CN1132816C - 2-吡啶基甲胺衍生物及其应用和杀虫剂组合物 - Google Patents
2-吡啶基甲胺衍生物及其应用和杀虫剂组合物 Download PDFInfo
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Abstract
本发明揭示通式I的化合物及其盐,式中A1是取代的2-吡啶基;A2是任意取代的苯基;L是-(C=O)-、-SO2-或-(C=S)-;R1是氢,任意取代的烷基或酰基;R2是氢或任意取代的烷基。上述的化合物及其盐是有用的杀植物病原性真菌剂。
Description
本发明涉及具有杀真菌活性的化合物及其制备方法和制备用的中间体。
式中
A1是取代的2-吡啶基;
A2是任意取代的苯基;
L是-(C=O)-、-SO2-或-(C=S)-;
R1是氢,任意取代的烷基或酰基;和
R2是氢或任意取代的烷基。
2-吡啶基(A1)最多可有四个取代基,较好最多有两个取代基。这些取代基可以相同或不同。取代基较好位于2-吡啶基的3和/或5位。
2-吡啶基(A1)上的优选取代基是卤素、羟基、氰基、硝基、SF5、三烷基甲硅烷基、任意取代的氨基、酰基、或基团E、OE或SE(式中E是烷基、链烯基、链炔基、环烷基、环烯基、苯基或杂环基,这些基团都可被任意取代)、或基团-C(E)=N-Q(式中Q是E、OE、SE或任意取代的氨基);或者两个相邻的取代基与相连的原子一起形成任意取代的环,这种环最多可含有3个杂原子。特别优选的取代基是烷氧基、烷基、氰基、卤素、硝基、烷氧基羰基、烷基亚磺酰基、烷基磺酰基和三氟甲基,最好是氯和三氟甲基。
苯基A2可最多具有5个取代基,较好最多有3个取代基,更好最多有2个取代基,这些取代基可以相同或不同。优选的取代基与A1中所述的取代基相同。特别优选的取代基是烷氧基、烷基、卤素、硝基或三氟甲基。
优选的连接基团L是-(C=O)-。
R1较好是氢。当它不是氢时,较好是烷基(被苯基任意取代)或烷氧基羰基。
许多用通式I表示的化合物是新颖的。因此,本发明的第二方面提供用通式I表示的化合物,式中A1是在3和/或5位有取代基而在其它位置没有取代基的2-吡啶基,R1和R2是氢,A2和L与上述定义相同。
本发明也包括下面具体列举的化合物。
分子中的烷基较好含1-10个碳原子,更好含1-7个碳原子,特别好含1-5个碳原子。
分子中的链烯基或链炔基较好含2-7个碳原子,例如烯丙基、乙烯基或炔丙基。
分子中的环烷基、环烯基或环炔基较好含3-7个碳原子,如环丙基、环戊基、环己基或环己烯基。
当烷基、链烯基、链炔基、环烷基、环烯基、环炔基上有取代基时,该取代基例如是卤素、氰基、任意取代的烷氧基、任意取代的烷硫基、巯基、羟基、硝基、任意取代的氨基、酰基、酰氧基、酰硫基、任意取代的苯基、任意取代的杂环基、任意取代的苯硫基、任意取代的苯氧基、任意取代的杂环氧基或任意取代的杂环硫基。
烷基、链烯基或链炔基上的优选取代基是烷氧基、卤代烷氧基或烷硫基(上述取代基都含有1-5个碳原子);卤素;或任意取代的苯基。特别优选的基团是三氟甲基。
环烷基、环烯基、环炔基也可被任意取代的烷基、链炔基或链烯基等取代。反过来也可以。
当苯基或杂环基有取代基时,取代基较好是上述A2上的取代基。
术语杂环基包括芳族和非芳族杂环基。杂环基一般是至多含4个杂原子的5、6或7元环,上述的杂原子选自氮、氧或硫。杂环基的例子是呋喃基、噻吩基、吡咯基、吡咯啉基、吡咯烷基、咪唑基、二氧戊环基、噁唑基、噻唑基、咪唑基、咪唑啉基、咪唑烷基、吡唑基、吡唑啉基、吡唑烷基、异噁唑基、异噻唑基、噁二唑基、***基、噻二唑基、吡喃基、吡啶基、哌啶基、二噁烷基、吗啉代、二噻烷基、硫代吗啉代、哒嗪基、嘧啶基、吡嗪基、哌嗪基、三嗪基、噻唑啉基、苯并咪唑基、四唑基、苯并噁唑基、咪唑并吡啶基、1,3-苯并噁嗪基、1,3-苯并噻嗪基、噁唑并吡啶基、苯并呋喃基、喹啉基、喹唑啉基、喹喔啉基、环丁砜基、二氢喹唑啉基、苯并噻唑基、苯二甲酰亚胺基、苯并呋喃基、吖庚因基、噁吖庚因基、噻吖庚因基、二吖庚因基和苯并二吖庚因基。
氨基例如可被一个或两个E或酰基取代,每个取代基可以相同或不同,或两个取代基与相连的氮一起形成环,较好是5-7元环。这种环可被取代,且可含有其它杂原子,如吗啉、硫代吗啉或哌啶。这种环一样被取代如A。
术语酰基包括含硫、磷的酸和羧酸的残基。酰基的实例是-COR5a、-COOR5a、-CXNR5aR6a、-CON(R5a)OR6a、-COONR5aR6a、-CON(R5a)NR6aR7a、-COSR5a、-CSSR5a、-S(O)yR5a、-S(O)2OR5a、-S(O)yNR5aR6a、-P(=X)(OR5a)(OR6a)、CO-COOR5a,式中R5a、R6a和R7a可以相同或不同,且为氢、任意取代的烷基、任意取代的链烯基、任意取代的链炔基、任意取代的环烷基、任意取代的环烯基、任意取代的环炔基、任意取代的苯基或任意取代的杂环基,或R5a和R6a、R6a和R7a与相连的原子一起形成一个环,y是1或2,X是O或S。
取代时,苯基或烷基上的取代基是上述的取代基。
在本发明的优选化合物中,
A1是3位和/或5位被氯和/或三氟甲基取代的一取代或二取代的2-吡啶基,如2-(5-氯-3-三氟甲基)吡啶基;X是-C(=O)-;和
R1是氢、烷基,如甲基,特别是氢;
R2是氢、烷基(如甲基)、苄基或烷氧基羰基(如乙氧基羰基),特别是氢。
A2苯基上特别优选的取代基是卤素。
本发明的化合物具有作为杀真菌剂,特别是防治植物真菌疾病的活性,如谷类白粉病菌(Erysiphe graminis)和葡萄霜霉病(Plasmopara viticola)、稻瘟病(Pyricularia oryzae)、谷类眼状斑(Pseudocercosporella herpotrichoides)、稻鞘枯萎病(Pellicularia sasakii)、灰霉病(Botrytis cinerea)、猝倒病(Rhizoctonia solani)、小麦褐锈病(Puccinia recondita)、西红柿或马铃薯晚疫(Phytophthora infestans)、苹果疮痂病(Venturia inaequalis)、麦类颖斑病(Leptosphaeria nodorum)。本发明化合物对其有活性的其它真菌包括其它白粉菌、其它锈菌、以及半知菌纲、子囊菌纲、藻状菌纲和担子菌纲的常规植物病原菌。
因此,本发明也提供在真菌感染或可能感染的地方防治真菌的方法。该方法包括在所述的地方施加通式I表示的化合物。
本发明也提供含有通式I的化合物与农业上可接受的稀释剂或载体混合的农用组合物。
当然,本发明的组合物可包括一种以上的本发明的化合物。
本发明的组合物还可含有一种或多种附加的活性成分,如已知具有植物生长调节剂、除草剂、杀真菌剂、杀虫剂或杀螨剂性能的化合物。或者,本发明的化合物可顺序与其它这些活性成分使用。
