→4)-β-D-glucopyranosyl-(1→β)-β-D-glucopyranosyl-(1→3)]-[β-D-glucopyranosyl-(1→2)]- β-D-fucopyranoside 4. Their structures were elucidated on the basis of interpretation of NMR and MS data and from chemical evidence.     

CF_3I在238 nm的光解碎片平动能谱研究:CF_3光解碎片的振动态分布和势能曲线交叉穿越几率

利用高分辨弱电场加速型光解碎片平动能谱仪,对CF3I在238 nm的光解动力学进行了研究.结果表明,来自3Q0平行跃迁的I*通道[CF3I(X)hν→‖CF3I(3Q0)→CF3(ν1,ν2)+I*],信号最强,并可以分辨出碎片CF3(ν1,ν2)的振动峰.通过对峰间距的分析,可以基本分辨出同时具有CF3碎片的振动波带CF3(ν1,ν2=0)与CF3(ν1,ν2=1).其中ν1=701 cm-1为对称伸缩振动,ν2=1086 cm-1为CF3伞形振动.测量了这些振动态的分布及振动波带分配比为∑P(ν1,1)/∑P(ν1,0)=0.48/0.52.还测得238 nm处4个光解通道的分支比:通道1(X→3Q0→I*)为0.664,通道2(X→3Q0→1Q1→I)为0.084,通道3(X→1Q1→I)为0.178,通道4(X→1Q1→3Q0→I*)为0.074.实验结果表明,3Q0→1Q1过程中的势能曲线交叉穿越几率P0→1=0.112,1Q1→3Q0过程中P1→0=0.294;I*通道的各向异性参数β(I*)=1.70,I通道β(I)=-0.04.     

A1掺杂量对正极材料LiNi_(1/3)Co_(2/3-x)A1_xO_2结构和电化学性能的影响

以共沉淀法合成的前驱体Ni_(1/3)Co_(2/3-x)Al_x(OH)_2与低共熔锂盐0.38LiOH·H_2O-0.62LiNO_3制备了锂离子电池正极材料LiNi_(1/3)Co_(2/3-x)Al_xO_2(x=1/12,1/3,1/2,7/12).采用X射线衍射(XRD)、扫描电镜(SEM)和电化学性能测试对其结构、形貌和电化学性质进行表征.结果表明,LiNi_(1/3)Co_(2/3-x)Al_xO_2在1/12≤x≤1/3范围内可以保持单一的六方层状a-NaFeO_2结构,当A1掺杂量(x)高于1/3时,会出现杂相.其中,LiNi_(1/3)Co_(1/3)Al_(1/3)O_2结晶程度最高,阳离子混排效应最小,并且颗粒小而均匀,振实密度可以达到2.88 g·cm~(-3),首次放电容量为151.5 mAh·g~(-1),循环50次后放电容量保持在91.4%,在1C和2C倍率下放电容量仍可达到133.7和120.9 mAh·g~(-1)     

Two New Steroidal Glycosides from Fermented Leaves of Agave americana

Two new spirostanol glycosides named agamenoside A and B, ere isolated from the fermented leaves of Agave americana. Their structures were elucidated as (23S,25R)-5α-spirostan-3β,6α，23－triol 3-O-α-L-rhamnopyranosyl-(1→3)-β-D-glucopyranosyl-(1→2)-[β-D-xylopyranosyl-(1→3)]-β-D-glucopyranosyl-(1→4)-β-D-galactopyranoside(1) and (25R)-5α-spiro-stan-3β,6α-diol 3-O-β-D-glucopyranosyl-(1→2)-[β-D-xylopyranosyl-(1→3)]-β-D-glucopyra-nosyl-(1→4)-β-D-galactopyranoside(2) by a combination of chemical and spectral methods.     

Two New Steroidal Saponins from Tacca plantaginea

Two new C27 steroidal glycosides, named taccaoside A(1) and B(2), were isolated from the traditional Chinese herb Tacca plantaginea. The spectroscopic and chemical evidences revealed their structures to be 26-O-β-D-glucopyranosyl-(25R)-3β,26-dihydroxy furost-5,20-diene-3-O-[α-L-rhamnopyranosyl(1→2)]-[α-L-rhamnopyranosyl(1→3)]-β-D-glucopyranoside(1) and 26-O-β-D-glucopyranosyl-(25R)-3β,26-dihydroxy furost-5,20-diene-3-O-[α-L-rhamnopyranosyl-(1→2)]-[β-D-glucopyranosyl(1→3)-α-L-rhamnopyranosyl(1→3)]-β-D-glucopyranoside(2),respectively.     

