δ-（甲酰乙烯基）二氢卟吩衍生物的合成

以脱镁叶绿酸-a甲酯为原料,利用Vilsmeier反应合成δ-(甲酰乙烯基)二氢卟吩衍生物.镍(II)脱镁叶绿酸-a甲酯和镍(II)红紫素-18与Vilsmeier试剂作用,生成了E环被打开的镍(II)δ-(甲酰乙烯基)红紫素-7-三甲酯和镍(II)δ-(甲酰乙烯基)二氢卟吩P6三甲酯.镍(II)N-乙酰氧基红紫素-18-酰亚胺和Vilsmeier试剂作用,生成了镍(II)δ-(甲酰乙烯基)-N-乙酰氧基红紫素-18-酰亚胺.当这些化合物脱去镍离子后,吸收波长明显红移,δ-(甲酰乙烯基)-N-乙酰氧基红紫素-18-酰亚胺的吸收波长达到742nm.同时保留了对δ-位再进行化学修饰的可能性.合成的新化合物均由核磁共振、红外光谱、元素分析和质谱予以证实.     

单一手性锌配位聚合物：晶体结构，荧光及介电性质

在原位水热条件下,单一手性有机配体(S)-甲基-2-(4-氰基苯胺)-3-(4-羟基苯)丙酸甲酯与叠氮化钠和氯化锌反应,得到了一个新的四唑锌配位聚合物{[Zn(TBHPA)H2O].H2O}n(1,TBHPA=(S)-2-(4-(2H-tetrazol-5-yl)benzylamino)-3-(4-hydroxy-phenyl)propa-noic acid)。单晶结构表明该化合物结晶在手性空间群P212121,CD谱进一步证实该化合物固体粉末具有单一手性。倍频实验结果表明化合物1的SHG(倍频效应)响应大概是尿素的0.6倍。荧光测定结果显示该化合物在428 nm处有较强的荧光发射峰(激发波长319 nm)。另外,还研究了化合物1在室温条件下不同频率的介电常数变化。     

Synthesis,Structure and Fluorescence Property of New Cd-MOFs Based on a Tetraphenylethylene(TPE)Ligand

A very stable Cd^Ⅱ-organic framework,{[Cd₃(Tipe)_1.5(bpodc)₂Cl₂]·(H₂O)₂}_n(compound 1,Tipe=1,1,2,2-tetrakis(4-(imidazol-1-yl)phenyl)ethene,bpodc=benzophenone-4,4-dicarboxylic acid),has been successfully synthesized under hydrothermal conditions.Compound 1 crystallizes in the triclinic system,space group P1^-,with a=12.289(3),b=15.951(4),c=20.755(5)?,α=81.248(2)°,β=83.905(2)°,γ=89.452(2)°,V=3998.2(17)?³,Z=2,M_r=1839.59,D_c=1.528 g/cm³,μ=0.925 mm^-1,F(000)=1844,R=0.0508 and wR=0.1571 for 13998 observed reflections(I>2σ(I)).Its overall structure is a three-dimensional stacking with a porosity of 10.1%based on a calculation by PLATON.Compound 1 shows a blue fluorescence emission with the peak maximum of 501 nm(λ_ex=397 nm)by ligand-to-ligand charge transfer of TPE chromophore.And it exhibits excellent performance in detecting Fe³⁺and Cr₂O₇^2-ions in aqueous solutions as a multi-response sensor.     

微波辐射下合成3-芳基-9-氨基-1,2,3,4-四氢吖啶-1-酮衍生物

在微波辐射和对甲基苯磺酸的催化作用下, 5-芳基-1,3-环己二酮与邻氨基苯甲腈进行缩合反应, 得到了N-取代的2-氨基苯甲腈衍生物, 在K₂CO₃和Cu₂Cl₂的催化作用下进一步合环, 得到3-芳基-9-氨基-1,2,3,4-四氢吖啶-1-酮衍生物, 用LiAlH₄还原羰基得到3-芳基-9-氨基-1,2,3,4-四氢吖啶-1-醇衍生物. 新合成化合物的结构均经元素分析、红外光谱和核磁共振光谱予以确认.     

