CN111316987B - 一种杀真菌组合物及其应用 - Google Patents

一种杀真菌组合物及其应用 Download PDF

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CN111316987B
CN111316987B CN201811531834.XA CN201811531834A CN111316987B CN 111316987 B CN111316987 B CN 111316987B CN 201811531834 A CN201811531834 A CN 201811531834A CN 111316987 B CN111316987 B CN 111316987B
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王军锋
李志念
刘君丽
关爱莹
司乃国
刘长令
兰杰
孙芹
赵杰
单忠刚
孙庚�
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Shenyang Sinochem Agrochemicals R&D Co Ltd
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Abstract

本发明属于农用杀菌剂领域,具体的说是一种杀真菌组合物及其应用。组合物为A、B两种活性组分,活性组分A和活性组分B之间的重量比为1:99‑99:1;活性组分A选自如下通式I‑1F所示的化合物及其盐,活性组分B选自甲氧基丙烯酸酯类的杀菌剂。本发明杀真菌组合物特别适合防治多种植物病原性真菌病害,如植物白粉病、锈病、霜霉病、晚疫病、疫病、霜疫霉病、黑痣病或纹枯病。

Description

一种杀真菌组合物及其应用
技术领域
本发明属于农用杀菌剂领域,具体涉及一种含嘧啶的取代吡唑类化合物与甲氧基丙烯酸酯类杀菌剂的杀真菌组合物及其应用。
背景技术
专利WO2016184378公开了一种含嘧啶的取代吡唑类化合物及其用途,其中报道了如下通式I-1F所示的化合物对多种真菌病害具有良好的活性。
Figure BDA0001905854090000011
在杀菌剂应用的实践中,人们经常发现一种药剂长期使用,田间药效显著下降,甚至是失去了防病作用。
发明内容
本发明目的在于提供一种含嘧啶的取代吡唑类化合物与甲氧基丙烯酸酯类杀菌剂的杀真菌组合物及其应用,以延缓病原菌抗药性的产生,延长药剂的使用寿命。
为实现上述目的,本发明采用技术方案为:
一种杀真菌组合物,组合物为A、B两种活性组分,活性组分A和活性组分B之间的重量比为1:99-99:1;
活性组分A为通式I-1F所示的化合物或其盐:
Figure BDA0001905854090000012
式中:
R3选自氢、羟基、甲酰基、C1-C4烷基、卤代C1-C4烷基、C1-C4烷氧基、卤代C1-C4烷氧基、C3-C4环烷基、C1-C4烷硫基、C2-C4烯基硫基、C2-C4烯基、C2-C4炔基、卤代C2-C4烯基、卤代C2-C4炔基、C1-C4烷氧基C1-C4烷基、卤代C1-C4烷氧基C1-C4烷基、C1-C4烷硫基C1-C4烷基、卤代C1-C4烷硫基C1-C4烷基、C1-C4烷基亚磺酰基、卤代C1-C4烷基亚磺酰基、C1-C4烷基磺酰基、卤代C1-C4烷基磺酰基、C1-C4烷基氨基磺酰基、二(C1-C4烷基)氨基磺酰基、C1-C4烷基磺酰基氨基羰基、C1-C4烷基羰基氨基磺酰基、C3-C4环烷基氧基羰基、C1-C4烷基羰基、卤代C1-C4烷基羰基、C1-C4烷氧基羰基、