本发明组合物中的稀释剂或载体可以是任选地含有表面活性剂,如分散剂、乳化剂或湿润剂的固体或液体。合适的表面活性剂包括阴离子化合物,例如羧酸盐,如长链脂肪酸的羧酸金属盐;N-酰基肌氨酸盐;磷酸与脂肪醇乙氧基化物的单酯或二酯或这些酯的盐;脂肪醇硫酸酯,如十二烷基硫酸钠、十八烷基硫酸钠或十六烷基硫酸钠;乙氧基化脂肪醇硫酸酯;乙氧基化烷基苯酚硫酸酯、木质素磺酸盐;石油磺酸盐;烷基-芳基磺酸盐,如烷基苯磺酸盐或低级烷基萘磺酸盐,如丁基萘磺酸盐;磺化萘-甲醛缩合物的盐;磺化酚-甲醛缩合物的盐;或更复杂的磺酸盐,如酰胺磺酸盐,如油酸与N-甲基牛磺酸或磺基丁二酸二烷基酯的磺化缩合产物,如丁二酸二辛酯的磺酸钠。非离子型表面活性剂包括脂肪酸酯、脂肪醇、脂肪酸酰胺或脂族烷基或链烯基取代的苯酚与环氧乙烷的缩合产物、多元醇醚的脂肪酸酯(如失水山梨糖醇脂肪酸酯)、这些酯与环氧乙烷的缩合产物(如聚氧乙烯失水山梨糖醇脂肪酸酯)、环氧乙烷与环氧丙烷的嵌段共聚物、炔属二醇(如2,4,7,9-四甲基-5-癸炔-4,7-二醇)或乙氧基化炔属二醇。
阳离子表面活性剂的实例包括作为乙酸盐、环烷酸盐或油酸盐存在的脂族一元胺、二元胺或多胺;含氧的胺,如氧化胺或聚氧乙烯烷基胺;经羧酸与二元胺或多胺缩合制得的与酰胺连接的胺;季铵盐。
本发明的组合物可以取本领域中已知的农用化学品制剂的任何形式,如溶液、分散体、水乳液、撒粉、种子涂剂、薰剂、烟剂、可分散的粉末、可乳化的浓缩物或粒状物。另外,它可以是适于直接施用的形式或施用前需用适量的水或其它稀释剂稀释的浓缩物或初级组合物。
可乳化的浓缩物包含溶解在与水不混溶的溶剂中的本发明化合物。这种化合物在乳化剂的存在下与水形成乳状液。
撒粉含有与固体粉状稀释剂(如高岭土)充分混合并碾细的本发明化合物。
粒状固体包含与撒粉中所用的相似稀释剂混合的本发明化合物,但这种混合物用已知的方法造粒。或者,这种粒状固体包含吸收或吸附在预制成颗粒的稀释剂(漂白土、石绒或石灰石粉)上的活性成分。
可湿性粉末、细粒或颗粒通常包含与合适表面活性剂和惰性粉末稀释剂(如陶土)混合的活性成分。
另一种合适的浓缩物是可流动的悬浮液浓缩物。它可通过将本发明的化合物与水或其它液体、湿润剂和悬浮剂一起研磨制得。
施用到植物上时,本发明组合物中活性成分的浓度较好为0.0001-1.0%重量,更好为0.0001-0.01%重量。在初级组合物中,活性成分的量可以在较宽的范围内变化,且例如占组合物的5-95%重量。
在本发明的方法中,化合物一般施用到种子、植物或它们的生长环境中。因此,本发明的化合物可以在播种前、播种时或播种后直接施用于土壤,从而使土壤中存在的活性化合物能控制可能侵害种子的真菌的生长。当直接处理土壤时,该活性化合物可用任何能让其与土壤充分混合的方法施用,如喷雾法、播撒固体颗粒、或在播种时同时施用活性成分。合适的施用量为5-1000克/公顷,更好为10-500克/公顷。
在植物上开始出现真菌时,或者在植物上出现真菌前作为保护措施,例如用喷雾法或撒粉法将活性化合物直接施用在植物上。在这两种情况下,优选的施用方式是叶面喷雾法。一般来说重要的是在植物生长的早期获得对真菌的良好防治,因为这一时期植物损害最严重。如有必要,喷雾剂或撤粉中一般含有萌前或萌后除草剂。有时,宜在栽种前或栽种时处理植物的根,例如将根浸在合适的液体或固体组合物中。当活性化合物直接施用于植物上时,合适的施用量为0.025-5千克/公顷,较好为0.05-1千克/公顷。
另外,本发明的化合物可用于经遗传修饰而具有耐真菌性、耐害虫性和/或耐除草剂性之类特性的植物或植物部分。
用通式I表示的化合物可通过按反应式I使通式II的化合物或其盐酸盐与通式III的化合物反应制得,式中X是离去基团,如卤素。当L是-(C=O)-或-SO2-时,优选的反应条件是在三乙胺的存在下将II与相应的苯甲酰或磺酰氯混合。
通式III化合物是已知的,或可用已知的方法制得。
如下中间体通式IIa的一些化合物是已知的,即R1和R2为氢的通式II化合物。然而,现有技术中没有通式IIa化合物的高产率制备方法。我们现已开发了这样一种方法。
因此,本发明的第三方面提供通式IIa化合物的制备方法。该方法包括如下步骤:
a)在碱性条件下使通式IV化合物与通式V化合物反应,产生通式VI的中间体,
b)将通式VI的中间体转化为通式VII中间体,
c)将通式VII中间体转化为通式IIa化合物,式中
Ra和Rb,可以相同或不同,且为烷基、链烯基、链炔基、环烷基、环烯基、杂环基或苯基(都可被取代,较好为任意取代的苯基)或氢;
E1是吸电子基团或按步骤c)用熟练化学技术人员已知的方法可被氢取代的基团(较好是羧基或羧酸酯基);
X1是离去基团(较好是卤素);
A1和R1与本发明第一方面中的定义相同。
步骤a)中优选的碱性条件包括与碱金属氢化物、醇盐或碳酸盐反应。
步骤b)中优选的反应条件包括用稀酸,特别是稀盐酸处理。
当E1是羧基或羧酸酯基时,脱羧反应(步骤c)的合适反应条件对熟练化学技术人员来说是已知的。优选的脱羧条件包括用稀盐酸水溶液加热VII。
通式IV化合物是已知的,或可用已知的方法制备,可以分离中间体VI和VII。或者可以原位制备,无需分离和提纯直接用于随后的反应步骤。较好是原位制备中间体VI,但较好分离中间体VII。
在本说明书中,除非上下文另有要求,术语“包括”可理解为包括所述的某一整体或一组整体,但不排斥其它任何整体或一组整体,包括方法步骤。
通式IIb化合物的盐酸盐,即R1为任意取代的烷基且R2为氢的通式II化合物,可按反应式2制得。X2是离去基团,如溴,碱较好是叔丁醇钾。转化为IIb的盐酸盐的优选反应条件是用稀盐酸进行处理。
2-吡啶基(A1)至多可有4个取代基,较好至多有2个取代基。这些取代基可以相同或不同。这些取代基较好位于2-吡啶基的3和/或5位上。
取代时,通式IIb中2-吡啶基(A1)上优选取代基是卤素、羟基、氰基、硝基、SF5、三烷基甲硅烷基、任意取代的氨基、酰基、或基团E、OE或SE(式中E是烷基、链烯基、链炔基、环烷基、环烯基、苯基或杂环基,这些基团都可被任意取代)、或基团-C(E)=N-Q(式中Q是E、OE、SE或任意取代的氨基);或者两个相邻的取代基与相连的原子一起形成任意取代的环,这种环最多可含有3个杂原子。特别优选的取代基是烷氧基、烷基、卤素、硝基和三氟甲基,最好是氯和三氟甲基。
A1较好是被氯和/或三氟甲基取代的一或二取代2-吡啶基。
现参照如下的实施例说明本发明。分离得到的新颖化合物的结构用NMR和/或其它合适的分析方法加以确认。
实施例1
N-[(3-氯-5-三氟甲基-2-吡啶基)甲基]-α,α,α-三氟-邻-甲苯甲酰胺(化合物1)
将(3-氯-5-三氟甲基-2-吡啶基)甲胺(0.35克)的干燥***(2毫升)溶液加入到2-三氟甲基苯甲酰氯(0.39克)和三乙胺(0.27毫升)的干燥***(5毫升)溶液中,将该混合物搅拌过夜。加入水(20毫升)和乙酸乙酯(10毫升),分离有机相,用碳酸氢钠水溶液洗涤,干燥,减压下进行蒸馏。用硅胶色谱纯化残留物,得到标题产物,熔点为127-30℃。
实施例2
