CN103483313A - 新型酰肼衍生物及其制备方法和应用 - Google Patents
新型酰肼衍生物及其制备方法和应用 Download PDFInfo
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Abstract
本发明涉及一种酰肼衍生物及其制备方法和应用。具有如下通式:各基团如权利要求1所示。本发明在改善了原有化合物脂溶性的同时,也提高了杀虫活性,此类衍生物具有优异的杀虫活性,施药后虫体片刻即出现肌肉失去控制,进食停止,虫体有明显的缩小、瘫痪,最后导致昆虫死亡,同时还能引起昆虫的异常蜕皮,特别对鳞翅目害虫如东方粘虫,小菜蛾,甜菜夜蛾等十分有效,是一种具有广阔应用前景的杀虫剂。
Description
技术领域
本发明涉及农用化学杀虫剂的合成技术,特别是一种酰肼衍生物及其制备方法和应用。
背景技术
无脊椎动物害虫的防治在实现高种植效率中极为重要。无脊椎动物害虫对生长和贮存的农作物的损害会引起生产率的显著降低,并因此导致消费者的花费增加。同时害虫的防治在林、牧、副、渔以及公共卫生中也很重要。虽然市场上出现了一些新害虫防治剂,但是由于市场的不断扩大以及害虫的抗性、药物的使用寿命等问题和人们对环境生态的日益重视,需要科学家们不断研究,进而开发出更有效、低成本、低毒、对环境生态安全和具有新型作用方式的杀虫剂品种。
鱼尼丁受体类杀虫剂是近几年开发的防治鳞翅目害虫的有效杀虫剂。日本农药公司、美国杜邦公司以及拜耳农科申请了不少专利,报道了大量的化合物。
为设计并合成具有杀虫生物活性的新衍生物,我们将新型双酰肼桥引入了化合物中设计并首次合成了未见文献报道的一类双酰肼类衍生物,生物活性测试表明,此类衍生物具有优异的杀虫活性,施药后虫体片刻即出现肌肉失去控制,进食停止,虫体有明显的缩小、瘫痪,最后导致昆虫死亡,同时还首次观测到引起昆虫的异常蜕皮现象。
发明内容
本发明的目的在于一种酰肼衍生物及其制备方法和应用,该酰肼衍生物能够改善原有化合物抗药性和提高杀虫活性的双酰肼类化合物,改善了原有化合物脂溶性的同时,也提高了杀虫活性,此类衍生物施药后虫体片刻即出现肌肉失去控制,进食停止,虫体有明显的缩小、瘫痪,最后导致昆虫死亡,同时还能引起昆虫的异常蜕皮,特别对鳞翅目害虫如东方粘虫,小菜蛾,甜菜夜蛾等十分有效,是一种具有广阔应用前景的杀虫剂,用于农业上防治作物的病害和虫害。
本发明提供的酰肼衍生物具有以下结构式:
式中:X是C或N;
R1是H、卤素、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基、C1-C6烷基羰基、C1-C6烷氧基羰基、卤代C1-C6烷基羰基或NH-R9;
R2是H、卤素、硝基、氨基、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基、C1-C6烷硫基、C1-C6烷磺酰基;R3是H、卤素、C1-C6烷基、硝基;R4是H、卤素、氰基、硝基;
R5是卤素、氰基、C1-C6烷氧基、卤代C1-C6烷氧基、C1-C6烷硫基、卤代C1-C6烷硫基、C2-C6烯氧基、卤代C2-C6烯氧基、C2-C6炔氧基、卤代C2-C6炔氧基、C2-C6烷酰氧基或卤代C2-C6烷酰氧基、C1-C6烷基羰基、C1-C6烷氧基C1-C6烷基、卤代C1-C6烷氧基C1-C6烷基、C1-C6烷硫基C1-C6烷基、CH2N3、CH2NH2;
R6是H或卤素;
R7是H、C1-C6烷氧基、卤代C1-C6烷氧基、C1-C6烷硫基、卤代C1-C6烷硫基;
R8是H、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基、C1-C6烷基羰基、卤代C1-C6烷基羰基、C1-C6烷氧草酰基、C1-C6烷氧羰基;
R9是H、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基、C1-C6烷基羰基、卤代C1-C6烷基羰基、C1-C6烷氧草酰基、C1-C6烷氧羰基;
在上述衍生物的定义中,所用术语不论单独使用还是用在复合词中,代表如下取代基:
卤素为氟、氯、溴或碘;
烷基为直链烷基或支链烷基;
卤代烷基为卤代直链或支链烷基,在这些烷基上的氢原子可以部分或全部被卤原子取代;“卤代烯基”、“卤代炔基”和“卤代环烷基”的定义与术语“卤代烷基”相同;
烯基为有2-6个碳原子的直链或支链并可在任何位置上存在有双键;
炔基为有2-6个碳原子的直链或支链并可在任何位置上存在有三键。
本发明提供的酰肼衍生物的制备方法包括的步骤:
酰肼衍生物(I)合成方法一:
通式III化合物在溶于有机溶剂中,加入草酰氯和微量的催化剂,在室温下反应3-12小时制得酰氯,然后与通式Ⅳ化合物摩尔比1∶1,溶于有机溶剂中,加入适量的碱,在温度为0-25℃下反应0.5-48小时制得目标化合物I;反应式中各基团如权利要求1所示(R1除外,R1为氨基以及取代氨基以外的基团)。
所述的有机溶剂选自二氯甲烷、氯仿、四氯化碳、苯、甲苯、二甲苯、环己烷、正己烷、乙酸乙酯、四氢呋喃、1,4-二氧六环、N,N-二甲基甲酰胺或二甲基亚砜。
所述的碱选自有机碱:三乙胺、吡啶、1,8-二氮杂-双环(5,4,0)十一碳-7-烯或N,N-二甲基苯胺;或无机碱:氢氧化钠、氢氧化钾、碳酸钠、碳酸钾、甲醇钠、叔丁醇钠或叔丁醇钾。
酰肼衍生物(I)合成方法二:
通式III化合物在溶于有机溶剂中,加入草酰氯和微量的催化剂,在室温下反应3-12小时制得酰氯,然后与通式V化合物摩尔比1∶1,溶于有机溶剂中,加入适量的碱,在温度为0-25℃下反应0.5-48小时制得化合物II。通式II化合物溶于有机溶剂,加入通式Ⅶ化合物和适量的碱,在温度为0-25℃下反应0.5-48小时制得化合物I。反应式中各基团如权利要求1所示。
所述的有机溶剂选自二氯甲烷、氯仿、四氯化碳、苯、甲苯、二甲苯、环己烷、正己烷、 乙酸乙酯、四氢呋喃、1,4-二氧六环、N,N-二甲基甲酰胺或二甲基亚砜。
所述的碱选自有机碱:三乙胺、吡啶、1,8-二氮杂-双环(5,4,0)十一碳-7-烯或N,N-二甲基苯胺:或无机碱:氢氧化钠、氢氧化钾、碳酸钠、碳酸钾、甲醇钠、叔丁醇钠或叔丁醇钾。
通式III化合物参考文献Chin J.Chem.,2013,30,1748-1758制备。
通式IV或V化合物可通过如下方法制备:
取代的苯甲酸在二氯亚砜的作用下生成酰氯,再与不同取代的肼的盐酸盐或水合肼(80%)在温度0-10℃下以适合的碱为缚酸剂反应0.5-12小时制得目标化合物IV或V。反应式中各基团如上述所定义,所述的碱选自有机碱:三乙胺、吡啶、1,8-二氮杂-双环(5,4,0)十一碳-7-烯或N,N-二甲基苯胺;或无机碱:氢氧化钠、氢氧化钾、碳酸钠、碳酸钾、甲醇钠、叔丁醇钠或叔丁醇钾。
本发明所述的双酰肼衍生物用于制备农用化学杀虫剂。特别是用于东方粘虫,小菜蛾和甜菜夜蛾等昆虫的防治。
本发明提供的双酰肼衍生物作为活性成分配以农业可以接受的助剂组成的农药组合物用于防治昆虫的用途。
本发明提供的新型酰肼类衍生物具有很高的杀虫活性。不仅改善了原有化合物抗药性,也提高了杀虫活性和降低了生产成本。具体讲,本发明在改善了原有化合物脂溶性的同时,也提高了杀虫活性,此类衍生物具有优异的杀虫活性,施药后虫体片刻即出现肌肉失去控制,进食停止,虫体有明显的缩小、瘫痪,最后导致昆虫死亡,同时还能引起昆虫的异常蜕皮,特别对鳞翅目害虫如东方粘虫,小菜蛾,甜菜夜蛾等十分有效,是一种具有广阔应用前景的杀虫剂。
附图说明
图1是本发明提供的双酰肼衍生物合成路线示意图。
具体实施方式
以下结合实施例来进一步说明本发明,其目的是能更好的理解本发明的内容乃体现本发明的实质性特点,因此所举之例不应视为对本发明保护范围的限制。
实施例1
3-溴-N-叔丁基-1-(3-氯-2-吡啶基)-N’-(4-三氟甲基苯甲酰基)-1H-吡唑-5-甲酰肼(衍生物01)的合成:
步骤A:制备N’-叔丁基-4-三氟甲基苯甲酰肼
在100mL的圆底烧瓶中加入4-三氟甲基苯甲酸(0.57g,3mmol),SOCl2,回流,减压脱去过量的SOCl2,得到粗品酰氯,滴加到混有适量叔丁基肼盐酸盐,氢氧化钠,二氯甲烷和水的混合物中,滴毕,室温反应,加入乙酸乙酯,分出有机层,有机层脱溶后,得到标题化合物,0.57g白色粉末,m.p.77-78℃。
步骤B:制备3-溴-N-叔丁基-1-(3-氯-2-比啶基)-N'-(4-三氟甲基苯甲酰基)-1H-吡唑-5-甲酰肼
在100mL的单口圆底烧瓶中加入3-溴-1-(3-氯-2-吡啶基)-1H-比唑-5-甲酸(0.30g,1.00mm0l)、草酰氯和二氯甲烷,滴加2滴DMF,室温反应后,减压脱去溶剂得酰氯粗品。将N'-叔丁基-4-三氟甲基苯甲酰肼和三乙胺混合,冰水浴冷却下滴加粗品酰氯,滴毕,室温搅拌,加入乙酸乙酯,分出有机层,有机层脱溶后,得到标题化合物,0.34g白色粉末,m.p.83-84℃。
实施例2
N’-(2-氨基-5-氯-3-甲基苯甲酰基)-3-溴-N-叔丁基-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酰肼(衍生物17)的合成
步骤A:制备2-氨基-3-甲基-5-氯苯甲酸
将2-氨基-3-甲基苯甲酸(15.10g,100mmol)溶于DMF,其中加入过量NCS,然后加热,冷却后倒入500mL冰水中,有棕红色固体出现,过滤,干燥,得标题化合物12.3g。
步骤B:制备N’-叔丁基-2-氨基-3-甲基-5-氯苯甲酰肼
在100mL的圆底烧瓶中加入2-氨基-3-甲基-5-氯苯甲酸(0.56g,3mmol),SOCl2,回流,减压脱去过量的SOCl2,得到粗品酰氯,在冰水浴冷却下滴加到混有叔丁基肼盐酸盐,氢氧化钠,二氯甲烷和水的混合物中,室温反应,加入100mL的乙酸乙酯,分出有机层,有机层脱溶后,得到标题化合物,0.46g白色粉末,m.p.131-132℃。
步骤C:制备N'-(2-氨基-5-氯-3-甲基苯甲酰基)-3-溴-N-叔丁基-1-(3-氯-2-比啶基)-1H-比唑-5-甲酰肼
在100mL的单口圆底烧瓶中加入3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酸(0.30g,1.00mmol)、草酰氯和二氯甲烷,滴加2滴DMF,室温反应,减压脱去溶剂得酰氯粗品。将N’-叔丁基-2-氨基-3-甲基-5-氯苯甲酰肼和三乙胺溶于二氯甲烷中,滴加粗品酰氯溶液,滴毕,室温搅拌,加入50mL的乙酸乙酯,分出有机层,有机层脱溶后,得到标题化合物,0.25g白色粉末,m.p.241-242℃。
实施例3
N-[2-(2-(3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酰基)-2-(叔丁基)肼基羰基)-4-氯-6-甲基苯基]氨基甲酸甲酯(衍生物45)的合成
在100mL的单口圆底烧瓶中加入N’-(2-氨基-5-氯-3-甲基苯甲酰基)-3-溴-N-叔丁基-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酰肼(0.32g,0.6mmol),三乙胺和二氯甲烷,滴加乙酰氯,滴毕,室温搅拌,反应结束后,加入乙酸乙酯,分出有机层,有机层脱溶后,得到标题化合物,0.14g白色粉末,m.p.264-265℃。
实施例4
N-[2-(1-乙酰基-2-(3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酰基)-2-(叔丁基)肼基羰基)-4-氯-6-甲基苯基]氨基甲酸甲酯(衍生物52)的合成
在50mL的单口圆底烧瓶中加入N'-(2-氨基-5-氯-3-甲基苯甲酰基)-3-溴-N-叔丁基-1-(3-氯-2-比啶基)-1H-比唑-5-甲酰肼(0.32g,0.6mmol)和乙酸酐,加热回流,反应完将反应液倒入冰水中,有固体析出,抽滤,烘干得到标题化合物,0.11g白色粉末,m.p.102-103℃。