四核铜配合物 [CuBrP(p-OCH_3Ph) _3]_4 ·1.5CH_3OH的合成和晶体结构

CuXP(p OCH3Ph) 3]4·1 .5CH3OH (X =Br,I)的合成和Cu4Br4C85.5H90 O1 3.5P4的晶体结构。该晶体属于三方晶系 ,空间群为R3,晶胞参数为 :a =2 3.959(2 ) ,c =2 6.376(4) ,γ =1 2 0 .0 0°,V =1 31 1 2 (3) 3,μ(MoKα) =2 .92 1mm- 1 ,Z =6,Dc=1 .543g .cm- 3,F(0 0 0 ) =61 62 ,R =0 .0 4 1 9,wR =0 .0 792 .可观察衍射点 471 3个 (I 2σ(I) )。该分子中 4个Cu原子和 4个Br原子构成立方烷结构 ,每个Cu与 3个Br原子 ,1个P(p OCH3Ph) 3中的P原子形成畸变四面体配位。     

BINUCLEAR COPPER(Ⅱ) COMPLEXES OF SOME PLANT GROWTH-STIMULATING SUBSTANCES Ⅱ. SYNTHESES AND STRUCTURES OF BIS(N,N-DIMETHYLFORMAMIDE)-TETRAKIS-[μ-(N-p-(AND m-)METHYLPHENYLPHTHALAMINO)]DICOPPER(Ⅱ)TETRAKIS(N,N-DIMETHYLFORMAMIDE) SOLVATE

<正> [Cu2( -C-N-C6H4CH3-p)4(DMF)2]-4DMF(1), Mr = 1582.7, triclinic,Pl, a = 10.761(1), b = 13.930(3), c = 15.116(3) A;α= 114.74(1),β= 101.82 (1),r= 95.85(1)°,V = 1969.0 A3,Z=1,Dm= 1.36,DC =1.335 g/cm3.[Cu2(-C-N-C6H4Ch3-M)4.(DF)2].4DMF(2), Mr = 1582.7, triclinic, Pl,a = 10.588(5), b = 13.699(2), c = 15.759(4) A;α= 114.88(2),β= 103.89(3), γ=92.56(3)°, V =1985.3 A3, Z = 1, 0. = 1.39,Dc= 1.324 g/cm3.The four phthalamine groups in molecules of (1) and (2) are all biden-tate bridging ligands to Cu atoms and there are two terminal DMF ligands, one on each Cu atom. The Cu-Cu distances are 2.635(1) and 2.641(1) A for (1) and (2) respectively.     

新型2,6-双(3,5-二取代吡唑基-1-羰基)吡啶的合成

报道了四种吡唑衍生物和它们四种新型的杂环酰胺衍生物的合成 ,它们是 3 ,5 二甲基吡唑 (1) ,5 甲基 3 苯基吡唑(2 ) ,3 ,5 二苯基吡唑 (3 ) ,5 甲基 3 二茂铁基吡唑 (4 ) ,2 ,6 双 (3 ,5 二甲基吡唑基 1 羰基 )吡啶 (5 ) ,2 ,6 双 (5 甲基 3 苯基吡唑基 1 羰基 )吡啶 (6) ,2 ,6 双 (3 ,5 二苯基吡唑基 1 羰基 )吡啶 (7)和 2 ,6 双 (5 甲基 3 二茂铁基吡唑基 1 羰基 )吡啶 (8) .并对它们进行了元素分析 ,FT IR ,1HNMR和13 CNMR等波谱分析 .     

