Synthesis and Crystal Structure of the Optical Activity of (Z)-Nitromethylene Neonicotinoid Analogue

A novel （Z）-nitromethylene neonicotinoid analogue （C23H27Cl2N5O4·2H2O） （II） with optical activity has been synthesized, the structure was characterized by elemental analysis, IR and 1H NMR spectra, and the （Z）-configuration was confirmed by single-crystal X-ray diffraction. The crystal belongs to triclinic, space group P1 with a = 7.4638（3）, b = 12.6232（5）, c = 15.2990（6）, α = 71.907（1）, β = 89.397（2）, γ = 80.314（1）°, V = 1349.28（9）3, Z = 2, Dc = 1.340 g/cm3, μ = 0.286 mm-1, Mr = 544.43, F（000） = 572, S = 1.056, R = 0.0801 and wR = 0.2366 for 4998 unique reflections with 3012 observed ones （I 〉 2σ（I））. In the crystal, the dihedral angle between the pyridine and 4-Cl-phenyl rings is 58.13°. Intermolecular O-H···O, C-H···O and C-H···Cl hydrogen bonds involving water molecules stabilize the crystal structure.

(Z)-N-(3-(2-Chloro-4-nitrophenyl)-4-methylthiazol-2(3H)-ylidene) Pivalamide: Synthesis and Crystal Structure

Synthesis of the title compound was carried out by base-catalyzed cyclization of 1-pivaloyl-3-(2-chloro-4-nitrophenyl) thiourea with α-bromoacetone produced in situ. The structure was confirmed by the spectroscopic and elemental analysis and single crystal X-ray diffraction data. It crystallizes in the triclinic space group P-1 with unit cell dime sions a = 8.7137(10), b = 10.2010(14), c = 10.6593(13), α = 62.671(9), β = 82.701(10), γ = 79.762(10), V = 827.21(8) ?3, Z = 2.

Synthesis, Crystal Structure and Fungicidal Activity of (Z)-3,3-Dimethyl-1-(1H-1,2,4-triazol-1-yl)butan-2-one O-2-Chlorobenzyl Oxime Nitrate

The title compound has been synthesized by the reaction of 3,3-dimethyl-1-（1H-1,2,4-triazol-1-yl）butan-2-one oxime with 2-chlorobenzyl chloride, and then treated with 65～68% HNO3. Its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group P21/c with a = 14.5481（8）, b = 9.3351（5）, c = 13.1911（7） , β = 98.9450（10）°, Z = 4, V = 1769.67（17） 3, Mr = 369.81, Dc = 1.388 g/cm3, S = 1.06, μ = 0.247 mm-1, F（000） = 776, the final R = 0.0352 and wR = 0.0960 for 3069 observed reflections （I 2σ（I））. X-ray crystal structure presents the intramolecular N–H…O hydrogen bond. The packing is nearly parallel without π-π stacking interactions between two adjacent phenyl rings and stabilized by Van der Waals force. The preliminary bioassay shows that the title compound possesses fungicidal activity against Gibberella zeae at the dosage of 25 mg/L.

Synthesis and Crystal Structure of (Z)-Methyl-3-methoxy-2-{2-[(4-(E-3-p-tolylacryloyl)phenoxy)methyl]phenyl}acrylate

The title compound,（Z）-methyl-3-methoxy-2-{2-[（4-（E-3-p-tolylacryloyl）phenoxy）-methyl]phenyl}acrylate,was synthesized and determined by X-ray single-crystal diffraction. The crystal belongs to the triclinic system,space group P1 with a = 8.0157（8）,b = 12.5748（13）,c = 13.3768（14） ,α = 64.770（2）,β = 75.720 （2）,γ = 89.784（2）°,μ = 0.085 mm-1,Mr = 442.49,V = 1174.1（2） 3,Z = 2,Dc = 1.252 g/cm3,F（000） = 468,T = 294（2） K,R = 0.0603 and wR = 0.1498 for 2644 observed reflections with I 〉 2σ（I）. X-ray diffraction analysis reveals that the single crystal contains strong non-classical hydrogen bonds. The preliminary bioassay showed that the title compound exhibits inhibitory activity against the Pseudoperoniospora cubensis and Rhizoctonia solani at the test concentration of 200 mg/L.

