Synthesis,crystal structure,and insecticidal evaluation of novel aryl pyrazole compounds containing aminophosphonate moiety

A series of novel aryl pyrazole derivatives containing aminophosphonate were designed and synthesized on the basis of the commercial insecticide Fipronil. Their structures were confirmed by ¹H NMR, FT-IR, elemental analysis, and compound 4 m was characterized by a single crystal X-ray diffraction analysis. The results of the preliminary bioassays showed that title compounds exhibited satisfactory insecticidal activities against Culex pipiens and Musca domestica. The introduction of an electron-withdrawing group to the para-position of the benzene ring was essential for high bioactivity.     

Design,synthesis, and insecticidal activity of novel isoxazole derivatives containing bisamide moiety

In this study, a total of 31 novel isoxazole derivatives containing bisamide moiety were synthesized and evaluated for their insecticidal activity against Plutella xylostella (P. xylostella). Bioassays indicated that some of the target compounds exhibited good insecticidal activity against P. xylostella. In particular, compound E26 revealed excellent insecticidal activity against P. xylostella, with a 50% lethal concentration (LC₅₀) value of 4.6 μg/mL, which was even better than those of chlorpyrifos (7.7 μg/mL), beta‐cypermethrin (12.8 μg/mL), and azadirachtin (10.2 μg/mL). These results indicated that isoxazole derivatives containing bisamide moiety could be developed as novel and promising insecticides. To the best of our knowledge, it is the first report on the insecticidal activity of this series of novel isoxazole derivatives containing bisamide moiety.     

新型N-取代苯甲酰基-N′-(4-甲基苯并噻唑-2-基)硫脲衍生物的合成、晶体结构及抑菌活性

以取代苯甲酸和2-氨基-4-甲基苯并噻唑为原料合成5个新型N-取代苯甲酰基-N′-(4-甲基苯并噻唑-2-基)硫脲衍生物,化合物结构经元素分析、IR、1 H NMR和13 C NMR表征,X-射线单晶衍射测定了N-(4-甲氧苯甲酰基)-N′-(4-甲基苯并噻唑-2-基)硫脲(化合物1)的晶体结构,该晶体为单斜晶系,P21/c空间群,选择广西主要经济作物中常见的病原菌,对目标化合物进行室内抑菌活性测试,实验结果发现该类化合物具有一定的抑菌活性.     

Novel pyrethrin derivatives containing hydrazone and 1,3,4-oxadiazole thioether moieties: Design,synthesis, and insecticidal activity

Abstract

A series of novel pyrethrin derivatives containing hydrazone and 1,3,4-oxadiazole thioether moieties were designed, synthesized, and evaluated for their insecticidal activity. Bioassays indicated that some of the target compounds exhibited good insecticidal activities against Plutella xylostella (P. xylostella), Vegetable aphids (V. aphids), and Empoasca vitis (E. vitis). In particular, compound (E)-2-((5-(2,2-dimethyl-3-(2-methylprop-1-en-1-yl)cyclopropyl)-1,3,4-oxadiazol-2-yl)thio)-N'-(4-(trifluoromethyl)benzylidene)acetohydrazide (6s) revealed excellent insecticidal activities against P. xylostella, V. aphids, and E. vitis with the 50% lethal concentration (LC₅₀) values of 5.23, 7.07, and 1.61?mg/L, respectively, which were similar to or even better than those of chlorpyrifos, beta cypermethrin, spinosad, and azadirachtin. These results indicated that novel pyrethrin derivatives containing hydrazone and 1,3,4-oxadiazole thioether moieties could be developed as novel and promising insecticides.     

Synthesis,characterization, crystal structure,and antimicrobial studies of novel thiourea derivative ligands and their platinum complexes

N,N-Di-R-N′-(4-chlorobenzoyl)thiourea (Di-R: diethyl, di-n-propyl, di-n-butyl and diphenyl) ligands (HL^1–4) and their Pt(II) complexes (cis-[Pt(L^1–4-S,O)₂]) have been synthesized and structurally characterized by elemental analyses, FT-IR and NMR spectroscopy. HL² ligand and cis-[Pt(L⁴-S,O)₂] metal complex have been also characterized by a single-crystal X-ray diffraction study. HL², C₁₄H₁₉ClN₂OS, crystallizes in the monoclinic space group P2₁/n (no. 14), with Z = 4, and unit cell parameters, a = 11.1405(16) Å, b = 9.7015(12) Å, c = 14.790(2) Å, β = 106.547(7)°. The cis-[Pt(L⁴-S,O)₂], C₄₀H₂₈Cl₂N₄O₂PtS₂: triclinic, space group P-1 (no. 2), a = 8.9919(3) Å, b = 14.7159(6) Å, c = 15.7954(6) Å, α = 113.9317(18)°, β = 97.4490(18)°, and γ = 105.0492(16)°. Single crystal analysis of complex, cis-[Pt(L^1–4-S,O)₂], revealed that a square planar coordination geometry is formed around the platinum atom by two sulfur and two oxygen atoms of the related ligands, which are in a cis configuration. In addition, the thiourea derivative ligands and their complexes were evaluated for both their in-vitro antibacterial and antifungal activity. The results have been reported, explained, and compared with fluconazole and ampicillin, used as reference drugs.     