Y_2O_3前驱体热分解过程及动力学研究

用热重-差热分析法对Y_2O_3前驱体Y_2(CO_3)_3和Y_2(C_2O_4)_3水合物热分解过程及动力学进行分析,通过Kissinger法、 Ozawa法和Coast-Redfern法等对实验数据进行处理,得出Y_2(C_2O_4)_3水合物的热分解分四步进行,前两步为脱水过程,后两步为分解过程,四步反应对应的活化能E_c分别为64.24, 59.48, 146.20和112.37 kJ·mol~(-1);指前因子A_c分别为:4.09×10~8, 3.83×10~5, 6.86×10~(10)和6.18×10~5。每一步的机制函数分别是:1-(1-α)~(1/2)=kt, 1-(1-α)~(1/3)=kt,[(1-α)~(-2)-1]/2=kt和[-ln(1-α)]~(1/3)=kt。而Y_2(CO_3)_3在空气中热分解只有两步,第一步脱3个H_2O和1个CO_2分子,第二步脱2个CO_2分子生成Y_2O_3,两步对应的活化能E_c分别为88.29和116. 53 kJ·mol~(-1),指前因子A_c分别为1.5×10~(13)和9.4×10~7。它们的机制函数分别为(1-α)~(-1)-1=kt和[1-(1-α)~(1/3)]~2=kt。前驱体Y_2(CO_3)_3水合物相对来说比Y_2(C_2O_4)_3水合物更易分解生成Y_2O_3,两种前驱体的热分解都是最后一步为控速步骤。     

3-((1R,3aS,3aS,10aR)-十氢-(1H,4H)-吡啶并[1,6]萘啶-1-基)丙-1-胺的合成

以廉价易得的苦参碱为起始原料,经过开环、酯化反应、水解等步骤,得到4-((3aS,3aS,10aR)-2-(叔丁氧基羰基)十氢-(1H,4H)-吡啶并[1,6]萘啶-1-基)丁酸(5)。5再经过Curtius重排反应,得到叔丁基(1R,3aS,3aS,10aR)-1-(3-(((苄氧基)羰基)氨基)丙基)八氢-(1H,4H)-吡啶并[1,6]萘啶-2(3H)-羧酸叔丁酯(6)。然后,6脱去Cbz基团得到(1R,3aS,3aS,10aR)-1-(3-氨基丙基)八氢-(1H,4H)-吡啶并[1,6]二氮杂萘-2(3H)-羧酸叔丁酯(7),最后,7脱去Boc基团成功得到苦参碱衍生物的重要中间体3-((1R,3aS,3aS,10aR)-十氢-(1H,4H)-吡啶并[1,6]萘啶-1-基)丙-1-胺(8),总收率28%。目标化合物和中间体的结构经¹H NMR, ¹³C NMR和HR-MS确证。      

6H-吲哚[2,3-b]并喹喔啉衍生物的合成及荧光性能研究

报道了以7-甲(乙)基靛红(1a,1b)为原料,对其1-烃基化得1-烃基-7-甲(乙)基靛红(2a1-2a5,2b1-2b5)。1a,1b,2a1-2a5,2b1-2b5与邻苯二胺在冰醋酸为溶剂或以水为溶剂,四丁基溴化铵(TBAB)为相转移催化剂,采用改进的工艺进行缩合反应,以70.0%-85.8%的收率合成了一系列结构新颖的含有1,4-二氮杂萘结构的吲哚类化合物3a-3b,3a1-3a5,3b1-3b5。化合物3a1-3a5,3b1-3b5为新化合物,其结构经红外光谱、质谱、核磁氢谱(碳谱)确认。荧光光谱测定表明,化合物3a-3b,3a1-3a5,3b1-3b5具有很好的荧光性能。     

Syntheses,Crystal Structures and Bioactivities of Two Novel Isatin Derivatives

Two novel compounds 1-(4-fluorobenzyl)-4-chloro-(Z)-3-benzoylhydrazono-2-indolinone(1) and 1-(4-methoxybenzyl)-(Z)-3-benzoylhydrazono-2-indolinone(2) were synthesized and their crystal structures were determined by single-crystal X-ray diffraction.Compound 1(C22H15ClFN3O2) crystallized in the triclinic system,space group P1·with a=0.94198(19) nm,b=1.4339(3) nm,c=1.5018(3) nm,α=101.58(3)°,β=102.96(3)°,γ=102.73°,V=1.8602(6) nm3,Mr=407.82,Dc=1.456 g/cm3,μ=0.240 mm-1,F(000)=840,Z=4,R1=0.0442 and wR2=0.1064.Comp...     