N-[(3-氯-5-三氟甲基-2-吡啶基)甲基]-N-甲基-2,6-二氯苯甲酰胺(化合物63)
在氮气氛中、室温和搅拌下将氢化钠(0.077克60%油分散体)加入化合物21(参见下表)的干燥四氢呋喃溶液中。将该混合物温热至30℃,10分钟后在室温下再搅拌30分钟。加入甲基碘(0.12毫升),然后在室温下搅拌过夜。通过先滴加甲醇的四氢呋喃溶液,后滴加水,使该混合物猝灭。减压下蒸馏掉四氢呋喃,然后在水和***之间分配所得的残留物。水层用***萃取两次,合并的萃取液用水洗涤,然后以盐水洗涤,干燥。萃取液在减压下进行蒸发,得到标题产物,熔点为83-4℃。
实施例3
N-[(3,5-二氯-2-吡啶基)甲基]-2,6-二氯苯甲酰胺(化合物59)
室温下向步骤b)制得的产物(见下)(0.30克)和三乙胺(0.4毫升)的搅拌着的四氢呋喃(5毫升)溶液中滴加2,6-二氯苯甲酰氯(0.20毫升)。继续搅拌12小时。浓缩反应混合物,加入水(10毫升),然后将混合物搅拌15分钟。过滤混合物,所得的固体先用水洗涤,然后用石油醚(沸点为40-60℃)洗涤。固体用二异丙醚重结晶,得到标题产物,熔点为161-5℃。
制备原料
a)2-(3,5-二氯-2-吡啶基)氨基乙酸乙酯
向0℃的搅拌着的氢化钠(0.445克)的干燥二甲基甲酰胺(4毫升)溶液加入N-(二苯基亚甲基)氨基乙酸乙酯(1.485克)的干燥二甲基甲酰胺(3毫升)溶液,继续搅拌20分钟。然后在5℃下滴加2,3,5,-三氯吡啶(1.58克)的干燥二甲基甲酰胺(4毫升)溶液,历时10分钟,然后在室温下将反应混合物搅拌2小时。加入2M盐酸(25毫升),继续搅拌2小时。然后用***洗涤所得的溶液,并进行分层。水相用饱和碳酸氢钠水溶液中和,然后用乙酸乙酯进行萃取。合并的乙酸乙酯层用盐水洗涤两次,用硫酸镁干燥,过滤,蒸去溶剂后得到残留物。该残留物以硅胶色谱进行提纯,用乙酸乙酯/石油醚(40-60℃)洗脱得到标题产物。
b)(3,5-二氯-2-吡啶基)甲胺盐酸盐
将步骤a)中制得的产物(0.24克)与3M盐酸(20毫升)的混合物回流加热4小时。冷却后,该混合物用***进行洗涤,然后分层。与甲苯共沸蒸馏(3次),从水相中除去水,得到标题产物。
实施例4
N-[1-(3-氯-5-三氟甲基-2-吡啶基)-2-苯基乙基]-2,6-二氯苯甲酰胺(化合物83)
在步骤c)中制得的产物(见下)(0.31克)的二氯甲烷(10毫升)溶液中,加入三乙胺(0.28毫升),然后加入2,6-二氯苯甲酰氯(0.15毫升)。将该混合物在室温下搅拌1.5小时,然后蒸发至干。加入***(20毫升)。该溶液然后依次用2M盐酸(10毫升)、水(10毫升)、碳酸氢钠溶液(10毫升)和水(10毫升)洗涤。分离有机层,干燥(MgSO4),然后除去溶剂。残留物用硅胶色谱(沸点为40-60℃的石油醚∶***(1∶1))提纯,得到标题产物,为固体,熔点为164-8℃。
制备原料
N-[(3-氯-5-三氟甲基-2-吡啶基)甲基]二苯酮亚胺
在10℃向二苯酮亚胺(1.67毫升)的干燥二氯甲烷(25毫升)溶液中加入(3-氯-5-三氟甲基-2-吡啶基)甲胺盐酸盐(2.47克)。该溶液在室温下搅拌3小时,然后过滤。将滤液蒸发至干,用硅胶色谱(石油醚∶***(4∶1))提纯,得到标题产物。
b)N-[1-(3-氯-5-三氟甲基-2-吡啶基)-2-苯基乙基]二苯酮亚胺
在-60℃向叔丁醇钾(0.33克)的四氢呋喃(5毫升)溶液中加入步骤a)中制得的产物的四氢呋喃(10毫升)溶液。在-60℃搅拌10分钟后,在-50℃滴加苄基溴(0.36毫升)的干燥四氢呋喃(20毫升)溶液。让该溶液慢慢达到室温,继续搅拌过夜。然后将该混合物蒸发至干,加入***(35毫升)和乙酸(2毫升)。该混合物用水洗涤(3×10毫升),然后进行分层。将有机层干燥(MgSO4),除去溶剂后得到标题产物。
c)1-(3-氯-5-三氟甲基-2-吡啶基)-2-苯基乙胺盐酸盐
室温下在步骤b)中制得的产物(1.29克)的***(5毫升)溶液中加入1M盐酸(10毫升),然后将该溶液在室温下搅拌2小时。将该混合物过滤后得到固体。该固体先用水(15毫升)洗涤,然后用***(15毫升)洗涤。真空干燥后得到标题产物。与甲苯共沸蒸馏(3次)从水相中除去水,得到额外量的标题产物。
表1
化合物 | R1 | R2 | (R3)q | (R4)p | 熔点(℃) |
1 | H | H | 3-Cl,5-CF3 | 2-CF3 | 127-30 |
2 | H | H | 3-Cl,5-CF3 | 2-丁二酰亚胺基 | 173-4 |
3 | H | H | 3-Cl,5-CF3 | 3-Br | 88 |
4 | H | H | 3-Cl,5-CF3 | 3,5-Cl2 | 138-9 |
5 | H | H | 3-Cl,5-CF3 | 3,4-Cl2 | 147-50 |
6 | H | H | 3-Cl,5-CF3 | 2,5-Cl2 | 123 |
7 | H | H | 3-Cl,5-CF3 | 2,4-Cl2 | 128 |
8 | H | H | 3-Cl,5-CF3 | 2,3-Cl2 | 146-7 |
9 | H | H | 3-Cl,5-CF3 | 2,4-(OMe)2 | 166 |
10 | H | H | 3-Cl,5-CF3 | 3-OPri | 98-100 |
11 | H | H | 3-Cl,5-CF3 | 2-OCOMe | 100-4 |
12 | H | H | 3-Cl,5-CF3 | 4-But | 139-41 |
13 | H | H | 3-Cl,5-CF3 | 2-NO2 | 137-40 |
14 | H | H | 3-Cl,5-CF3 | 2,6-F2 | 152-4 |
15 | H | H | 3-Cl,5-CF3 | 2,4-F2 | 135 |
16 | H | H | 3-Cl,5-CF3 | 4-Cl | 108-10 |
17 | H | H | 3-Cl,5-CF3 | 2,3-Me2 | 158 |
化合物 | R1 | R2 | (R3)q | (R4)p | 熔点(℃) |
18 | H | H | 3-Cl,5-CF3 | 2-F | 116-7 |
19 | H | H | 3-Cl,5-CF3 | 2-Me | 135-6 |
20 | H | H | 3-Cl,5-CF3 | 2-Br | oil |
21 | H | H | 3-Cl,5-CF3 | 2,6-Cl2 | 130-3 |
22 | H | H | 3-Cl,5-CF3 | 2-OMe | 140-4 |
23 | H | H | 3-Cl,5-CF3 | 2-Cl | 77-80 |
24 | H | H | 3-Cl,5-CF3 | - | 98-100 |
25 | H | H | 5-CF3 | 2,6-Cl2 | 152-3 |
26 | H | H | 3-Cl,5-CF3 | 2,6-Me2 | 123 |