实施例5
N’-(2-氨基-5-氯-3-甲基苯甲酰基)-1-(3-氯-2-吡啶基)-3-三氟甲基-1H-吡唑-5-甲酰肼(衍生物197)的合成
步骤A:制备2-氨基-3-甲基-5-氯苯甲酰肼
在100mL的圆底烧瓶中加入2-氨基-3-甲基-5-氯苯甲酸(0.56g,3mmol),SOCl2,回流,减压脱去过量的SOCl2,得到粗品酰氯,在冰水浴冷却下滴加到80%水合肼的四氢呋喃溶液,滴毕,室温反应,加入乙酸乙酯,分出有机层,有机层脱溶后,得到标题化合物,0.48g白色粉末,m.p.121-122℃。
步骤B:制备N’-(2-氨基-5-氯-3-甲基苯甲酰基)-3-三氟甲基-1-(3-氯-2-比啶基)-1H-吡唑-5-甲酰肼
在100mL的单口圆底烧瓶中加入3-三氟甲基-1-(3-氯-2-比啶基)-1H-吡唑-5-甲酸(0.29g,1.00mmol)、草酰氯和二氯甲烷,滴加2滴DMF,室温反应,减压脱去溶剂得酰氯粗品。将2-氨基-3-甲基-5-氯苯甲酰肼和三乙胺溶于的四氢呋喃中,滴加粗品酰氯,滴毕,室温搅拌,加入乙酸乙酯,分出有机层,有机层脱溶后,得到标题化合物,0.38g白色粉末,m.p.94-96℃。
实施例6
[(4-氯-2-(2-(1-(3-氯-2-吡啶基)-3-三氟甲基)-1H-吡唑-5-甲酰基)甲酰肼)-6-甲基苯基]氨基甲酸乙酯(衍生物296)
在50mL的单口圆底烧瓶中将N’-(2-氨基-5-氯-3-甲基苯甲酰基)-1-(3-氯-2-吡啶基)-3-三氟甲基-1H-吡唑-5-甲酰肼(0.27g,0.5mmol)和吡啶溶于四氢呋喃,滴加氯甲酸乙酯,滴毕,室温搅拌,加入乙酸乙酯,分出有机层,有机层脱溶后,经柱层析得到标题化合物,0.16g白色粉末,m.p.111-112℃。
实施例7
[4-氯-2-(2-(1-(3-氯-2-吡啶基)-3-三氟甲基-1H-吡唑-5-甲酰基)甲酰胼)-6-甲基苯基]氨基草酰甲酯(衍生物368)的合成
在50mL的单口圆底烧瓶中将N’-(2-氨基-5-氯-3-甲基苯甲酰基)-1-(3-氯-2-吡啶基)-3-三氟甲基-1H-吡唑-5-甲酰肼(0.27g,0.5mmol)和吡啶溶于四氢呋喃,滴加氯草酸甲酯,滴毕,室温搅拌,加入乙酸乙酯,分出有机层,有机层脱溶后,经柱层析得到标题化合物,0.16g白色粉末,m.p.134-136℃。
现将根据实施例1~7的制备方法而采用不同的原料制备的该类衍生物01~509,列入表1,部分衍生物1H NMR(Bmker AV400 spectrometer using tetramemylsilane as the internal standard)数据列入表2。
表l
编号 | X | R1 | R2 | R3 | R4 | R5 | R6 | R7 | R8 | 熔点 |
1 | N | H | H | CF3 | H | Br | Cl | t-C4H9 | H | 83-84 |
2 | N | H | H | Cl | H | Br | Cl | t-C4H9 | H | 96-97 |
3 | N | H | H | Br | H | Br | Cl | t-C4H9 | H | 92-93 |
4 | N | F | H | H | H | Br | Cl | t-C4H9 | H | 163-165 |
5 | N | Cl | H | H | H | Br | Cl | t-C4H9 | H | 199-200 |
6 | N | I | H | H | H | Br | Cl | t-C4H9 | H | 207-208 |
7 | N | Br | H | H | H | Br | Cl | t-C4H9 | H | - |
8 | N | H | H | CH3 | H | Br | Cl | t-C4H9 | H | - |
9 | N | H | H | CF3 | H | Cl | Cl | t-C4H9 | H | - |
10 | N | H | H | Cl | H | Cl | Cl | t-C4H9 | H | - |
11 | N | H | H | Br | H | Cl | Cl | t-C4H9 | H | - |
12 | N | F | H | H | H | Cl | Cl | t-C4H9 | H | - |
[0076]
13 | N | Cl | H | H | H | Cl | Cl | t-C4H9 | H | - |
14 | N | I | H | H | H | Cl | Cl | t-C4H9 | H | - |
15 | N | Br | H | H | H | Cl | Cl | t-C4H9 | H | - |
16 | N | H | H | CH3 | H | Cl | Cl | t-C4H9 | H | - |
17 | N | NH2 | CH3 | H | Cl | Br | Cl | t-C4H9 | H | 241-242 |
18 | N | NH2 | CH3 | H | Cl | Cl | Cl | t-C4H9 | H | - |
19 | N | NH2 | CH3 | H | Cl | CN | Cl | t-C4H9 | H | - |
20 | N | NH2 | CH3 | H | Cl | OCH2CF3 | Cl | t-C4H9 | H | - |
21 | N | NH2 | CH3 | H | Cl | OCF3 | Cl | t-C4H9 | H | - |
22 | N | NH2 | CH3 | H | Cl | SCH3 | Cl | t-C4H9 | H | - |
23 | N | NH2 | CH3 | H | Cl | CF3 | Cl | t-C4H9 | H | - |
24 | N | NH2 | CH3 | H | Br | Br | Cl | t-C4H9 | H | 227-228 |
25 | N | NH2 | CH3 | H | Br | Cl | Cl | t-C4H9 | H | - |
26 | N | NH2 | CH3 | H | Br | CN | Cl | t-C4H9 | H | - |
27 | N | NH2 | CH3 | H | Br | OCH2CF3 | Cl | t-C4H9 | H | - |
28 | N | NH2 | CH3 | H | Br | OCF3 | Cl | t-C4H9 | H | - |
29 | N | NH2 | CH3 | H | Br | SCH3 | Cl | t-C4H9 | H | - |
30 | N | NH2 | CH3 | H | Br | CF3 | Cl | t-C4H9 | H | - |
31 | N | NH2 | H | H | Cl | Br | Cl | t-C4H9 | H | - |
32 | N | NH2 | H | H | Cl | Cl | Cl | t-C4H9 | H | - |
33 | N | NH2 | H | H | Cl | CN | Cl | t-C4H9 | H | - |
34 | N | NH2 | H | H | Cl | OCH2CF3 | Cl | t-C4H9 | H | - |
35 | N | NH2 | H | H | Cl | OCF3 | Cl | t-C4H9 | H | - |
36 | N | NH2 | H | H | Cl | SCH3 | Cl | t-C4H9 | H | - |
37 | N | NH2 | H | H | Cl | CF3 | Cl | t-C4H9 | H | - |
38 | N | NH2 | H | H | Br | Br | Cl | t-C4H9 | H | - |
39 | N | NH2 | H | H | Br | Cl | Cl | t-C4H9 | H | - |
40 | N | NH2 | H | H | Br | CN | Cl | t-C4H9 | H | - |
41 | N | NH2 | H | H | Br | OCH2CF3 | Cl | t-C4H9 | H | - |
42 | N | NH2 | H | H | Br | OCF3 | Cl | t-C4H9 | H | - |
43 | N | NH2 | H | H | Br | SCH3 | Cl | t-C4H9 | H | - |
44 | N | NH2 | H | H | Br | CF3 | Cl | t-C4H9 | H | - |
45 | N | NHCOCH3 | CH3 | H | Cl | Br | Cl | t-C4H9 | H | 264-265 |
46 | N | NHCOCH3 | CH3 | H | Cl | Cl | Cl | t-C4H9 | H | - |
47 | N | NHCOCH3 | CH3 | H | Cl | CN | Cl | t-C4H9 | H | - |
48 | N | NHCOCH3 | CH3 | H | Cl | OCH2CF3 | Cl | t-C4H9 | H | - |
49 | N | NHCOCH3 | CH3 | H | Cl | OCF3 | Cl | t-C4H9 | H | - |
[0077]
50 | N | NHCOCH3 | CH3 | H | Cl | SCH3 | Cl | t-C4H9 | H | - |
51 | N | NHCOCH3 | CH3 | H | Cl | CF3 | Cl | t-C4H9 | H | - |
52 | N | NHCOCH3 | CH3 | H | Cl | Br | Cl | t-C4H9 | COCH3 | 102-103 |
53 | N | NHCOC2H5 | CH3 | H | Cl | Br | Cl | t-C4H9 | H | - |
54 | N | NHCOC2H5 | CH3 | H | Cl | Cl | Cl | t-C4H9 | H | - |
55 | N | NHCOC2H5 | CH3 | H | Cl | CN | Cl | t-C4H9 | H | - |
56 | N | NHCOC2H5 | CH3 | H | Cl | OCH2CF3 | Cl | t-C4H9 | H | - |
57 | N | NHCOC2H5 | CH3 | H | Cl | OCF3 | Cl | t-C4H9 | H | - |
58 | N | NHCOC2H5 | CH3 | H | Cl | SCH3 | Cl | t-C4H9 | H | - |
59 | N | NHCOCH(CH3)2 | CH3 | H | Cl | Br | Cl | t-C4H9 | H | 236-237 |
60 | N | NHCOCH(CH3)2 | CH3 | H | Cl | Cl | Cl | t-C4H9 | H | - |
61 | N | NHCOCH(CH3)2 | CH3 | H | Cl | CN | Cl | t-C4H9 | H | - |
62 | N | NHCOCH(CH3)2 | CH3 | H | Cl | OCH2CF3 | Cl | t-C4H9 | H | - |
63 | N | NHCOCH(CH3)2 | CH3 | H | Cl | OCF3 | Cl | t-C4H9 | H | - |
64 | N | NHCOCH(CH3)2 | CH3 | H | Cl | SCH3 | Cl | t-C4H9 | H | - |
65 | N | NHCOCH(CH3)2 | CH3 | H | Cl | CF3 | Cl | t-C4H9 | H | - |
