含硫(氧)肟醚化合物杀虫活性三维定量构效关系研究

打破文献[1～3]中芳基烷基肟醚化合物的结构框架,将杂原子硫(氧)引入到其烷基中,设计并合成了一系列全新结构的含硫(氧)肟醚化合物．其生物活性研究结果表明,该系列化合物具有优良的杀鳞翅目、同翅目和直翅目等害虫的作用,且具有拟除虫菊酯农药快速击倒的活性特点．     

(αE,E)-α-(甲氧亚氨基)-2-[1-(芳香醛酮肟氧基)甲基]苯乙酸甲酯的立体选择性合成及生物活性研究

使用邻甲苯基重氮盐与乙醛酸甲酯肟偶联反应高立体选择性合成出 (E)-2-(羟基亚氨基)-2-邻甲基苯乙酸甲酯,经硫酸二甲酯的甲基化反应可得到重要的中间体(E)-2-(甲氧亚氨基)-2-邻甲基苯乙酸甲酯, 再经NBS溴化后与 (E)-芳香醛酮肟进行醚化反应最终得到目标物(αE,E)-α-(甲氧亚氨基)-2-[1-(芳香醛酮肟氧基)甲基]苯乙酸甲酯, 这些化合物多数具有很好的广谱杀菌活性.     

3-(4-β-D-吡喃阿洛糖苷苯基)-4-胺羰基-5-甲氧羰基异噁唑衍生物的 合成及其镇静活性的研究

4-(β-D-吡喃阿洛糖苷)-α-氯代苯甲醛肟与N-芳基马来酰亚胺在三乙胺作用下, 以甲醇为溶剂, 通过1,3-偶极环加成, 合成了一系列未见文献报道的3-(4-β-D-吡喃阿洛糖苷苯基)-4-胺羰基-5-甲氧羰基异噁唑衍生物; 其结构经1H NMR, IR, MS (HRMS)加以确证. 并对4a～4h和5a进行了药理活性筛选, 结果表明, 部分化合物具有良好的镇静活性. 其中, 化合物4b (200 mg•kg－1), 4c (200 mg•kg－1), 4h (200 mg•kg－1), 与豆腐果苷相比较具有更强的活性.     

2-{5-[(1H-1,2,4-三唑-1-基)甲基]-4-苯基-4H-1,2,4-三唑-3-硫基}-1-芳基乙酮类化合物的合成、表征及生物活性测试

通过α-卤代芳基乙酮和5-[(1H-1,2,4-三唑-1-基)甲基]-4-苯基-2H-1,2,4-三唑-3(4H)-硫酮反应, 合成了11个新的2-{5-[(1H-1,2,4-三唑-1-基)甲基]-4-苯基-4H-1,2,4-三唑-3-硫基}-1-芳基乙酮类化合物. 其结构经元素分析, IR, ¹H NMR等确证, 并用X射线单晶衍射测定了化合物6f的晶体结构. 生物活性测试结果表明, 部分化合物具有一定的杀菌活性.     

含肟醚的新型四唑啉酮衍生物的合成及除草活性研究

1-(4-氯苯基)-1,4-二氢-四唑-5-酮(1)与氯丙酮反应生成1-(4-氯苯基)-4-(2-氧代丙基)-1,4-二氢-四唑-5-酮(2). 中间体2、盐酸羟胺和卤化物通过三组分一锅法合成了目标化合物3. 初步生物活性测试结果表明: 目标化合物3具有较好的除草活性.     

γ－芳基取代烯丙醇菊酯的合成及杀虫活性

γ－芳基取代烯丙醇菊酯的合成及杀虫活性陈亚娟，黄润秋，马军安（南开大学元素有机化学研究所，天津，３０００７１）关键词γ－芳基取代烯丙醇，拟除虫菊酯，杀虫活性第一个人工合成除虫菊酯烯丙菊酯保留了天然除虫菊酯醇部分的环戊烯醇酮结构，至今仍广泛用作卫生杀虫...     

不对称环磷酸肟酯的合成和生物活性研究

通过反式-2-氯-2-氧-4-苯基-5,5-二甲基-1,3,2-二氧磷杂环己烷(Ⅱ)和α-氰基-芳基甲醛肟(Ⅰa-Ⅰf)在相转移催化条件下反应,制得新型的1,3,2-二氧磷杂环磷酸肟酯(Ⅲa_Ⅲf),产物中的非对映异构体经¹HNMR、³¹PNMR和单晶X射线衍射确证.但化合物Ⅱ与芳基甲醛肟反应,得到芳基甲腈和环磷酸,这可能是生成不稳定的环磷酸醛肟酯(Ⅳ)经Beckmann裂解所致.生物活性测试表明,化合物cis-Ⅲd具有很好的抗烟草花叶病毒活性.     

