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:     

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(Ⅱ)

非酯型拟除虫菊酯杀虫剂是近年来菊酯类杀虫剂研究的新进展。这是传统拟除虫菊酯结构中的酯基被其它官能团如肟醚基、醚键、亚甲基、羰基等替代后的化合物。作者曾报道用酰胺基替代酯基合成非酯型酰胺类菊酯化合物,所得化合物对家蝇亦具有一定的杀     

新型含异噁唑环醚菊酯的合成及生物活性研究

4异丙基 3 取代苯基 5 羟基异唑和 3 苯氧基苄基溴为原料 ,三乙胺为缚酸剂 ,设计并合成了 1 4个未见报道的 4 异丙基 3 取代苯基 5 异唑基 (3′ 苯氧基 )苄基醚。通过红外光谱、核磁共振、元素分析等手段 ,确证了它们的化学结构。初步的试验表明 ,其中 9个异唑醚菊酯化合物具有较强的生物活性 ,为新型拟除虫菊酯的创制提供了参考依据。Ｆｏｕｒｔｅｅｎｎｅｗｐｙｒｅｔｈｒｏｉｄｓｃｏｎｔａｉｎｉｎｇｉｓｏｘａｚｏｌｅｗｅｒｅｄｅｓｉｇｎｅｄａｎｄｓｙｎｔｈｅｓｉｚｅｄｆｒｏｍ 4 ｉｓｏｐｒｏｐｙ1 3 ｓｕｂｓ…     

丁香油酚酯新型杀虫剂的设计合成

拟除虫菊酯是一类在天然除虫菊酯化学结构研究的基础上发展起来的仿生杀虫剂,具有低毒、高效、广谱等特点,在农药及卫生方面得到广泛的应用[1-3]。为了进一步研究出对害虫和螨类具有高活性的除虫菊酯类化合物,设计各种各样的环和醚类除虫菊酯衍生物正成为努力的方向[4]。近年来     

α[O-烷基-O'-烷基(苯基)二硫代磷(膦)酸酯基]异戊酸间-苯氧基-α'-氰基苄酯的合成

本文合成了三类十个含磷拟除虫菊酯类新化合物-α-二硫代磷(膦)酸酯基异戊(乙)酸间-苯氧基-α'氰基苄酯,研究了其纯化条件.对部分中间体的制备方法作了改进.产物的结构经IR,^1H NMR 及元素分析证实,测定了部分产物的MS.对波谱中"异常"现象进行了讨论.     

含吡啶环拟除虫菊酯的合成及其杀虫杀螨活性

在新农药的创制中 ,吡啶作为苯环的生物等排体常被用作分子设计的有效基团 [1,2 ] ,近年来若干含有吡啶环的高效农药如吡虫啉 (Imidacloprid) [3 ] 、盖草能 (Haloxyfop) [4 ] 、啶氧菌酯 (Picoxystrobin) [5]等已被开发应用 .为合成筛选高生物活性化合物 ,我们在前期研究[6 ,7] 的基础上 ,将吡啶环引入拟除虫菊酯的酸部分 ,合成了与戊菊酯 (S- 5 4 3 9) [8] 和氰戊菊酯 (Fenvalerate) [8] 结构相近的新化合物 (5 ,6 ) ,并分离得到化合物 6的两对对映异构体 (α-和β-体 ) .生物活性测试表明 ,这些新化合物具有较高的杀虫或杀螨活性 .目标…     

一些炔菊酯类化合物的合成及其生物活性

拟除虫菊酯是一类高效低毒低残留的杀虫剂,１－芳氧基－４－氯－２－丁炔类化合物具有良好的生物活性［１,２］．为了寻找结构简单、新颖、高效、低毒、低残留的拟除虫菊酯类化合物,我们用此炔类化合物与拟除虫菊酯的菊酸部分相结合,合成了１６个未见报道的化合物,并...     