Synthesis and Crystal Structure of (Z)-Ethyl-4-(4-methoxy)benzylidene-2-(3,5-dimethoxypheny-tetrahydrofuran-3,3-dicarboxylate

The title compound （Z）-ethyl-4-（4-methoxy）benzylidene-2-（3,5-dimethoxyphenyl）- tetrahydrofuran-3,3-dicarboxylate has been synthesized, and its crystal structure was characterized by X-ray single-crystal diffraction. The crystal belongs to triclinic, space group P1, with a = 8.140（3）, b = 11.966（4）, c = 13.771（5）Aα= 67.366（4）, β= 85.165（5）, γ= 75.806（4）°, V = 1200.1（7） A3, Z = 2, C26H3008, Mr = 470.50, Dc = 1.302 g/cm^3, F（000） = 500,λ（MoKa） = 0.71073 A, μ= 0.096 mm^-1, R = 0.0659 and wR = 0.1841 for 3080 observed reflections （I 〉 2σ（I））. As a key intermediate of HIV-1 integrase inhibitor, the synthesis and structure confirmation of the title compound are important for further studies.

Synthesis and Crystal Structure of(E)-Ethyl 2-(4-(2,4-dimethoxybenzylideneamino)-5-(3,4,5-trimethoxyphenyl)-4H-1,2,4-triazol-3-ylthio)acetate

The crystal structure of the title compound（E）-ethyl 2-（4-（2,4-dimethoxy benzylide-neamino）-5-（3,4,5-trimethoxyphenyl）-4H-1,2,4-triazol-3-ylthio）acetate（4,C24H28N4O7S,Mr = 516.17） was synthesized and determined by X-ray single-crystal diffraction.The crystal belongs to the monoclinic system,space group P21/n with a = 13.162（2）,b = 8.4506（13）,c = 22.602（4） ,β = 99.888（3）°,μ = 0.183 mm-1,V = 2476.5（7）3,Z = 4,Dc = 1.385 g/cm3,F（000） =1088,T = 110（2） K,R = 0.0426 and wR = 0.1216 for 3859 observed reflections with I 2σ（Ⅰ）.

S-(+)-(E)-1-(2-furfuryl)-5-substituted-1,3,5-hexahydrotriazine-2-N-nitroimines:Synthesis,Crystal Structure and DFT Calculations

A novel neonicotinoid analogue（C13H19N5O5,3a）had been synthesized,the structure was characterized by elemental analysis,IR and 1H NMR spectra,and the S-（＋）-（E）-configuration was confirmed by single-crystal X-ray diffraction.The crystal belongs to monoclinic,space group P21 with a = 8.7076（17）,b = 8.3211（17）,c = 10.642（2）,β = 92.370（3）o,V = 770.4（3）3,Z = 2,Dc = 1.402 g/cm3,μ = 0.110 mm-1,Mr = 325.33,F（000）= 344,S = 1.027,R = 0.0543 and wR = 0.1229 for 3601 unique reflections with 2919 observed ones（I 2σ（I））.Compound 3a is stabilized by intramolecular hydrogen bonds and intermolecular force.In addition,the structure of compound 3a was optimized by the B3LYP/6-31G（d,p）.DFT/B3LYP optimizations were performed based on X-ray geometries applying 6-31G（d,p）basis set.The optimized structure of compound 3a by the B3LYP/6-31G（d,p）method is more bent than in the crystal.IR spectrum of the solid compound is consistent with the X-ray structure.The HOMO-LUMO gap in 3a（5.3 eV）indicates high kinetic stabilities of compound 3a.The preliminary bioassay test showed that 3a exhibited good activities against Nilaparvata legen,Pseudaletia separate Walker and Aphis medicagini at 500 mg/L.

(Z)-1-苯基-1-对氟苯基-2-对甲苯磺酰基-1，4-戊二烯的合成及其晶体结构

通过1-苯基-2-对甲苯磺酰基乙炔、对氟苯基氯化锌及烯丙基溴的三组分串联反应,合成了(Z)-1-苯基-1-对氟苯基-2-对甲苯磺酰基-1,4-戊二烯(1),其结构经1H NMR,13C NMR,IR,HR-MS和XRD表征。1为Z-构型,属单斜晶系,空间群P21/c,a=9.899 1(20),b=9.621 9(20),c=21.812 9(15),β=95.575(10)°,V=2067.8(6)3,Z=4,Dc=1.254 g.cm3,μ=0.181 mm-1,λ=0.710 73,F(000)=816,R=0.046 3,wR=0.134 1。共收集到3 684个独立衍射点,其中I>2σ(I)的可观察点为2 989。