Design,synthesis, crystal structure and bioactivity evaluation of novel diethyl (arylfuranyl)(arylpyrazolylamino)methanephosphonates

A series of novel arylpyrazole derivatives containing aminomethanephosphonate and phenylfuran moieties were designed, synthesized and characterized by ¹H NMR, ³¹P NMR and IR spectroscopy and elemental analyses. The single crystal structure of diethyl [5-(4-chlorophenyl)furan-2-yl][3-cyano-1-(2,3,4-trifluorophenyl)-1H-pyrazol-5-ylamino]methanephosphonate (4l) was determined by X-ray diffraction. Preliminary bioassays showed that these phosphonates exhibit satisfactory insecticidal activities against Culexpipiens and Musca domestica at 0.1%. In particular, compound 4l exhibited a most promising KT50 value, which is superior to that of Dextraltetramethrin® and similar to Prallehtrin®. The structure-activity relationship was also preliminarily investigated.     

Synthesis,spectroscopic characterization,crystal structure and antifungal activity of thiourea derivatives containing a thiazole moiety

Four novel thiourea derivatives containing a thiazole moiety were synthesized and characterized by IR, ¹H and ¹³C NMR, mass spectrometry and elemental analysis. The crystal structure of 1a was determined from single crystal X-ray diffraction data. It crystallizes in monoclinic space group P2₁/n with unit cell dimensions a = 11.7752(6) Å, b= 3.8677(2) Å, c= 27.4126(13) Å and β = 92.734(5) Å. There is a strong intramolecular hydrogen bond of the type N-H?O, with H?O distance of 2.5869(19) Å. The mass fragmentation pattern has also been discussed. The antifungal activity of the synthesized compounds was studied by broth micro-dilution method and poisoned food technique. The compounds 1b and 1c possessed a broad spectrum of antifungal activity.

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Design,synthesis and insecticidal activities of novel anthranilic diamides containing polyfluoroalkyl pyrazole moiety

In order to discover new molecules with good insecticidal activities, a series of anthranilic diamides containing polyfluoroalkyl pyrazole were designed and synthesized, and their structures were characterized by ¹H NMR and HRMS. Bioassays demonstrated that some of the title compound exhibited excellent insecticidal activities. The larvicidal activities of compound 8a, 8c, 8g, 8k and 8l against Mythimna separata Walker were 100% at 0.8 mg/L. The insecticidal activities of compound 8a, 8c, 8e, 8g, 8k and 8l against Plutella xylostella Linnaeus were 100% at 0.4 mg/L. Surprisingly compounds 8a and 8c still showed 100% larvicidal activities against Plutella xylostella Linnaeus at 0.08 mg/L comparable to the commercialized Chlorantraniliprole. The LC₅₀ of compound 8a and 8c against M. separata is 0.048 and 0.043 mg/L respectively.     

Design, synthesis and antifungal/insecticidal evaluation of novel cinnamide derivatives

Twenty novel cinnamamide derivatives were designed and synthesized using as lead compound pyrimorph, whose morpholine moiety was replaced by β-phenylethylamine. All the compounds were characterized by their spectroscopic data. The fungicidal and insecticidal activities were also evaluated. The preliminary results showed that all the title compounds had certain fungicidal activities against seven plant pathogens at a concentration of 50 μg/mL, and compounds 11a and 11l showed inhibition ratios of up to 90% against R. solani. Most of the title compounds exhibited moderate nematicidal activities. In general, the morpholine ring may be replaced by other amines and a chlorine atom in the pyridine ring is helpful to fungicidal activity.     

Novel pyrethrin derivatives containing an 1,3,4-oxadiazole thioether moiety: Design,synthesis, and insecticidal activity

In this study, a series of novel pyrethrin derivatives containing an 1,3,4-oxadiazole thioether moiety were designed and synthesized. Bioassay results revealed that some of the target compounds possessed excellent insecticidal activities against Plutella xylostella (P. xylostella), Vegetable aphids (V. aphids), and Empoasca vitis (E. vitis), respectively. In particular, compound 4l revealed the best insecticidal activities against P. xylostella and V. aphids, with the 50% lethal concentration (LC₅₀) values of 1.78 and 1.61 mg/L, respectively, meanwhile, compound 4k revealed the best insecticidal activity against E. vitis, with the LC₅₀ value of 1.06 mg/L, which were superior to those of the commercial insecticidal agents of chlorpyrifos, beta cypermethrin, spinosad, and azadirachtin. These results indicated that novel pyrethrin derivatives containing an 1,3,4-oxadiazole thioether moiety could effectively inhibit P. xylostella, V. aphids, and E. vitis.     