新型非酯型拟除虫菊酯类化合物的合成及其生物活性的研究(Ⅰ)

传统的拟除虫菊酯类杀虫剂均含有1个酯基。近些年来,相继合成了一些非酯型拟除虫菊酯化合物。在保持分子整体空间结构不变的情况下,用其它功能团替换酯基,已开发出肟醚菊酯、醚菊酯、烃菊酯和酮菊酯等高效低毒、结构简化的杀虫剂,其中醚菊酯已正式作为农药商品。作为拟除虫菊酯类化合物结构变化的新尝试,我们合成了10种非酯型拟除虫菊酯新化合物,它们属于N-芳基-3-甲基-3-(对乙氧基苯基)丁酰胺类化合物,结构如下:     

含肟酯类姜黄素衍生物的合成及其抗病毒活性

采用生物活性因子拼接法将肟酯引入单羰基姜黄素衍生物1,5-二取代芳基-1,4-戊二烯-3-酮中,合成了11个新型不对称1,5-二取代-1,4-戊二烯-3-酮肟酯类姜黄素衍生物,其结构经1H NMR,IR和元素分析表征.初步生物活性测试结果表明,部分化合物具有一定的抗黄瓜花叶病毒(CMV)活性.     

水相中2-氨基-4-芳基-5,6-二氢化-4H-吡喃并[3,2-c]喹啉-5-酮衍生物的合成

以芳亚甲基丙二腈或2-氰基-3-芳基丙烯酸酯和4-羟基喹啉-2-酮为原料, 水为溶剂, 在TEBA(三乙基苄基氯化铵)催化下90 ℃, 合成了2-氨基-4-芳基-5,6-二氢化-4H-吡喃[3,2-c]喹啉-5-酮衍生物. 和其它方法相比, 该反应具有反应条件温和, 产率高(87%～96%)和环境友好等优点. 产物的结构通过熔点, IR, ¹H NMR和元素分析表征. 化合物3m的结构通过X单晶衍射分析确证.     

超声辐射和相转移催化下肟苄醚的合成

在超声辐射和苄基十四烷基二甲基氯化铵作用下, 肟和苄基溴在NaOH水溶液中于室温反应30～60 min, 肟苄基醚的收率60%～96%, 反应时间短, 收率高, 对环境友好.     

Versatile Synthesis of Fused Tricyclic 1,2,4-Triazole Derivatives

ABSTRACT

A rapid and general method for the synthesis of symmetrical disulfides involves reaction of sulfur with sodium hydroxide under PTC-microwave irradiation condition to give sodium disulfide, which reacts with alkyl halides to afford the disulfides in good to excellent isolated yields.     

Efficient Synthesis of Some New 1,3,4‐Thiadiazoles and 1,2,4‐Triazoles Linked to Pyrazolylcoumarin Ring System as Potent 5α‐Reductase Inhibitors

The current study in this article concerned with construction of five‐membered heterocycles with multiple heteroatoms as nitrogen and sulfur from readily available starting materials and reagents. Treatment of 1‐(2‐oxo‐2H‐chromene‐3‐carbonyl)‐3‐phenyl‐1H‐pyrazol‐5(4H)‐one with each of phenylisothiocyanate in alcoholic potassium hydroxide and carbon disulfide in basic medium gave rise to a thioanilide and methylthio derivatives, respectively. Treatment of the latter compounds with a variety of hydrazonoyl halides resulted in construction of thiadiazole moiety linked to pyrazole ring. Furthermore, triazole derivatives were synthesized from the thioanilide derivative through its reaction with methyl iodide followed by reaction with hydrazonoyl halides. 5α‐Reductase inhibition activity for the prepared compounds was investigated against the reference drug anastrozole, and the results showed that the inhibition activity of compounds 5g and 11g is more potent than anastrozole. Also compounds bearing triazole moiety is more potent than compounds bearing thiadiazole one. Moreover, the anti‐prostate cancer screening anti‐androgenic bioassay in human prostate cancer cells for the tested compounds was evaluated, and the results showed great inhibition growth and potential antiandrogens.     

Replacing the carbonyl's oxygen with the difluoromethyl group

Aldehydes or ketones were reacted with 2-(trimethylsilyl)-1,3-dithiane (1) and the products reduced to the corresponding dithianes using tetrafluoroboric acid and sodium borohydride. These sulfur containing compounds were reacted with bromine trifluoride under mild conditions (1-2 min, 0 °C) with a net result of replacing the carbonyls' oxygen with the desired difluoromethyl moiety.     

Synthesis and biological activities of dithiocarbamates containing1,2,3-triazoles group

Twelve novel dithiocarbamates containing 1,2,3-trizaoles group were prepared via one step starting from organic halides, dithiocarbamic acid prop-2-ynyl ester, and sodium azide, using a very simple catalytic system composed of copper（I） chloride and water at 70 8C. The structures of the new compounds were characterized and screened for their in vitro anti-tumor. Four of the compounds displayed varying levels of anti-tumor activity against the CDC25 B.     