卤代C1-C4烷氧基羰基、C1-C4烷基羰基C1-C4烷基、C1-C4烷氧基羰基C1-C4烷基、C1-C4烷基氨基羰基、二(C1-C4烷基)氨基羰基、C2-C4烯氧基羰基、C2-C4炔氧基羰基、C1-C4烷氧基C1-C4烷氧基羰基、C1-C4烷基氨基硫基、二(C1-C4烷基)氨基硫基、未取代的或被1-5个如下基团进一步取代的(杂)芳基羰基C1-C4烷基、(杂)芳基羰基、(杂)芳氧基羰基、(杂)芳基C1-C4烷基氧基羰基、(杂)芳基C1-C4烷基,卤素、硝基、氰基;
R4、R5可相同或不同,分别选自氢、卤素、C1-C4烷基、卤代C1-C4烷基、C1-C4烷氧基或卤代C1-C4烷氧基;其中,R4、R5与其相连的C还可以组成C3-C4的环;
R6、R7可相同或不同,分别选自氢、卤素、C1-C4烷基、卤代C1-C4烷基、C1-C4烷氧基或卤代C1-C4烷氧基;其中,R6、R7与其相连的C还可以组成C3-C4的环;
R8、R9可相同或不同,分别选自氢、氰基、卤素、C1-C4烷基、卤代C1-C4烷基、C1-C4烷氧基羰基、卤代C1-C4烷氧基羰基、未取代的或被1-5个R11取代的(杂)芳基、(杂)芳甲基、(杂)芳基羰基、(杂)芳甲基羰基或(杂)芳氧基羰基;
R11选自卤素、羟基、氨基、氰基、硝基、C1-C4烷基、卤代C1-C4烷基、C1-C4烷氧基、卤代C1-C4烷氧基、C3-C4环烷基、C1-C4烷基氨基、卤代C1-C4烷基氨基、二(C1-C4烷基)氨基、卤代二(C1-C4烷基)氨基、C1-C4烷硫基、卤代C1-C4烷硫基、C2-C4烯基、C2-C4炔基、C2-C4烯氧基、卤代C2-C4烯氧基、C2-C4炔氧基、卤代C2-C4炔氧基、C1-C4烷基磺酰基、卤代C1-C4烷基磺酰基、C1-C4烷基羰基、卤代C1-C4烷基羰基、C1-C4烷氧基羰基、卤代C1-C4烷氧基羰基、C1-C4烷氧基C1-C4烷基、卤代C1-C4烷氧基C1-C4烷基、C1-C4烷硫基C1-C4烷基、卤代C1-C4烷硫基C1-C4烷基、C1-C4烷氧基羰基C1-C4烷基、卤代C1-C4烷氧基羰基C1-C4烷基、C1-C4烷硫基羰基C1-C4烷基、卤代C1-C4烷硫基羰基C1-C4烷基、C1-C4烷基羰基氧基、卤代C1-C4烷基羰基氧基、C1-C4烷氧基羰基氧基、卤代C1-C4烷氧基羰基氧基、C1-C4烷基磺酰基氧基、卤代C1-C4烷基磺酰基氧基、C1-C4烷氧基C1-C4烷氧基或卤代C1-C4烷氧基C1-C4烷氧基;n选自0至5的整数,当n大于1时,R11可相同或不同;
R14、R15、R16或R17可相同或不同,分别选自氢、卤素、羟基、氨基、氰基、硝基、C1-C4烷基、卤代C1-C4烷基、C1-C4烷氧基、卤代C1-C4烷氧基或C3-C4环烷基;
W选自氢、卤素、C1-C4烷基、卤代C1-C4烷基、C3-C4环烷基、C1-C4烷氧基、C1-C4烷硫基或C1-C4烷基磺酰基;
活性组分B选自甲氧基丙烯酸酯类杀菌剂中的一种或几种。
所述活性组分A为通式I-1F所示化合物的盐,其中通式I-1F所示化合物的盐为通式I-1F所示的化合物与盐酸、硫酸、磷酸、甲酸、乙酸、三氟乙酸、草酸、甲磺酸、对甲苯磺酸、苯甲酸、邻苯二甲酸、马来酸、富马酸、山梨酸、苹果酸或柠檬酸形成的盐;
本发明优选,所述组合物中A、B两种活性组分之间的重量比为1:50-50:1;
所述活性组分A为通式I-1F所示化合物或其盐;
通式中R3选自氢、羟基、甲酰基、C1-C4烷基、卤代C1-C4烷基、C1-C4烷氧基、卤代C1-C4烷氧基、C3-C4环烷基、C1-C4烷硫基、C2-C4烯基硫基、C2-C4烯基、C2-C4炔基、卤代C2-C4烯基或卤代C2-C4炔基;