27 | H | H | 3-Cl,5-CF3 | 2,3-F2 | 88-91 |
28 | H | H | 3-Cl,5-CF3 | 2,4,6-Me3 | 146-9 |
29 | H | H | 3-Cl,5-CF3 | 2,3-(CH)4- | 138-140 |
30 | H | H | 3-Cl,5-CF3 | 2-Cl-4-F | 111-3 |
31 | H | H | 3-Cl,5-CF3 | 2-Cl-6-F | 152-3 |
32 | H | H | 3-Cl,5-CF3 | 2,4,6-F3 | 126-8 |
33 | H | H | 3-Cl,5-CF3 | 2,3,6-F3 | 129 |
34 | H | H | 3-Cl,5-CF3 | 2,6-(OMe)2 | 151 |
35 | H | H | 3-Cl,5-CF3 | 2-OCF3 | 89-90 |
36 | H | H | 3-Cl,5-CF3 | 3-CF3 | 133-4 |
37 | H | H | 3-Cl,5-CF3 | 2-Cl,4-NO2 | 147-9 |
38 | H | H | 3-Cl,5-CF3 | 4-Ph | 146-8 |
39 | H | H | 3-Cl,5-CF3 | 2-F,6-CF3 | 118-120 |
化合物 | R1 | R2 | (R3)q | (R4)p | 熔点(℃) |
40 | H | H | 3-Cl,5-CF3 | 2-F,3-CF3 | 102-5 |
41 | H | H | 3-Cl,5-CF3 | 3-F,6-CF3 | 134-6 |
42 | H | H | 3-Cl,5-CF3 | 4-F,2-CF3 | 100-3- |
43 | H | H | 3-Cl,5-CF3 | F5 | 99-101 |
44 | H | H | 3-Cl,5-CF3 | 2-I | 118-9 |
45 | H | H | 3-Cl,5-CF3 | 2-Br,5-OMe | 122-5 |
46 | H | H | 3-Cl,5-CF3 | 2,6-(CF3)2 | 半固态 |
47 | H | Me | 5-CF3 | 2,6-Cl2 | 89-94 |
48 | H | Et | 5-CF3 | 2,6-Cl2 | 82-3 |
49 | H | H | 5-CF3 | 2-Cl | 91-3 |
50 | H | H | 5-CF3 | 2-F | 64-6 |
51 | H | H | 5-CF3 | 2-OMe | 86-9 |
52 | H | H | 5-CF3 | 2-CF3 | 128-130 |
53 | H | H | 5-CF3 | 2-NO2 | 124-6 |
54 | H | H | 5-CF3 | 2,6-F2 | 122-4 |
55 | H | H | 5-CF3 | 2,3-Me2 | 103-6 |
56 | H | H | 5-CF3 | 4-Cl | 107-10 |
57 | H | H | 5-CF3 | 2-Br | 116-9 |
58 | H | H | 3-Cl,5-CF3 | 2,4,6-Cl3 | 152-3 |
59 | H | H | 3,5-Cl2 | 2,6-Cl2 | 161-5 |
60 | H | H | 5-Cl | 2,6-Cl2 | 129-32 |
61 | H | H | 3-Cl,5-CF3 | 4-NMe2 | 143-4 |
化合物 | R1 | R2 | (R3)q | (R4)p | 熔点(℃) |
62 | H | H | 5-Cl | 2-NO2 | 129-32 |
63 | H | Me | 3-Cl,5-CF3 | 2,6-Cl2 | 83-4 |
64 | H | H | 3-Cl,5-CF3 | 2-NO2,4-Me | 138-9 |
65 | H | H | 3-Cl,5-CF3 | 2-OPh | 97-9 |
66 | H | H | 3-Cl,5-CF3 | 2-Cl,6-8r | 144-6 |
67 | H | H | 3-Cl,5-CF3 | 2-NO2,3-Cl | 118-9 |
68 | H | H | 3-Cl,5-CF3 | 2-NO2,5-Cl | 143-4 |
69 | H | H | 3-Cl,5-CF3 | 2-F,6-I | 133-5 |
70 | H | H | 3-Cl,5-CF3 | 2-SMe | 116-7 |
71 | H | H | 3-Cl,5-CF3 | 2,3,5,6-F4 | 112-4 |
72 | H | H | 3-Cl,5-CF3 | 2-Ph | 117-8 |
73 | H | H | 3-Cl,5-CF3 | 2-F,3-Me | 120-1 |
74 | H | H | 3-Cl,5-CF3 | 2-Me,4-Br | 107-8 |
75 | H | H | 3-Cl,5-CF3 | 2-Cl,5-Br | 119-20 |
76 | H | H | 3-Cl,5-CF3 | 2-OMe,5-Cl | 181-2 |
77 | H | H | 3-Cl,5-CF3 | 2-Cl,5-NO2 | 143-4 |
78 | H | H | 3-Cl,5-CF3 | 2-Cl,5-SMe | 94-5 |
79 | H | H | 3-Cl,5-CF3 | 2-OEt | 167-8 |
80 | H | H | 3-Cl,5-CF3 | 2-OCH2Ph | 134-5 |
81 | H | H | 3-Cl,5-CF3 | 2-OMe,4-SMe | 162-3 |
82 | H | H | 3-Cl,5-CF3 | 2-Me,5-NO2 | 129-30 |
83 | 苄基 | H | 3-Cl,5-CF3 | 2,6-Cl2 | 164-8 |
化合物 | R1 | R2 | (R3)q | (R4)p | 熔点(℃) |
84 | 苄基 | H | 3-Cl,5-CF3 | 2-NO2 | 147-9 |
85 | Me | H | 3-Cl,5-CF3 | 2,6-Cl2 | 115-8 |
86 | Me | H | 3-Cl,5-CF3 | 2-NO2 | 油状物 |
87 | Me | H | 3-Cl,5-CF3 | 2-Cl,6-F | 112-6 |
88 | H | H | 3-Cl,5-CF3 | 3-Me,5-NO2 | 油状物 |
89 | H | H | 3-Cl,5-CF3 | 4-Me,5-NO2 | 152 |
90 | H | H | 3-Cl,5-CF3 | 2,5-(OMe)2 | 165 |
91 | H | H | 3-Cl,5-CF3 | 2,3-(OMe)2 | 117 |