4个芘基查尔酮衍生物的合成及超快三阶非线性光学响应

本文合成了4个D-A-π-D型芘基查尔酮衍生物:1-(芘-1-基)-3-(3,4-二甲氧基苯基)丙烯酮(3a)、1-(芘-1-基)-3-(3,4,5-三甲氧基苯基)丙烯酮(3b)、1-(芘-1-基)-3-(3,5-二甲氧基苯基)丙烯酮(3c)及1-(芘-1-基)-3-(2,4-二甲氧基苯基)丙烯酮(3d).采用差示扫描...     

3,3,6,6-四甲基-9-对氯苯基-1,8-二氧代-2,3,4,5,6,7-六氢氧杂蒽的合成和晶体结构

标题化合物C2 3H2 5O3Cl是由对氯苯甲醛与 5,5 二甲基 1 ,3环己二酮在乙二醇中反应而得。结构通过单晶X 射线衍射法测定 ,其晶体属于单斜晶系 ,空间群P2 1 /n ,a =6.0 4 8(1 ) ,b =1 9.543(3) ,c =1 7.42 0 (3) ,β =97.2 9(1 )° ,V =2 0 4 2 .2 (6) 3,Mr=384.90 ,Dc=1 2 52 g/cm3,Z =4,μ(MoKα) =2 .0 6cm- 1 ,F(0 0 0 ) =81 6。晶体结构用直接法解出 ,经用全矩阵最小二乘法对原子参数进行修正 ,最终的偏离因子为R =0 .0 39,Rw=0 .0 4 7。X 射线衍射分析表明 :平面 1 (C(8) -C(9) -C(1 9) )与平面 2 (C(1 0 ) -C(1 1 ) -C(1 2 ) )之间的两面角为1 6.2 4° ;平面 1与平面 3(C(7) -C(8) -C(9) )之间的两面角为 1 77.37° ;平面 1与平面 4(C(1 )-C(5) -C(6) )之间的两面角为 98.2 1°;平面 2与平面 3之间的两面角为 1 61 .1 2° ;平面 2与平面 4之间的两面角为 81 .98°;平面 3与平面 4之间的两面角为 79.1 5°     

Synthesis and screening of some novel substituted indoles contained 1,3,4-oxadiazole and 1,2,4-triazole moiety

A series of novel 3-[5-(1H-indol-3-yl-methyl)-2-oxo-[1,3,4]oxadiazol-3-yl]propionitrile(5),3-[4- amino-3-(1H-indol-3-yl-methyl)-5-oxo-4,5-dihydro-[1,2.4]triazol-1-yljpropionitrile(6),3-[5-(1H- indol-3-yl-methyl)-2-thioxo-[1,3,4]oxadiazol-3-yl]propionitrile(7) and 3-[4-amino-3-(1H-indol-3-yl-methyl) -5-thioxo-4,5-dihydro-[1,2,4]triazol-l -yljpropionitrile(8) were synthesized in good yields from the intermediate(1H-indol-3-yl)-acetic acid N’-(2-cyanoethyl)hydrazide(4).The chemical structures of the newly synthesized compounds were elucidated by their IR,~1H NMR and MS.Further,all the compounds were screened for their antimicrobial activity against Gram-positive,Gram-negative bacteria and also tested their ability toward anti-inflammatory activity.     

新型有机-无机杂化材料(C_3H_5N_2)_4·PMo~ⅤMo_(11)~(Ⅵ)O_(40)·4DMF·2H_2O的合成、结构及抗前列腺癌活性研究

制备了有机 -无机杂化材料 (C3H5N2 ) 4PMo Mo 1 1 O4 0 · 4DMF· 2 H2 O.用元素分析、红外光谱和 X射线衍射对其进行了表征 ,该晶体属三斜晶系 ,P1空间群 ,晶胞参数为 a=1 .2 42 3 (3 ) nm,b=1 .2 666(3 )nm,c=1 .3 3 41 (3 ) nm,V=1 .742 3 (6) nm3,α=70 .5 6(3 )°,β=71 .1 6(3 )°,γ=64.1 8(3 )°,Z=1 ,R1 =0 .0 5 85 ,w R2 =0 .1 885 .结构解析表明 ,十二钼磷酸阴离子和质子化的咪唑分子通过静电引力和氢键相互作用 .采用 MTT法 ,对其体外抗前列腺癌活性及毒性进行了研究