Synthesis and Crystal Structure of 2-Oxo-3-phenyl-1-oxaspiro[4.5]dec-3-en-4-yl 4-chlorobenzoate

The title compound 2-oxo-3-phenyl-1-oxaspiro[4.5]dec-3-en-4-yl 4-chloro-benzoate 6 (C22H19ClO4, Mr = 382.82) has been synthesized by the condensation reaction of 4-hydroxy-3-phenyl-1-oxaspiro[4.5]dec-3-en-2-one 5 with 4-chlorobenzoyl chloride, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group P21/n with a = 10.6749(11), b = 6.0573(7), c = 29.680(2) , β = 94.073(3)o, V = 1914.3(3) 3, Z = 4, Dc = 1.328 g/cm3, F(000) = 800, μ = 0.224 mm–1, S = 1.003, the final R = 0.0605 and wR = 0.1500 for 1828 observed reflections with I > 2σ(I) and 244 variable parameters. The crystal analysis shows that the molecular structure of the title compound has one planar furan ring, one chair conformation cyclohexane ring and two benzene rings. The furan and cyclohexane rings adopt whorl conformations.     

超高效液相色谱-串联质谱法测定斑马鱼性腺中13种类固醇激素

建立了超高效液相色谱-串联质谱测定雌性斑马鱼性腺中13种类固醇激素的分析方法。雌鱼性腺分别经预冷的乙腈、乙酸乙酯浸提后,氨基(NH2)、亲水-亲脂平衡介质(HLB)固相萃取柱富集净化,ACQUITY UPLCBEH C18色谱柱进行梯度分离。采用多反应监测模式扫描,基质匹配外标法定量。研究了不同提取溶剂对13种类固醇激素的提取效果,考察了固相萃取柱的净化效果,并对斑马鱼性腺进行类固醇激素加标回收率实验,结果表明,13种分析物的平均加标回收率为74.8%~127.0%,相对标准偏差为3.9%~15.8%,方法检出限为0.006~0.300μg/kg。该方法简便、准确、灵敏,可应用于斑马鱼性腺类固醇激素生理水平的检测。     

Synthesis and Crystal Structure of Mesityl Acetic Acid 3-Mesityl-2-oxo- 1-oxaspiro [4,4] non-3-en-4-yl Ester

The title compound mesityl acetic acid 3-mesityl-2-oxo-1-oxaspiro[4,4]non-3-en-4-yl ester (5, C28H32O4, Mr = 432.56), as a spiromesifen derivative, has been synthesized by the conden- sation reaction of 2,4,6-trimethylphenylacetic chloride with 4-hydroxyl-3-mesityl-1-oxa-spiro[4,4]- non-3-en-2-one (4), and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the triclinic system, space group P1 with a = 7.9261(7), b = 8.2802(8), c = 18.7604(18) , α = 91.576(3), β = 93.277(2), γ = 95.306(12)o, V = 1223.3(2) 3, Z = 2, Dc = 1.174 g/cm3, F(000) = 464, μ = 0.077 mm-1, S = 1.001, the final R = 0.0624 and wR = 0.1415 for 2809 observed reflections with I 2σ(I) and 290 variable parameters. The crystal analysis results show that the five-membered cyclopentyl ring displays an envelope conformation with C(25) atom at the flap position, 0.537(3)  out of the mean plane formed by the other four atoms. The dihedral angles between the two benzene and furan rings are 70.0(2) and 80.67(3)o, respectively.     

Synthesis and Crystal Structure of 3-（2,4-Dichlorophenyl）- 4-dydroxy-5-cyclohexanyl-△3-dihydrofuran-2-one

The title compound 3-（2,4-dichlorophenyl）-4-dydroxy-3-（2,4-dichlorophenyl）-4- dydroxy-5-cyclohexanyl-A3-dihydrofuran-2-one 5 has been synthesized by the cyclization of methyl O-（2,4-dichlorophenyl-acetyl）-1-hydroxycyclo-hexane-carboxylate 4, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the triclinic system, space group Pi with a = 6.8192（3）, b = 10.5053（5）, c = 10.5811（5）A,α = 71.681（10）, β = 78.905（12）, γ = 81.036（12）°, C15H14C1203, Mr = 313.18, V= 702.44（6）A3, Z = 2, De= 1.481 g/cm^3, F（000） = 324,μ = 0.465 mm^-1, S = 1.006, the final R = 0.0331 and wR = 0.1363 for 2505 observed reflections with I 〉 2σ（I） and 183 variable parameters. The crystal analysis shows that the cyclohexene unit of the title compound has a quasi-chair conformation, and a one-dimensional chain structure is formed via the intermolecular hydrogen bond O（1）-H（101）…O（2）.     