92 | H | H | 3-Cl,5-CF3 | 2-OMe,4-Cl | 200 |
93 | H | H | 3-Cl,5-CF3 | 2,4,5-(OMe)3 | 184 |
94 | H | H | 3-Cl,5-CF3 | 2,4-(CF3)2 | 101 |
95 | H | H | 3-Cl,5-CF3 | 2-NO2,4-Cl | 116 |
96 | H | H | 3-Cl,5-CF3 | 2,3,4-(OMe)3 | 125 |
97 | H | H | 3-Cl,5-CF3 | 2,5-(CF3)2 | 112 |
98 | H | H | 3-Cl,5-CF3 | 2-NO2,3-OMe | 149 |
99 | H | H | 3-Cl,5-CF3 | 2,4-(NO2)2 | 152 |
100 | H | H | 3-Cl,5-CF3 | 2,5-Br2 | 136 |
101 | H | H | 3-Cl,5-CF3 | 2-NO2,5-OMe | 油状物 |
102 | H | H | 3-Cl,5-CF3 | 2-Br,3-NO2 | 148 |
103 | H | H | 3-Cl,5-CF3 | 2-NO2,4-CF3 | 138 |
104 | H | H | 3-Cl,5-CF3 | 2-Br,5-NO2 | 151 |
105 | H | H | 3-Cl,5-CF3 | 2-OPr | 122 |
化合物 | R1 | R2 | (R3)q | (R4)p | 熔点(℃) |
106 | H | H | 3-Cl,5-CF3 | 2-(1-吡咯基) | 油状物 |
107 | H | H | 3-Cl,5-CF3 | 2-Br,5-Cl | 138 |
108 | H | H | 3-Cl,5-CF3 | 2-[(2-CN-苯基)硫基 | 油状物 |
109 | H | H | 3-Cl,5-CF3 | 2-CN | 134 |
110 | H | H | 3-Cl,5-CF3 | 2-NO2,4,5-(OMe)2 | 143-4 |
111 | H | H | 3-Cl,5-CF3 | 4-Me | 137-8 |
112 | H | H | 3-Cl,5-CF3 | 4-OMe | 148-9 |
113 | H | H | 3-Cl,5-CF3 | 4-CF3 | 120-1 |
114 | H | H | 3-Cl,5-CF3 | 4-NO2 | 115-6 |
115 | H | H | 3-Cl,5-CF3 | 3-NO2 | 114-5 |
116 | H | H | 3-Cl,5-CF3 | 4-F | 78-9 |
117 | H | H | 3-Cl,5-CF3 | 3-NO2,4-Cl | 127-8 |
118 | H | H | 3-Cl,5-CF3 | 3,4-Me2 | 128-9 |
119 | H | H | 3-Cl,5-CF3 | 3-Cl,4-OMe | 122-3 |
120 | H | H | 3-Cl,5-CF3 | 4-CN | 108-10 |
121 | H | H | 3-Cl,5-CF3 | 3-CN | 122-3 |
122 | H | H | 3-Cl,5-CF3 | 3-CN,4-OMe | 1-1-6-7 |
123 | H | H | 3-Cl,5-CF3 | 3-苄氧基 | 油状物 |
124 | H | H | 3-Cl,5-CF3 | 3-苯氧基 | 71-2 |
125 | H | H | 3-Cl,5-CF3 | 3-F | 123-4 |
126 | Me | H | 3-Cl,5-CF3 | 2-Cl | 99 |
化合物 | R1 | R2 | (R3)q | (R4)p | 熔点(℃) |
127 | Me | H | 3-Cl,5-CF3 | 2,3-Me2 | 124 |
128 | Me | H | 3-Cl,5-CF3 | 2-Br | 113 |
129 | Me | H | 3-Cl,5-CF3 | 3-Br | 105 |
130 | Me | H | 3-Cl,5-CF3 | 2-CF3 | 100 |
131 | Me | H | 3-Cl,5-CF3 | 2,4,6-F3 | 121 |
132 | Me | H | 3-Cl,5-CF3 | 2-I | 129 |
133 | Me | H | 3-Cl,5-CF3 | 2-F | 半固态 |
134 | Me | H | 3-Cl,5-CF3 | 2-Cl | 136 |
135 | Me | H | 3-Cl,5-CF3 | 2,6-F2 | 111 |
136 | Me | H | 3-Cl,5-CF3 | 2,4-F2 | 102 |
137 | Me | H | 3-Cl,5-CF3 | 2-CF3,5-F | 100 |
138 | Me | H | 3-Cl,5-CF3 | 3-CF3,2-F | 油状物 |
139 | Me | H | 3-Cl,5-CF3 | 2-Me | 89 |
140 | Me | H | 3-Cl,5-CF3 | 4-NO2 | 133 |
141 | 苄基 | H | 3-Cl,5-CF3 | 2-Cl | 161 |
142 | 苄基 | H | 3-Cl,5-CF3 | 2,3-Me2 | 173 |
143 | 苄基 | H | 3-Cl,5-CF3 | 2-Br | 157 |
144 | 苄基 | H | 3-Cl,5-CF3 | 3-Br | 169 |
145 | 苄基 | H | 3-Cl,5-CF3 | 2-CF3 | 166 |
146 | 苄基 | H | 3-Cl,5-CF3 | 2,4,6-F3 | 154 |
147 | 苄基 | H | 3-Cl,5-CF3 | 2-I | 174 |
148 | 苄基 | H | 3-Cl,5-CF3 | 2-F | 127 |
化合物 | R1 | R2 | (R3)q | (R4)p | 熔点(℃) |
149 | 苄基 | H | 3-Cl,5-CF3 | 4-Cl | 197 |
150 | 苄基 | H | 3-Cl,5-CF3 | 2,6-F2 | 153 |
151 | 苄基 | H | 3-Cl,5-CF3 | 2,4-F2 | 129 |
152 | 苄基 | H | 3-Cl,5-CF3 | 2-F,3-CF3 | 147 |
153 | 苄基 | H | 3-Cl,5-CF3 | 3-F,6-CF3 | 182 |
154 | 苄基 | H | 3-Cl,5-CF3 | 2-Me | 176 |
155 | 苄基 | H | 3-Cl,5-CF3 | 4-NO2 | 197 |
156 | 苄基 | H | 3-Cl,5-CF3 | - | 199 |
157 | 苄基 | H | 3-Cl,5-CF3 | 2-Cl,6-F | 189 |