66 | N | NHCOCCl3 | CH3 | H | Cl | Br | Cl | t-C4H9 | H | 231-233 |
67 | N | NHCOCCl3 | CH3 | H | Cl | Cl | Cl | t-C4H9 | H | - |
68 | N | NHCOCCl3 | CH3 | H | Cl | CN | Cl | t-C4H9 | H | - |
69 | N | NHCOCCl3 | CH3 | H | Cl | OCH2CF3 | Cl | t-C4H9 | H | - |
70 | N | NHCOCCl3 | CH3 | H | Cl | OCF3 | Cl | t-C4H9 | H | - |
71 | N | NHCOCCl3 | CH3 | H | Cl | SCH3 | Cl | t-C4H9 | H | - |
72 | N | NHCOCCl3 | CH3 | H | Cl | CF3 | Cl | t-C4H9 | H | - |
73 | N | NHCOCH2Cl | CH3 | H | Cl | Br | Cl | t-C4H9 | H | 204-206 |
74 | N | NHCOCH2Cl | CH3 | H | Cl | Cl | Cl | t-C4H9 | H | - |
75 | N | NHCOCH2Cl | CH3 | H | Cl | CN | Cl | t-C4H9 | H | - |
76 | N | NHCOCH2Cl | CH3 | H | Cl | OCH2CF3 | Cl | t-C4H9 | H | - |
77 | N | NHCOCH2Cl | CH3 | H | Cl | OCF3 | Cl | t-C4H9 | H | - |
78 | N | NHCOCH2Cl | CH3 | H | Cl | SCH3 | Cl | t-C4H9 | H | - |
79 | N | NHCOCH2Cl | CH3 | H | Cl | CF3 | Cl | t-C4H9 | H | - |
80 | N | NHCOPh | CH3 | H | Cl | Br | Cl | t-C4H9 | H | 216-217 |
81 | N | NHCOPh | CH3 | H | Cl | Cl | Cl | t-C4H9 | H | - |
82 | N | NHCOPh | CH3 | H | Cl | CN | Cl | t-C4H9 | H | - |
83 | N | NHCOPh | CH3 | H | Cl | OCH2CF3 | Cl | t-C4H9 | H | - |
84 | N | NHCOPh | CH3 | H | Cl | OCF3 | Cl | t-C4H9 | H | - |
85 | N | NHCOPh | CH3 | H | Cl | SCH3 | Cl | t-C4H9 | H | - |
86 | N | NHCOPh | CH3 | H | Cl | CF3 | Cl | t-C4H9 | H | - |
[0078]
87 | N | NHCOCH3 | CH3 | H | Br | Br | Cl | t-C4H9 | H | 244-245 |
88 | N | NHCOCH3 | CH3 | H | Br | Cl | Cl | t-C4H9 | H | - |
89 | N | NHCOCH3 | CH3 | H | Br | CN | Cl | t-C4H9 | H | - |
90 | N | NHCOCH3 | CH3 | H | Br | OCH2CF3 | Cl | t-C4H9 | H | - |
91 | N | NHCOCH3 | CH3 | H | Br | OCF3 | Cl | t-C4H9 | H | - |
92 | N | NHCOCH3 | CH3 | H | Br | SCH3 | Cl | t-C4H9 | H | - |
93 | N | NHCOCH3 | CH3 | H | Br | CF3 | Cl | t-C4H9 | H | - |
94 | N | NHCOC2H5 | CH3 | H | Br | Br | Cl | t-C4H9 | H | - |
95 | N | NHCOC2H5 | CH3 | H | Br | Cl | Cl | t-C4H9 | H | - |
96 | N | NHCOC2H5 | CH3 | H | Br | CN | Cl | t-C4H9 | H | - |
97 | N | NHCOC2H5 | CH3 | H | Br | OCH2CF3 | Cl | t-C4H9 | H | - |
98 | N | NHCOC2H5 | CH3 | H | Br | OCF3 | Cl | t-C4H9 | H | - |
99 | N | NHCOC2H5 | CH3 | H | Br | SCH3 | Cl | t-C4H9 | H | - |
100 | N | NHCOCH(CH3)2 | CH3 | H | Br | Br | Cl | t-C4H9 | H | 241-242 |
101 | N | NHCOCH(CH3)2 | CH3 | H | Br | Cl | Cl | t-C4H9 | H | - |
102 | N | NHCOCH(CH3)2 | CH3 | H | Br | CN | Cl | t-C4H9 | H | - |
103 | N | NHCOCH(CH3)2 | CH3 | H | Br | OCH2CF3 | Cl | t-C4H9 | H | - |
104 | N | NHCOCH(CH3)2 | CH3 | H | Br | OCF3 | Cl | t-C4H9 | H | - |
105 | N | NHCOCH(CH3)2 | CH3 | H | Br | SCH3 | Cl | t-C4H9 | H | - |
106 | N | NHCOCH(CH3)2 | CH3 | H | Br | CF3 | Cl | t-C4H9 | H | - |
107 | N | NHCOCCl3 | CH3 | H | Br | Br | Cl | t-C4H9 | H | 234-236 |
108 | N | NHCOCCl3 | CH3 | H | Br | Cl | Cl | t-C4H9 | H | - |
109 | N | NHCOCCl3 | CH3 | H | Br | CN | Cl | t-C4H9 | H | - |
110 | N | NHCOCCl3 | CH3 | H | Br | OCH2CF3 | Cl | t-C4H9 | H | - |
111 | N | NHCOCCl3 | CH3 | H | Br | OCF3 | Cl | t-C4H9 | H | - |
112 | N | NHCOCCl3 | CH3 | H | Br | SCH3 | Cl | t-C4H9 | H | - |
113 | N | NHCOCCl3 | CH3 | H | Br | CF3 | Cl | t-C4H9 | H | - |
114 | N | NHCOCH2Cl | CH3 | H | Br | Br | Cl | t-C4H9 | H | 219-220 |
115 | N | NHCOCH2Cl | CH3 | H | Br | Cl | Cl | t-C4H9 | H | - |
116 | N | NHCOCH2Cl | CH3 | H | Br | CN | Cl | t-C4H9 | H | - |
117 | N | NHCOCH2Cl | CH3 | H | Br | OCH2CF3 | Cl | t-C4H9 | H | - |
118 | N | NHCOCH2Cl | CH3 | H | Br | OCF3 | Cl | t-C4H9 | H | - |
119 | N | NHCOCH2Cl | CH3 | H | Br | SCH3 | Cl | t-C4H9 | H | - |
120 | N | NHCOCH2Cl | CH3 | H | Br | CF3 | Cl | t-C4H9 | H | - |
121 | N | NHCOPh | CH3 | H | Br | Br | Cl | t-C4H9 | H | 231-233 |
122 | N | NHCOPh | CH3 | H | Br | Cl | Cl | t-C4H9 | H | - |
123 | N | NHCOPh | CH3 | H | Br | CN | Cl | t-C4H9 | H | - |
[0079]
124 | N | NHCOPh | CH3 | H | Br | OCH2CF3 | Cl | t-C4H9 | H | - |
125 | N | NHCOPh | CH3 | H | Br | OCF3 | Cl | t-C4H9 | H | - |
126 | N | NHCOPh | CH3 | H | Br | SCH3 | Cl | t-C4H9 | H | - |
127 | N | NHCOPh | CH3 | H | Br | CF3 | Cl | t-C4H9 | H | - |
128 | N | NH2 | H | H | H | Br | Cl | H | H | - |
129 | N | NH2 | H | H | H | Cl | Cl | H | H | - |
130 | N | NH2 | H | H | H | CN | Cl | H | H | - |
131 | N | NH2 | H | H | H | OCH2CF3 | Cl | H | H | - |
132 | N | NH2 | H | H | H | OCF3 | Cl | H | H | - |
133 | N | NH2 | H | H | H | SCH3 | Cl | H | H | - |
134 | N | NH2 | H | H | H | CF3 | Cl | H | H | - |
135 | N | NH2 | H | H | H | CO2C2H5 | Cl | H | H | - |
136 | N | NH2 | H | H | H | CH2N3 | Cl | H | H | - |
137 | N | NH2 | CH3 | H | H | Br | Cl | H | H | 114-115 |
138 | N | NH2 | CH3 | H | H | Cl | Cl | H | H | - |
139 | N | NH2 | CH3 | H | H | CN | C1 | H | H | - |
140 | N | NH2 | CH3 | H | H | OCH2CF3 | Cl | H | H | - |
141 | N | NH2 | CH3 | H | H | OCF3 | Cl | H | H | - |
142 | N | NH2 | CH3 | H | H | SCH3 | Cl | H | H | - |
143 | N | NH2 | CH3 | H | H | CF3 | Cl | H | H | - |
144 | N | NH2 | CH3 | H | H | CO2C2H5 | Cl | H | H | - |
145 | N | NH2 | CH3 | H | H | CH2N3 | Cl | H | H | - |
146 | N | NH2 | H | H | Cl | Br | Cl | H | H | 142-143 |
147 | N | NH2 | H | H | Cl | Cl | Cl | H | H | - |
