CN103864694A - 一种含氟苯甲酰脲苯并咪唑类化合物及其应用 - Google Patents
一种含氟苯甲酰脲苯并咪唑类化合物及其应用 Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/06—Benzimidazoles; Hydrogenated benzimidazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
- C07D235/10—Radicals substituted by halogen atoms or nitro radicals
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
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- Plant Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
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- Agricultural Chemicals And Associated Chemicals (AREA)
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Abstract
本发明公开了一种含氟苯甲酰脲苯并咪唑类化合物及其应用,其结构如式I所示:
Description
技术领域本发明属于化学合成农药领域,涉及一种含氟苯甲酰脲苯并咪唑类化合物及其作为杀虫剂、杀菌剂的应用。
背景技术酰基脲类化合物具有杀虫、杀螨、杀菌、抗病毒等方面的活性,含氟苯甲酰脲类杀虫剂具有活性高、杀虫谱广、选择性强、环境友好等特点,成为目前杀虫剂的重要品种之一,如已商品化的氟铃脲、氟酰脲、氟虫脲、伏虫隆、定虫隆等已有广泛应用。毛春晖等人报道了一些含有酰基脲桥结构的双酰肼衍生物具有杀幼虫活性(毛春晖,汪清民等,含有脲桥结构的双酰肼衍生物的合成和杀虫活性研究,有机化学,2006,26(1):60-64。)。苯并咪唑类化合物具有良好的杀菌活性(张英,杨松等,苯并咪唑类化合物杀菌活性的研究进展,农药,2008,47(3):164-170。),如已商品化的噻菌灵、苯菌灵、多菌灵是高效、广谱、低毒杀菌剂。有报道称在分子中引入三氟甲基可提高化合物的亲脂性,从而提高对生物体膜和组织的渗透性及同生物体反应时的电子吸引性,增强化合物的生理活性(李汝麟,含三氟甲基芳香化合物的特性与应用,有机氟工业,1992,2:14-30。)。刘晨江等报道了含三氟甲基苯并咪唑的硫脲类化合物的合成方法(刘晨江,时天昊,李燕萍等,含2-三氟甲基苯并咪唑的1,3,4-噻二唑的合成,化学通报,2006,12:948-950。时天昊,刘晨江,李燕萍等,含2-三氟甲基苯并咪唑的1,2,4-三唑的合成,精细化工,2006,23(4):411-413。)根据基团贡献加和原理,本发明将三氟甲基苯并咪唑和含氟苯甲酰脲基团引入同一分子中,设计合成了一种含氟苯甲酰脲苯并咪唑类化合物,具体为:N′-(2-三氟甲基-1-基)乙酰基-N-(2,6-二氟苯甲酰基)氨基甲酰肼,其结构式如式Ⅰ所示。并试验了该化合物的杀虫、杀菌活性,旨在提供一种高效低毒的杀虫杀菌剂。在现有技术中如本发明所述的式I化合物及应用性能未见公开。
发明内容本发明的目的在于提供一种含氟苯甲酰脲苯并咪唑类化合物及其制备方法,该化合物属于高效安全的绿色化学杀虫杀菌剂,它可用于农业或林业虫害菌害的防治。
本发明的技术方案如下:
一种含氟苯甲酰脲苯并咪唑类化合物为N′-(2-三氟甲基-1-基)乙酰基-N-(2,6-二氟苯甲酰基)氨基甲酰肼,其结构式如式Ⅰ所示。
本发明如式I所示化合物可由如下方法制备:
具体分为以下步骤:
1.2-三氟甲基苯并咪唑(II)的合成:
在有聚磷酸和磷酸存在下,邻苯二胺和三氟乙酸在乙二醇中搅拌加热回流反应,生成2-三氟甲基苯并咪唑(II)。
2.2-三氟甲基苯并咪唑-1-基乙酸乙酯(III)的合成:
2-三氟甲基苯并咪唑(II)在1,4-二氧六环中与NaH反应生成2-三氟甲基苯并咪唑钠盐,然后再与2-溴乙酸乙酯反应生成2-三氟甲基苯并咪唑-1-基乙酸乙酯(III)。在反应中加入促进剂KI和催化剂四丁基溴化铵,可以提高反应速度。
3.2-三氟甲基苯并咪唑-1-乙酰肼(Ⅳ)的合成:
2-三氟甲基苯并咪唑-1-基乙酸乙酯(III)与水合肼在乙醇中搅拌加热回流反应得2-三氟甲基苯并咪唑-1-乙酰肼(Ⅳ)。
4.2,6-二氟苯甲酰基异氰酸酯(Ⅴ)的合成:
2,6-二氟苯甲酰胺与草酰氯在甲苯中反应得2,6-二氟苯甲酰基异氰酸酯(Ⅴ)。
5.N′-(2-三氟甲基-1-基)乙酰基-N-(2,6-二氟苯甲酰基)氨基甲酰肼(I)的合成:
以二月桂酸二丁基锡作催化剂,2-三氟甲基苯并咪唑-1-乙酰肼(Ⅳ)与2,6-二氟苯甲酰基异氰酸酯(Ⅴ),在1,2-二氯乙烷中搅拌下加热回流反应,生成N′-(2-三氟甲基-1-基)乙酰基-N-(2,6-二氟苯甲酰基)氨基甲酰肼(I)。反应结束后旋蒸除去溶剂,剩余物加入冰水中析出固体。抽滤得淡黄色固体粗产物。将粗产物加入到二氯甲烷中搅拌溶解掉未反应的2,6-二氟苯甲酰基异氰酸酯,抽滤得白色固体,烘干即得产物。
本发明的优点和积极效果:由于本发明化合物既含有杀虫活性的2,6-二氟苯甲酰脲基团,又含有杀菌活性的三氟甲基苯并咪唑基团,故本化合物是一种兼具高杀虫活性与高杀菌活性的高效、低毒杀虫杀菌剂,而且苯并咪唑和酰脲类化合物易生物降解,属环境友好型产品。本化合物合成方法简单,不需要特殊设备,易于实现工业化生产。本发明化合物为具有杀虫、杀菌活性的新化合物,为新农药的研发提供了基础。
本发明化合物在防治病虫害时,可单独使用也可与其它活性物质组合使用以提高产品的综合性能。该杀虫或杀菌组合物还包括农业或林业上可接受的载体。
具体实施方式
下列合成实施例或生测实验结果可用来进一步说明本发明,但不意味着限制本发明。
合成实例
实施例1、化合物N′-(2-三氟甲基-1-基)乙酰基-N-(2,6-二氟苯甲酰基)氨基甲酰肼(I)的制备:
(1)2-三氟甲基苯并咪唑(Ⅱ)的合成:
在250mL三口烧瓶中,加入0.10mol(10.80g)邻苯二胺,0.12mol(13.68g)三氟乙酸,20mL聚磷酸,20mL磷酸,100mL乙二醇,搅拌下加热至回流反应3小时。用薄层色谱法(TLC法)跟踪反应进程,展开剂V(乙酸乙酯):V(石油醚)=1:1。待原料邻苯二胺的点基本消失后结束反应。加入NaOH饱和溶液中和至pH值约为8,析出沉淀,经抽滤、水洗、干燥后得淡紫色粉末16g,产率86%。毛细管法测熔点为:206~210℃。
1HNMR(500MHz,DMSO),δ/ppm:7.38-7.41(2H,ArH),7.72-7.74(2H,ArH),5.0(1H,NH)。
IR:υ(cm-1):1631(N-H),1463(C=N),1288(C-N),1553,1551,1402(Ar,C=C),1172(C-F),741(ArX-H)
(2)2-三氟甲基苯并咪唑-1-基乙酸乙酯(III)的合成:
在250mL三口烧瓶中,加入120mL经无水硫酸镁干燥的1,4-二氧六环,0.10mol(18.60g)2-三氟甲基苯并咪唑(Ⅰ),搅拌使其溶解。在冰水浴冷却下加入0.10mol(2.40g)NaH(以80%质量比例分散于硅胶中),搅拌反应半小时。将0.10mol(16.70g)2-溴乙酸乙酯溶于30mL1,4-二氧六环中,撤去冰水浴,在室温下缓慢滴加入反应瓶中。滴加完毕后,加入3~4gKI作反应促进剂,加入约0.4g四丁基溴化铵作反应催化剂,搅拌下回流反应约8~10小时。用薄层色谱法(TLC法)跟踪反应进程,展开剂V(乙酸乙酯):V(石油醚)=1:3。待原料Ⅰ的点基本消失后结束反应。先抽滤除去硅胶,将溶液以旋转蒸馏仪除去溶剂,剩余物加入水中溶解,再用乙酸乙酯萃取,分去水层,有机相用无水硫酸镁干燥,过滤,旋蒸除去乙酸乙酯得油状液25g,产率92%。