二茂铁衍生物的合成及单晶结构研究

近年来 ,二茂铁金属有机液晶材料因其特异的液晶性能和较高的应用价值 ,引起了人们广泛的研究兴趣 ,得到了迅速的发展 ,使该类液晶材料的种类不断增加[1～ 4] 。本文报道的二茂铁衍生物是一个含有苯基、酯基和Ｓｃｈｉｆｆｓ的金属有机化合物 ,是一种潜在的金属有机液晶材料 ,其合成路线如下 :1　实验1 1　仪器与试剂仪器 :显微熔点测定仪。核磁共振仪为ＲｒａＫｅｒＡＶＡＮＣＥ - 30 0Ｇ型 ,ＴＭＳ作为内标。红外光谱仪为Ｐｅｒｋｉｎ Ｅｌｍｅｒ1 730型 ,ＫＢｒ压片。单晶测定仪为ＳｉｅｍｅｎｓＰ4型衍射仪。试剂均为国产化学纯。1 2…     

Design,synthesis, and bioactivity evaluation of novel thiochromanone derivatives containing an oxime or oxime ether moiety

In this study, using botanical active component thiochromanone as the lead compound, a series of novel thiochromanone derivatives containing an oxime or oxime ether moiety were designed and synthesized. The half-maximal effective concentration (EC₅₀) values of compound 4a against Xanthomonas oryzae pv. oryzae (Xoo), Xanthomonas oryzae pv. oryzicolaby (Xoc), and Xanthomonas axonopodis pv. citri (Xac) were 6, 10, and 15 μg/ml, respectively, which were superior to those of Bismerthiazol and Thiodiazole-copper. Meanwhile, compound 4a also revealed better antifungal activity against Botrytis cinerea, with the EC₅₀ value of 18 μg/ml, than that of Carbendazim. To the best of our knowledge, this is the first report on the antibacterial and antifungal activities of this series of novel thiochromanone derivatives containing an oxime or oxime ether moiety.     

Design,synthesis and biological evaluation of novel 3-phenylpropanamide derivatives with acyl hydrazone units

In this study, a series of 3-phenylpropanamide derivatives with acyl hydrazone units were synthesized and characterized by ¹H NMR, ¹³C NMR and HR MS. And the structure of compound III₃₃ was confirmed by X-ray single crystal. The bioassay results showed that, compounds III₈, III₁₇, III₂₂, and III₃₄ showed excellent inhibition on Xanthomonas oryzae pv. pryzae (Xoo) with EC₅₀ values of 7.1, 8.8, 9.5, and 4.7 μg/mL in vitro. The EC₅₀ values of compounds III₁₂, III₁₄ and III₃₃ against Ralstonia solanacearum (Rs) were 7.6, 7.6 and 7.9 μg/mL, respectively, all lower than the values of thiadiazol copper (TC) was 66.8 μg/mL and bismerthiazol (BT) was 72.4 μg/mL. Compounds III₁₂, III₁₄, III₃₃, and III₃₄ exhibited excellent antibacterial activity of more than 80% against Xanthomonas axonopodis pv. citri (Xac) in vitro. Besides, compounds III₈ (51.4%) and III₃₄ (52.1%) were highly effective against Xoo in vivo, outperforming TC (49.5%) and BT (47.8%). Compounds III₈ (29.8%) and III₃₄ (24.6%) were close to TC (41.7%) and BT (47.8%) in terms of protective efficacy against Xoo in vivo. Meanwhile, some of title compounds also displayed inhibitory effects against phytopathogenic fungi. In a word, this study illustrated that the structures combined with phenylpropane amide derivatives of the acyl hydrazone units could be used as potential antibacterial reagents in the future.     

具有生物活性的1,4-二氢吡啶衍生物的水热法合成及结构表征

1,4-二氢吡啶衍生物具有很好的生理活性。在医学上用作心血管疾病的防治保健药物,不仅能治疗肠胃疾病、雷诺氏病、脂肪肝、中毒性肝炎,也有抗衰老、防早熟等作用,还可以用作治疗肺动脉高压和癫痫病的辅助药物[1-2]。近年又发现1,4-二氢吡啶衍生物不但是一类高效的钙拮抗剂,亦是一种绿色饲料添加剂。它的合成通常采用文献报道的Hantzsch法合成[3],即将干燥氨气通入乙酰乙酸乙酯与醛的混合溶液中。该反应时间长、操作复杂,且氨气易对环境造成污染。正因为此,越来越多的化学家和药物学家将有机合成的研究重点放在对环境无污染的绿色合成上。如…     