158 | H | H | 3-CF3 | 2-NO2 | 129-36 |
159 | H | H | 3-CF3 | 2-Br | 95-8 |
160 | H | H | 3-CF3 | 2-Cl | 108-10 |
161 | H | H | 3-CF3 | 2-CF3 | 110-15 |
162 | H | H | 3-CF3 | 2-I | 126-36 |
163 | H | H | 3-CF3 | 2-Cl,6-F | 161-2 |
164 | H | H | 3-CF3 | 2,6-F2 | 142-6 |
165 | H | H | 3-CF3 | 2,6-(OMe)2 | 128-9 |
166 | H | H | 3-CF3 | 2-CF3,5-F | 128-9 |
167 | H | H | 3-CF3 | 2,4,6-Cl3 | 181-4 |
168 | H | H | 3-CF3 | 2,3,6-F3 | 127-9 |
169 | H | H | 3-CF3 | 2-Br,6-Cl | 169-70 |
170 | H | H | 3-CF3 | 2,6-Cl2 | 169-71 |
化合物 | R1 | R2 | (R3)q | (R4)p | 熔点(℃) |
171 | H | H | 3-Cl,5-CF3 | 2-Me,6-NO2 | 164-5 |
172 | H | H | 3-Cl,5-CF3 | 2,6-(OMe),3-Cl | 177-8 |
173 | H | H | 3-Cl,5-CF3 | 2,6-(OMe)2,3-NO2 | 184-5 |
174 | H | H | 3-Cl,5-CF3 | 2,3,5-Cl3,6-OH | 300-10 |
175 | H | H | 3-Cl,5-CF3 | 2,6-Cl2,3-OH | 96-8 |
176 | H | H | 3-Cl,5-CF3 | 2-Cl,6-OH | 116-8 |
177 | Me | H | 3-Cl,5-CF3 | - | 110 |
178 | Me | H | 3-Cl,5-CF3 | 4-MeO | 146 |
179 | Me | H | 3-Cl,5-CF3 | 3,5-Cl2 | 157 |
180 | Me | H | 3-Cl,5-CF3 | 2,4-Cl2 | 油状物 |
181 | H | H | 3-Cl,5-CF3 | 2-Cl,6-MeS | 139-142 |
182 | H | H | 3-Cl,5-CF3 | 2-CH2Cl | 92-3 |
183 | H | H | 3-Cl,5-CF3 | 2-(2-Br-Ph)CH2S | 油状物 |
184 | Et | H | 3-Cl,5-CF3 | 2,6-Cl2 | 113-6 |
185 | Et | H | 3-Cl,5-CF3 | 2-Cl,6-F | 116-8 |
186 | Et | H | 3-Cl,5-CF3 | 4-Cl | 90-2 |
187 | Et | H | 3-Cl,5-CF3 | 4-F | 78-80 |
188 | Pr | H | 3-Cl,5-CF3 | 2,6-Cl2 | 121-3 |
189 | Pr | H | 3-Cl,5-CF3 | 2-Cl,6-F | 110-2 |
190 | Pr | H | 3-Cl,5-CF3 | 4-Cl | 88-90 |
191 | Pr | H | 3-Cl,5-CF3 | 4-F | 113-5 |
192 | Pr | H | 3-Cl,5-CF3 | 2,4-Cl2 | 油状物 |
化合物 | R1 | R2 | (R3)q | (R4)p | 熔点(℃) |
193 | Pri | H | 3-Cl,5-CF3 | 2,4-Cl2 | 148-52 |
194 | H | H | 3-Cl,5-CF3 | 4-BuO | 100-3 |
195 | H | H | 5-硝基 | 2,6-Cl2 | 176-8 |
196 | H | H | 5-硝基 | 2-Cl,6-F | 171-3 |
197 | H | H | 5-硝基 | 2-Br,6-Cl | 159-61 |
198 | H | H | 5-硝基 | 2-NO2 | 151-3 |
199 | H | H | 5-硝基 | 4-Cl | 116-8 |
200 | H | H | 3-Cl,5-CF3 | 2-苯二甲酰亚胺基 | 173-4 |
201 | Me | H | 3-Cl,5-CF3 | 4-BuO | 94-5 |
202 | H | H | 5-OCOMe | 2,6-Cl2 | 153-4 |
203 | H | H | 5-OCOMe | 2-Cl,6-F | 137-8 |
204 | H | H | 5-OCOMe | 2-Br,6-Cl | 158-9 |
205 | H | H | 5-OCOMe | 2-I | 144-5 |
206 | H | H | 5-OCOEt | 2,6-Cl2 | 98-100 |
207 | H | H | 5-OCOEt | 2-Br,6-Cl | 96-8 |
208 | H | H | 5-OCOEt | 2-Cl,6-F | 97-9 |
209 | H | H | 5-OCOEt | 4-Cl | 112-4 |
210 | H | H | 5-OCOEt | 2-Cl | 84-7 |
211 | H | H | 5-OCOEt | 2-NO2 | 85-9 |
212 | H | H | 5-OSO2Me | 2,6-Cl2 | 132-3 |
213 | H | H | 6-OH | 2,6-Cl2 | 269-70 |
214 | H | H | 6-Me-3-OSO2Me | 2,6-Cl2 | 185-6 |
化合物 | R1 | R2 | (R3)q | (R4)p | 熔点(℃) |
215 | H | H | 6-Cl | 2,6-Cl2 | 139-41 |
216 | H | H | 4-Cl | 2,6-Cl2 | 156-7 |
217 | Pri | H | 3-Cl,5-CF3 | 2,6-Cl2 | 135-7 |
218 | NC-CH2 | H | 3-Cl,5-CF3 | 2,6-Cl2 | 160-3 |
219 | NC-CH2 | H | 3-Cl,5-CF3 | 2-Cl,6-F | 155-6 |
221 | NC-CH2 | H | 3-Cl,5-CF3 | 4-Cl | 118-9 |
222 | NC-CH2 | H | 3-Cl,5-CF3 | 3,5-Cl2 | 122-4 |
223 | NC-CH2 | H | 3-Cl,5-CF3 | 2,4-Cl2 | 110-2 |
实施例5
