1-酰基苯并咪唑酮酰胺衍生物的合成及其抗菌活性

以邻苯二胺和乙酰乙酸乙酯为起始原料制得异丙烯基苯并咪唑酮(Ⅲ),再经N-酰化反应得到13个苯并咪唑酮酰胺衍生物(Ⅳ-01～Ⅳ-13)以及由Ⅳ-02脱异丙烯基的产物Ⅳ-02a,其中9个为未见文献报道的新化合物。通过核磁共振氢谱和碳谱、质谱以及元素分析对其结构进行了表征。抑菌活性测定结果表明,化合物Ⅳ-01～Ⅳ-03、Ⅳ-11及Ⅳ-02a对供试病原细菌和真菌均表现出明显的抑菌活性,其中化合物Ⅳ-02和Ⅳ-02a尤为突出,且二者活性相近,其中Ⅳ-02对蜡状芽孢杆菌Bacillus cereus(1.184 6)、枯草芽孢杆菌Bacillus subtilis(1.88)、金黄色葡萄球菌Staphylococcus aureus(1.89)和大肠杆菌Escherichia coil(1.157 4)的MIC(抑制生长的最低浓度)值分别为0.78、12.5、1.56和1.56 μg/mL,对番茄灰霉病菌Botrytis cinerea的有效抑制中浓度(EC50)为7.02 μg/mL。     

Synthesis and insecticidal activity of new pyrethroids

BACKGROUND: Pyrethroids are among the most potent pesticides known, with great potential for structural variation with retention or enhancement of potency. The simple methyl ester is easier to prepare (at least one step shorter) than the more complex pyrethroids modified on the alcohol moiety. The objective was to synthesise methyl esters of pyrethroid acids containing an aromatic ring on the acid moiety and evaluate their biological activity against Ascia monuste orseis Latr., Tuta absoluta Meyrick, Periplaneta americana (L.), Musca domestica L. and Sitophilus zeamais (Motsch.). RESULTS: The synthetic sequence required seven steps: protection of the hydroxyl groups of D ‐mannitol, diol oxidative cleavage with sodium metaperiodate, alkene formation by Wittig reaction with methoxycarbonylmethylidene(triphenyl)phosphorane, cyclopropanation, acetal hydrolysis with perchloric acid and oxidative cleavage with sodium metaperiodate gave methyl (1S, 3S)‐3‐formyl‐2,2‐dimethylcyclopropane‐1‐carboxylate. The final step comprised reaction of the aldehyde with five different aromatic phosphorus ylides to give the pyrethroids. CONCLUSION: An efficient and versatile synthesis of ten new pyrethroid methyl esters has been accomplished from the readily available D ‐mannitol in seven steps. All compounds showed insecticidal activity, and methyl (1S, 3S)‐3‐[(Z)‐2‐(4‐chlorophenyl)vinyl]‐2,2‐dimethylcyclopropane‐1‐carboxylate was the most active, killing 90% of A. monuste orseis and 100% of T. absoluta and P. americana. Copyright © 2009 Society of Chemical Industry     

含苯并咪唑环的1,3,4-噻二唑酰胺衍生物的合成与抑菌活性

为寻找新型活性杂环化合物,通过活性亚结构拼接,以取代苯酚和氯乙酸为起始原料,经醚化、缩合、烃基化和氨解反应,设计并采用微波辅助合成了6种未见文献报道的含苯并咪唑环的1,3,4-噻二唑酰胺衍生物,其结构经红外和核磁共振氢谱确证。初步抑菌活性测试结果表明,所有目标化合物对5种供试病原菌都表现出一定的抑菌活性,其中,化合物7c、7d、7e和7f在50 mg/L下对5种供试病原菌的抑制率均达到80%以上。     

姜黄素异噁唑和吡唑衍生物的合成及杀螨活性

为了开发基于天然产物的新型杀螨剂,以胡椒碱为先导化合物,设计并合成了26个含1,3,4-噁二唑杂环的胡椒碱类衍生物 8a ~ 8z ,并经核磁共振氢谱 (或碳谱)、红外光谱和高分辨质谱确证其结构。化合物 8g 通过X-射线单晶衍射确定其空间构型。采用玻片浸渍法测定了系列化合物对朱砂叶螨Tetranychus cinnabarinus Boisduval雌成螨的触杀活性。结果表明：化合物 8m (LC₅₀：0.41 mg/mL)、 8r (LC₅₀：0.36 mg/mL) 及 8u (LC₅₀：0.32 mg/mL) 表现出良好的杀螨活性,其活性分别为胡椒碱 (LC₅₀：15.64 mg/mL) 的38.1、43.4及48.9倍,且化合物 8u 在0.3 mg/mL质量浓度下对朱砂叶螨有较好的室内防治效果,施药后第5天的防治效果为61.8%。构效关系分析发现：在胡椒碱C2位引入1,3,4-噁二唑杂环有利于提高其杀螨活性,且杀螨活性与噁二唑苯环上的取代基密切相关。     