148 | N | NH2 | H | H | Cl | CN | Cl | H | H | - |
149 | N | NH2 | H | H | Cl | OCH2CF3 | Cl | H | H | - |
150 | N | NH2 | H | H | Cl | OCF3 | Cl | H | H | - |
151 | N | NH2 | H | H | Cl | SCH3 | Cl | H | H | - |
152 | N | NH2 | H | H | Cl | CF3 | Cl | H | H | - |
153 | N | NH2 | H | H | Cl | CO2C2H5 | C1 | H | H | - |
154 | N | NH2 | H | H | Cl | CH2N3 | Cl | H | H | - |
155 | N | NH2 | H | H | Br | Br | Cl | H | H | - |
156 | N | NH2 | H | H | Br | Cl | Cl | H | H | - |
157 | N | NH2 | H | H | Br | CN | Cl | H | H | - |
158 | N | NH2 | H | H | Br | OCH2CF3 | Cl | H | H | - |
159 | N | NH2 | H | H | Br | OCF3 | Cl | H | H | - |
160 | N | NH2 | H | H | Br | SCH3 | Cl | H | H | - |
[0080]
161 | N | NH2 | H | H | Br | CF3 | Cl | H | H | - |
162 | N | NH2 | H | H | Br | CO2C2H5 | Cl | H | H | - |
163 | N | NH2 | H | H | Br | CH2N3 | Cl | H | H | - |
164 | N | NH2 | H | H | I | Br | Cl | H | H | - |
165 | N | NH2 | H | H | I | Cl | Cl | H | H | - |
166 | N | NH2 | H | H | I | CN | Cl | H | H | - |
167 | N | NH2 | H | H | I | OCH2CF3 | Cl | H | H | - |
168 | N | NH2 | H | H | I | OCF3 | Cl | H | H | - |
169 | N | NH2 | H | H | I | SCH3 | Cl | H | H | - |
170 | N | NH2 | H | H | I | CF3 | Cl | H | H | - |
171 | N | NH2 | H | H | I | CO2C2H5 | Cl | H | H | - |
172 | N | NH2 | H | H | I | CH2N3 | Cl | H | H | - |
173 | N | NH2 | H | H | CN | Br | Cl | H | H | - |
174 | N | NH2 | H | H | CN | Cl | Cl | H | H | - |
175 | N | NH2 | H | H | CN | CN | Cl | H | H | - |
176 | N | NH2 | H | H | CN | OCH2CF3 | Cl | H | H | - |
177 | N | NH2 | H | H | CN | OCF3 | Cl | H | H | - |
178 | N | NH2 | H | H | CN | SCH3 | Cl | H | H | - |
179 | N | NH2 | H | H | CN | CF3 | Cl | H | H | - |
180 | N | NH2 | H | H | CN | CO2C2H5 | Cl | H | H | - |
181 | N | NH2 | H | H | CN | CH2N3 | Cl | H | H | - |
182 | N | NH2 | H | Cl | H | Br | Cl | H | H | 111-113 |
183 | N | NH2 | H | Cl | H | Cl | Cl | H | H | - |
184 | N | NH2 | H | Cl | H | CN | Cl | H | H | - |
185 | N | NH2 | H | Cl | H | OCH2CF3 | Cl | H | H | - |
186 | N | NH2 | H | Cl | H | OCF3 | Cl | H | H | - |
187 | N | NH2 | H | Cl | H | SCH3 | Cl | H | H | - |
188 | N | NH2 | H | Cl | H | CF3 | Cl | H | H | - |
189 | N | NH2 | H | Cl | H | CO2C2H5 | Cl | H | H | - |
190 | N | NH2 | H | Cl | H | CH2N3 | Cl | H | H | - |
191 | N | NH2 | CH3 | H | Cl | Br | Cl | H | H | 91-93 |
192 | N | NH2 | CH3 | H | Cl | Cl | Cl | H | H | 113-115 |
193 | N | NH2 | CH3 | H | Cl | CN | Cl | H | H | 130-131 |
194 | N | NH2 | CH3 | H | Cl | OCH2CF3 | Cl | H | H | 99-101 |
195 | N | NH2 | CH3 | H | Cl | OCF3 | Cl | H | H | - |
196 | N | NH2 | CH3 | H | Cl | SCH3 | Cl | H | H | - |
197 | N | NH2 | CH3 | H | Cl | CF3 | Cl | H | H | 94-96 |
198 | N | NH2 | CH3 | H | Cl | CO2C2H5 | Cl | H | H | 127-129 |
199 | N | NH2 | CH3 | H | Cl | CH2N3 | Cl | H | H | - |
200 | N | NH2 | CH3 | H | Br | Br | Cl | H | H | 136-137 |
201 | N | NH2 | CH3 | H | Br | Cl | Cl | H | H | - |
202 | N | NH2 | CH3 | H | Br | CN | Cl | H | H | - |
203 | N | NH2 | CH3 | H | Br | OCH2CF3 | Cl | H | H | - |
204 | N | NH2 | CH3 | H | Br | OCF3 | Cl | H | H | - |
205 | N | NH2 | CH3 | H | Br | SCH3 | Cl | H | H | - |
206 | N | NH2 | CH3 | H | Br | CF3 | Cl | H | H | - |
207 | N | NH2 | CH3 | H | Br | CO2C2H5 | Cl | H | H | - |
208 | N | NH2 | CH3 | H | Br | CH2N3 | Cl | H | H | - |
209 | N | NH2 | CH3 | H | I | Br | Cl | H | H | 138-140 |
210 | N | NH2 | CH3 | H | I | Cl | Cl | H | H | - |
211 | N | NH2 | CH3 | H | I | CN | Cl | H | H | - |
212 | N | NH2 | CH3 | H | 1 | OCH2CF3 | Cl | H | H | - |
213 | N | NH2 | CH3 | H | I | OCF3 | Cl | H | H | - |
214 | N | NH2 | CH3 | H | I | SCH3 | Cl | H | H | - |
215 | N | NH2 | CH3 | H | I | CF3 | Cl | H | H | - |
216 | N | NH2 | CH3 | H | I | CO2C2H5 | Cl | H | H | - |
217 | N | NH2 | CH3 | H | I | CH2N3 | Cl | H | H | - |
218 | N | NH2 | CH3 | H | CN | Br | Cl | H | H | 203-204 |
219 | N | NH2 | CH3 | H | CN | Cl | Cl | H | H | - |
220 | N | NH2 | CH3 | H | CN | CN | Cl | H | H | - |
221 | N | NH2 | CH3 | H | CN | OCH2CF3 | Cl | H | H | - |
222 | N | NH2 | CH3 | H | CN | OCF3 | Cl | H | H | - |
223 | N | NH2 | CH3 | H | CN | SCH3 | Cl | H | H | - |
224 | N | NH2 | CH3 | H | CN | CF3 | Cl | H | H | - |
225 | N | NH2 | CH3 | H | CN | CO2C2H5 | Cl | H | H | - |
226 | N | NH2 | CH3 | H | CN | CH2N3 | Cl | H | H | - |
227 | N | NHCO2CH3 | CH3 | H | Cl | Br | Cl | H | H | 128-130 |
228 | N | NHCO2CH3 | CH3 | H | Cl | Cl | Cl | H | H | 128-129 |
229 | N | NHCO2CH3 | CH3 | H | Cl | CN | Cl | H | H | 112-114 |
230 | N | NHCO2CH3 | CH3 | H | Cl | OCH2CF3 | Cl | H | H | 137-139 |
231 | N | NHCO2CH3 | CH3 | H | Cl | OCF3 | Cl | H | H | - |
232 | N | NHCO2CH3 | CH3 | H | Cl | SCH3 | Cl | H | H | - |
233 | N | NHCO2CH3 | CH3 | H | Cl | CF3 | Cl | H | H | 154-156 |
234 | N | NHCO2CH3 | CH3 | H | Cl | CO2C2H5 | Cl | H | H | 112-113 |
[0081]
235 | N | NHCO2CH3 | CH3 | H | Cl | CH2N3 | Cl | H | H | - |
236 | N | NHCO2CH3 | CH3 | H | Br | Br | Cl | H | H | 140-142 |
237 | N | NHCO2CH3 | CH3 | H | Br | Cl | Cl | H | H | - |
238 | N | NHCO2CH3 | CH3 | H | Br | CN | Cl | H | H | - |