R4、R5可相同或不同,分别选自氢、卤素、C1-C4烷基、卤代C1-C4烷基、C1-C4烷氧基或卤代C1-C4烷氧基;
R6、R7可相同或不同,分别选自氢、卤素、C1-C4烷基、卤代C1-C4烷基、C1-C4烷氧基或卤代C1-C4烷氧基;
R8、R9可相同或不同,分别选自氢、氰基、卤素、C1-C4烷基、卤代C1-C4烷基、C1-C4烷氧基羰基或卤代C1-C4烷氧基羰基;
R11选自卤素、羟基、氨基、氰基、硝基、C1-C4烷基、卤代C1-C4烷基、C1-C4烷氧基、卤代C1-C4烷氧基、C3-C4环烷基、C1-C4烷基氨基或卤代C1-C4烷基氨基;n选自0至5的整数,当n大于1时,R11可相同或不同;
R14、R15、R16或R17可相同或不同,分别选自氢、卤素、羟基、氨基、氰基、硝基、C1-C4烷基、卤代C1-C4烷基、C1-C4烷氧基或卤代C1-C4烷氧基;
W选自氢、卤素、C1-C4烷基、卤代C1-C4烷基、C3-C4环烷基、C1-C4烷氧基或C1-C4烷硫基;
活性组分B选自烯肟菌酯(Enestroburin)B1、烯肟菌胺(fenaminstrobin)B2、唑菌酯(pyraoxystrobin)B3、唑胺菌酯(pyrametostrobin)B4、嘧菌酯(azoxystrobin)B5、吡唑醚菌酯(pyraclostrobin)B6、啶氧菌酯(picoxystrobin)B7、醚菌酯(kresoxim-methyl)B8、肟菌酯(trifloxstrobin)B9、氟嘧菌酯(fluoxastrobin)B10、丁香菌酯(coumoxystrobiun)B11、苯醚菌酯(ZJ0712)B12、氯啶菌酯(triclopyricarb)B13、苯氧菌胺(metominostrobin)B13、肟醚菌胺(orysastrobin)B14或苯噻菌酯(benzothiostrobin)B15中的一种或几种。
所述活性组分A为通式I-1F所示化合物的盐,其中通式I-1F所示化合物的盐为通式I-1F所示的化合物与盐酸、硫酸、磷酸、甲酸、乙酸、三氟乙酸、草酸、甲磺酸、对甲苯磺酸、苯甲酸、邻苯二甲酸或马来酸形成的盐。
本发明进一步优选,所述组合物中A、B两种活性组分之间的重量比为1:20-20:1;
所述活性组分A为通式I-1F中的化合物或其盐;
通式中R3选自氢、羟基、甲酰基、C1-C4烷基或卤代C1-C4烷基;R4、R5可相同或不同,分别选自氢、卤素、C1-C4烷基或卤代C1-C4烷基;R6、R7可相同或不同,分别选自氢、卤素、C1-C4烷基或卤代C1-C4烷基;R8、R9可相同或不同,分别选自氢、氰基、卤素、C1-C4烷基或卤代C1-C4烷基;R11选自卤素、羟基、氨基、氰基、硝基、C1-C4烷基或卤代C1-C4烷基;n选自0至5的整数,当n大于1时,R11可相同或不同;R14、R15、R16或R17可相同或不同,分别选自氢、卤素、羟基、氨基、氰基、硝基、C1-C4烷基或卤代C1-C4烷基;W选自氢、卤素、C1-C4烷基或卤代C1-C4烷基;
活性组分B选自烯肟菌酯B1、烯肟菌胺B2、唑菌酯B3、嘧菌酯B5、吡唑醚菌酯B6、啶氧菌酯B7、醚菌酯B8、肟菌酯B9、氟嘧菌酯B10、丁香菌酯B11、苯醚菌酯B12或氯啶菌酯B13中的一种或几种。
所述活性组分A为通式I-1F所示化合物的盐,其中通式I-1F所示化合物的盐为通式I-1F所示的化合物与盐酸、硫酸、磷酸、甲酸、乙酸、三氟乙酸、草酸或甲磺酸形成的盐。
本发明再进一步优选,所述组合物为A、B两种活性组分之间的重量比为1:10-10:1;