含嘧啶环的新拟除虫菊酯的合成及其生物活性的研究

拟除虫菊酯是一类高效、低毒、广谱性杀虫剂。嘧啶环是生物分子和医药中有较好活性的基团。本文拟在菊酯分子中引入嘧啶杂环,并测试其生物活性。我们以β-二酮为起始原料,分别与尿素、甲酰胺和脒缩合关环形成嘧啶,并进一步合成含嘧啶环的新拟除虫菊酯。所合成化合物的生物试验表明其中一些化合物对家蝇具有较好的击倒效应和杀虫效能。     

具有拟除虫菊酯活性的肟醚类化合物

本文报导一类具有拟除虫菊酯活性的肟醚类化合物的合成、结构特性及生物活性。其中某些化合物对粘虫等有很高杀虫活性而对温血动物急性毒性很低,有希望发展成一类新型杀虫剂。     

拟除虫菊酯学术讨论会在南京召开

江苏省化学化工学会和昆虫学会联合举办的拟除虫菊酯学术讨论会,于1979年3月18日至21日在南京召开。参加会议的有全国从事拟除虫菊酯研制工作的科研、教学、生产和行政等80多个单位,共100多位代表。拟除虫菊酯,是一类新型的高效、低毒、低残留杀虫剂。由于它杀虫效力强、治虫谱广、用药量少,对人畜无害又不污染环境等优点,所以被视为一类较理想的新农药,当前在国内外受到极大的重视。拟除虫菊酯在国际上发展很快。二氯苯醚菊酯,是拟除虫菊酯中第一个具有较高耐光性能、可用于防治农业害虫的新杀虫剂,1973年英国首先合成。以后,又相继出现了速灭菊酯(S-5602)、溴氰菊酯(Decis)等结构简单、特别高效的新拟除虫菊酯。对此,江苏省农药研究所副所长程暄生同志在会上作了“近代拟除虫菊酯杀虫剂的新进展”的报告,受到了与会者的好评。     

Fluoride-induced chemiluminescent decomposition of 1,2-dioxetanes bearing a phenyl moiety substituted with a methyl having an electron-withdrawing group

A new type of dioxetane bearing a 3-(cyanomethyl)phenyl (1a), 3-(methoxycarbonylmethyl)phenyl (1b), 3-(benzoylmethyl)phenyl (1c), or 3-[cyano(methoxycarbonyl)methyl]phenyl group (1d) decomposed through an intermediary dioxetane bearing a benzylic carbanion to afford crimson to yellow light on treatment with TBAF in DMSO.     

间氯苯基锰卟啉-5-氟尿嘧啶配合物的合成及其对癌细胞的抑制活性

合成了4种新5-氟尿嘧啶-卟啉衍生物：5-[3-(2-(5-氟尿嘧啶-1-基)乙氧基)苯基]-10,15,20-三(3-氯苯基)卟啉(1a)、5-[3-(2-(5-氟尿嘧啶-1-基)乙氧基)苯基]- 10,15,20-三(3-氯苯基)锰卟啉(2a)、5-[3-(3-(5-氟尿嘧啶-1-基)丙氧基)苯基]-10,15,20-三(3-氯苯基)锰卟啉(2b)和5-[3-(4-(5-氟尿嘧啶-1-基)丁氧基)苯基]-10,15,20-三(3-氯苯基)锰卟啉(2c),通过UV-Vis、IR、MS及元素分析表征了它们的结构。 用噻唑蓝法（MTT法）测定了化合物2a、2b和2c对人胃癌细胞株BGC-823的抑制活性。 化合物2b的半数抑制浓度IC50为1.34 μmol/L,表明有一定的细胞毒作用。     

Synthesis of 3‐phenyl‐5‐(trifluoromethyl)isoxazole and 5‐phenyl‐3‐(trifluoromethyl)isoxazole

Reaction of 4,4,4‐trifluoro‐1‐phenyl‐1,3‐butanedione with hydroxylamine led to the formation of 5‐hydroxy‐3‐phenyl‐5‐(trifluoromethyl)‐4,5‐dihydroisoxazole which was dehydrated to 3‐phenyl‐5‐(trifluoro‐methyl)isoxazole. This isomer can also be synthesized by reaction of 4‐chloro‐4‐phenyl‐1,1,1‐trifluoro‐3‐buten‐2‐one with sodium azide. The regioisomer, 5‐phenyl‐3‐(trifluoromethyl)isoxazole was synthesized by reaction of 1,1,1‐trifluoro‐4‐phenylbut‐3‐yn‐2‐one with hydroxylamine and by the reaction of 3‐chloro‐1‐phenyl‐4,4,4‐trifluorobut‐2‐en‐1‐one with sodium azide. Both isomers were characterized by mass and NMR spectroscopy.     