Design,synthesis, insecticidal,and acaricidal activities of novel pyrimidinamine derivatives containing a biphenyl ether

A series of original pyrimidinamine derivatives containing a biphenyl ether moiety were designed and synthesized. Their structures were confirmed by ¹H NMR, MS, and elemental analyses. Their insecticidal activities against lepidopteran and hemiptera insects and acaricidal activities were tested. The results of bioassay demonstrated that 9k showed the best activity (LC₅₀ = 2.08 mg/L) against Tetranychus urticae, which is comparable with the positive control, spirotetramat (LC₅₀ = 2.27 mg/L), and 9g showed better activity (LC₅₀ = 0.52 mg/L) against Aphis fabae than the positive control, imidacloprid (LC₅₀ = 1.02 mg/L), and relatively good activity (LC₅₀ = 2.49 mg/L) against T urticae. Their structure‐activity relationships indicated that both an ethyl group on the 4‐position of the pyrimidine ring and alkyl chain as a para‐substituent group of the benzene ring showed good biological activity.     

Hydrothermal synthesis,crystal structure,and properties of a novel magnesium phosphonate with a 1D chain structure

A novel 1D chain magnesium phosphonate with a 1D channel system along the c-axis, [Mg(H₄L)(H₂O)₃]_n (1) (H₄L^2-=HN(CH₂PO₃H)₃)^2-, has been synthesized under hydrothermal condition using triphosphonate ligand. The MgO₆ polyhedra and NC₃ planes are connected by phosphonate groups to form a 1D chain. The chains are interlinked by hydrogen bonds into 2D layers. Adjacent layers are further linked via hydrogen bonds to build a 3D network structure. The luminescent property of complex 1 has been also studied. For the complex 1, a blue fluorescent emission band with a maximum peak at 460 nm was observed.     

Design,synthesis, and pesticidal activities of novel pyrimidin-4-amine derivatives containing trifluoroethyl sulfide moiety

In order to overcome the problem of pesticide resistance, it is necessary to discover novel pesticides with new mechanisms of action. Herein, a series of novel pyrimidin-4-amine derivatives containing trifluoroethyl sulfide moiety were designed and synthesized. Bioassays indicated that the title compounds synthesized possessed excellent acaricidal activity against Tetranychus urticae and fungicidal activity against Erysiphe graminis and Puccinia sorghi. Especially, the acaricidal activity of 5-chloro-6-(difluoromethyl)-N-(2-(2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl)thio)phenoxy)ethyl)pyrimidin-4-amine (compound T4 , LC₅₀ = 0.19 mg/L) against T. urticae was close to commercial acaricide cyenopyrafen, and the fungicidal activity of 5-chloro-6-(difluoromethyl)-2-methyl-N-(2-(3-((2,2,2-trifluoroethyl)thio)phenoxy)ethyl)pyrimidin-4-amine (compound T15 , EC₅₀ = 1.32 mg/L) against P. sorghi. was superior to commercial fungicide tebuconazole. The synthesis and characterization of these compounds were given and the structure–activity relationships were discussed.     

新型N-(取代芳氧乙酰胺基)-N'-(1-甲基环己基酰基)硫脲及其环合产物的合成及其杀虫活性

采用亚结构拼接法,将苯氧乙酸类结构引入酰基硫脲中,设计并合成了8个新型的硫脲类化合物——N-(取代苯氧乙酰胺基)-N'-(1-甲基环己基酰基)硫脲(5a~5h);5a~5h在酸性条件下关环形成8个新型的含1,3,4-噻二唑的酰胺类化合物——1-甲基-N-(5-取代基-1,3,4-噻二唑-2-基)环氧甲酰胺(6a~6h),其结构经1H NMR和ESI-MS表征。初步的生物活性测试结果表明,在用药量为500mg·L-1时,N-(2,4-二氯苯氧乙酰胺基)-N'-(1-甲基环己基酰基)硫脲对粘虫的抑制率为80%。     

新型笼状钼磷超分子化合物的水热合成与晶体结构

用水热法首次合成了含有２ 种有机胺的新型笼状钼磷超分子化合物〔ＮＨ３（ＣＨ２）６ＮＨ３〕７〔ＮＨ３（ＣＨ２）２ＮＨ３〕２（Ｈ３Ｏ）６〔Ｐ２ Ｍｏ５Ｏ２３〕４·１１Ｈ２Ｏ,并通过元素分析、红外和Ｘ－ 射线单晶衍射法进行了结构表征．晶体属三斜晶系,空间群ｐ１杂多阴离子中的每个〔Ｐ２Ｍｏ５Ｏ２３〕６－ 是由５ 个ＭｏＯ６ 八面体和两个ＰＯ４ 四面体键合而成,其中Ｍｏ,Ｐ原子成一个畸变五角双锥构型．