Synthesis and insecticidal activity of nitroguanidine derivatives

Nitroguanidine derivatives with thiazol-5-ylmethyl moieties were prepared and their insecticidal activities against homopterous pests were tested. New synthetic routes for 2-chloro-5-chloromethylthiazole from 2,3-dichloro-1-propene and for substituted nitroguanidines from S-methyl-N-nitroisothiourea were established. Biological evaluation led to a novel insecticide (E)-1-(2-chlorothiazol-5-ylmethyl)-3-methyl-2-nitroguani dine (TI-435) which has a broad activity spectrum and is under development. ©1999 Society of Chemical Industry     

嘧啶酮类衍生物的合成及杀虫活性

为了创制高效广谱的绿色杀虫剂,以(E)-4,5-二氢-6-甲基-4-(3-吡啶亚甲基氨基)-1,2,4-三嗪-3(2H)-酮(吡蚜酮)为先导,用带有不同电荷密度的五元、六元取代苯环或杂环取代其结构中的吡啶环部分,合成了10个全新的嘧啶酮类衍生物,特别对其中所包含的三嗪环和二氢喹唑啉酮合成部分进行了重点研究。所有目标化合物的结构均经过核磁共振氢谱、高分辨质谱及红外光谱的确认。初步杀虫活性测试结果表明,目标化合物对蚜虫Aphis craccivora未表现出明显的杀虫活性,初步暗示了先导化合物吡蚜酮结构中所含的吡啶环部分可能对其杀虫活性起了重要作用。     

新型氯虫苯甲酰胺衍生物的合成及其杀虫活性

以氯虫苯甲酰胺为先导,设计并合成了一系列结构新颖的邻氨基苯甲酰胺类衍生物,其结构均经核磁共振氢谱和质谱确证。初步杀虫活性测试结果表明,在质量浓度为1μg/mL时,部分化合物对小菜蛾Plutella xylostella的致死率均超过90%,高于先导化合物氯虫苯甲酰胺。     

细交链孢菌酮酸及其衍生物的合成与杀虫活性

为了寻找具有较高杀虫活性的特胺酸化合物,以天然活性产物细交链孢菌酮酸(TeA)作为先导化合物,利用酰基化米氏酸作为酰基化试剂,设计、合成了26个3-位不同酰基取代和5-位不同取代的含特胺酸骨架衍生物 4a~4s、5a~5g、7a 和 8a ,其中14个化合物未见文献报道,所有目标化合物的结构均经核磁共振氢谱、碳谱和高分辨质谱确证。初步杀虫活性测定结果表明,在100 μg/mL下处理72 h内,所有目标化合物对麦长管蚜Macrosiphum avenae (Fabricius)均表现出良好的杀虫活性,并具有内吸性,其中化合物 5d 和 7a 48 h致死率为100%,高于对照药剂螺虫乙酯,具有作为先导化合物进一步研究的价值。对处理后的小麦植株进行残留量测定,结果表明目标化合物 4e、5c、7a 和 8a 能被植株较好的吸收 。 该研究结果可为进一步研究具有特胺酸骨架化合物的构效关系提供参考。     

Synthesis,insecticidal activity and pyrethroidal mode of action of new tin ether derivatives

A novel range of trimethylstanniomethyl ethers of well known pyrethroid alcohols were synthesised, and their insecticidal activities and modes of action as insecticides were investigated. Among them, ethers from three types of alcohol (3-phenoxybenzyl, 4-fluoro-3-phenoxybenzyl and 6-phenoxy-2-pyridylmethyl) showed remarkable insecticidal activities against rice stem borers, houseflies and German cockroaches. According to electrophysiological studies on the abdominal nerve cords of German cockroaches, trimethylstanniomethyl 6-phenoxy-2-pyridylmethyl ether induced a rapid decline in spontaneous firing similar to that from tetramethrin. However, insecticidal trimethyltin chloride caused an entirely different response. These observations suggest that the present tin ether derivatives resemble pyrethroids, rather than the insecticidal tin compounds known so far.     