所述活性组分A为通式I-1F所示化合物或其盐,通式中R3选自氢、羟基、甲酰基或C1-C4烷基;R4、R5可相同或不同,分别选自氢、卤素或C1-C4烷基;R6、R7可相同或不同,分别选自氢、卤素或C1-C4烷基;R8、R9可相同或不同,分别选自氢、氰基、卤素或C1-C4烷基;R11选自卤素、羟基、氨基、氰基、硝基或C1-C4烷基;n选自0至5的整数,当n大于1时,R11可相同或不同;R14、R15、R16或R17可相同或不同,分别选自氢、卤素、羟基、氨基、氰基、硝基或C1-C4烷基;W选自氢、卤素或C1-C4烷基;
活性组分B选自烯肟菌酯B1、烯肟菌胺B2、唑菌酯B3、嘧菌酯B5、吡唑醚菌酯B6、啶氧菌酯B7、醚菌酯B8、肟菌酯B9或丁香菌酯B11中的一种或几种。
所述活性组分A为通式I-1F所示化合物的盐,其中通式I-1F所示化合物的盐为通式I-1F所示的化合物与盐酸、硫酸、磷酸、甲酸或乙酸形成的盐。
本发明更进一步优选,所述组合物为A、B两种活性组分之间的重量比为1:4-4:1;
所述活性组分A为通式I-1F所示化合物或其盐,式中R3选自氢,R4、R5分别选自氢,R6、R7分别选自氢,R8、R9分别选自氢,R11选自4-氯,R14、R15、R16或R17分别选自氢,W选自氢。
活性组分B选自烯肟菌酯B1、烯肟菌胺B2、唑菌酯B3、嘧菌酯B5、吡唑醚菌酯B6、啶氧菌酯B7、肟菌酯B9或丁香菌酯B11中的一种或几种。
所述活性组分A为通式I-1F所示化合物的盐,其中通式I-1F所示化合物的盐为通式I-1F所示的化合物与硫酸形成的盐。
一种杀真菌组合物的应用,所述杀真菌组合物用于制备防治植物病原性真菌病害的药物。
所述植物病原性真菌病害为植物白粉病、锈病、霜霉病、晚疫病、疫病、霜疫霉病、黑痣病或纹枯病。
一种杀菌制剂,制剂有效成分为所述的杀真菌组合物,杀真菌组合物的重量百分含量为0.1-95%。
根据农作物病害的发生程度,在农作物种植区域内,本发明组合物的使用浓度为5-500mg/L(有效成分含量,下同),优选50-200mg/L。
本发明组合物中活性组分A和至少一种活性组分B按照本发明提供的合适配比,预先配制好或在使用现场配制或将两组分单独依次使用。
本发明组合物适合用于树木(苹果、橡胶、梨、柑橘、山楂、板栗、花椒、枸杞、芒果、木瓜、荔枝等)、藤蔓植物(葡萄)、瓜菜类(番茄、茄子、辣椒、黄瓜、甜瓜、冬瓜、西瓜、南瓜、苦瓜、丝瓜、佛手瓜、葫芦、西葫芦、胡萝卜、莴苣、马铃薯)、豆类(大豆、豌豆、芸豆、豇豆)、禾谷类(小麦、水稻、玉米)、葱蒜类(葱、蒜、洋葱)、花卉植物和草坪的真菌病害防治,以及种子处理、水果保鲜等应用。
本发明杀真菌组合物特别适合防治下列植物病害:苹果树白粉病、苹果树锈病、橡胶树白粉病、梨树锈病、柑橘白粉病、山楂白粉病、板栗白粉病、花椒白粉病、枸杞白粉病、芒果白粉病、木瓜白粉病、荔枝霜疫霉病、棒子白粉病、葡萄白粉病、葡萄霜霉病、番茄白粉病、番茄晚疫病、茄子白粉病、辣椒白粉病、辣椒疫病、黄瓜白粉病、黄瓜霜霉病、甜瓜白粉病、甜瓜霜霉病、冬瓜白粉病、西瓜白粉病、南瓜白粉病、苦瓜白粉病、苦瓜霜霉病、丝瓜白粉病、丝瓜霜霉病、佛手瓜白粉病、葫芦白粉病、西葫芦白粉病、胡萝卜白粉病、莴苣白粉病、大豆锈病、豌豆锈病、豌豆白粉病、芸豆锈病、芸豆白粉病、豇豆锈病、马铃薯黑痣病、马铃薯晚疫病、小麦锈病、小麦纹枯病、小麦白粉病、水稻纹枯病、玉米锈病、葱锈病、蒜锈病、洋葱锈病、月季白粉病、玫瑰白粉病、菊花白粉病、草坪草白粉病、草坪草锈病等。
本发明所具有优点:
本发明按不同比例将活性组分A和杀菌剂活性组分B组合,有效的提高病害防治效果。采用专业公式科学计算后,组合物试验配比的观察效力值均远高于计算效力值,协同增效作用十分明显。