239 | N | NHCO2CH3 | CH3 | H | Br | OCH2CF3 | Cl | H | H | - |
240 | N | NHCO2CH3 | CH3 | H | Br | OCF3 | Cl | H | H | - |
241 | N | NHCO2CH3 | CH3 | H | Br | SCH3 | Cl | H | H | - |
242 | N | NHCO2CH3 | CH3 | H | Br | CF3 | Cl | H | H | 115-117 |
243 | N | NHCO2CH3 | CH3 | H | Br | CO2C2H5 | Cl | H | H | - |
244 | N | NHCO2CH3 | CH3 | H | Br | CH2N3 | Cl | H | H | - |
245 | N | NHCO2CH3 | CH3 | H | I | Br | Cl | H | H | 139-141 |
246 | N | NHCO2CH3 | CH3 | H | I | Cl | Cl | H | H | - |
247 | N | NHCO2CH3 | CH3 | H | I | CN | Cl | H | H | - |
248 | N | NHCO2CH3 | CH3 | H | I | OCH2CF3 | Cl | H | H | - |
249 | N | NHCO2CH3 | CH3 | H | I | OCF3 | Cl | H | H | - |
250 | N | NHCO2CH3 | CH3 | H | I | SCH3 | Cl | H | H | - |
251 | N | NHCO2CH3 | CH3 | H | I | CF3 | Cl | H | H | - |
252 | N | NHCO2CH3 | CH3 | H | I | CO2C2H5 | Cl | H | H | - |
253 | N | NHCO2CH3 | CH3 | H | I | CH2N3 | Cl | H | H | - |
254 | N | NHCO2CH3 | CH3 | H | CN | Br | Cl | H | H | - |
255 | N | NHCO2CH3 | CH3 | H | CN | Cl | Cl | H | H | - |
256 | N | NHCO2CH3 | CH3 | H | CN | CN | Cl | H | H | - |
257 | N | NHCO2CH3 | CH3 | H | CN | OCH2CF3 | Cl | H | H | - |
258 | N | NHCO2CH3 | CH3 | H | CN | OCF3 | Cl | H | H | - |
259 | N | NHCO2CH3 | CH3 | H | CN | SCH3 | Cl | H | H | - |
260 | N | NHCO2CH3 | CH3 | H | CN | CF3 | Cl | H | H | - |
261 | N | NHCO2CH3 | CH3 | H | CN | CO2C2H5 | Cl | H | H | - |
262 | N | NHCO2CH3 | CH3 | H | CN | CH2N3 | Cl | H | H | - |
263 | N | NHCO2CH3 | H | Cl | H | Br | Cl | H | H | 122-124 |
264 | N | NHCO2CH3 | H | Cl | H | Cl | Cl | H | H | - |
265 | N | NHCO2CH3 | H | Cl | H | CN | Cl | H | H | - |
266 | N | NHCO2CH3 | H | Cl | H | OCH2CF3 | Cl | H | H | - |
267 | N | NHCO2CH3 | H | C1 | H | OCF3 | Cl | H | H | - |
268 | N | NHCO2CH3 | H | Cl | H | SCH3 | Cl | H | H | - |
269 | N | NHCO2CH3 | H | Cl | H | CF3 | Cl | H | H | - |
270 | N | NHCO2CH3 | H | Cl | H | CO2C2H5 | Cl | H | H | - |
271 | N | NHCO2CH3 | H | Cl | H | CH2N3 | Cl | H | H | - |
[0082]
272 | N | NIHCO2CH3 | H | H | Cl | Br | Cl | H | H | 167-168 |
273 | N | NHCO2CH3 | H | H | Cl | Cl | Cl | H | H | - |
274 | N | NHCO2CH3 | H | H | Cl | CN | Cl | H | H | - |
275 | N | NHCO2CH3 | H | H | Cl | OCH2CF3 | Cl | H | H | - |
276 | N | NHCO2CH3 | H | H | Cl | OCF3 | Cl | H | H | - |
277 | N | NHCO2CH3 | H | H | Cl | SCH3 | Cl | H | H | - |
278 | N | NHCO2CH3 | H | H | Cl | CF3 | Cl | H | H | - |
279 | N | NHCO2CH3 | H | H | Cl | CO2C2H5 | Cl | H | H | - |
280 | N | NHCO2CH3 | H | H | Cl | CH2N3 | Cl | H | H | - |
281 | N | NHCO2CH3 | CH3 | H | H | Br | Cl | H | H | 151-152 |
282 | N | NHCO2CH3 | CH3 | H | H | Cl | Cl | H | H | - |
283 | N | NHCO2CH3 | CH3 | H | H | CN | Cl | H | H | - |
284 | N | NHCO2CH3 | CH3 | H | H | OCH2CF3 | Cl | H | H | - |
285 | N | NHCO2CH3 | CH3 | H | H | OCF3 | Cl | H | H | - |
286 | N | NHCO2CH3 | CH3 | H | H | SCH3 | Cl | H | H | - |
287 | N | NHCO2CH3 | CH3 | H | H | CF3 | Cl | H | H | - |
288 | N | NHCO2CH3 | CH3 | H | H | CO2C2H5 | Cl | H | H | - |
289 | N | NHCO2CH3 | CH3 | H | H | CH2N3 | Cl | H | H | - |
290 | N | NHCO2C2H5 | CH3 | H | Cl | Br | Cl | H | H | 126-128 |
291 | N | NHCO2C2H5 | CH3 | H | Cl | C1 | Cl | H | H | - |
292 | N | NHCO2C2H5 | CH3 | H | Cl | CN | Cl | H | H | - |
293 | N | NHCO2C2H5 | CH3 | H | Cl | OCH2CF3 | Cl | H | H | - |
294 | N | NHCO2C2H5 | CH3 | H | Cl | OCF3 | Cl | H | H | - |
295 | N | NHCO2C2H5 | CH3 | H | Cl | SCH3 | Cl | H | H | - |
296 | N | NHCO2C2H5 | CH3 | H | Cl | CF3 | Cl | H | H | 111-112 |
297 | N | NHCO2C2H5 | CH3 | H | Cl | CO2C2H5 | Cl | H | H | - |
298 | N | NHCO2C2H5 | CH3 | H | Cl | CH2N3 | Cl | H | H | - |
299 | N | NHCO2C2H5 | CH3 | H | Br | Br | Cl | H | H | - |
300 | N | NHCO2C2H5 | CH3 | H | Br | Cl | Cl | H | H | - |
301 | N | NHCO2C2H5 | CH3 | H | Br | CN | Cl | H | H | - |
302 | N | NHCO2C2H5 | CH3 | H | Br | OCH2CF3 | Cl | H | H | - |
303 | N | NHCO2C2H5 | CH3 | H | Br | OCF3 | Cl | H | H | - |
304 | N | NHCO2C2H5 | CH3 | H | Br | SCH3 | Cl | H | H | - |
305 | N | NHCO2C2H5 | CH3 | H | Br | CF3 | Cl | H | H | - |
306 | N | NHCO2C2H5 | CH3 | H | Br | CO2C2H5 | Cl | H | H | - |
307 | N | NHCO2C2H5 | CH3 | H | Br | CH2N3 | Cl | H | H | - |
308 | N | NHCO2C2H5 | CH3 | H | I | Br | Cl | H | H | - |
[0083]
309 | N | NHCO2C2H5 | CH3 | H | I | Cl | Cl | H | H | - |
310 | N | NHCO2C2H5 | CH3 | H | I | CN | Cl | H | H | - |
311 | N | NHCO2C2H5 | CH3 | H | I | OCH2CF3 | Cl | H | H | - |
312 | N | NHCO2C2H5 | CH3 | H | I | OCF3 | Cl | H | H | - |
313 | N | NHCO2C2H5 | CH3 | H | I | SCH3 | Cl | H | H | - |
314 | N | NHCO2C2H5 | CH3 | H | I | CF3 | Cl | H | H | - |
315 | N | NHCO2C2H5 | CH3 | H | I | CO2C2H5 | Cl | H | H | - |
316 | N | NHCO2C2H5 | CH3 | H | I | CH2N3 | Cl | H | H | - |
317 | N | NHCO2C2H5 | CH3 | H | CN | Br | Cl | H | H | - |
318 | N | NHCO2C2H5 | CH3 | H | CN | Cl | Cl | H | H | - |
319 | N | NHCO2C2H5 | CH3 | H | CN | CN | Cl | H | H | - |
320 | N | NHCO2C2H5 | CH3 | H | CN | OCH2CF3 | Cl | H | H | - |
321 | N | NHCO2C2H5 | CH3 | H | CN | OCF3 | Cl | H | H | - |
322 | N | NHCO2C2H5 | CH3 | H | CN | SCH3 | Cl | H | H | - |
323 | N | NHCO2C2H5 | CH3 | H | CN | CF3 | Cl | H | H | - |
