[Co(N-(3-Aminopropyl)-1,3-propanediamine)(2-(Aminomethyl)pyridine) Cl][ZnCl_4]的一对差向异构体的合成及晶体结构

用过氧化物法合成了 [Co(3,3-tri)(amp)Cl][ZnCl4]的两个经式异构体,晶体结构解析表明两者互为差向异构体。其中反式异构体 (仲氢相对于 Cl)晶体属单斜晶系,空间群 C2/c, a=2.7663(7)nm, b=0.9505(1)nm, c=1.8288(4)nm,β =105.57(2)°, V=4.632(1)nm3, Dc=1.706g· cm-3, Z=8, F000=2432.00,μ (MoKα )=23.51cm-1, R=0.033, Rw=0.041;顺式异构体 (仲氢相对于 Cl)晶体属三斜晶系,空间群, a=1.0790(2)nm, b=1.1749(1)nm, c=0.8920(1)nm,α =90.73(1)°,β =109.573(9)°,γ =80.60(1)°, V=1.0500(2)nm3, Dc=1.71g· cm-3, Z=2, F000=548.00,μ (MoKα )=25.73cm-1, R=0.022, Rw=0.030。两异构体中 Co3＋为六配位,其差异仅表现在 3,3-tri仲胺上氢的取向不同。     

2-(2-氨基-3-吡啶基)-苯并咪唑的合成、晶体结构和荧光特性研究

在合成2-(2-氨基-3-吡啶基)-苯并咪唑的基础上,利用NMR(1H、13C、COSY、HSQC和HMBC)、MS、IR和UV进行了详细表征;通过X-ray单晶衍射仪测定了该化合物的晶体结构,实验结果表明该晶体属于三方晶系(空间群R3,a=1.833 7(3)nm,b=1.833 7(2)nm,c=1.777 7(4)nm,V=5.176 4(15)nm3,Z=18),很好地支持了波谱表征的结果。同时,结合密度泛函计算,研究了2-(2-氨基-3-吡啶基)-苯并咪唑的荧光光谱。结果表明,化合物的双荧光不是由同一种异构体发射的,而是来源于不同异构体:长波区500~600 nm的荧光由K构型发射,短波区350~450 nm的发射由异构体E1和E2共同产生,理论预测的光谱与实验一致。     

2-芳基-4-甲基-2,3,4,5-四氢-(1,5)-苯并硫氮杂(艹卓)的晶体结构研究

本文报道2-p-硝基苯基-4-甲基-2,3,4,5-四氢-(1,5)-苯并硫氮杂(艹卓)的两个顺反式异构体的晶体结构.顺式异构体属正交晶系,空间群为 D_(2h)~(10)—Pbnb,晶胞参数:a=8.326(1),b=14.865(5),c=24.533(4)(?);d_c=1.31g/cm~3;Z=8;F(000)=1264;μ_(MoKα)=2.2cm~(-1).反式异构体属单斜晶系,空间群为 C_(2h)~6-C2/c,晶胞参数:a=22.366(3),b=12.488(2),c=12.483(2)(?);β=121.01(1)°;d_o=1.34g/cm~3;Z=8;F(000)=1264;μ(MoKα)=2.2cm~(-1).晶体结构由 SHELXTL 直接法程序解出,用块矩阵最小二乘法修正,最后的偏离因子:顺式异构体 R=0.0661,R_w=0.0661;反式异构体,R=0.0705,R_w=0.0571.结构分析表明:顺式异构体为类椅式构象,反式异构体为类扭船式构象.这为进一步归纳这类化合物的结构特征和立体化学规律提供了条件.     

(R)-N-乙酰基-四氢噻唑-2-硫酮-4-甲酰TT的合成及其晶体结构

由N-乙酰(R)-四氢噻唑-2-硫酮-4-羧酸在三聚氯氰及三乙胺存在下与四氢噻唑-2-硫酮反应得到标题化合物，[α]^2^0~D +11.18°。用X射线衍射法测得其晶体结构，属单斜晶系，空间群为P2~1/c。晶体学数据：a=0.9959(4)nm，b=1.1469(4)nm，c=1.1108(3)nm，β=92.72(3)°，V=1.2673(8)nm^3，Z=4。分子中两个C=O基，两个C=S基团处于C(1)-N(1)-C(4)及C(6)-N(2)-C(7)键两侧呈反式。用PM3分子轨道方法研究了该化合物的电子结构，电荷和键序分布，得到该化合物前线轨道性质。     