1HNMR(500MHz,DMSO),δ/ppm:7.258-7.704(m,4H,ArH),4.702(s,2H,CH2),4.122-4.136(q,J=7.2Hz,2H,CH2),1.306-1.320(t,J=7.2Hz,3H,CH3)。
(3)2-三氟甲基苯并咪唑-1-乙酰肼(Ⅳ)的合成:
在250mL三口烧瓶中,加入0.08mol(21.76g)2-三氟甲基苯并咪唑-1-基乙酸乙酯(Ⅱ),0.2mol(12.50g)80%的水合肼溶液,100mL95%乙醇,搅拌加热回流反应10小时。用薄层色谱法(TLC法)跟踪反应进程,展开剂V(乙酸乙酯):V(石油醚)=1:5。待原料Ⅱ的点基本消失后结束反应。将反应液倒入水中析出固体,抽滤。滤液旋蒸除去乙醇,再抽滤,合并固体,烘干得略带粉色的白色固体15.50g,产率75.1%。用95%乙醇进行重结晶得白色固体,毛细管法测熔点为:230~232℃。
1HNMR(500MHz,DMSO),δ/ppm:9.502(s,1H,CONH),7.374-7.403(t,J=14.5Hz,1H,ArH),7.450-7.481(t,J=15.5Hz,1H,ArH),7.678-7.695(d,J=8.5Hz,1H,ArH),7.821-7.837(d,J=8.0Hz,1H,ArH),5.066(s,2H,CH2),4.081-4.112(q,J=5Hz,2H,NH2)
(4)2,6-二氟苯甲酰基异氰酸酯(Ⅴ)的合成:
在装有搅拌器、温度计、恒压漏斗、顶端连接干燥管的回流冷凝管和氯化氢吸收装置(5~10%的氢氧化钠水溶液)的250mL四口烧瓶中加入0.1mol(15.8g)2,6-二氟苯甲酰胺,120mL甲苯作溶剂,常温搅拌约5分钟,搅拌下缓慢滴加0.16mol(20g)草酰氯。滴加完毕后升温至50℃左右反应2~3小时。用薄层色谱法(TLC法)跟踪反应进程,展开剂V(乙酸乙酯):V(石油醚)=2:1。待原料2,6-二氟苯甲酰胺的点基本消失后结束反应。将反应液旋蒸除去甲苯溶剂和过量的草酰氯,蒸出物测定草酰氯的含量,可循环套用。剩余物冷却后析出白色固体,抽滤,固体用少量甲苯洗涤,烘干,得白色粉末17.57g,产率96%。毛细管法测熔点为:138~141℃。
1HNMR(500MHz,CD3Cl),δ/ppm:6.93-6.95(2H,ArH),7.51-7.53(1H,ArH)。
IR:υ(cm-1):3199(Ar-H),1628(C=O),1652(N=C=O),1499(Ar,C=C),1008,1104(C-F)。
(5)N′-(2-三氟甲基-1-基)乙酰基-N-(2,6-二氟苯甲酰基)氨基甲酰肼(I)的合成:
在250mL三口烧瓶中,加入0.05mol(12.90g)2-三氟甲基苯并咪唑-1-乙酰肼(Ⅲ),0.06mol(11.00g)2,6-二氟苯甲酰基异氰酸酯(Ⅳ),1mmol(0.63g)二月桂酸二丁基锡作催化剂,150mL1,2-二氯乙烷作溶剂,搅拌下加热回流反应8~10小时。用薄层色谱法(TLC法)跟踪反应进程,展开剂V(乙酸乙酯):V(石油醚)=5:1。待原料Ⅲ的点基本消失后结束反应。旋蒸除去溶剂,剩余物加入冰水中析出固体。抽滤,得淡黄色固体粗产物。将此固体加入到盛有20mL二氯甲烷的烧杯中,搅拌溶解未反应的2,6-二氟苯甲酰基异氰酸酯(Ⅳ),抽滤,得白色固体,烘干得产物Ⅴ20.07g,产率91%。毛细管法测熔点为:236~238℃。