324 | N | NHCO2C2H5 | CH3 | H | CN | CO2C2H5 | Cl | H | H | - |
325 | N | NHCO2C2H5 | CH3 | H | CN | CH2N3 | Cl | H | H | - |
326 | N | NHCO2CH(CH3)2 | CH3 | H | Cl | Br | Cl | H | H | 118-119 |
327 | N | NHCO2CH(CH3)2 | CH3 | H | Cl | Cl | Cl | H | H | - |
328 | N | NHCO2CH(CH3)2 | CH3 | H | Cl | CN | Cl | H | H | - |
329 | N | NHCO2CH(CH3)2 | CH3 | H | Cl | OCH2CF3 | Cl | H | H | - |
330 | N | NHCO2CH(CH3)2 | CH3 | H | Cl | OCF3 | Cl | H | H | - |
331 | N | NHCO2CH(CH3)2 | CH3 | H | Cl | SCH3 | Cl | H | H | - |
332 | N | NHCO2CH(CH3)2 | CH3 | H | Cl | CF3 | Cl | H | H | 115-117 |
333 | N | NHCO2CH(CH3)2 | CH3 | H | Cl | CO2C2H5 | Cl | H | H | - |
334 | N | NHCO2CH(CH3)2 | CH3 | H | Cl | CH2N3 | Cl | H | H | - |
335 | N | NHCO2CH(CH3)2 | CH3 | H | Br | Br | Cl | H | H | - |
336 | N | NHCO2CH(CH3)2 | CH3 | H | Br | Cl | Cl | H | H | - |
337 | N | NHCO2CH(CH3)2 | CH3 | H | Br | CN | Cl | H | H | - |
338 | N | NHCO2CH(CH3)2 | CH3 | H | Br | OCH2CF3 | Cl | H | H | - |
339 | N | NHCO2CH(CH3)2 | CH3 | H | Br | OCF3 | Cl | H | H | - |
340 | N | NHCO2CH(CH3)2 | CH3 | H | Br | SCH3 | Cl | H | H | - |
341 | N | NHCO2CH(CH3)2 | CH3 | H | Br | CF3 | Cl | H | H | - |
342 | N | NHCO2CH(CH3)2 | CH3 | H | Br | CO2C2H5 | Cl | H | H | - |
343 | N | NHCO2CH(CH3)2 | CH3 | H | Br | CH2N3 | Cl | H | H | - |
344 | N | NHCO2CH(CH3)2 | CH3 | H | I | Br | Cl | H | H | - |
345 | N | NHCO2CH(CH3)2 | CH3 | H | I | Cl | Cl | H | H | - |
[0084]
346 | N | NHCO2CH(CH3)2 | CH3 | H | I | CN | Cl | H | H | - |
347 | N | NHCO2CH(CH3)2 | CH3 | H | I | OCH2CF3 | Cl | H | H | - |
348 | N | NHCO2CH(CH3)2 | CH3 | H | I | OCF3 | Cl | H | H | - |
349 | N | NHCO2CH(CH3)2 | CH3 | H | I | SCH3 | Cl | H | H | - |
350 | N | NHCO2CH(CH3)2 | CH3 | H | I | CF3 | Cl | H | H | - |
351 | N | NHCO2CH(CH3)2 | CH3 | H | I | CO2C2H5 | Cl | H | H | - |
352 | N | NHCO2CH(CH3)2 | CH3 | H | I | CH2N3 | Cl | H | H | - |
353 | N | NHCO2CH(CH3)2 | CH3 | H | CN | Br | Cl | H | H | - |
354 | N | NHCO2CH(CH3)2 | CH3 | H | CN | Cl | Cl | H | H | - |
355 | N | NHCO2CH(CH3)2 | CH3 | H | CN | CN | Cl | H | H | - |
356 | N | NHCO2CH(CH3)2 | CH3 | H | CN | OCH2CF3 | Cl | H | H | - |
357 | N | NHCO2CH(CH3)2 | CH3 | H | CN | OCF3 | Cl | H | H | - |
358 | N | NHCO2CH(CH3)2 | CH3 | H | CN | SCH3 | Cl | H | H | - |
359 | N | NHCO2CH(CH3)2 | CH3 | H | CN | CF3 | Cl | H | H | - |
360 | N | NHCO2CH(CH3)2 | CH3 | H | CN | CO2C2H5 | Cl | H | H | - |
361 | N | NHCO2CH(CH3)2 | CH3 | H | CN | CH2N3 | Cl | H | H | - |
362 | N | NHCOCO2CH3 | CH3 | H | Cl | Br | Cl | H | H | 195-197 |
363 | N | NHCOCO2CH3 | CH3 | H | Cl | Cl | Cl | H | H | - |
364 | N | NHCOCO2CH3 | CH3 | H | Cl | CN | Cl | H | H | - |
365 | N | NHCOCO2CH3 | CH3 | H | Cl | OCH2CF3 | Cl | H | H | - |
366 | N | NHCOCO2CH3 | CH3 | H | Cl | OCF3 | Cl | H | H | - |
367 | N | NHCOCO2CH3 | CH3 | H | Cl | SCH3 | Cl | H | H | - |
368 | N | NHCOCO2CH3 | CH3 | H | Cl | CF3 | Cl | H | H | 134-136 |
369 | N | NHCOCO2CH3 | CH3 | H | Cl | CO2C2H5 | Cl | H | H | - |
370 | N | NHCOCO2CH3 | CH3 | H | Cl | CH2N3 | Cl | H | H | - |
371 | N | NHCOCO2CH3 | CH3 | H | Br | Br | Cl | H | H | - |
372 | N | NHCOCO2CH3 | CH3 | H | Br | Cl | Cl | H | H | - |
373 | N | NHCOCO2CH3 | CH3 | H | Br | CN | Cl | H | H | - |
374 | N | NHCOCO2CH3 | CH3 | H | Br | OCH2CF3 | Cl | H | H | - |
375 | N | NHCOCO2CH3 | CH3 | H | Br | OCF3 | Cl | H | H | - |
376 | N | NHCOCO2CH3 | CH3 | H | Br | SCH3 | Cl | H | H | - |
377 | N | NHCOCO2CH3 | CH3 | H | Br | CF3 | Cl | H | H | - |
378 | N | NHCOCO2CH3 | CH3 | H | Br | CO2C2H5 | Cl | H | H | - |
379 | N | NHCOCO2CH3 | CH3 | H | Br | CH2N3 | Cl | H | H | - |
380 | N | NHCOCO2CH3 | CH3 | H | I | Br | Cl | H | H | - |
381 | N | NHCOCO2CH3 | CH3 | H | I | Cl | Cl | H | H | - |
382 | N | NHCOCO2CH3 | CH3 | H | I | CN | Cl | H | H | - |
[0085]
383 | N | NHCOCO2CH3 | CH3 | H | I | OCH2CF3 | Cl | H | H | - |
384 | N | NHCOCO2CH3 | CH3 | H | I | OCF3 | Cl | H | H | - |
385 | N | NHCOCO2CH3 | CH3 | H | I | SCH3 | Cl | H | H | - |
386 | N | NHCOCO2CH3 | CH3 | H | I | CF3 | Cl | H | H | - |
387 | N | NHCOCO2CH3 | CH3 | H | I | CO2C2H5 | Cl | H | H | - |
388 | N | NHCOCO2CH3 | CH3 | H | I | CH2N3 | Cl | H | H | - |
389 | N | NHCOCO2CH3 | CH3 | H | CN | Br | Cl | H | H | - |
390 | N | NHCOCO2CH3 | CH3 | H | CN | Cl | Cl | H | H | - |
391 | N | NHCOCO2CH3 | CH3 | H | CN | CN | Cl | H | H | - |
392 | N | NHCOCO2CH3 | CH3 | H | CN | OCH2CF3 | Cl | H | H | - |
393 | N | NHCOCO2CH3 | CH3 | H | CN | OCF3 | Cl | H | H | - |
394 | N | NHCOCO2CH3 | CH3 | H | CN | SCH3 | Cl | H | H | - |
395 | N | NHCOCO2CH3 | CH3 | H | CN | CF3 | Cl | H | H | - |
396 | N | NHCOCO2CH3 | CH3 | H | CN | CO2C2H5 | Cl | H | H | - |
397 | N | NHCOCO2CH3 | CH3 | H | CN | CH2N3 | Cl | H | H | - |
398 | N | NHCOCO2C2H5 | CH3 | H | Cl | Br | Cl | H | H | 111-112 |
399 | N | NHCOCO2C2H5 | CH3 | H | Cl | Cl | Cl | H | H | - |
400 | N | NHCOCO2C2H5 | CH3 | H | Cl | CN | Cl | H | H | - |
401 | N | NHCOCO2C2H5 | CH3 | H | Cl | OCH2CF3 | Cl | H | H | - |
402 | N | NHCOCO2C2H5 | CH3 | H | Cl | OCF3 | Cl | H | H | - |
403 | N | NHCOCO2C2H5 | CH3 | H | Cl | SCH3 | Cl | H | H | - |
