1,10-邻菲咯啉衍生物的合成及其晶体结构

以1,10-邻菲咯啉为原料,经氧化反应合成了1,10-邻菲咯啉-5,6-二酮(1);1与对氟苯甲醛反应合成了2-苯基(4-氟)-咪唑[4,5]-1,10-邻啡咯啉(2).1和2的结构经1H NMR,MS和X-射线单晶衍射表征.1为正交晶系,Pna21空间群,晶胞参数为:a=14.329 0(4)(A),b=12.370 0(3)(A),c=6.395 6(16)(A),α=90°,β=90°,γ=90°,V=1 133.5(5)(A)~3,Z=14,Dc=2.521 g·cm~(-3),μ=12.430 mm~(-1),F(000)=789,最终偏离因子R=0.039 8,wR=0.114 7.2为单斜晶系,P21/n,空间群晶胞参数为:a=9.810 0(4)(A),b=10.951 0(4)(A),c=17.3670(7)(A),α=90.000°,β=99.042(5)°,γ=90.000°,V=1 842.5(12)(A)~3,Z=4,Dc=1.292 g·cm~(-3),μ=0.095mm~(-1),F(000)=732,最终偏离因子R=0.091 2,wR=0.334 9.     

3-叠氮-4-氨基呋咱的合成及其晶体结构

以乙二醛和盐酸羟胺为原料,经加成,闭环和氮化反应制备了新型含能化合物3-叠氮-4-氨基呋咱(AAF),其结构经NMR,IR,X-射线单晶衍射仪及元素分析表征。AAF晶体属单斜晶系,P21/c空间群,晶胞参数为:a=0.5329(16)nm,b=1.0722(3)nm,c=0.8492(2)nm,α=90.00°,β=99.03(2)°,γ=90.00°,V=0.5046(2)nm3,Dc=1.660g.cm-3,Z=4,F(000)=256,μ(MoKα)=0.138mm-1。最终偏离因子R1=0.0768,wR2=0.1983。AAF晶体存在分子间氢键。     

4，6-二甲基-2-巯基嘧啶乙酸·邻菲咯啉双核铜配合物的合成及晶体结构

合成了标题化合物[Cu2（phen）2（C8H9N2O2S）（H2O）（OH）]·（ClO4）2,用元素分析和X射线单晶衍射法对其进行了表征和结构分析．该化合物为单斜晶系,空间群：P2（1）．晶胞参数a=8．2295（7）nm,b=18．0274（15）nm,c=24．5459（19）nm,β=96．240（2）°,V=3620．0（5）nm^2,Z=4,Dc=1．686g／cm^3,Mr=918．64,F（000）=1864,μ（Mo—Kα）=1．452mm^-1,R1=0．1091,ωR2=0．1380．两个铜原子通过来自羟基的氧、水分子和4,6-二甲基-2-巯基嘧啶乙酸根桥连．2个铜原子的配位环境基本相同,都具有5配位扭曲的四方锥构型,Cu…Cu之间的距离为0．30189（8）nm．     

以邻菲咯啉衍生物及1，3-间苯二甲酸为配体的一维链状Cd(Ⅱ)配位聚合物的合成及结构

在水热条件下,我们利用邻菲咯啉衍生物配体(L=2-(3-fluorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline)和1,3-间苯二甲酸(1,3-H2BDC)反应得到了一维配位聚合物[Cd2(L)2(1,3-BDC)2]n,并对该化合物进行了元素分析、红外和单晶X-射线表征。该化合物属于三斜晶系,空间群Pī,晶胞参数a=1.080 8(4)nm,b=1.149 5(4)nm,c=1.924 8(7)nm,α=106.482(5)°,β=99.436(6)°,γ=93.093(6)°,V=2 249.2(14)nm3,Z=4,C27H15CdFN4O4,Mr=590.83,Dc=1.745 g.cm-3,F(000)=1 176,μ(Mo Kα)=1.024 mm-1,R=0.044 5和wR=0.111 7。该化合物为一维链状结构,链与链之间又进一步地通过CH-π相互作用形成二维层状超分子结构。     

稀土-反式-2,3-二甲基丙烯酸-邻菲咯啉混配配合物的合成与表征

合成了一种新的双核稀土配合物[REL₃(phen)]₂(RE=La,Ce,Pr,Nd,Sm,Eu,L=反式CH₃CHC(CH₃)COO^-,phen=phenanthroline),并且用红外光谱、紫外光谱、核磁共振谱和元素分析等进行了表征,其中测定了[LaL₃phen]₂的晶体结构.晶体属单斜晶系,P2₁/n空间群,Z=2,晶胞参数a=1.2962(4)nm,b=1.3283(4)nm,c=1.5485(5)nm,β=95.45(2)°,最终偏差因子R=0.033,R_W=0.040.配合物分子为一个中心对称的双核分子,镧离子由两个双齿羧基和两个μ₂-O羧基桥联,La…La^*距离为0.4094nm.中心离子为九配位,形成畸变的三帽三棱柱配位多面体.La-O和La-N的键长范围分别为0.2460～0.2756nm和0.2718～0.2760nm.     