具体实施方式
本发明组合物对有害真菌的协同增效作用可通过下列实施例作进一步说明,但本发明绝非仅限于此。其中所述的活性组分即为本发明的杀真菌组合物中的化合物A与甲氧基丙烯酸酯类杀菌剂B;且活性物A的制备参见WO2016184378中的记载。
测试方法及评价方法如下:
待测活性样品分别为活性组分A、活性组分B、活性组分A与活性组分B的组合物。
活性组分A为活性组分A1或活性组分A2。
活性组分A为通式I-1F所示的化合物A1:
Figure BDA0001905854090000061
式中,R3选自氢,R4、R5分别选自氢,R6、R7分别选自氢,R8、R9分别选自氢,R11选自4-氯,R14、R15、R16或R17分别选自氢,W选自氢,即为化合物A1;
活性组分A2为化合物A1与硫酸形成的盐。
活性组分B为烯肟菌胺B2、嘧菌酯B5、吡唑醚菌酯B6、啶氧菌酯B7、肟菌酯B9、丁香菌酯B11。
待测组合物为活性组分A1分别与烯肟菌酯B1或烯肟菌胺B2、唑菌酯B3、嘧菌酯B5、吡唑醚菌酯B6、啶氧菌酯B7、肟菌酯B9、丁香菌酯B11组成的组合物;或活性组分A2与烯肟菌酯B1或烯肟菌胺B2、唑菌酯B3、嘧菌酯B5、吡唑醚菌酯B6、啶氧菌酯B7、肟菌酯B9或丁香菌酯B11组成的组合物。
具体方式:
将上述各活性组分或组合物用丙酮或水溶解(丙酮量与喷液量的体积比等于或小于0.05),用含有0.1%吐温80的水稀释,配制成所需浓度待测液,另按设定比例配制组合物的待测液。在作物喷雾机上,将待测液喷施于病害寄主植物上,24小时后进行病害接种。依据病害特点,将需要控温保湿培养的病害植物接种后放在气候室中培养,待病害完成侵染后,移入温室培养。待对照充分发病后,测定病原物侵染作物叶面积百分数,使用Abbot公式计算,即得到观察效力(W):
W=(1-α/β)×100
式中:
α:处理作物的真菌侵染百分数;
β:未处理(空白对照)作物的真菌侵染百分数;
效力为“0”表示处理作物的侵染水平与未处理对照作物的侵染水平相同;效力为“100”表示处理作物未受侵染。
组合物的预期效力(计算效力)使用Colby公式(见R.S.Colby,杂草(Weeds),1967,15,20-22)确定,并与观察效力比较。
E=X+Y–XY/100
式中:
E:使用浓度为a和b的活性组分A和B的组合物时的预期效力(以下各表中的计算效力),以未处理对照的%表示;
X:使用浓度为a时的活性组分A的效力,以未处理对照的%表示;
Y:使用浓度为b时的活性组分B的效力,以未处理对照的%表示。
当观察效力值大于计算效力值时,表示组合物具有增效作用;当观察效力值等于计算效力值时,表示组合物为加合作用;当观察效力值小于计算效力值时,表示组合物为拮抗作用。
实施例1防治小麦白粉病试验
将品种为“辽春15”的盆栽两叶期小麦幼苗用各活性组分或组合物的水溶液(有效成分浓度如下表所述)喷雾处理,24小时后,将小麦白粉病菌孢子抖落在小麦叶片上,并在温室内培养,7天后测定叶片上病菌侵染的发展程度。
各单独活性组分及本发明组合物防治小麦白粉病的活性数据见表1和表2。
表1单独活性组分的活性
Figure BDA0001905854090000071
表2本发明组合物的活性
Figure BDA0001905854090000081
Figure BDA0001905854090000091
由上述表1和表2结果显示,组合物的观察效力值均大于计算效力值,组合物在试验配比范围内表现为增效作用。
实施例2防治黄瓜霜霉病试验