水合5-(4-羟基苯酚)四氮唑的溶剂热合成及其晶体结构

以4-羟基苯氰为原料,用溶剂热法合成了水合5-(4-羟基苯酚)四氮唑晶体[(C7H6N4O)·1.5H2O,1],其结构经1H NMR,IR,元素分析及X-单晶衍射表征.1属单斜晶系,C2/c空间群,晶胞参数:a=1.487 2(3) nm,b=0.992 3(2) nm,c=1.304 8(2) nm,β=113.724(3)°,V=1.762 8(5) nm3,Dc=1.365 g*cm-3,F(000)=760,Z=8,μ(MoKα)=0.104 mm-1,R1=0.050 5,wR2=0.117 6.1中存在强烈的分子间氢键和π-π堆积作用.     

硝酸二(α-羟基异丁酸)二水合钕的合成、表征及晶体结构

合成的标题配合物Nd(C_4H_7O_3)_2·NO_3·2H_2O晶体属C2/c空间群,晶胞参数:a=0.8996(1)nm,b=0.8601(1)nm,c=2.1111(3)nm,β=92.38(1)°Z=4,晶体中配合物呈聚合链状结构,硝酸根无序分布在靠近对称中心的2个相关位置,钕的配位数为8。     

六亚甲基四胺锑(Ⅲ)、铋(Ⅲ)配合物的固相合成与表征

通过固相反应,合成了新的配合物六亚甲基四胺锑(Ⅲ)、铋(Ⅲ):SbCl3(C6H12N4)2·H2O(1)、BiCl3(C6H12N4)2·H2O(2).经元素分析、X 射线粉末衍射、远红外光谱和差热 热重分析进行表征,确定了配合物的组成和结构.对XRD谱指标化,确定其晶系和晶胞参数.SbCl3(C6H12N4)2·H2O(1):a=1.2490nm,b=1.4583nm,c=1.6870nm,β=91.78°,V=3.0706nm3;BiCl3(C6H12N4)2·H2O(2):a=1.3250nm,b=1.3889nm,c=1.7449nm,β=98.94°,V=3.1725nm3.     

K_4H_(2.2)PTi_(1.60)W_(10.40)4O_(40)·13H_2O的合成、表征、晶体结构及抗菌活性

Na2WO4·2H2O与NaH2PO4及TiCl4在常规条件下反应合成Keggin型钨钛磷酸钾K4H2.2PTi1.60W10.40O40·13H2O(1),并通过元素分析,IR,UV,X-ray单晶衍射表征。化合物1晶体属于四方晶系,P4/mnc空间群,a=1.4158(2)nm,b=1.4158(2)nm,c=1.2449(3)nm,V=2.4955(7)nm3,Z=2,R1=0.0583,wR2=0.1447。该晶体沿a轴方向晶胞堆积有一截面为0.72nm×0.62nm的孔道,水分子填充在孔道内。183WNMR谱表明多阴离子在溶液中主要以C2对称性的异构体存在。该化合物对绿脓杆菌和β-溶血链球菌有较强的抑制活性。     

对咪唑基苯甲酸镉(Ⅱ)配合物的合成及结构研究

利用水热法合成了2个新的对咪唑基苯甲酸镉配合物Cd(C10N2O2H7)2·H2O(1)和Cd2(H2O)5(C10N2O2H7)(C9O6H3)·4H2O(2),通过元素分析、红外光谱和X-射线单晶衍射进行了表征.结果表明:化合物1属于正交晶系,Pnna空间群,a=1.389 5(5)nm,b=1.665 4(5)nm,c=0.828 2(5)nm,V=1.916 5(15)nm3,Z=4,R1=0.026 3,wR2=0.0793;化合物2属于单斜晶系,P21/c空间群,晶胞参数a=1.370 2nm,b=1.751 1nm,c=1.255 7(4)nm,β=114.819(6)°,V=2.734 6(14)nm3,Z=4,R1=0.057 3,wR2=0.166 7.     

