10-氯-5-二乙氧基甲基-1,3-二甲基色烯并[4,3-d]吡唑并[3,4-b]吡啶-6(3H)-酮的合成和晶体结构

利用L-脯氨酸催化的5-氯水杨醛(1)与6-甲基-4-羟基吡喃酮(2)的缩合反应及硫酸铜催化下与1,3-二甲基-5-氨基吡唑(3)的串联反应,合成得到了10-氯-1,3-二甲基-5-(2-氧代丙基)色烯并[4,3-d]吡唑并[3,4-b]吡啶-6(3H)-酮(4)和10-氯-5-二乙氧基甲基-1,3-二甲基色烯并[4,3-d]吡唑并[3,4-b]吡啶-6(3H)-酮(5).化合物5的结构通过单晶X射线衍射法确定:晶体属于三斜晶系,空间群P-1;相对分子质量Mr=803.68;晶胞参数a=1.03160(10)nm,b=1.42900(13)nm,c=1.44268(15)nm;V=1.9448(3)nm~3;Z=2;晶胞密度Dc=1.372g/cm~3;吸收系数μ=0.228mm-1;单胞中电子的数目F(000)=840.晶体结构用直接法解出,经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=0.0681,w R=0.2051.在晶体结构中色烯环与吡啶环及吡唑环近似于共平面.     

简便的双环化反应合成3,7-二甲基-4a,16-二羟基-1H-苯并[5,6]茚并[2,1-1]氧杂蒽-1,9-二酮化合物及其结构表征

标题化合物C26H26O5以2,3-萘二甲醛和5-甲基-1,3-环己二酮为原料,在醋酸溶剂中,室温下经搅拌多组分一锅法合成得到.其结构通过单晶X-射线衍射法确定,晶体属单斜晶系,空间群P21,相对分子质量Mr=418.47,晶胞参数a=0.990 04(8) nm,b=1.090 98(9)nm,c=1.042 46(11) nm,V=1.087 53(17) nm3,Z=2,晶胞密度Dc=1.278 g/cm3,吸收系数μ=0.088mm-1,单胞中电子的数目F(000) =444.晶体结构用直接法解出,经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R1 =0.053 3,wR2=0.129 3.在晶体结构中新形成的吡喃环为半椅式构象,而茚中五元环则为信封式构象.     

简便的双环化反应合成3,7-二甲基-4a,16-二羟基-1H-苯并[5,6]茚并[2,1-l]氧杂蒽-1,9-二酮化合物及其结构表征

标题化合物C26H26O5以2,3-萘二甲醛和5-甲基-1,3-环己二酮为原料,在醋酸溶剂中,室温下经搅拌多组分一锅法合成得到.其结构通过单晶X-射线衍射法确定,晶体属单斜晶系,空间群P21,相对分子质量Mr=418.47,晶胞参数a=0.990 04(8)nm,b=1.090 98(9)nm,c=1.042 46(11)nm,V=1.087 53(17)nm3,Z=2,晶胞密度Dc=1.278g/cm3,吸收系数μ=0.088mm-1,单胞中电子的数目F(000)=444.晶体结构用直接法解出,经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R1=0.053 3,wR2=0.129 3.在晶体结构中新形成的吡喃环为半椅式构象,而茚中五元环则为信封式构象.     

9,9-二甲基-2-(4-硝基苯基)-4-苯基-9H-吡啶并[1,2-a]吲哚高氯酸盐的微波合成及晶体结构

在微波辐射条件下,由2,3,3-三甲基-3H-吲哚高氯酸盐、1-苯基-3-(4'-硝基苯基)-2-丙烯-1-酮与哌啶合成了标题化合物.在甲醇/乙醇=1/1(V/V)中培养出单晶,通过X射线单晶结构分析法测定了分子结构和晶体结构,晶体属于单斜晶系,P2(1)/n空间群,其晶胞参数为:a=1.2507(4)nm,b=1.4378(4)nm,c=1.3033(4)nm,V=2.3366(12)nm3,Dc=1.401g/cm3,μ=0.210mm-1,F(000)=1024,Z=4,R1=0.0553,wR2=0.0732.     