无溶剂无催化剂微波促进下 1-苯基-3-甲基-5-吡唑啉酮与芳醛的反应研究

无溶剂无催化剂条件下,微波促进1-苯基-3-甲基-5-吡唑啉酮与芳醛的缩合反应选择不同辐射功率将分别得到4-芳亚甲基-3-甲基-1-苯基-5-吡唑啉酮和4,4′-芳亚甲基-双(1-苯基-3-甲基-5-吡唑啉酮),产率良好.产物结构经1H NMR,13CNMR和IR进行了表征.     

Preparation of Optically Active Six‐Membered P‐Heterocycles: A 3‐Phosphabicyclo[3.1.0] hexane 3‐oxide,a 1,2‐Dihydrophosphinine 1‐oxide,and a 1,2,3,6‐Tetrahydrophosphinine 1‐oxide

The earlier described a 3‐methyl‐1‐phenyl‐3‐phospholene 1‐oxide ( 1 ) → 6,6‐dichloro‐1‐methyl‐3‐phenyl‐3‐phosphabicyclo[3.1.0]hexane 3‐oxide ( 2 ) → 4‐chloro‐1‐phenyl‐1,2‐dihydrophosphinine 1‐oxide ( 3 ) → 4‐chloro‐5‐methyl‐1‐phenyl‐1,2,3,6‐tetrahydrophosphinine 1‐oxide ( 4 ) reaction sequence was investigated from the point of view of preparing optically active intermediates/products ( 2–4 ). In principle, both the resolution of the corresponding racemic products and the transformation of the optically active starting materials are suitable approaches for the preparation of optically active six‐membered P‐heterocycles ( 2–4 ). Racemization occurred during the dichlorocyclopropanation reaction of (S)‐3‐methyl‐1‐phenyl‐3‐phospholene 1‐oxide ((S)‐ 1 ), but the thermolytic ring opening of (−)‐ 2, and the selective reduction of α,β‐double bond of (−)‐ 3 did not cause the loss of optical activity. First in the literature, the resolution of a 3‐phosphabicyclo[3.1.0]hexane 3‐oxide ( 2 ) and a 1,2,3,6‐tetrahydrophosphinine 1‐oxide ( 4 ) was elaborated. © 2013 Wiley Periodicals, Inc. Heteroatom Chem 24:179–186, 2013; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.21080     

Studies on the Reactivity of Amino‐1‐(6‐phenyl‐pyridazin‐3‐yl)‐1H‐pyrazole‐4‐carboxylic Acid Hydrazide Towards Some Reagents for Biological Evaluation

Novel 5‐amino‐1‐(6‐phenyl‐pyridazin‐3‐yl)‐1H‐pyrazole‐4‐carboxylic acid ethyl ester ( 2 ) was formed using (6‐phenyl‐pyridazin‐3‐yl)‐hydrazine ( 1 ) and ethyl(ethoxymethylene)cyanoacetate. The β‐enaminoester derivative 2 was in turn used as precursor for the preparation of 1‐(6‐phenyl‐pyridazin‐3‐yl)‐pyrazoles ( 3 , 4 , 7 , 8 , 9 , 10 , 11 , 12 , 15 , 16 ), 1‐(6‐phenyl‐pyridazin‐3‐yl)‐pyrazolo[3,4‐d]pyrimidines ( 5 , 6 , 14 ) and 1‐(6‐phenyl‐pyridazin‐3‐yl)‐pyrazolo[3,4‐d][1,2,3]triazine ( 13 ). The in vitro antimicrobial activity of the synthesized compounds was evaluated by measuring the inhibition zone diameters where some of them showed potent antimicrobial activity in compared with well‐known drugs (standards).     

Quinolone Analogues 15: Synthesis and Antimalarial Activity of 4‐Phenyl‐1‐(1‐triazolylmethyl‐4‐quinolon‐3‐ylcarbonyl)semicarbazide and Related Compounds

The 1‐hydrazinocarbonylmethyl‐4‐quinolone‐3‐carboxylate ( 10 ) was converted into the 1‐(4‐amino‐1,2,4‐triazol‐3‐ylmethyl)‐4‐quinolone‐3‐carboxylic acid ( 13 ), whose reaction with arylcarbaldehydes gave the 1‐(4‐arylmethyleneamino‐1,2,4‐triazol‐3‐ylmethyl)‐4‐quinolone‐3‐carboxylic acids ( 5a , 5b , 5c , 5d , 5e , 5f , 5g ). Compound 10 was also transformed into the 1‐(4‐amino‐1,2,4‐triazol‐3‐ylmethyl)‐4‐quinolone‐3‐carbohydrazide ( 15 ), whose reaction with phenyl isocyanate or phenyl isothiocyanate afforded the 4‐phenyl‐1‐(1‐triazolylmethyl‐4‐quinolon‐3‐ylcarbonyl)semicarbazide ( 6a ) or 4‐phenyl‐1‐(1‐triazolylmethyl‐4‐quinolon‐3‐ylcarbonyl)thiosemicarbazide ( 6b ), respectively. Compounds 6a , 6b showed the in vitro antimalarial activity to chloroquine‐resistant Plasmodium falciparum, wherein their IC₅₀ was 3.89 and 3.91 μM, respectively.     