Synthesis and insecticidal evaluation of N-substituted 2-nitroiminoimidazolidines

N-substituted and N,N′-disubstituted 2-nitroiminoimidazolidines were prepared from 2-nitroiminoimidazoline. The feeding-contact and systemic activities as insecticides of some of these new compounds have been evaluated. © 1998 Society of Chemical Industry     

Comparison of anti-feedant and insecticidal activity of nimbin and salannin photo-oxidation products with neem (Azadirachta indica) limonoids

Photo-oxidation of the neem limonoids nimbin and salannin with UV light in the presence of oxygen gives two isomeric lactone products per limonoid, nimbinolide and isonimbinolide, and salanninolide and isosalanninolide, respectively. When compared in insect tests with the important limonoids of neem seeds, azadirachtin, nimbin and salannin, isonimbinolide and isosalanninolide show activity greater than that of nimbin or salannin and in some respects show activity approaching that of azadirachtin. The photo-oxidation products were tested for anti-feedant activity and toxicity against larvae of three species of Lepidoptera, Spodoptera littoralis (Boisd), Spodoptera frugiperda (FE Smith) and Helicoverpa armigera (Hübner) and nymphs of the locusts Schistocerca gregaria (Forsk?l) and Locusta migratoria (L).     

2-噻唑酰氨基环己烷基磺酰胺的合成与杀菌活性

为进一步研究环烷基磺酰胺类化合物的杀菌活性与构效关系,在前期工作基础上,合成了11个未见文献报道的2-噻唑酰氨基环己烷基磺酰胺类化合物 ( 7a ~ 7k ),其结构均经1H NMR、13C NMR、质谱和元素分析确证。分别采用菌丝生长速率法、黄瓜活体叶片法、孢子萌发法和番茄活体盆栽法对目标化合物进行了生物活性测定。结果表明:目标化合物对番茄灰霉病菌Botrytis cinerea表现出较好的抑制活性,其中化合物 7a 和 7c 在10 mg/L下对番茄灰霉病菌孢子萌发的抑制率分别为90%和67%;在200 mg/L 施药剂量下,对活体黄瓜叶片、番茄叶片和番茄花上灰霉病的防治效果,化合物 7a 分别为75%、78%和30%,化合物 7c 分别为78%、62%和44%,均优于对照药剂腐霉利,有进一步研究的价值。     

Synthesis and structure–activity relationships of carbohydrazides and 1,3,4‐oxadiazole derivatives bearing an imidazolidine moiety against the yellow fever and dengue vector,Aedes aegypti

BACKGROUND

1,3,4‐Oxadiazole and imidazolidine rings are important heterocyclic compounds exhibiting a variety of biological activities. In this study, novel compounds with oxadiazole and imidazolidine rings were synthesized from 3‐(methylsulfonyl)‐2‐oxoimidazolidine‐1‐carbonyl chloride and screened for insecticidal activities. The proposed structures of the 17 synthesized compounds were confirmed using elemental analysis, infrared (IR), proton nuclear magnetic resonance (¹H‐NMR), and mass spectroscopy.

RESULTS

None of the compounds showed larvicidal activity at the tested concentrations against first‐instar Aedes aegypti larvae. However, nine compounds exhibited promising adulticidal activity, with mortality rates of ≥80% at 5 µg per mosquito. Further dose–response bioassays were undertaken to determine median lethal dose (LD₅₀) values. Compounds 1 , 2b , 2c , 2d , 2 g , 3b , 3c , 3 g, and 3 h were effective, with typical LD₅₀ values of about 5 ? 10 µg per mosquito against female Ae. aegypti. Compounds 2c (bearing a nitro group on the aromatic ring; LD₅₀ = 2.80 ± 0.54 µg per mosquito) and 3 h ( double halogen groups at 2,4 position on the phenyl ring; LD₅₀ = 2.80 ± 0.54 µg per mosquito) were the most promising compounds.

CONCLUSION

Preliminary mode of action studies failed to show consistent evidence of either neurotoxic or mitochondria‐directed effects. Further chemical synthesis within this series may lead to the development of new effective insecticides. © 2017 Society of Chemical Industry

     

松油烯-4-醇酯类衍生物的合成及杀虫活性

松油烯-4-醇具有较高的生物活性,在前期研究基础上,以松油烯-4-醇为原料,对其羟基进行改造,合成了12个松油烯-4-醇酯类衍生物 Z1~Z12,其中Z3、Z4、Z8、Z9、Z10、Z11、Z12为新化合物。所有化合物的结构均经核磁共振氢谱、碳谱及质谱确证。初步杀虫活性测定结果表明:各化合物对粘虫均有一定的触杀作用,其中Z5 活性最高,其LD50值为0.072 8 mg/头,为松油烯-4-醇的1.32倍;除 Z9 外,其余11个化合物对家蝇均具有一定的熏蒸作用,但其毒力均低于松油烯-4-醇。