[Cu(1,10-phen)(L-Ile)(H2O)]·NO3的合成、结构及其表征

合成了三元混配配合[Cu(1,10-phen)(L-Ile)(H2O)]NO3(1,10-phen=1,10-邻菲咯啉,L-Ile=L-异亮氨酸),并用元素分析、X射线衍射、摩尔电导、红外、紫外等手段对混配配合物进行了表征.晶体结构分析表明配合物晶体的空间群为P21,晶胞参a=1.1835(5)nm,b=0.6775(5)nm,c=1. 3328(5)nm,β=90. 745(5)°,V=1.0686(10)mm3,μ=1. 062mm-1,Dc= 1.411g/cm3,F(000)=470,R=0.0551,Rw=0.0469.分子中Cu(Ⅰ)离子与一个L-Ile(N,O)配体、一个1,10-phen(N,N)配体及H2O(O)配位形成五配位的变形四方锥构型.     

3-(2-羟基苯基)-5-苯基-6-乙氧羰基-2-环己烯酮的合成与晶体结构

合成了3-(2-羟基苯基)-5-苯基-6-乙氧羰基-2-环己烯酮.通过元素分析、红外光谱、紫外光谱、核磁共振氢谱和质谱对其组成和结构进行了表征.利用X射线衍射分析方法测定了它的晶体结构.该化合物的晶体属单斜晶系,空间群P21/c,a=1.41946(17)nm,b=0.58445(7)nm,c=2.1756(3)nm,β=104.795(2)°,V=1.7450(4)nm3,Z=4,Dc=1.280 g·cm-3,F(000)=712,μ=0.088mm-1,R1[I＞2σ(I)]=0.0627,wR2[I＞2σ(I)]=0.1484.晶体结构测定结果表明化合物分子中的环己烯部分为半椅式构象,分子间通过氢键形成具有16元环的二聚体.     

芳醛缩N-(2-乙胺)-9,10-二氢蒽-9,10-桥-α,β-琥珀酰亚胺Schiff碱衍生物的合成及晶体结构

合成了2个N-(2-乙胺)-9,10-二氢蒽-9,10-桥-α,β-琥珀酰亚胺希夫碱衍生物,利用单晶X-射线衍射法测定了它们的晶体结构.化合物1为正交晶系,Pca21空间群,晶胞参数a=1.132 59(15)nm,b=2.535 6(4)nm,c=0.835 82(12)nm;α=90.00°,β=90.00°,γ=90.00°,V=2.4003(6)nm3,Z=4;化合物2为三斜晶系,P-1空间群,晶胞参数a=1.012 9(15)nm,b=1.190 1(16)nm,c=1.307 5(18)nm;α=67.17(3)°,β=72.88(3)°,γ=75.41(3)°,V=1.371(3)nm3,Z=2.     

配合物[Cu(H2O)(C12H8N2)2]·2ClO4的合成、性质及晶体结构

合成了配合物 [Cu(H2 O) (C12 H8N2 ) 2 ]·2ClO4 (C12 H8N2 为 1,10 邻菲咯啉 ) ,用元素分析、摩尔电导、红外光谱及电子光谱进行了表征 ,并测定了配合物的晶体结构。该晶体属单斜晶系 ,空间群为CC;晶胞参数 :a =1.9177(2 )nm ,b =0 .81994(0 )nm ,c=1.6 2 45 8(14)nm ,β =10 0 .10 4(6 )° ;V =2 .5 419(4)nm3,Z =4,F(0 0 0 ) =130 0 ,DC=1.6 93g/cm3,R =0 .0 430 ,wR =0 .1195。中心铜 (Ⅱ )离子与两个 1,10 邻菲咯啉的四个N原子和一个水分子的氧原子配位 ,形成了一个变形的三角双锥结构     

配合物[Co(PHEN)2(EA)](ClO4)2·H2O·CH3OH的合成及其晶体结构

以2-氨基乙醇(EA)和邻菲咯啉(PHEN)为配体合成了新配合物[Co(PHEN)2(EA)](ClO4)2.H2O.CH3OH,其结构经IR,元素分析和X-射线单晶衍射法表征。1属单斜晶系,空间群为P2(1)/n,晶胞参数a=0.863 0(7)nm,b=1.348 8(11)nm,c=2.520 6(20)nm,β=91.503(12)°,V=2.933(4)nm3,Z=4,R=0.074 4,wR=0.170 3。衍射数据[I>2σ(I)]为2 602。在1中,Co(Ⅱ)原子与五个氮原子和一个氧原子配位,处于畸变的八面体配位环境。     

