A series of novel 5-aryl-1-(aryloxyacetyl)-3-(tert-butyl or phenyl)-4-(1H-1,2,4-triazol-1-yl)-4,5-dihydropyrazole 3a-3n were synthesized by the annulation of 2-aryloxyacetohydrazides with 3-aryl-1-t-butyl(or phenyl)-2-(1H-1,2,4-triazol-1-yl)prop-2-en-1-ones(1)in the presence of a catalytic amount of acetic acid.Compounds 2 were obtained by the Knoevenagel reactions of 1-t-butyl(or phenyl)-2-(1H-1,2,4-triazol-1-yl)ethanone(2)with aromatic aldehydes in the presence of piperidine.Their structures were confirmed by IR,1H-NMR,ESIMS,and elemental analyses.The preliminary bioassay indicated that some compounds displayed moderate to excellent fungicidal activity.For example,compounds 31,3m,and 3n possessed100%inhibition against Cercospora arachidicola Hori at the concentration of 50 mg/L.
The crystal structure of the title compound （C25H28N5O5P,Mr=509.49） has been determined by single-crystal X-ray diffraction.The crystal is of monoclinic,space group P21/c with a=13.0726（4）,b=13.4513（4）,c=15.103（1）,β=93.650（1）°,V=2650.29（14）3,Z=4,Dc= 1.277 g/cm3,F（000）=1072,μ（MoKα）=0.147 mm-1,the final R=0.0748 and wR=0.1956 for 3186 observed reflections （I 〉 2σ（I））.The fused triazolopyrimidine system ring is coplanar,the dihedral angles between the triazolopyrimidine and C（1）-C（3）-C（5） phenyl,the triazolopyrimidine and C（17）-C（19）-C（21） phenyl,and the two phenyl rings are 66.87,58.79 and 80.11o,respectively.Intramolecular N（5）-H（5A）…O（3） and intermolecular C（2）-H（2）…N（4）,C（18）-H（18）…O（3）,C（19）-H（19）…O（2） and C（24）-H（24C）…N（4） hydrogen bonds together with C-H…π interactions contribute to the stability of the structure and result in a three-dimensional framework.The preliminary bioassay indicates that the title compound exhibits moderate herbicidal activity against dicotyledonous plants （Brassica campestris L） at the concentration of 100 mg/L.
The crystal structure of the title compound （C22H17BrOs, Mr = 441.27） has been determined by single-crystal X-ray diffraction. The crystal is of orthorhombic system, space group Pna21 with a = 11.76（I）, b = 14.58（1）, c = 11.52（1）A, V= 1973.9A3, Z= 4, Dc = 1.485 g/cm3, F（000） = 896,μ（MoKa） = 2.113 mm-1, the final R = 0.0394 and wR = 0.0809 for 3918 observed reflections （1 〉 2o（/））. The single-crystal X-ray diffraction data indicate that the C=C bond is in an E-configuration. The intramolecular C（10）-H（10B）...O（4） and intermolecular C（17）-H（I 7）...0（4） hydrogen bonds contribute to the stability of the structure.
双酰肼化合物作为一类重要的昆虫生长调节剂广泛用于植物保护中.为了发现新型高效低毒性的双酰肼杀虫剂先导化合物,通过在双酰肼化合物分子骨架中引入1,2,3-噻二唑杂环,设计合成了一类含1,2,3-噻二唑的双酰肼衍生物3,其结构经IR、1 H NMR、ESI-MS和元素分析测试技术确证;生物活性测定结果表明,部分目标化合物在200mg/L质量浓度下对甜菜夜蛾幼虫(spodopteraexigua hubner)和小菜蛾幼虫(plutella xylostella)显示出良好的杀虫活性,如化合物3f对甜菜夜蛾和小菜蛾分别显示出100%和95%的杀死率;但目标化合物对蚜虫(Aphis)的杀死率较微弱.
The crystal structure of the title compound （C18H18N4O, Mr = 306.36） has been determined by single-crystal X-ray diffraction. The crystal is of triclinic, space group P1 with α = 4.783（0）, b = 13.577（1）, c = 13.830（1） A, α = 63.581（2）, β = 88.326（2）, γ = 86.161（2）°, V= 802.5（1） A3, Z= 2, Dc = 1.268 g/cm^3, F（000） = 324, μ（MoKa） = 0.082 mm^-1, the final R = 0.0497 and wR = 0.1199 for 3094 observed reflections （I 〉 2σ（I））. The dihedral angles between the phenyl （C（1）-C（4）-（6）） and triazole, the phenyl （C（13）-C（15）-C（18）） and triazole, and the two phenyl rings are 7.9（1）, 69.9（1） and 67.8（1）°, respectively. Strong C-H…π interaction joins molecules into a chain along the c axis and contributes to the stability of the structure. Preliminary bioassay results show that the title compound possesses excellent and selective fungicidal activity against Colletotrichum gossypii but displays moderate to weak insecticidal activity against aphides.