以1-(3-羧苯基)-5-甲基-1氢-1,2,3-三唑-4-羧酸为配体构筑的两个配合物的合成、晶体结构及性质(英文)

1-(3-羧苯基)-5-甲基-1氢-1,2,3-三唑-4-羧酸为配体与锰金属盐、锌金属盐在水热合成法得到2个配位聚合物:{Mn(cpmtc)2(H2O)2}n(1),{Zn(cpmtc)3(H2O)}n(2)。通过单晶衍射仪测得这2个晶体结构,配位聚合物1为单斜晶系,P21/c空间群;a=1.183 52(19)nm,b=1.198 01(19)nm,c=0.998 76(16)nm,β=113.201°。配位聚合物2属于单斜晶系,P21/c空间群;a=1.023 3(3)nm,b=1.172 0(4)nm,c=1.023 3(3)nm,β=92.8700°。除此之外,这2个配位聚合物通过红外和荧光进行表征。     

Stereoselective synthesis of (S)-3-(methylamino)-3-((R)-pyrrolidin-3-yl)propanenitrile

(S)-3-(methylamino)-3-((R)-pyrrolidin-3-yl)propanenitrile (1) is a key intermediate in the preparation of PF-00951966, (1) a fluoroquinolone antibiotic for use against key pathogens causing community-acquired respiratory tract infections including multidrug resistant (MDR) organisms. The current work describes the development of a highly efficient and stereoselective synthesis of 1 in 10 steps with an overall yield of 24% from readily available benzyloxyacetyl chloride. Two key transformations in the synthetic sequence involve (a) catalytic asymmetric hydrogenation with chiral DM-SEGPHOS-Ru(II) complex to afford β-hydroxy amide 11b in good yield (73%) and high stereoselectivity (de 98%, ee >99%) after recrystallization and (b) S(N)2 substitution reaction with methylamine to provide diamine 14 with inversion of configuration at the 1'-position in high yield (80%), after efficient purification using a simple acid/base extraction protocol.     

Preparation,molecular structures,and characteristic properties of (E)-1-(2-furyl)- and (E)-1-(2-thienyl)-2-(3-guaiazulenyl)ethylenes and (E)-1-(3-furyl)- and (E)-1-(3-thienyl)-2-(3-guaiazulenyl)ethylenes

Wittig reactions of 2-furaldehyde (20) [and thiophene-2-carbaldehyde (21)] with (3-guaiazulenylmethyl)triphenylphosphonium bromide (19) in ethanol containing NaOEt at 25 °C for 24 h under argon give (E)-1-(2-furyl)-2-(3-guaiazulenyl)ethylene (22E) and (E)-1-(2-thienyl)-2-(3-guaiazulenyl)ethylene (23E) in 53 and 36% yields. Similarly, Wittig reactions of 3-furaldehyde (29) [and thiophene-3-carbaldehyde (30)] with 19 under the same reaction conditions as for 20 and 21 afford (E)-1-(3-furyl)-2-(3-guaiazulenyl)ethylene (31E) and (E)-1-(3-thienyl)-2-(3-guaiazulenyl)ethylene (32E) in 32 and 46% yields. Molecular structures and characteristic properties as well as preparation of the title E (i.e., one of the geometrical isomers) forms, with a view to comparative study, are reported. Moreover, reactions of those conjugated π-electron systems with TCNE (=tetracyanoethylene) in benzene [and in DMF (=N,N-dimethylformamide)] at 25 °C for 24 h under argon yield unique products, possessing interesting molecular structures, respectively, whose characteristic properties and crystal structures are documented, also.     

3-(Carbazol-2-yl)- and 3-(Carbazol-3-yl)-dl-alanines

A facile transformation of 2- and 3-methylcarbazoles into 3-(carbazol-2-yl)-and 3-(carbazol-3-yl)-dl-alanines compounds is described.     

3-(3''''-羟基丁基)异苯并呋喃-1(3H)-酮的合成

由邻苯二甲酸酐为原料 ,经中间体 3 羟基苯酞 (3 ) ,再经溴丙烯及锡存在下 3的烯丙基化、硼氢化氧化、铬酐氧化、二甲基锌甲基化 ,共 6步反应合成了 3 (3’ 羟基丁基 )异苯并呋喃 1(3H) 酮。     

Practical synthesis of methyl(E)-2-(3-(3-(2-(7-chloro-2- quinolinyl)ethenyl)phenyl)-3-oxopropyl)benzoate,a key intermediate of Montelukast

A novel and practical synthetic route is presented for the preparation of methyl-(E)-2-(3-(3-(2-(7-chloro-2-quinolinyl)ethenyl) phenyl)-3-oxopropyl)benzoate,the key intermediate of Montelukast,a leukotriene antagonist.The main diarylpropane framework was prepared via a polarity conversation reaction resulting in an acyl anion equivalent followed by a nucleophilic substitution reaction.The overall yield of this approach was 61%.This method is simple for operation and suitable for industrial production.