将品种为“新泰密刺”的盆栽两叶期黄瓜幼苗用各活性组分或组合物的水溶液(有效成分浓度如下表所述)喷雾处理,24小时后,将黄瓜霜霉病菌孢子囊水悬浮液接种在黄瓜叶片上,并在气候室中培养,待病害完成侵染后,移入温室培养,7天后测定叶片上病菌侵染的发展程度。
各单独活性组分及本发明组合物防治黄瓜霜霉病的活性数据见表3和表4。
表3单独活性组分的活性
Figure BDA0001905854090000092
表4本发明组合物的活性
Figure BDA0001905854090000093
Figure BDA0001905854090000101
结果显示,组合物的观察效力值均大于计算效力值,组合物在试验配比范围内表现为增效作用。
实施例3防治黄瓜白粉病试验
将品种为“新泰密刺”的盆栽三叶期黄瓜苗用各活性组分或组合物的水溶液(浓度如下表所述)喷雾处理,24小时后,将黄瓜白粉病菌孢子悬浮液接种在黄瓜叶片上,并在温室内培养,15天后测定叶片上病菌侵染的发展程度。
各单独的活性组分及本发明组合物防治黄瓜白粉病的活性数据见表5和表6。
表5单独活性组分的活性
Figure BDA0001905854090000111
表6本发明组合物的活性
Figure BDA0001905854090000112
Figure BDA0001905854090000121
结果显示,组合物的观察效力值均大于计算效力值,组合物在试验配比范围内表现为增效作用。
将品种为“金黄糯”的盆栽两叶期玉米苗用各活性组分或组合物的水溶液(浓度如下表所述)喷雾处理,24小时后,将玉米锈病菌孢子悬浮液接种在玉米叶片上,并在气候室中培养,待病害完成侵染后,移入温室培养,12天后测定叶片上病菌侵染的发展程度。
各单独的活性组分及本发明组合物玉米锈病的活性数据见表7和表8。
表7单独活性组分的活性
Figure BDA0001905854090000122
Figure BDA0001905854090000131
表8本发明组合物的活性
Figure BDA0001905854090000132
Figure BDA0001905854090000141
结果显示,组合物的观察效力值均大于计算效力值,组合物在试验配比范围内表现为增效作用。

Claims (6)

1.一种杀真菌组合物,其特征在于:组合物为A、B两种活性组分,活性组分A和活性组分B之间的重量比为1:99-99:1;
活性组分A为通式
Figure DEST_PATH_IMAGE001
-1F所示的化合物或其硫酸盐:
Figure DEST_PATH_IMAGE003
式中:
R3选自氢;
R4、R5分别选自氢;
R6、R7分别选自氢;
R8、R9分别选自氢;
R11选自4-氯;
R14、R15、R16或R17分别选自氢;
W选自氢;
活性组分B为烯肟菌胺、嘧菌酯、吡唑醚菌酯、啶氧菌酯、烯肟菌酯、唑菌酯、肟菌酯、丁香菌酯。
2.根据权利要求1所述的杀真菌组合物,其特征在于:所述组合物中A、B两种活性组分之间的重量比为1:50-50:1。
3.根据权利要求2所述的杀真菌组合物,其特征在于:所述组合物中A、B两种活性组分之间的重量比为1:20-20:1。
4.根据权利要求3所述的杀真菌组合物,其特征在于其特征在于:所述组合物为A、B两种活性组分之间的重量比为1:10-10:1。
5.一种根据权利要求1所述的杀真菌组合物的应用,其特征在于:所述杀真菌组合物用于制备防治植物病原性真菌病害的药物。
6.根据权利要求5所述的杀真菌组合物的应用,其特征在于:所述植物病原性真菌病害为植物白粉病、锈病、霜霉病、晚疫病、疫病、霜疫霉病、黑痣病或纹枯病。
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