CN1655679A - 膦酸酯及其衍生物用作杀虫剂活性增强剂 - Google Patents

膦酸酯及其衍生物用作杀虫剂活性增强剂 Download PDF

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CN1655679A
CN1655679A CNA038117185A CN03811718A CN1655679A CN 1655679 A CN1655679 A CN 1655679A CN A038117185 A CNA038117185 A CN A038117185A CN 03811718 A CN03811718 A CN 03811718A CN 1655679 A CN1655679 A CN 1655679A
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D·斯托克
C·J·派珀
J·L·拉姆齐
M·S·伯切默尔
P·J·穆勒奎恩
R·B·佩里
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Abstract

一种杀虫组合物，含有膦酸酯或其烷氧基化衍生物或二聚物作为助剂。优选的膦酸酯是双－(2－乙基己基)－2－乙基己基膦酸酯、双－(2－乙基己基)－辛基膦酸酯和双－(丁基)－丁基膦酸酯。

Description

膦酸酯及其衍生物用作杀虫剂活性增强剂
本发明涉及一种组合物，特别是涉及杀虫组合物，更具体地说涉及含有机膦酸酯助剂的杀虫组合物。
USP2927014公开了一系列有机膦酸酯和亚膦酸酯化合物作为除草剂的应用。WO9304585公开了某些有机亚膦酸酯和膦酸酯作为增强某些除草剂活性的助剂的应用。WO9418837教导了一种特定的膦酸酯，双(2-乙基己基)2-乙基己基膦酸酯作为增强特定除草剂的生物性能的助剂的应用。在WO9800021中公开了某些膦酸酯或亚膦酸酯化合物与某些杀菌剂如氟喹唑和嘧菌酯组合能提供改良的杀菌活性。
本申请人现已发现通过使用有机膦酸酯助剂能惊人地增强杀虫剂活性。
根据本发明，提供了一种杀虫组合物，该组合物含有杀虫剂和式(I)的膦酸酯或其烷氧基化衍生物或二聚物
其中R1和R2独立地是含4-20个碳原子的烷氧基或-[OCH2CHR4]n-OR5基团，其中R4是氢、甲基或乙基，n是0-50，R5是氢或含1-20个碳原子的烷基；R3是(i)含4-20个碳原子的烷基或烯基(ii)任选被取代的苯基或(iii)式(II)的基团
Figure A0381171800042
其中R6是含4-20个碳原子的烷氧基或如本文定义的-[OCH2CHR4]n-OR5基团和R7是含4-20个碳原子的烷氧基或如本文定义的-[OCH2CHR4]n-OR5基团。
本文所用术语“烷基”包括直链或支链烷基，包括当该术语用于表述如“烷氧基”时。可能存在于任选被取代的苯基中的任选取代基包括C1-4烷基和卤素。
某些式(I)化合物可能含有二聚物或以二聚物的形式存在，所述二聚物包含在本发明范围内。
任选烷氧基化的酯基用如本文定义的-[OCH2CHR4]n-OR5基团代表。优选n是0-10，更优选0-5。如果存在一定范围的烷氧基化度，n可代表平均值，并且不必是整数。同样的，可能出现混合的烷氧基化，这样在基团-[OCH2CHR4]n中会存在不同的R4值。优选R5是含1-8个碳原子的烷基。如果n是0，-[OCH2CHR4]n-OR5基团成为烷氧基，因此，当n是0，基团-OR5适宜是含4-20个碳原子的烷氧基。
优选每个基团R1和R2都是含4-10个碳原子的烷氧基并且R3是含4-10个碳原子的烷基。适宜的膦酸酯公开于WO98/00021，本发明还包括等价物，其中相应的烷基链长小于WO98/00021所公开的那些。特别优选的是每个R1、R2和R3均含有4-8个碳原子。优选的膦酸酯是双-(2-乙基己基)-2-乙基己基膦酸酯、双-(2-乙基己基)-辛基膦酸酯和双-(丁基)-丁基膦酸酯。