1HNMR(500MHz,DMSO),δ/ppm:10.413(s,1H,-CONHCO),7.388-7.655(m,7H,ArH),7.811-7.824(d,J=6.5Hz,2H,-NHNH),5.193(s,2H,CH2)。
IR:υ(cm-1):3145(N-H),1689,1686,1606,1486,(C=O),1551,1502,1448(Ar,C=C),1170,1110,1012(C-F)。
生物活性测定
实施例2、杀虫活性测试
杀小菜蛾活性测定方法:化合物(I)对小菜蛾活性测定采用浸叶法,采用国际抗性行动委员会(IRAC)提出的浸叶法。用配制好的待测药液,用直头眼科镊子浸渍甘蓝叶片,时间3-5秒,甩掉余液,每次1片,每个样品共3片,按样品标记顺序依次放在处理纸上。待药液干后,放入具有标记的10cm长的直型管内,接入2龄小菜蛾幼虫30头,用纱布盖好管口。将试验处理置于标准处理室内,48h检查结果以拔针轻触虫体,不动者为死亡。计算死亡率。试验做3次重复,取平均值。化合物(I)在浓度10ppm时对小菜蛾的致死率达95%。
实施例3、杀菌活性测试
将一定量药剂溶解在适量N,N-二甲基甲酰胺(DMF)内,然后用含有一定量吐温20乳化剂水溶液稀释至50mg/L。采用离体平皿法,供试病原菌:番茄早疫病菌(Alternariasolani)、黄瓜枯萎病菌(Fusariumoxysporum)、花生褐斑病菌(CercosporaarachidicolaHori)。
采用菌体生长速率测定法,具体过程是:在无菌条件下各吸取1mL药液注入培养皿内,加入9mLPDA培养基(马铃薯葡萄糖琼脂培养基),摇匀后制成50mg/L含药平板,以添加1mL灭菌水的平板做空白对照。用直径4mm的打孔器沿菌丝外缘切取菌盘,移至含药平板上,每次处理重复三次。将培养皿放在24±1℃恒温培养箱内培养,72h后调查各处菌盘扩展直径,求平均值,与空白对照比较计算相对抑菌率。
防效(%)=(空白菌落直径-处理菌落直径)/(空白菌落直径-4)×100%
测试浓度为50μg/mL下化合物(I)对番茄早疫病菌的抑菌率为81%;对黄瓜枯萎病菌的抑菌率为78%;对花生褐斑病菌的抑菌率为70%。
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106008472A (zh) * | 2016-06-14 | 2016-10-12 | 青岛科技大学 | 脲基连接的吲哚-苯并咪唑衍生物及其合成 |
CN114805191A (zh) * | 2022-05-30 | 2022-07-29 | 重庆医药高等专科学校 | 一种新型杀虫剂氟啶脲的合成方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
PL205592B1 (pl) * | 2001-07-12 | 2010-05-31 | Akad Medyczna | Nowe pochodne 3-[metylo-1,2,4-triazol-1-yl]-4-podstawione-1,2,4-triazolino-5-onu oraz sposób ich otrzymywania |
CN102060780A (zh) * | 2010-12-27 | 2011-05-18 | 苏州雅本化学股份有限公司 | 2-(n-取代)-氨基苯并咪唑衍生物的制备方法 |
CN102174030A (zh) * | 2011-03-24 | 2011-09-07 | 南开大学 | 一类5-甲基-1,2,3-噻二唑-4-甲酰脲类化合物及其制备方法和用途 |
-
2014
- 2014-03-10 CN CN201410085872.2A patent/CN103864694B/zh not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