404 | N | NHCOCO2C2H5 | CH3 | H | Cl | CF3 | Cl | H | H | - |
405 | N | NHCOCO2C2H5 | CH3 | H | Cl | CO2C2H5 | Cl | H | H | - |
406 | N | NHCOCO2C2H5 | CH3 | H | Cl | CH2N3 | Cl | H | H | - |
407 | N | NHCOCO2C2H5 | CH3 | H | Br | Br | Cl | H | H | - |
408 | N | NHCOCO2C2H5 | CH3 | H | Br | Cl | Cl | H | H | - |
409 | N | NHCOCO2C2H5 | CH3 | H | Br | CN | Cl | H | H | - |
410 | N | NHCOCO2C2H5 | CH3 | H | Br | OCH2CF3 | Cl | H | H | - |
411 | N | NHCOCO2C2H5 | CH3 | H | Br | OCF3 | Cl | H | H | - |
412 | N | NHCOCO2C2H5 | CH3 | H | Br | SCH3 | Cl | H | H | - |
413 | N | NHCOCO2C2H5 | CH3 | H | Br | CF3 | Cl | H | H | - |
414 | N | NHCOCO2C2H5 | CH3 | H | Br | CO2C2H5 | Cl | H | H | - |
415 | N | NHCOCO2C2H5 | CH3 | H | Br | CH2N3 | Cl | H | H | - |
416 | N | NHCOCO2C2H5 | CH3 | H | I | Br | Cl | H | H | - |
417 | N | NHCOCO2C2H5 | CH3 | H | I | Cl | Cl | H | H | - |
418 | N | NHCOCO2C2H5 | CH3 | H | I | CN | Cl | H | H | - |
419 | N | NHCOCO2C2H5 | CH3 | H | I | OCH2CF3 | Cl | H | H | - |
[0086]
420 | N | NHCOCO2C2H5 | CH3 | H | I | OCF3 | Cl | H | H | - |
421 | N | NHCOCO2C2H5 | CH3 | H | I | SCH3 | Cl | H | H | - |
422 | N | NHCOCO2C2H5 | CH3 | H | I | CF3 | Cl | H | H | - |
423 | N | NHCOCO2C2H5 | CH3 | H | I | CO2C2H5 | Cl | H | H | - |
424 | N | NHCOCO2C2H5 | CH3 | H | I | CH2N3 | Cl | H | H | - |
425 | N | NHCOCO2C2H5 | CH3 | H | CN | Br | Cl | H | H | - |
426 | N | NHCOCO2C2H5 | CH3 | H | CN | Cl | Cl | H | H | - |
427 | N | NHCOCO2C2H5 | CH3 | H | CN | CN | Cl | H | H | - |
428 | N | NHCOCO2C2H5 | CH3 | H | CN | OCH2CF3 | Cl | H | H | - |
429 | N | NHCOCO2C2H5 | CH3 | H | CN | OCF3 | Cl | H | H | - |
430 | N | NHCOCO2C2H5 | CH3 | H | CN | SCH3 | Cl | H | H | - |
431 | N | NHCOCO2C2H5 | CH3 | H | CN | CF3 | Cl | H | H | - |
432 | N | NHCOCO2C2H5 | CH3 | H | CN | CO2C2H5 | Cl | H | H | - |
433 | N | NHCOCO2C2H5 | CH3 | H | CN | CH2N3 | Cl | H | H | - |
434 | N | NHCOCO2CH(CH3)2 | CH3 | H | Cl | Br | Cl | H | H | - |
435 | N | NHCOCO2CH(CH3)2 | CH3 | H | Cl | Cl | Cl | H | H | - |
436 | N | NHCOCO2CH(CH3)2 | CH3 | H | Cl | CN | Cl | H | H | - |
437 | N | NHCOCO2CH(CH3)2 | CH3 | H | Cl | OCH2CF3 | Cl | H | H | - |
438 | N | NHCOCO2CH(CH3)2 | CH3 | H | Cl | OCF3 | Cl | H | H | - |
439 | N | NHCOCO2CH(CH3)2 | CH3 | H | Cl | SCH3 | Cl | H | H | - |
440 | N | NHCOCO2CH(CH3)2 | CH3 | H | Cl | CF3 | Cl | H | H | - |
441 | N | NHCOCO2CH(CH3)2 | CH3 | H | Cl | CO2C2H5 | Cl | H | H | - |
442 | N | NHCOCO2CH(CH3)2 | CH3 | H | Cl | CH2N3 | Cl | H | H | - |
443 | N | NHCOCO2CH(CH3)2 | CH3 | H | Br | Br | Cl | H | H | - |
444 | N | NHCOCO2CH(CH3)2 | CH3 | H | Br | Cl | Cl | H | H | - |
445 | N | NHCOCO2CH(CH3)2 | CH3 | H | Br | CN | Cl | H | H | - |
446 | N | NHCOCO2CH(CH3)2 | CH3 | H | Br | OCH2CF3 | Cl | H | H | - |
447 | N | NHCOCO2CH(CH3)2 | CH3 | H | Br | OCF3 | Cl | H | H | - |
448 | N | NHCOCO2CH(CH3)2 | CH3 | H | Br | SCH3 | Cl | H | H | - |
449 | N | NHCOCO2CH(CH3)2 | CH3 | H | Br | CF3 | Cl | H | H | - |
450 | N | NHCOCO2CH(CH3)2 | CH3 | H | Br | CO2C2H5 | Cl | H | H | - |
451 | N | NHCOCO2CH(CH3)2 | CH3 | H | Br | CH2N3 | Cl | H | H | - |
452 | N | NHCOCO2CH(CH3)2 | CH3 | H | I | Br | Cl | H | H | - |
453 | N | NHCOCO2CH(CH3)2 | CH3 | H | I | Cl | Cl | H | H | - |
454 | N | NHCOCO2CH(CH3)2 | CH3 | H | I | CN | Cl | H | H | - |
455 | N | NHCOCO2CH(CH3)2 | CH3 | H | I | OCH2CF3 | Cl | H | H | - |
456 | N | NHCOCO2CH(CH3)2 | CH3 | H | I | OCF3 | Cl | H | H | - |
[0087]
457 | N | NHCOCO2CH(CH3)2 | CH3 | H | I | SCH3 | Cl | H | H | - |
458 | N | NHCOCO2CH(CH3)2 | CH3 | H | I | CF3 | Cl | H | H | - |
459 | N | NHCOCO2CH(CH3)2 | CH3 | H | I | CO2C2H5 | Cl | H | H | - |
460 | N | NHCOCO2CH(CH3)2 | CH3 | H | I | CH2N3 | Cl | H | H | - |
461 | N | NHCOCO2CH(CH3)2 | CH3 | H | CN | Br | Cl | H | H | - |
462 | N | NHCOCO2CH(CH3)2 | CH3 | H | CN | Cl | Cl | H | H | - |
463 | N | NHCOCO2CH(CH3)2 | CH3 | H | CN | CN | Cl | H | H | - |
464 | N | NHCOCO2CH(CH3)2 | CH3 | H | CN | OCH2CF3 | Cl | H | H | - |
465 | N | NHCOCO2CH(CH3)2 | CH3 | H | CN | OCF3 | Cl | H | H | - |
466 | N | NHCOCO2CH(CH3)2 | CH3 | H | CN | SCH3 | Cl | H | H | - |
467 | N | NHCOCO2CH(CH3)2 | CH3 | H | CN | CF3 | Cl | H | H | - |
468 | N | NHCOCO2CH(CH3)2 | CH3 | H | CN | CO2C2H5 | Cl | H | H | - |
469 | N | NHCOCO2CH(CH3)2 | CH3 | H | CN | CH2N3 | Cl | H | H | - |
470 | N | NHCOCO2CH2CH=CH2 | CH3 | H | Cl | Br | Cl | H | H | 117-119 |
471 | N | NHCOCO2CH2CH=CH2 | CH3 | H | Cl | Cl | Cl | H | H | - |
472 | N | NHCOCO2CH2CH=CH2 | CH3 | H | Cl | CN | Cl | H | H | - |
473 | N | NHCOCO2CH2CH=CH2 | CH3 | H | Cl | OCH2CF3 | Cl | H | H | - |
474 | N | NHCOCO2CH2CH=CH2 | CH3 | H | Cl | OCF3 | Cl | H | H | - |
475 | N | NHCOCO2CH2CH=CH2 | CH3 | H | Cl | SCH3 | Cl | H | H | - |
476 | N | NHCOCO2CH2CH=CH2 | CH3 | H | Cl | CF3 | Cl | H | H | - |
477 | N | NHCOCO2CH2CH=CH2 | CH3 | H | Cl | CO2C2H5 | Cl | H | H | - |
478 | N | NHCOCO2CH2CH=CH2 | CH3 | H | Cl | CH2N3 | Cl | H | H | - |
479 | N | NHCOCO2CH2CH=CH2 | CH3 | H | Br | Br | Cl | H | H | - |
480 | N | NHCOCO2CH2CH=CH2 | CH3 | H | Br | Cl | Cl | H | H | - |
481 | N | NHCOCO2CH2CH=CH2 | CH3 | H | Br | CN | Cl | H | H | - |