Photochromic dihetarylethenes. 10. Photochromic 1,2-bis[2-(benzothiazol-2-yl)-3-thienyl]- and 1,2-bis[2-(benzothiazol-2-yl)benzothiophen-3-yl]ethenes

Dithienylethenes containing the thiophene rings with benzothiazolyl substituents in position 2 were synthesized. 1,2-Bis[2-(benzothiazol-2-yl)benzothiophen-3-yl]hexafluorocyclopentene and 1,2-bis[2,5-di(benzothiazol-2-yl)-3-thienyl]hexafluorocyclopentene possess photochromic properties. The open forms of 1,2-bis(2-benzothiazolylhetaryl)ethenes fluoresce, but introduction of the benzothiazole rings into dihetarylethenes significantly lowers the fatigue resistance of photochromes and favors thermal reversibility.     

5-(1-芳基-1-吡咯-2-基)-1氢-四唑类化合物的合成与表征

利用阳极氧化反应, 将一系列N-芳基吡咯电氰化, 区域专一地得到吡咯氰化物2, 分离收率为76%~85%. 将其与叠氮化钠反应, 合成了一系列具有潜在血管紧张素Ⅱ受体(AT)拮抗活性的新型四唑化合物. 该合成路线的原料易得, 并以阳极氰化芳香氮杂环引入氰基为关键步骤, 可作为在芳香氮杂环上引入四唑基团的通用合成路线.     

2-Amino-3-(benzimidazol-2-yl)benzo[b]furans

The corresponding 2-amino-3-(benzimidazol-2-yl)benzo[b]furans were obtained by reaction of 2,3,5-trimethyl-1,4-benzoquinone with 2-cyanomethylbenzimidazoles. It is shown that new benzo[b]furo[2′,3′∶4,5]pyrimido[1,6-a]benzimidazole polynuclear heterocyclic systems (bases and quaternary salts) are formed in the reaction of these products with acylating agents. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 164–166, February, 1980.     

Photocyclization of 2-[1]benzothien-3-yl)-3-phenylpropenoic acids

Photocyclization of the substituted 2-([1]benzothien-3-yl)-3-phenylpropenoic acids 3a-c in the presence of iodine and air in a benzene-cyclohexane mixture afforded a separable mixture of three compounds, benzo[b]naphtho[2,1-d]thiophene-6-carboxylic acids 4a-c , 6H-benzo[b]naphtho[2,3-d]thiopyran-6-ones 5a-c , and 10-methoxy-2-methyl-6H-benzo[b]naphtho[2,3-d]pyran-6-one ( 6 ).     

Synthesis of 2-(pyridin-3-yl)-1-azabicyclo[3.2.2]nonane, 2-(pyridin-3-yl)-1-azabicyclo[2.2.2]octane, and 2-(pyridin-3-yl)-1-azabicyclo[3.2.1]octane, a class of potent nicotinic acetylcholine receptor-ligands

In an attempt to generate nicotinic acetylcholine receptor (nAChR) ligands selective for the alpha4beta2 and alpha7 subtype receptors we designed and synthesized constrained versions of anabasine, a naturally occurring nAChR ligand. 2-(Pyridin-3-yl)-1-azabicyclo[2.2.2]octane, 2-(pyridin-3-yl)-1-azabicyclo[3.2.2]nonane, and several of their derivatives have been synthesized in both an enantioselective and a racemic manner utilizing the same basic synthetic approach. For the racemic synthesis, alkylation of N-(diphenylmethylene)-1-(pyridin-3-yl)methanamine with the appropriate bromoalkyltetrahydropyran gave intermediates which were readily elaborated into 2-(pyridin-3-yl)-1-azabicyclo[2.2.2]octane and 2-(pyridin-3-yl)-1-azabicyclo[3.2.2]nonane via a ring opening/aminocyclization sequence. An alternate synthesis of 2-(pyridin-3-yl)-1-azabicyclo[3.2.2]nonane via the alkylation of N-(1-(pyridin-3-ylethylidene)propan-2-amine has also been achieved. The enantioselective syntheses followed the same general scheme, but utilized imines derived from (+)- and (-)-2-hydroxy-3-pinanone. Chiral HPLC shows that the desired compounds were synthesized in >99.5% ee. X-ray crystallography was subsequently used to unambiguously characterize these stereochemically pure nAChR ligands. All compounds synthesized exhibited high affinity for the alpha4beta2 nAChR subtype ( K i < or = 0.5-15 nM), a subset bound with high affinity for the alpha7 receptor subtype ( K i < or = 110 nM), selectivity over the alpha3beta4 (ganglion) receptor subtype was seen within the 2-(pyridin-3-yl)-1-azabicyclo[2.2.2]octane series and for the muscle (alpha1betagammadelta) subtype in the 2-(pyridin-3-yl)-1-azabicyclo[3.2.2]nonane series.