PL205592B1 (pl) * | 2001-07-12 | 2010-05-31 | Akad Medyczna | Nowe pochodne 3-[metylo-1,2,4-triazol-1-yl]-4-podstawione-1,2,4-triazolino-5-onu oraz sposób ich otrzymywania |
CN102060780A (zh) * | 2010-12-27 | 2011-05-18 | 苏州雅本化学股份有限公司 | 2-(n-取代)-氨基苯并咪唑衍生物的制备方法 |
CN102174030A (zh) * | 2011-03-24 | 2011-09-07 | 南开大学 | 一类5-甲基-1,2,3-噻二唑-4-甲酰脲类化合物及其制备方法和用途 |
Non-Patent Citations (7)
Title |
---|
GUAN-PING YU,等: "Synthesis and QSAR studies on 1-[(5-substituted-1,3,4-thiadiazol-2-yl)methyl]-1H-1,2,4-triazole as antifungal agents", 《STRUCT CHEM》, no. 20, 31 December 2009 (2009-12-31), pages 569 - 576 * |
刘晨江,等: "含2-三氟甲基苯并咪唑的1,3,4-噻二唑的合成", 《化学通报》, no. 12, 31 December 2006 (2006-12-31), pages 948 - 950 * |
孙乐,等: "1-[5-(4-硝基苄基)-2H-四唑乙酰基]-4-芳酰氨基硫脲的合成", 《兰州大学学报(自然科学版)》, vol. 34, no. 3, 30 September 1998 (1998-09-30), pages 77 - 81 * |
张万权,等: "微波辐射下合成1-( 2-三氟甲基苯并咪唑-1-乙酰基)-4-芳酰基氨基硫脲", 《应用化学》, vol. 26, no. 1, 31 January 2009 (2009-01-31), pages 59 - 62 * |
张万权,等: "微波辐射下合成2-芳甲酰氨基-5-(2-三氟甲基苯并咪唑-1-亚甲基)-1,3,4-噻二唑", 《有机化学》, vol. 28, no. 12, 31 December 2008 (2008-12-31), pages 2166 - 2169 * |
时天昊,等: "含2-三氟甲基苯并咪唑的1,2,4-三唑的合成", 《精细化工》, vol. 23, no. 4, 30 April 2006 (2006-04-30), pages 411 - 413 * |
李耀先,等: "1-苯并三氮唑乙酰基-4-取代苯甲酰基硫脲的合成", 《吉林大学自然科学学报》, no. 3, 30 September 1992 (1992-09-30), pages 122 - 124 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106008472A (zh) * | 2016-06-14 | 2016-10-12 | 青岛科技大学 | 脲基连接的吲哚-苯并咪唑衍生物及其合成 |
CN114805191A (zh) * | 2022-05-30 | 2022-07-29 | 重庆医药高等专科学校 | 一种新型杀虫剂氟啶脲的合成方法 |
CN114805191B (zh) * | 2022-05-30 | 2023-12-05 | 重庆医药高等专科学校 | 一种杀虫剂氟啶脲的合成方法 |
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