本发明组合物还可含混合物。因此，该组合物可含有两种或多种本发明的有机膦酸酯化合物和/或其他添加剂(一般称为助剂)，所述添加剂可以是表面活性剂和/或油。
本发明组合物中的杀虫活性成分可包括一种或多种：
(a)乙酰胆碱酯酶抑制剂。这些化合物充当乙酰胆碱酯酶的抑制剂。乙酰胆碱酯酶切断中枢神经系统中神经介质乙酰胆碱的酯官能团，因此防止重复刺激乙酰胆碱受体。该酶在活性位点有亲核丝氨酸残基，能催化酯的水解，产生胆碱和乙酰化的酶，乙酰化的酶被迅速水解还原成其活性形式。杀虫乙酰胆碱酯酶抑制剂用一个基团将此丝氨酸残基酰化，其水解速度比乙酸酯低得多，因此阻断此酶的作用。这导致昆虫的胆碱能神经系统兴奋过度，最终导致痉挛和死亡。具有这种作用模式的代表性的杀虫剂包括有机磷杀虫剂。
根据磷官能团的具体性质(磷酸酯、膦酸酯、磷酰胺、硫醇磷酸酯、硫代磷酸酯和二硫醇磷酸酯)，可将有机磷杀虫剂分成六个小类，但所有的有机磷杀虫剂都含有亲电子的磷原子，磷原子上连接一良好(good)的离去基。还可根据离去基的性质(脂族的、苯氧基或芳氧基)将其分类。P＝S化合物在昆虫体内代谢成更有活性的P＝O化合物，而哺乳动物易于更迅速地断裂P-OR键，导致更强的选择性。具体的实例包括毒死蜱、甲基嘧啶磷、二嗪磷、丙溴磷、杀扑磷、特丁磷、乐果和噻唑膦(fozthiazate)和氨基甲酸酯类杀虫剂如抗蚜成、丙硫克百威、甲萘威和涕灭威；
(b)乙酰胆碱激动剂
乙酰胆碱是中枢神经系统的主要神经介质，负责在突触传递神经冲动并且还调节神经-肌肉界面的肌肉刺激。根据结合哪种天然产物最好-蕈毒碱或烟碱，已将乙酰胆碱受体分成两种主要亚型。现有许多通过此机制起作用的杀虫剂，并且其中包括硝基亚甲基类，该类杀虫剂对哺乳动物的毒性较低，但对昆虫显示出有效的广谱内吸活性。硝基亚甲基类对刺吸口器害虫和咀嚼口器害虫都有活性，并且通过胃和接触发挥作用。这些硝基亚甲基杀虫剂(也称为新-烟碱类)包括吡虫啉、啶虫脒、烯啶虫胺、噻虫胺、噻虫啉、噻虫嗪、MTI-446(来自Mitsui)。另一种此类化合物是多杀菌素，这是spinosyn和spinosyn B的混合物。多杀菌素也作用于烟碱受体，尽管其产生的效果与硝基亚甲基类有点不同；
(c)氯化物通道阻断剂(disruptors)
这些化合物通过阻断γ-氨基丁酸(GABA)的作用发挥作用，GABA是CNS的主要的抑制性神经递质。GABA从突触前膜中释放出来，并穿过突触，结合于GABA受体。此受体与氯离子通道连结，在GABA存在下该通道被打开。此打开使得氯离子净流入极化的神经细胞，因此降低了横跨神经细胞膜的电势(由于在静止状态中，神经细胞膜内侧比外侧阳性强)。这意味着当神经激动时，电势的改变小于缺乏GABA时的情况，因此神经冲动被有效地阻抑。
GABA激动剂包括齐墩螨素类，此类物质是能阻断多种氯离子通道的大环天然产物。这类物质实际上模拟GABA的作用，导致氯离子通道长期打开，最终导致昆虫麻痹。齐墩螨素、埃玛菌素(通常以盐的形式)和弥拜菌素是此类化学物质的实例。GABA拮抗剂的实例包括苯基吡唑类(fiprils)，例如氟虫腈和较老的化合物如“环二烯类”有机氯化合物如硫丹。
(d)钠离子通道阻断剂