б-(甲酰乙烯基)二氢卟吩衍生物的合成

以脱镁叶绿酸-a甲酯为原料,利用Vilsmeier反应合成б-(甲酰乙烯基)二氢卟吩衍生物.镍(II)脱镁叶绿酸-a甲酯和镍(II)红紫素-18与Vilsmeier试剂作用,生成了E环被打开的镍(II)б-(甲酰乙烯基)红紫素-7-三甲酯和镍(II)б-(甲酰乙烯基)二氢卟吩P6三甲酯.镍(II)N-乙酰氧基红紫素-18-酰亚胺和Vilsmeier试剂作用,生成了镍(II)б-(甲酰乙烯基)-N-_乙酰氧基红紫素-18-酰亚胺.当这些化合物脱去镍离子后,吸收波长明显红移,б-(甲酰乙烯基)-N-乙酰氧基红紫素-18-酰亚胺的吸收波长达到742 nm.同时保留了对б-位再进行化学修饰的可能性.合成的新化合物均由核磁共振、红外光谱、元素分析和质谱予以证实.     

Synthesis,Structure and Fluorescence Property of a New Mn-MOFs Based on a Tetraphenylethane (TPE) Ligand

A new 3D luminescent Mn-MOF is synthesized based on a tetraphenylethane-core ligand 1,1,2,2-tetrakis(4-(1H-imidazol-1-yl)phenyl)ethene(tipe),with the formula[Mn(tipe)(bcpf)·(DMF)]_n(1,bcpf=4,4?-sulfonyldibenzoic acid).Compound 1 crystallizes in the triclinic system,space group ■,with a=12.951(2),b=14.235(2),c=14.375(2)?,α=90.015(2)°,β=108.181(2)°,γ=99.368(2)°,V=2480.6(6)?~3,Z=2,M_r=1028.98,D_c=1.378 g/cm~3,μ=0.372 mm~(-1),F(000)=1066,R=0.0479 and wR=0.1066 for 5927 observed reflections(Ⅰ2σ(Ⅰ)).Its topological analysis displays that 1 is a double interpenetrating architecture.The Mn atom bridges the tipe ligands to form the 1-dimensional chains into a 2-dimensional layered structure,and then connects the auxiliary ligands to get a 3-dimensional structure.What’s more,luminescent spectra of 1 show that it emits strong blue light caused by ligand-to-ligand charge transfer of TPE chromophore.     

Syntheses and Crystal Structures of Pyridyl Substituted Dibenzo[b,e]-[1,4]diazepin-1-one Derivatives

A new series °f 11-pyridyl substituted dibenz°-diazepin-1-°ne derivatives 1 was synthesized by a tw° step cycl°c°ndensati°n reacti°n. All the c°mp°unds were characterized by IR,MS, and 1H NMR. And crystals °f 1a and 1b were °btained and determined by X-ray single-crystal diffracti°n. Crystal data °f 1a: C48H52N6O7, m°n°clinic system, space gr°up C2/c, a = 28.39(4), b =9.275(12), c = 16.84(2) A, β = 104.98(3)°, V = 4284(10) A3, Z = 4, F(000) = 1752, Dc = 1.279 g/cm3,R = 0.0603, and wR = 0.1314. Crystal data °f 1b: C24H21N3 O, m°n°clinic system, space gr°up P21/c,a = 11.625(5), b = 19.055(9), c = 8.741(4) A, β = 95.547(6)°, V = 1927.2(15) A3, Z = 4, F(000) =776, Dc = 1.266 g/cm3, R = 0.0494, and wR = 0.1287.     

利用脱镁叶绿酸甲酯的化学修饰合成红紫素酰亚胺衍生物

A series of novel purpurin-18 imide derivatives exhibiting long wavelength absorption and amphiphilicity wereobtained from methyl pheophorbide-a(MPa)by modification of the peripheral functional groups.The vinyl groupat 3-position was oxidized with OsO_4 and NaIO_4 to form the formyl group and the Grignard reaction of this alde-hyde with the alkyl magnesium bromide was carried out to give the corresponding 3-(1-hydroxylalkyl)pheophor-bide-a.The E-ring of these chlorines was converted into anhydride ring to give purpurin derivatives by air oxidation.The trans-3~2-alkyl purpurin derivatives were obtained by dehydration of hydroxyl group at 3~1-position.TheN-hydroxyl purpurin imide was generated by treatment of the anhydride ring with bydroxylamine hydrochloride.The 3~1-alkylacyl-N-hydroxyl purpurin imides were obtained by oxidation of hydroxyl group at 3~1-position.Theacylation of N-hydroxyl group was completed to afford N-acyloxy purpurin imides.The photocytoxicity of severalcompounds in vitro were tested.