482 | N | NHCOCO2CH2CH=CH2 | CH3 | H | Br | OCH2CF3 | Cl | H | H | - |
483 | N | NHCOCO2CH2CH=CH2 | CH3 | H | Br | OCF3 | Cl | H | H | - |
484 | N | NHCOCO2CH2CH=CH2 | CH3 | H | Br | SCH3 | Cl | H | H | - |
485 | N | NHCOCO2CH2CH=CH2 | CH3 | H | Br | CF3 | Cl | H | H | - |
486 | N | NHCOCO2CH2CH=CH2 | CH3 | H | Br | CO2C2H5 | Cl | H | H | - |
487 | N | NHCOCO2CH2CH=CH2 | CH3 | H | Br | CH2N3 | Cl | H | H | - |
488 | N | NHCOCO2CH2CH=CH2 | CH3 | H | I | Br | Cl | H | H | - |
489 | N | NHCOCO2CH2CH=CH2 | CH3 | H | I | Cl | Cl | H | H | - |
490 | N | NHCOCO2CH2CH=CH2 | CH3 | H | I | CN | Cl | H | H | - |
491 | N | NHCOCO2CH2CH=CH2 | CH3 | H | I | OCH2CF3 | Cl | H | H | - |
492 | N | NHCOCO2CH2CH=CH2 | CH3 | H | I | OCF3 | Cl | H | H | - |
493 | N | NHCOCO2CH2CH=CH2 | CH3 | H | l | SCH3 | Cl | H | H | - |
[0088]
494 | N | NHCOCO2CH2CH=CH2 | CH3 | H | I | CF3 | Cl | H | H | - |
495 | N | NHCOCO2CH2CH=CH2 | CH3 | H | I | CO2C2H5 | Cl | H | H | - |
496 | N | NHCOCO2CH2CH=CH2 | CH3 | H | I | CH2N3 | Cl | H | H | - |
497 | N | NHCOCO2CH2CH=CH2 | CH3 | H | CN | Br | Cl | H | H | - |
498 | N | NHCOCO2CH2CH=CH2 | CH3 | H | CN | Cl | Cl | H | H | - |
499 | N | NHCOCO2CH2CH=CH2 | CH3 | H | CN | CN | Cl | H | H | - |
500 | N | NHCOCO2CH2CH=CH2 | CH3 | H | CN | OCH2CF3 | Cl | H | H | - |
501 | N | NHCOCO2CH2CH=CH2 | CH3 | H | CN | OCF3 | Cl | H | H | - |
502 | N | NHCOCO2CH2CH=CH2 | CH3 | H | CN | SCH3 | Cl | H | H | - |
503 | N | NHCOCO2CH2CH=CH2 | CH3 | H | CN | CF3 | Cl | H | H | - |
504 | N | NHCOCO2CH2CH=CH2 | CH3 | H | CN | CO2C2H5 | Cl | H | H | - |
505 | N | NHCOCO2CH2CH=CH2 | CH3 | H | CN | CH2N3 | Cl | H | H | - |
506 | N | NH2 | CH3 | H | Cl | Br | Cl | H | t-C4H9 | - |
507 | N | NHCOCH3 | CH3 | H | Cl | Br | Cl | H | t-C4H9 | - |
508 | N | NHCO2CH3 | CH3 | H | Cl | Br | Cl | H | t-C4H9 | - |
509 | N | NHCOCO2CH3 | CH3 | H | Cl | Br | Cl | H | t-C4H9 | - |
表2
实施例8
利用本发明提供的衍生物(01~509)进行测试,验证对害虫生物活性评价:
将本发明提供的任一种衍生物(01~509)溶于溶剂、水和表面活性剂,混合成为均一水相,使用时可用水稀释至任何所需的浓度,测试对象和测试方法如下:
1)对东方粘虫的生物活性评价:供试昆虫是东方粘虫(Mythimna separata Walker),室内用玉米叶饲养的正常群体。采用浸叶法,浸渍苗期玉米叶于已配置好的溶液中,晾干后放入直径7cm培养皿中,接入4龄幼虫,每个浓度重复3次;对照用丙酮溶液浸渍玉米叶饲养幼虫;24小时、48小时、72小时后观察试验结果;
2)对小菜蛾的生物活性评价:供试昆虫是小菜蛾2龄幼虫(Plutella xylostella(L.)),为室内正常饲养的正常群体;采用浸叶法,用镊子浸渍甘蓝叶片于已配置好的溶液中,时间2--3秒,甩掉余液;每次1片,每个样品共3片;待药液干后,放入10cm长的直型试管内,接入2龄小菜蛾幼虫,用纱布盖好管口;将试验处理置于标准处理室内,24小时、48小时、72小时后观察试验结果;
3)对甜菜夜蛾的生物活性评价:供试昆虫是甜菜夜蛾3龄幼虫(Laphygma exigua Hubner),为室内正常饲养的正常群体;采用浸叶法,用镊子浸渍甘蓝叶片于已配置好的溶液中,时间2--3秒,甩掉余液;每次1片,每个样品共3片;待药液干后,放入直径7cm培养皿中,接入甜菜夜蛾3龄幼虫,将试验处理置于标准处理室内,24小时、48小时、72小时后观察试验结果;
4)蜕皮激素实验:以东方粘虫(Mythimna separata Walker)作为受试昆虫,化合物进行了杀虫活性筛选,为了对照,在相同条件下对商业品种米螨(mimic)也进行了测试。测试采用浸叶法,将样品用丙酮配制成不同浓度的溶液,浸渍苗期玉米叶,晾干后放入7cm培养皿中,接入3龄幼虫,重复2~4次。对照用丙酮溶液浸渍玉米叶饲养幼虫。24h后随时添加新鲜的玉米叶片。在24,48,72,96h观察试验结果,直至对照幼虫正常蜕皮变成4龄。以粘虫幼虫完全死亡,即触之不动为幼虫的死亡标准。
上述试验的测试结果如表3所示。
表3
表中死亡率等级:A级为100%-90%;B级为90%-70%;C级为70%-50%:D级为50%-0%。
Claims (8)
1.一类吡唑酰肼衍生物,其特征在于具有以下结构式:
式中:
X是C或N;
R1是H、卤素、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基、C1-C6烷基羰基、C1-C6烷氧基羰基、卤代C1-C6烷基羰基或NH-R9;
R2是H、卤素、硝基、氨基、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基、C1-C6烷硫基、C1-C6烷磺酰基;
R3是H、卤素、C1-C6烷基、硝基;
R4是H、卤素、氰基、硝基;
R5是卤素、氰基、C1-C6烷氧基、卤代C1-C6烷氧基、C1-C6烷硫基、卤代C1-C6烷硫基、C2-C6烯氧基、卤代C2-C6烯氧基、C2-C6炔氧基、卤代C2-C6炔氧基、C2-C6烷酰氧基或卤代C2-C6烷酰氧基、C1-C6烷基羰基、C1-C6烷氧基C1-C6烷基、卤代C1-C6烷氧基C1-C6烷基、C1-C6烷硫基C1-C6烷基、CH2N3、CH2NH2;
R6是H或卤素;
R7是H、C1-C6烷氧基、卤代C1-C6烷氧基、C1-C6烷硫基、卤代C1-C6烷硫基;
R8是H、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基、C1-C6烷基羰基、卤代C1-C6烷基羰基、C1-C6烷氧草酰基、C1-C6烷氧羰基;
R9是H、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基、C1-C6烷基羰基、卤代C1-C6烷基羰基、C1-C6烷氧草酰基、C1-C6烷氧羰基;
在上述衍生物的定义中,所用术语不论单独使用还是用在复合词中,代表如下取代基:
卤素为氟、氯、溴或碘;
烷基为直链或支链烷基;
卤代烷基为直链或支链烷基,在这些烷基上的氢原子可以部分或全部被卤原子取代;“卤代烯基”、“卤代炔基”和“卤代环烷基”的定义与术语“卤代烷基”相同;
烯基为有2-6个碳原子的直链或支链并可在任何位置上存在有双键;
炔基为有2-6个碳原子的直链或支链并可在任何位置上存在有三键。
2.根据权利要求1所述的酰肼衍生物,其特征在于:
R1=H、卤素、NH2、NHCOCH3、NHCOCH(CH3)2、NHCOCH2Cl、NHCOPh、NHCOC2H5、NHCO2CH3、NHCO2C2H5、NHCO2CH(CH3)2、NHCOCO2CH3、NHCOCO2C2H5、NHCOCO2CH(CH3)2、NHCOCO2CH2CH=CH2;
R2=H、CH3;R3=H、卤素、CH3、CF3;R4=H、卤素、CN;R5=卤素、CN、OCH2CF3、OCF3、SCH3、CF3、CO2C2H5、CH2N3;R6=Cl;R7=H、t-C4H9;R8=H、t-C4H9、COCH3。
3.根据权利要求1所述的酰肼衍生物,其特征在于:
R1=H、卤素、NH2、NHCOCH3、NHCOCH(CH3)2、NHCOCCl3、NHCOCH2Cl、NHCOPh、
NHCO2C2H5、NHCO2CH(CH3)2、NHCOCO2CH3、NHCOCO2C2H5、NHCOCO2CH2CH=CH2;
R2=H、CH3;R3=H、卤素、CH3、CF3;R4=H、卤素、CN;R5=卤素、CN、OCH2CF3、SCH3、CF3、CO2C2H5;R6=Cl;R7=H、t-C4H9;R8=H、COCH3。
4.权利要求1所述的酰肼衍生物的制备方法,其特征在于包括如下的步骤:
酰肼衍生物(I)合成方法一:
通式III化合物在溶于有机溶剂中,加入草酰氯和微量的催化剂,在室温下反应3-12小时制得酰氯,然后与通式IV化合物摩尔比1∶1,溶于有机溶剂中,加入碱,在温度为0-25℃下反应0.5-48小时制得目标化合物I;反应式中各基团如权利要求1所示,R1除外,R1为氨基以及取代氨基以外的基团;或
酰肼衍生物(I)合成方法二:
通式III化合物在溶于有机溶剂中,加入草酰氯和微量的催化剂,在室温下反应3-12小时制得酰氯,然后与通式V化合物摩尔比1∶1,溶于有机溶剂中,加入碱,在温度为0-25℃下反应,0.5-48小时制得化合物II;通式II化合物溶于有机溶剂,加入通式VII化合物和适量的碱,在温度为0-25℃下反应,0.5-48小时制得化合物,反应式中各基团如权利要求1所示。
5.根据权利要求4所述的制备方法,其特征在于所述的有机溶剂选自二氯甲烷、氯仿、四氯化碳、苯、甲苯、二甲苯、环己烷、正己烷、乙酸乙酯、四氢呋喃、1,4-二氧六环、N,N.二甲基甲酰胺或二甲基亚砜。
6.根据权利要求4所述的制备方法,其特征在于所述的碱选自有机碱:三乙胺、吡啶、1,8-二氮杂-双环(5,4,0)十一碳-7-烯或N,N-二甲基苯胺;或无机碱:氢氧化钠、氢氧化钾、碳酸钠、碳酸钾、甲醇钠、叔丁醇钠或叔丁醇钾。
7.权利要求1所述的酰肼衍生物或其在农业上适用的盐,或其立体异构体用于制备农用化学杀虫剂。
8.权利要求1所述的酰肼衍生物作为活性成分与农业可以接受的助剂组成的农药组合物,用作杀虫剂。
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