N-[1-(3-氯-5-三氟甲基-2-吡啶基)-2,4-二氯苯磺酰胺(化合物501)
在(3-氯-5-三氟甲基-2-吡啶基)甲胺盐酸盐(0.25克)的四氢呋喃(6毫升)悬浮液中加入三乙胺(0.28毫升)。15分钟后,过滤白色的悬浮液,用四氢呋喃洗涤。将滤液和洗涤液加入2,4-二氯苯磺酰氯(0.25克)中,室温下将该混合物搅拌过夜,然后加入水,再搅拌30分钟。收集形成的白色固体。这种白色固体是标题产物,熔点为125-6℃(化合物501)
按相似的方法制得如下通式Ia的化合物。下表也包括上述实施例中所述的化合物。
化合物 | (R4)p | 熔点(℃) |
501 | 2,4-Cl2 | 125-6 |
502 | 4-Me | 113-4 |
503 | 2-Cl | 114-5 |
504 | 2-Cl,4-F | 99-101 |
505 | 2-F | 126-8 |
506 | 2,3-N=CH-CH=CH- | 145-6 |
507 | 2-CN | 154-7 |
508 | 2-Br | 134-6 |
509 | 2,6-Cl2 | 160-1. |
510 | 2,5-(OMe)2 | 119-23 |
511 | 2,6-F2 | 141-3 |
512 | 2-Cl-6-Me | 170-2 |
513 | 2-NO2 | 116-8 |
514 | 6-Me-3-NO2 | 113-5 |
515 | 2,3-CH=CH-CH=CH- | 94-5 |
516 | 2,4-F2 | 93-5 |
517 | 2,5-Cl2 | 92-3 |
518 | 3,4-Cl2 | 117-8 |
519 | 5-Cl-2-MeO | 94-5 |
520 | 2,4,6-Cl3 | 137-9 |
化合物 | (R4)p | 熔点(℃) |
521 | 4-Cl-2,5-Me2 | 130-2 |
522 | 2,4-Cl2-5-Me | 155-7 |
523 | 4-Cl | 132-3 |
524 | 2,3-Cl2 | 104-6 |
525 | 2-CF3 | 102-4 |
526 | - | 99-100 |
527 | 3-PhO | 88-9 |
528 | 3,4-(OMe)2 | 126-7 |
529 | 3,5-Cl2 | 125-7 |
530 | 5-F-2-Me | 88-9 |
实施例6
2-(3-氯-5-三氟甲基-2-吡啶基)-N-(3,4-二甲氧基苯甲酰)氨基乙酸乙酯(化合物601)
搅拌下将三乙胺(0.28毫升)加入2-(3-氯-5-三氟甲基-2-吡啶基)氨基乙酸乙酯(1克,按与实施例3中原料相似的制备方法制得)的二甲基甲酰胺(10毫升)溶液中,然后加入3,4-二甲氧基苯甲酰氯(0.70克)。将该混合物搅拌45分钟,然后蒸发。残留物用乙酸乙酯萃取,对所得的萃取液进行后处理,得到标题产物,熔点为40-3℃(化合物601)。
表3
化合物 | Qz | R2 | L | (R4)p | 熔点(℃) |
601 | H | H | -C(=O)- | 3,4-Me2 | 40-3 |
602 | H | 苄基 | -C(=O)- | 4-MeO | 116-9 |
603 | H | H | -C(=O)- | 2,4-Cl2 | 107-10 |
604 | H | H | -SO2- | 3,4-Cl2 | 89-92 |
605 | H | H | -C(=O)- | - | 油状物 |
606 | H | H | -C(=O)- | 2-Me | 油状物 |
607 | H | H | -C(=O)- | 4-MeO | 油状物 |
608 | H | H | -C(=O)- | 3-NO2 | 油状物 |
609 | H | H | -C(=O)- | 4-叔丁基 | 油状物 |
610 | H | H | -C(=O)- | 2-CF3 | 油状物 |
611 | H | H | -C(=O)- | 2,6-Cl2 | 油状物 |
612 | H | H | -SO2- | 3-CF3 | 74-6 |
613 | H | H | -C(=O)- | 2-F | 油状物 |
614 | H | H | -C(=O)- | 2-Cl | 油状物 |
615 | H | H | -C(=O)- | 3-Br | 62-4 |
616 | H | H | -SO2- | 2,5-Cl2 | 油状物 |
617 | H | 乙基 | -C(=O)- | - | 油状物 |
618 | H | 乙基 | -C(=O)- | 2-Cl | 油状物 |
619 | H | 乙基 | -C(=O)- | 3-NO2 | 油状物 |
化合物 | Qz | R2 | L | (R4)p | 熔点(℃) |
620 | H | 乙基 | -C(=O)- | 4-MeO | 油状物 |
621 | H | H | -C(=O)- | 2-Br | 155-6 |
622 | H | H | -C(=O)- | 3,4-(OMe)2 | 40-3 |
623 | H | 苄基 | -C(=O)- | 4-MeO | 116-9 |
实施例7
N-[(3-氯-5-三氟甲基-2-吡啶基)甲基]-2-氯苯硫代酰胺(化合物701)
将化合物23(3.84克)和劳森(Lawesson)试剂(4.45克)的甲苯(50毫升)溶液在80℃加热1小时。用硅胶色谱提纯该混合物,得到标题化合物,熔点为102-3℃。
按相似的方法制得如下的化合物。下表包括上述实施例中所述的化合物。
化合物 | R1 | (R4)p | 熔点(℃) |
701 | H | 2-Cl | 102-5 |
702 | H | 4-Me | 97-9 |
703 | H | 3-Me | 72-5 |
704 | H | 2-MeO | 172-5 |
705 | H | 3-MeO | 86-8 |
706 | H | 4-MeO | 107-9 |
707 | H | 3-Cl | 92-5 |
化合物 | R1 | (R4)p | 熔点(℃) |
708 | H | 4-Cl | 123-5 |
709 | H | 4-Me2N | 145-7 |
710 | H | 3-EtO | 62-4 |
711 | H | 4-EtO | 115-8 |
712 | H | 3-NO2 | 108-9 |
713 | H | 4-叔丁基 | 88-91 |
714 | H | 4-NO2 | 190-2 |
715 | H | 4-PrO | 95-8 |
716 | H | 4-PriO | 86-8 |
717 | H | 3-Cl,4-MeO | 147-9 |
718 | H | 3-BuO | 油状物 |
719 | H | 3-Cl,4-Me2N | 107-9 |
720 | H | 4-Br | 122-4 |