Derivatization of prostaglandins and related compounds to (methoxime) alkyl ester alkyl ether derivatives for gas chromatographic analysis

Rapid and convenient methods are described for the exhaustive derivatization of carbonyl, carboxyl and hydroxyl groups of prostaglandins and related compounds to methoxime, alkyl ester and alkyl ether compounds respectively. Optimal reaction conditions were established for each group. The reactions were carried out in polar aprotic solvents. Alkyl ester alkyl ether derivatives were obtained quantitatively and rapidly in one step with n-alkyl (C1-C4) halides in the presence of sodium hydroxide. Methyl ester methyl ether derivatives have the highest volatility, but propyl ester propyl ether derivatives improved the separation of complex mixtures. The carbonyl group sometimes induced side-products, so the carbonyl group was converted into methoxime. Methoximation was achieved quantitatively by using methoxylamine in the presence of hydrochloric acid or sodium hydroxide, followed by alkylation in same reaction medium. Methoximation gave syn- and anti-isomers, which were separated chromatographically, decreasing the resolution for complex samples.     

Preparation of trisodium O-monoalkyl and O-monoaryl diphosphates

Trisodium O-methyl, O-butyl, O-phenyl, and O-(4-nitrophenyl) diphosphates were synthesized from sodium dimethylamido-O-(2-cyanoethyl) phosphate and O-alkyl-and O-aryl phosphoric acids. While in the previously described method, sodium hydroxide was used for the preparation of O-phenyl diphosphate, in our current work, we present an improved protocol, where sodium methoxide is used to increase the yields of O-alkyl and O-aryl diphosphates. The structures of final compounds were determined by ¹H NMR, ³¹P NMR, and IR spectroscopy. The sodium O-alkyl- and O-aryl diphosphate salts prepared by this method may be used for the study of biological activity of diphosphate analogues.     

A Regioselective Synthesis of Novel Functionalized Organochalcogen Compounds by Chalcogenocyclofunctionalization Reactions Based on Chalcogen Halides and Natural Products

The regioselective synthesis of novel functionalized condensed organochalcogen compounds by chalcogenocyclofunctionalization reactions based on chalcogen halides and the natural products thymol and carvacrol has been developed. The reactions of selenium dibromide with allyl thymol and allyl carvacrol proceeded in methylene chloride at room temperature in the presence of NaHCO₃ affording bis[(7-isopropyl-4-methyl-2,3-dihydro-1-benzofuran-2-yl)methyl] and bis[(4-isopropyl-7-methyl-2,3-dihydro-1-benzofuran-2-yl)methyl] selenides in 90–92% yield. Similar sulfides were obtained in 70–72% yields by the reaction of sulfur dichloride in chloroform under reflux. Trihalotellanes containing the same organic moieties were synthesized from allyl thymol, allyl carvacrol and tellurium tetrachloride or tetrabromide in quantitative yields. Corresponding functionalized ditellurides were prepared in 91–92% yields by the reduction of the trichlorotellanes with sodium metabisulfite in two-phase solvent system. The comparison of reactivity of sulfur, selenium and tellurium halides in chalcogenocyclofunctionalization and distinguishing features of each reaction were discussed.     

Chemotherapeutic agents. IX. Synthesis and pesticidal activities of bis[4-aryl/alkyl-1, 2, 4-triazoline-5-thione-3-yl]alkanes and 1 -Aryl/alkyl-3-[4-(4-aryl/alkyl-1, 2, 4-triazoline-5-thione-3-yl)phenyl]thiourea and related compounds

Various bis[4-aryl/alkyl-1, 2, 4-triazoline-5-thione-3-yl]alkanes ( 3 ) were prepared from base cyclization of bis thiosemicarbazide 2 and transformed into sulphides by reaction with different alkyl halides in alkaline medium. These compounds were further oxidised to sulphones 5 with acidic potassium permanganate. 1-Aryl-3-[4-(4-aryl/alkyl-1, 2, 4-triazoline-3-thione-5-yl)phenyl]thioureas ( 8 ) were prepared in two steps from p-aminophenylhydrazide ( 6 ) and aryl/alkylisothiocyanates. Alkylation of 8 with different alkyl halides yielded exclusively sulphides 9 . Some sulphides 12 and Mannich bases 13 from 5-(p-fluorophenyl)-1, 3, 4-oxadiazol-2-thione ( 11 ) were also prepared to evaluate their pesticidal activities. All the prepared compounds were screened for pesticidal activities but none of them exhibited any significant activity.     

First enantioselective synthesis of vinyl oxiranes from aldehydes and ylides generated from allyl halides and chiral sulfides

Asymmetric allylidenation of aldehydes with sulfur ylides is possible with proper substitution of the initial sulfide, to avoid the [2,3] sigmatropic rearrangement of the unsaturated ylides. One-pot reaction of (2R,5R)-dimethylthiolane with allyl halides, aldehydes, and sodium hydroxide in tert-butyl alcohol affords vinyl oxiranes in good yields. Enantiomeric excesses up to 90% and trans selectivities have been achieved with methallyl-type halides.