3-甲基-1,6-二苯基-4-(噻吩-2-基)-1H-吡唑并[3,4-b]吡啶-5-甲腈的绿色合成和结构表征

标题化合物(C24H16N4S)以噻吩-2-甲醛、苯甲酰乙腈和3-甲基-1-苯基-1H-吡唑-5-胺为原料,在离子液体[bmim]Br溶剂中,在80℃搅拌合成得到.其结构通过单晶X射线衍射法确定,晶体属于三斜晶系,空间群P-1,相对分子质量Mr=392.47,晶胞参数a=0.936 12(8)nm,b=1.030 63(12)nm,c=1.166 24(16)nm,V=0.968 53(19)nm3,Z=2,晶胞密度Dc=1.346g/cm3,吸收系数μ=0.185mm-1,单胞中电子的数目F(000)=408.晶体结构用直接法解出,经全矩阵最小二乘法对原子参数进行修正,最终的偏离因子R=0.058 5,wR=0.133 7.在晶体结构中新形成的吡啶环与吡唑环近似于共平面结构.     

5-甲基-2-苯基-3-噻吩基-7-噻吩亚甲基-3,3a,4,5,6,7-六氢吡唑并[4,3-c]吡啶的微波合成和结构表征

标题化合物(C22H21N3S2)以3,5-二-(2-噻吩基)-1-甲基哌啶-4-酮、苯肼为原料,乙二醇为溶剂,在微波辐射下合成得到.其结构通过单晶X射线衍射法确定,属三斜晶系,空间群P1,相对分子质量Mr=391.54,晶胞参数a=0.804 14(10)nm,b=2.993 9(3)nm,c=0.851360(11)nm,V=1.956 9(3)nm3,Z=4,晶胞密度Dc=1.329 g/cm3,吸收系数μ=0.284 mm-1,单胞中电子的数目F(000)=824.晶体结构用直接法解出,经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=0.072 7,ωR=0.087 8.     

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.     

2-乙氨基-6H-5-(1-苯基-3-甲基/苯基-5-吡唑啉酮-4-基)-1,3,4-噻二嗪的合成和晶体结构

利用1-苯基-3-甲基/苯基-4-氯乙酰基-吡唑啉酮-5(PMCP/DPCP)与4-乙基氨基硫脲(ETSC)发生缩合反应,生成了2个新的双杂环化合物2-乙氨基-6H-5-(1-苯基-3-甲基/苯基-5-吡唑啉酮-4-基)-1,3,4-噻二嗪(PMCP-ETSC/DPCP-ETSC),并对其进行元素分析、红外光谱、核磁共振表征和晶体结构分析.PMCP-ETSC晶体属于单斜晶系,Pm空间群,晶胞参数:a=0.7947(1)nm,b=0.8348(1)nm,c=1.1990(2)nm,β=106.07(1)°,V=0.77269(2)nm3,Z=2,Dc=1.356g/cm3,μ=0.219mm-1,F(000)=332,R=0.0298,wR=0.0704.该化合物通过分子间氢键形成沿c轴无限延伸的一维链状结构.DPCP-ETSC晶体属于正交晶系,Pna21空间群,晶胞参数:a=1.1478(2)nm,b=1.3545(2)nm,c=1.1994(2)nm,V=1.8646(4)nm3,Z=4,Dc=1.345g/cm3,μ=0.194mm-1,F(000)=792,R=0.0345,wR=0.0694,此化合物通过分子间氢键形成沿c轴成链状,沿ab平面成波浪状的超分子结构.     

1,2-双(4-溴苯基)-6,7-二氢-3-甲氧基-6,6-二甲基-1H-吲哚-4(5H)-酮的简便合成和结构表征

以1-(4-溴苯基)-2,2-二羟基-乙酮、3-((4-溴苯基)氨基)-5,5-二甲基环己-2-烯酮为原料,甲醇既为醚化试剂也是反应介质,采用对-甲基苯磺酸(p-TsOH)为催化剂,通过多组分的多米诺反应微波辐射下合成多取代的四氢吲哚类衍生物--1,2-双(4-溴苯基)-6,7-二氢-3-甲氧基-6,6-二甲基-1H-吲哚-4(5H)-酮.其结构通过单晶X射线衍射法确定,晶体属三斜晶系,空间群P-1,相对分子质量Mr=503.23,晶胞参数a=0.884 19(9)nm,b=0.969 36(11)nm,c=1.348 97(13)nm,V=1.070 96(19)nm3,Z=2,晶胞密度Dc=1.561g/cm3,吸收系数μ=3.803mm-1,单胞中电子的数目F(000)=504.晶体结构用直接法解出,经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=0.058 4,wR=0.107 8.在晶体结构中新形成的吡咯杂环近似于平面结构.     