1-[(Z)-2-(-苯基二溴化锡基)乙烯基]环戊醇的合成及晶体结构

通过１［（Ｚ）２（三苯基锡基）乙烯基］环戊醇与Ｂｒ２反应制得了新化合物１［（Ｚ）２（苯基二溴化锡基）乙烯基］环戊醇．通过元素分析、锡含量测定、ＩＲ、１ＨＮＭＲ对其进行了表征并用Ｘ射线衍射法测得了所合成化合物的晶体结构．该化合物属正交晶系，Ｐ２１２１２１空间群，晶胞参数：ａ＝０８６７５（４）ｎｍ，ｂ＝１２５２３（７）ｎｍ，ｃ＝１４００９（８）ｎｍ；Ｚ＝４，Ｖ＝１５２１９ｎｍ３，Ｄｃ＝２．３９ｃｍ３，ｕ＝２３．７２ｃｍ－１．结构分析表明，标题化合物分子为畸变的三角双锥构架，双键的两个氢取顺式结构，分子中Ｏ与Ｓｎ配位。

(Z)-2-羟基-3-苯甲酰丙烯酸甲酯的合成及晶体结构

标题化合物C11H10O4的晶体结构用X-射线单晶衍射法测定。晶体属单斜晶系, P21/c空间群, 晶胞参数a = 12.136(1), b = 5.559(1), c = 14.615(2) ? b = 96.758(3), V = 979.1(3) ?, Z = 4, Mr = 206.19, Dc = 1.399 g/cm3, F(000) = 432, m(MoKa) = 0.107 mm-1。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 = 0.0453, wR = 0.0990。标题化合物形成了1个大的共轭体系, 含有1个稳定的烯醇结构。结构测定表明还存在着1个分子内氢键的结构, 它使烯醇结构更加稳定。

含2,2'-联吡啶配体簇合物的合成、晶体结构及非线性光学性质

The Cluster compound [Cu3BrWOS3(bipy)2] was synthesized by reaction of (NH4)2WOS3, CuBr, 2,2′ bipyridine and n Bu4NBr at room temperature and characterized by IR, UV and elemental analyses. The structure of [Cu3BrWOS3(bipy)2] wasdetermined by single crystal X ray diffraction revealing that the cluster consist of a nest shaped core. The W atom is tetrahedrally coordinated by three S atoms and one O atom. There are two types of copper atoms in the WOS3Cu3 aggregate: two copper atoms are tetrahedrally coordinated and another copper atom is trigonally coordinated. The nonlinear optical properties were studied with an 8ns pulsed laser at 532nm. Its optical responses to the incident light exhibit considerably optical absorptive and strong self focusing effect with α2=0.90×10-10m·W-1, n2=2.72×10-18m2·W-1. CCDC: 196348.

N-[(Z)-2-氰基亚胺-1,3-噻唑-3-基]-4-溴苯甲酰胺的合成、晶体结构及量子化学计算

含噻唑(噻唑烷)杂环的化合物具有广谱的抑菌、杀虫,抗癌、抗肿瘤等活性,因此设计合成含噻唑(噻唑烷)杂环的新化合物成为当今药物设计合成的热点。鉴于此,本研究以(Z)-2-氰基亚胺-1,3-噻唑烷和4-溴苯甲酰氯为原料,在丙酮和三乙胺体系中合成了标题化合物,采用IR、~1H NMR分析方法对其进行了表征。并采用X射线衍射(XRD)测定了其晶体结构,为单斜晶系,P2_(1/c)空间群,晶胞参数:a=16.579(3)A,b=5.6471(11)A,c=13.611(3)A;α=90°,β=112.91(3)°,γ=90°,Z=4,M_r=310.17,D_c=1.755Mg/m^3,F(000)=616,μ=3.67mm^(-1),R_1=0.037,ωR_2=0.108。接着采用量子化学理论,在DFT-B3LYP/6-311G(d,p)基组下计算了该化合物的优化结构参数、电荷分布、分子总能量及前线轨道能量,为标题化合物的深入研究提供了理论依据。

新型双环新烟碱类似物的合成及其生物活性

设计合成了六个新型双环新烟碱类似物,通过1H NMR,13C NMR,高分辨质谱和单晶结构对目标化合物的结构进行了表征.初步的生物活性测试表明:在500 mg?L-1浓度下,目标化合物6a,6c^6f对豆蚜(Aphis craccivora)具有很好的杀虫活性.通过分子对接比较并解释了目标化合物6a和吡虫啉的活性和作用模式的差异,其结果表明目标化合物6a的吡啶环和受体残基色氨酸147的芳香环侧链具有?-?堆积作用,与吡虫啉的作用方式存在一定差异.