721 | H | 3,4,5-(OMe)3 | 132-3 |
722 | Me | 3-Me | 119-21 |
723 | Me | 3-MeO | 107-8 |
724 | Me | 4-MeO | 122-3 |
725 | Me | 2-Cl | 114-5 |
726 | Me | 3-Cl | 112-5 |
727 | Me | 4-Cl | 127-9 |
728 | Me | 3-EtO | 100-1 |
729 | Me | 4-EtO | 101-4 |
730 | Me | 3-NO2 | 117-9 |
731 | Me | 4-叔丁基 | 112-4 |
化合物 | R1 | (R4)p | 熔点(℃) |
732 | Me | 4-NO2 | 246-8 |
733 | Me | 4-PrO | 97-8 |
734 | Me | 4-PriO- | 92-3 |
735 | Me | 3-Cl,4-MeO | 103-5 |
736 | Me | 3-BuO | 73-6 |
737 | Me | 3-Cl,4-Me2N | 85-8 |
738 | Me | 4-Br | 140-2 |
739 | Me | 3,4,5-(OMe)3 | 118-120 |
740 | H | 2-Me | 101-4 |
741 | H | 2,3-CH=CH-CH=CH- | 154-6 |
742 | H | 4-BuO | 76-80 |
743 | H | 4-PhCH2O- | 110-4 |
744 | Me | 4-Me | 134-5 |
745 | Me | 2-MeO | 109-12 |
746 | Me | 4-Me2N | 177-80 |
747 | Me | 2,3-CH=CH-CH=CH- | 123-5 |
748 | Me | 4-BuO | 100-3 |
749 | Me | 4-PhCH2O- | 132-4 |
测试实施例
用如下一种或多种植物病原真菌评价化合物的活性:
致病疫霉(Phytophthora infestans):晚疫
葡萄生单轴霉(Plasmopara viticola):葡萄霜霉病
禾白粉菌(Erysiphe graminis f.sp.tritici):小麦白粉病
稻瘟霉(Pyricularia oryzae):稻瘟病
小球腔菌(Leptosphaeria nodorum):麦类颖斑病
灰葡萄孢(Botrytis cinerea):灰霉病
按适当的方法将所需浓度的化合物水溶液(包括湿润剂)喷洒或浸湿试验植物的茎的底部。经给定的时间后,在施用合适的化合物之前或之后用合适的试验病原菌接种到植物或植物部分上,然后保持在适于保持植物生长和病菌繁殖的控制环境条件下。适当的时间后,目测受影响植物部分的感染程度。按1-3级评价化合物,1级表示很少或没有防治作用,2级表示有中等防治作用,3级表示有优良防治作用。在500ppm(w/v)或更低浓度下,本发明化合物对上述真菌有2级以上防治作用。
致病疫霉
1、3、6、7、13、14、17-21、22、23、25、27、29、31-34、37-46、59、62-64、66、68-71、85、87、98、101、107、110、122-124、128、130、132、171、173、180和701。
葡萄生单轴霉
1、3、13、14、15、17-21、22、23、25、27、29、31-34、39、41-46、59、63、64、66、69、71、84、86、87、102-110、124、128、130、132、150和171。
禾白粉菌
16、25、28、146、147、148、151、155、156、165、150和151。
稻瘟霉(Pyricularia oryzae)
16、25、31、38、41、45、65、89、97、146、157、169、150、151、152、156、158和176。
小球腔菌
15、16、18、22、33、34、92、63、128、130、143、149和150。
灰葡萄孢
127、130、134和139。
Claims (4)
式中
A1是3和/或5位有取代基而其它位置没有取代基的2-吡啶基,所述的取代基选自卤素、含1-5个碳原子的卤代烷基、氰基、-COOR5a和-OSO2R5a,其中R5a是含1-5个碳原子的烷基;
A2是最多可被5个取代基取代的苯基,所述的取代基可以相同或不同,且选自卤素、羟基、氰基、硝基、-COOR5a、基团E、OE、SE、可被两个含1-5个碳原子的烷基取代的氨基、2-苯二甲酰亚胺基和丁二酰亚胺基,其中R5a是含1-5个碳原子的烷基,E是含1-5个碳原子的烷基、苯基或吡咯基,所述基团可被卤素、氰基、苯基或卤代苯基取代;
L是-(C=O)-、-SO2-或-(C=S)-;
R1和R2是氢。
2.一种杀虫剂组合物,其特征在于它含有与农业上可接受的稀释剂或载体混合的权利要求1所述的化合物。
3.一种在真菌感染或可能感染的地方防治植物病原真菌的方法,该方法包括在所述的地方施加如权利要求1所述的通式1的化合物。
4.权利要求1所述的化合物作为杀植物病原真菌剂的应用。
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
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GB9803413.5 | 1998-02-19 | ||
GBGB9803413.5A GB9803413D0 (en) | 1998-02-19 | 1998-02-19 | Fungicides |
GBGB9813998.3A GB9813998D0 (en) | 1998-06-30 | 1998-06-30 | Fungicides |
GB9813998.3 | 1998-06-30 | ||
GBGB9817353.7A GB9817353D0 (en) | 1998-08-11 | 1998-08-11 | Fungicides |
GB9817353.7 | 1998-08-11 |
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CN1291187A CN1291187A (zh) | 2001-04-11 |
CN1132816C true CN1132816C (zh) | 2003-12-31 |
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CN998030589A Expired - Lifetime CN1132816C (zh) | 1998-02-19 | 1999-02-16 | 2-吡啶基甲胺衍生物及其应用和杀虫剂组合物 |
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