Synthesis and Crystal Structure of 2-Methoxy-benzoic Acid 2-Oxo-3-（2,4,6-trimethyl-phenyl）-1-oxa-spiro[4.4]non-3-en-4-yl Ester

The new title compound 2-methoxy-benzoic acid 2-oxo-3-(2,4,6-trimethyl-phenyl)-1-oxa-spiro[4.4]non-3-en-4-yl ester(3,C25H26O5) has been synthesized by the condensation reaction of 4-hydroxy-3-(2,4,6-trimethyl-phenyl)-1-oxa-spiro[4.4]non-3-en-2-one(2) with 2-methoxylben-zoyl chloride,and characterized by 1H NMR and MS spectra.Its crystal structure was determined by single-crystal X-ray diffraction.The crystal is of monoclinic,space group P21/c with a = 10.6945(7),b = 12.8176(7),c = 16.4223(10) ,β = 103.5665(17)o,V = 2188.3(2) 3,Z = 4,Dc = 1.234 g/cm3,F(000) = 864.000,μ = 0.085 mm-1,the final R = 0.0520 and wR = 0.1132 for 2732 observed reflections with I 2σ(I).In the crystal structure,the C(1)-C(2)(1.478 ) bond is significantly shorter than the normal single C-C bond(1.53 ),suggesting that the carbonyl group on C(1) has formed a conjugated system with a double bond on C(2) and C(12).     

N-(取代噻唑-2-基)-菊酰胺类化合物的合成及生物活性研究

为了寻求新颖的氨基噻唑类先导化合物,以含各种取代基的2-氨基噻唑在其氨基位置与拟除虫菊酯类农药的活性基团——菊酸采用亚结构对接的方法合成了35个N-(取代噻唑-2-基)-菊酰胺类化合物,经1HNMR,ESI-MS和元素分析对化合物的结构进行了表征.初步生物活性测定表明,化合物3d,6a,6d,4a,4b,4c和4e在600mg/L下对小菜蛾具有100%的杀虫活性,化合物3d和7c在50mg/L下对多种常见病原菌具有显著的杀菌活性,全部化合物没有明显的除草活性.     

N-[3-氰基-1-(2,6-二氯-4-三氟甲基苯基)-1H-吡唑-5-基]菊酰胺类化合物的合成及生物活性

为了寻求新的N-芳基吡唑类先导化合物, 用5种拟除虫菊酯类农药的活性基团——菊酸与高活性杀虫剂氟虫腈和其中间体5-氨基-3-氰基-1-(2,6-二氯-4-三氟甲基-苯基)吡唑在其氨基位置采用亚结构对接的方法合成得到了10个新的芳基吡唑菊酰胺类化合物. 经¹H NMR, ESI-MS和元素分析对化合物的结构进行了表征. 初步生物活性测定结果表明, 在37.5 mg/L浓度下, N-[3-氰基-1-(2,6-二氯-4-三氟甲基苯基)-4-(三氟甲基亚磺酰基)-1H-吡咯-5-基]-3-(2,2-二氯乙烯基)-2,2-二甲基环丙酰胺(3b)对小菜蛾Amaranthus spinosus抑制活性达到100%, LC₅₀为15.1 mg/L. 初步雌雄大鼠急性经口毒性综合评价属中毒级, 同时还检测了2-(4-氯苯基)-N-[3-氰基-1-(2,6-二氯-4-三氟甲基苯基)-1H-吡唑-5-基]-3-甲基丁酰胺(3i)的晶体结构.