1-(4-(1H-吲哚-3-基)-2-甲基-5-苯基-1-对甲苯基-1H-吡咯-3-基)乙酮的简便合成和结构表征

标题化合物(C28H24N2O)以N-对甲苯基烯胺酮,2,2-二羟基-1-苯基乙酮和吲哚为原料,在醋酸溶剂中,经微波辐射合成得到.其结构通过单晶X射线衍射法确定,晶体属单斜晶系,空间群P21/n,相对分子质量Mr=404.49,晶胞参数a=0.806 93(8)nm,b=1.473 70(13)nm,c=1.865 12(18)nm,V=2.213 5(4)nm3,Z=4,晶胞密度Dc=1.214g/cm3,吸收系数μ=0.074mm-1,单胞中电子的数目F(000)=856.晶体结构用直接法解出,经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=0.0491,ωR=0.115 4.在晶体结构中新形成的吡咯杂环近似于平面结构.     

[3]Parycyclo− and [3]metacyclo[3](3,7)-p-tropoquinonophanes

The title phanes were synthesized. Examination of their physical properties including X-ray crystallography disclosed that 1) the p-tropoquinone ring is still bent in both compounds though to a lesser extent than in the corresponding [2.2]phanes, 2) the metacyclo compound prefers syn conformation in solution, and 3) the intramolecular CT interaction is very similar in two compounds.     

Die Kristallstrukturen von [Et3PNAsPh3]2[Ag2Br4] und [Et3PNAsPh3]2[Pd2Br6]

Crystal Structures of [Et₃PNAsPh₃]₂[Ag₂Br₄] and [Et₃PNAsPh₃]₂[Pd₂Br₆] Colourless single crystals of [Et₃PNAsPh₃]₂[Ag₂Br₄]( 1 ) and red single crystals of [Et₃PNAsPh₃]₂[Pd₂Br₆]( 2 ) have been isolated from saturated solutions in acetonitrile of equivalent mixtures of [Et₃PNAsPh₃]Br with AgBr and PdBr₂, respectively. Both complexes were characterized by IR spectroscopy and by crystal structure determinations. 1 : Space group P1¯, Z = 1, lattice dimensions at ‐70°C: a = 985.0(2), b = 1042.2(5), c = 1345.8(5) pm, α = 102.88(2)°, β = 105.73(2)°, γ = 94.94(2)°, R₁ = 0.0577. 2 : Space group P2₁/c, Z = 2, lattice dimension at ‐70°C: a = 1003.0(1), b = 1371.8(2), c = 1974.0(1) pm, β = 93.30(1)°, R₁ = 0.0458. The dimeric anions of 1 and 2 form planar, centrosymmetric complex units.     

Translational isomerism in a [3]catenane and a [3]rotaxane

[structure: see text] Post-assembly covalent modification using Wittig chemistry of [2]rotaxane ylides, wherein NH(2)(+) centers in the dumbbell-shaped components are recognized by dibenzo[24]crown-8 (DB24C8) rings, has afforded a [3]catenane and a [3]rotaxane with a precise and synthetically prescribed shortage of DB24C8 rings. The nondegenerate pairs of translational isomers present in both of these interlocked molecular compounds provide the fundamental platform on which to construct sensory devices and nanochemomechanical systems.     

Tetraazadibora[3, 3]paracyclophane

Starting from the para‐phenylenediamine derivative HN(SiMe₃)‐C₆H₄‐NH(SiMe₃), a lithiation and subsequent borylation give [(MeO)₂B]N(SiMe₃)‐C₆H₄‐N(SiMe₃)[B(OMe)₂] ( 1 ), the hydridation of which yields Li₂[(H₃B)N(SiMe₃)‐C₆H₄‐N(SiMe₃)(BH₃)] ( 2 ). Applying ZrCl₄ upon 2 initiates a condensation to give the title compound [‐N(SiMe₃)‐p‐C₆H₄‐N(SiMe₃)‐BH‐]₂, a hetero[3, 3]paracyclophane with two N‐B‐N chains that connect the para‐phenylene units. The product 3 crystallizes in the orthorhombic space group P2₁2₁2₁.     

Synthesis of 3H[1,2]diazepino[5,6-b]indole and 3H[1,2]diazepino[4,5-b]indole derivatives

The synthesis of two new derivatives of 3H[1,2]diazepino[5,6-b]indole, 5 and 11 , and one new derivative of 3H[1,2]diazepino[4,5-b]indole, 16 , are described. Compound 5 was obtained by the reaction of methyl 2-(3-methoxycarbonyl-1-methylindole)acetate 2 , with hydrazine. Compound 11 was obtained in two ways from ethyl 2-(1-methylindole)acetate ( 8 ) by formylation and reaction with hydrazine. Compound 16 was obtained treating 3-(2-ethoxycarbonylindole)acetonitrile ( 14 ) with hydrazine.