钠离子通道对于神经传递很重要。静止时，由于外侧的钠离子比内侧的多，神经细胞膜的横跨电势差为约60mV。当神经冲动沿细胞传导时，膜中的钠离子通道打开，使钠离子大量地涌入细胞，导致电势正峰沿神经细胞流动。通常，这些通道非常快速地关闭，钠离子被泵出细胞以恢复静止电势。钠离子通道阻断剂使这些通道较长期地保持开放，阻止复极化。I型拟除虫菊酯(和藜芦碱类)阻止复极化0.001-0.1秒，这导致神经元的多波峰刺激(firing)，最终导致痉挛，而II型拟除虫菊酯能阻止复极化几分钟或更长的时间，导致缺乏协调。拟除虫菊酯是此作用模式的实例。拟除虫菊酯是来自菊属花的天然产物的合成类似物，在菊花中通常存在的是I型除虫菊酯。根据醇部分，可将拟除虫菊酯分成两种类型。I型拟除虫菊酯是第一代，易于光化学上较不稳定。II型拟除虫菊酯衍生自γ-氰基-3-苯氧基苯甲醇，效力高大约10倍。此外，一些II型拟除虫菊酯具有改变的酸部分，插入一个苯环。此类化学物质包括七氟菊酯、氯菊酯、氟氯菊酯、α-氯氰菊酯、溴氰菊酯、β-氟氯氰菊酯、λ-氯氟氰菊酯、γ-氯氟氰菊酯、S-氰戊菊酯和氟胺氰菊酯。其他钠离子通道阻断剂包括茚虫威；
(e)呼吸作用抑制剂
包括化学物质种类如(i)位点-1抑制剂，例如唑螨酯、喹螨醚、吡螨胺、唑虫酰胺和嘧螨醚以及解偶联剂。解偶联剂具有将呼吸作用与ATP生产相分离的作用。呼吸作用电子传递链中的蛋白质使用由呼吸作用产生的能量将质子泵越内侧线粒体膜。然后，ATP合成酶利用此pH梯度驱动ATP的合成。解偶联剂是亲脂的弱酸，能够以中性和阴离子形式通过膜扩散，因此能运送质子跨越内侧线粒体膜。这破坏了pH梯度，因此消除了用于ATP合成的驱动力。溴虫腈是此类型杀虫剂的一个实例；
(f)章鱼胺拮抗剂
章鱼胺是昆虫中枢神经系统的另一种神经递质(不存在于脊椎动物中)。它调节昆虫的行为唤醒。章鱼胺结合受体导致c-AMP的生产增加，这启动了神经元的兴奋。脒类造成对这些过程的过度刺激，从而导致产生如痉挛和持续飞行的行为。
章鱼胺拮抗剂的一个实例是双甲脒；
(g)昆虫生长调节剂-IGR’s
苯甲酰基脲类是此作用模式的实例。这些化合物抑制几丁质的生物合成，几丁质是作为昆虫外骨骼的主要结构成分(大约50％)的多糖。当昆虫蜕皮时，在这些化合物存在的情况下，没有足够的几丁质完成新的外骨骼的构建，因此昆虫在蜕皮过程中或蜕皮后立即死亡。在激素意义上，这些化合物实际上不是“生长调节剂”，但由于被这些化合物处理后死亡的昆虫的畸形躯干而杜撰了该术语。这些化合物对经常蜕皮的昆虫(例如鳞翅目)效果最好，但其使用受到限制，因为这些化合物仅能通过摄食吸收并且其活性依赖于生长阶段，因此易于作用缓慢。然而，这也导致非常清白的环境毒性特征，因此这些化合物经常被用于害虫综合防治项目。此类杀虫剂的实例包括除虫脲、氟虫脲、定虫隆、氟铃脲、虱螨脲(lufenuron)和双苯氟脲。其他昆虫生长调节剂化合物(具有与苯甲酰基脲类不同的效果)包括噻嗪酮、蚊蝇醚、灭蝇胺、虫酰肼、甲氧苯酰肼和乙螨唑；
(h)其他作用模式
在此部分有许多重要的具有新的作用模式(或不明确的作用模式)的杀虫化合物。包括杀螨隆、吡蚜酮和炔螨特。
优选的杀虫剂包括毒死蜱、丙溴磷、抗蚜威、吡虫啉、啶虫脒、烯啶虫胺、噻虫胺、噻虫啉、噻虫嗪、MTI-446(来自Mitsui)、多杀菌素、齐墩螨素、埃玛菌素、氟虫腈、λ-氯氟氰菊酯、χ-氯氟氰菊酯、茚虫威、唑螨酯、吡螨胺、溴虫腈、虱螨脲、灭蝇胺、杀螨隆和吡蚜酮。本发明组合物特别适用于杀虫剂噻虫嗪、多杀菌素、齐墩螨素、埃玛菌素、氟虫腈、λ-氯氟氰菊酯、γ-氯氟氰菊酯、茚虫威、唑螨酯、吡螨胺、溴虫腈、虱螨脲、灭蝇胺、杀螨隆和吡蚜酮。
本发明组合物可含有能在植物体内内吸移动的活性成分或接触性杀虫剂，特别是如果靶标害虫是隐蔽性取食者(如潜叶虫)时。
上述组合物特别适用于防治某些昆虫种类如咀嚼口器式害虫例如鳞翅目，和刺吸口器式害虫如蚜虫物种。
意外的是已发现本发明组合物在可接受的用量下对寄主植物没有过度的植物毒性。
式(I)化合物的混合物和杀虫剂混合物均可用于本发明组合物中。本发明的组合物可含有杀虫组合物中常规加入的其他添加剂，包括其他助剂如表面活性剂和杀虫剂增效剂或其他成分如防冻剂、聚合物、粘着剂、光保护剂、矿物油、植物油和衍生物。许多杀虫剂增效剂是本领域技术人员已知的，一个具体的实例是胡椒基丁醚。