Synthesis of 4‐(1‐phenyl‐1H‐pyrazol‐3‐yl)‐[1,2,4]triazolo[4,3‐a]quinoxalines and their 4‐halogenopyrazolyl analogs

Synthesis of {3‐[1‐(ethoxycarbonyl)‐[1,2,4]triazolo[4,3‐a]quinoxalin‐4‐yl]‐1‐phenyl‐1H‐pyrazol‐5‐yl}methyl ethyl oxalate ( 2 ), ethyl 4‐[5‐(acetoxymethyl)‐1‐phenyl‐1H‐pyrazol‐3‐yl]‐[1,2,4]triazolo[4,3‐a]quioxaline‐1‐carboxylate ( 4 ), [4‐halo‐1‐phenyl‐3‐(1‐phenyl‐[1,2,4]triazolo[4,3‐a]quioxalin‐4‐yl)‐1H‐pyrazol‐5‐yl]methyl acetate ( 11 ), {4‐halo‐3‐[1‐methyl‐[1,2,4]triazolo[4,3‐a]quinoxalin‐4‐yl]‐1‐phenyl‐1H‐pyraz‐ol‐5‐yl}methyl acetate ( 13 ), and [3‐([1,2,4]triazolo‐[4,3‐a]quinoxalin‐4‐yl)‐4‐halo‐1‐phenyl‐1H‐pyrazol‐5‐yl] methyl formate ( 15 ) was accomplished. The structural investigation of the new compounds is based on chemical and spectroscopic evidences. J. Heterocyclic Chem., (2011)     

对甲苯磺酸催化下二乙酰苯与含有羟基的苯甲醛的Aldol缩合反应

以对甲苯磺酸(p-TsOH)作催化剂, 二乙酰苯与含有羟基的苯甲醛发生aldol缩合反应, 合成了3个1,3-双[3-(取代苯基)丙烯酰基]苯衍生物1～3, 3个1,4-双[3-(取代苯基)丙烯酰基]苯衍生物4～6和2个中间体7, 8, 中间体7, 8再与含有羟基的苯甲醛发生aldol反应合成了3个1-[3-(4-羟基苯基)丙烯酰基]-4-[3-(取代苯基)丙烯酰基]苯衍生物9～11, 反应均能在2～6 d内完成, 操作和后处理简便. 以上11个新化合物均未见报道, 其结构经1H NMR, IR, MS和HRMS加以确证.     

Synthesis and electropolymerization studies of non-aggregated (4-{3-[3-(dimethylamino,diethylamino)phenoxy]propoxy}phenyl)propanoxy substituted silicon naphthalocyanines

In this study, 3-(4-{3-[3-(dimethylamino)phenoxy]propoxy}phenyl)propan-1-ol, 3-(4-{3-[3-(diethylamino)phenoxy]propoxy}phenyl)propan-1-ol and axially disubstituted silicon naphthalocyanines (SiNc) bearing electropolymerizable bis-[(4-{3-[3-(dimethylamino)phenoxy]propoxy}phenyl)propanoxy] and bis-[(4-{3-[3-(diethylamino)phenoxy]propoxy}phenyl)propanoxy] units were synthesized for the first time. Aggregation behavior of SiNcs was examined in different solvents and concentrations in DMSO. In all solvents and concentrations, SiNcs were non-aggregated. Also, electrochemical studies of SiNcs were investigated by cyclic and square wave voltammetry. While SiNcs gave only naphthalocyanine-based reduction process during the cathodic potential scans, they were electropolymerized on the working electrode during the anodic potential scan because of the oxidative electropolymerization of (4-{3-[3-(dimethylamino)phenoxy]propoxy}phenyl)propanoxy and (4-{3-[3-(diethylamino)phenoxy]propoxy}phenyl)propanoxy groups on the substituents of the complexes.