式(I)化合物可在桶混阶段添加到杀虫组合物中，本发明的组合物包括上述桶混组合物，该桶混组合物是稀释的并即可施用。作为选择，可将式(I)化合物掺入设计成施用前稀释的浓缩组合物中。式(I)化合物的性质可根据取代基的性质而改变，由液体到固体，由微溶于水到非常不溶于水。本领域技术人员应能使用常规技术提供例如由适宜的固体载体运载的固体或液体形式的本发明组合物，包括例如可湿性粉剂(WP或SP-可溶性粉剂)，可湿性颗粒剂(WG-水可分散性颗粒剂或SG-可溶性颗粒剂)，固体或液体在液体中的分散体如胶悬剂、油基胶悬剂、油悬浮剂如SC(胶悬剂)或OF(油悬浮剂)，乳剂和混合物如EW(水乳剂)、EO(油乳剂)、SE(悬乳剂)，液剂如EC(乳油)、DC(可分散液剂)、UL(超低容量液剂)、SL(可溶液剂)和特殊制剂如微胶囊化组合物。优选的式(I)化合物一般是具有有限的水溶性的油状液体。因此，易于通过常规的混合掺入到油溶液中，任选结合一种或多种乳化剂，或者吸收到固体载体如粘土或二氧化硅上用于掺入到干产品中。同样的，油状液体的式(I)化合物可用于制备杀虫剂在式(I)化合物中的分散体或制备含式(I)化合物和杀虫剂的溶液或制备混合的分散体系，其中例如杀虫剂以胶悬剂的形式存在，而式(I)化合物以水包油乳剂的形式存在。本领域技术人员能够想到其他组合。
助剂的用量通常以每公顷施用的喷雾体积的百分率表示。每公顷的水体积一般是大约200l/ha，但用于果树树冠特殊施用时可从50到超过3000范围内变化。助剂一般施用的体积是每公顷喷雾体积的0.05％至1.0％。取200l/ha为平均值，因此助剂的通常用量在每公顷100g(0.05％)至2000g(1.0％)范围内。杀虫剂的通常用量范围是10g/ha至5Kg/ha。因此，本领域技术人员应能预料涵盖活性成分和助剂的通常用量的比率。直接涉及杀虫剂与式(I)化合物的比率(重量比)是50∶1至1∶400。优选杀虫剂与式(I)化合物的重量比是25∶1至1∶25，特别是10∶1至1∶10。
尽管预期这些组合物通常在水中稀释后用于靶标作物的施用，但本发明的范围包括施用超低容量形式的本发明制剂用于例如干旱地区。在希望杀虫剂能迅速渗透树皮的情况下，本发明组合物还可以例如树皮渗透试剂(bark penetration formulation)的形式使用。此外，通过使用技术人员已知的剂型，本发明组合物还可用于处理和保护植物种子。
通过下列实施例对本发明进行说明。
实施例1
在治疗性防治L1/L2南美斑潜蝇(Liriomyza huidobriensis)的试验中，比较与0.5％双(2-乙基己基)-2-乙基己基膦酸酯(BEEP)结合的一系列杀虫剂的活性与不含双(2-乙基己基)-2-乙基己基膦酸酯的相应制剂的活性。结果列于表1中并且显示对菜豆叶片内此潜叶虫的防治％。
                                 表1
用量ppm     噻虫嗪     溴虫腈       氟虫腈     多杀菌素
  单独   +BEEP   单独   +BEEP   单独   +BEEP   单独   +BEEP
  对照     0     0     0     0     0     0     0     0
  400     0     20     0     100     60     100     42     100
  600     0     43     15     100     69     100     73     100
  800     0     63     0     100     66     100     82     100
  1000     12     68     28     100     83     100     81     100
用量ppm    齐墩螨素
单独 +BEEP
对照 0 0
3.13 27 99
6.25 48 100
12.5 74 100
25 96 100
用量ppm      灭蝇胺
单独 +BEEP
对照 0 0
25 27 28
50 57 83
100 81 100
200 100 100
                       实施例2
在对菜蛾(Plutella xylostella)的摄食/接触试验中，比较结合0.5％双(2-乙基己基)-2-乙基己基膦酸酯(BEEP)的λ-氯氟氰菊酯、丙溴磷和茚虫威的活性与不含双(2-乙基己基)-2-乙基己基膦酸酯的相应制剂的活性。结果列于表2并显示防治％。
           表2
用量 λ-氯氟氰菊酯
单独 +BEEP
对照 21 11
0.31ppm 54 100
0.63ppm 66 100
1.25ppm 83 100
2.5ppm 95 100
用量 丙溴磷
单独 +BEEP
对照 21 11
12.5ppm 16 65
25ppm 41 95
50ppm 95 100
100ppm 100 100
用量 茚虫威
单独 +BEEP
对照 15 20
0.16ppm 32 57
0.31ppm 26 80
0.63ppm 32 98
1.25ppm 80 100
                     实施例3
在对R2桃短尾蚜(Myzus persicae)的穿壁(translaminar)试验(评价时间3天)中，比较结合0.5％双(2-乙基己基)-2-乙基己基膦酸酯(BEEP)的λ-氯氟氰菊酯(以Karate 10CS制剂形式)的活性与不含双(2-乙基己基)-2-乙基己基膦酸酯的Karate 10CS的活性。结果列于表3并显示防治％。
      表3
用量ppm λ-氯氟氰菊酯
单独 +BEEP
对照 10 4
62 41 72
125 45 98
250 26 98
                     实施例4
在对棉蚜(Aphis gossypii)的穿壁试验(评价时间3天)中，比较结合0.5％双(2-乙基己基)辛基膦酸酯(BEOP)的噻虫嗪的Actara 25WG制剂的活性与不含双(2-乙基己基)辛基膦酸酯的Actara的活性。结果列于表4并显示防治％。
          表4
  用量ppm     噻虫嗪
  单独   +BEOP
  对照     11     3
  15.6     45     45
  31.2     68     48
  62.5     72     96

Claims (6)

1.一种杀虫组合物，含有杀虫剂和式(I)的膦酸酯或其烷氧基化衍生物或二聚物
Figure A038117180002C1
其中R1和R2独立地是含4-20个碳原子的烷氧基或-[OCH2CHR4]n-OR5基团，其中R4是氢、甲基或乙基，n是0-50，R5是氢或含1-20个碳原子的烷基；R3是(i)含4-20个碳原子的烷基或烯基(ii)任选被取代的苯基或(iii)式(II)的基团
Figure A038117180002C2
其中R6是含4-20个碳原子的烷氧基或如这里所定义的-[OCH2CHR4]n-OR5基团，R7是含4-20个碳原子的烷氧基或如R1和R2定义中所述的-[OCH2CHR4]n-OR5基团。
2.根据权利要求1所述的杀虫组合物，其中R1和R2是含4-10个碳原子的烷氧基，R3是含4-10个碳原子的烷基。
3.根据权利要求2所述的杀虫组合物，其中的R1、R2和R3含4-8个碳原子。
4.根据权利要求3所述的杀虫组合物，其中的膦酸酯是双-(2-乙基己基)-2-乙基己基膦酸酯、双-(2-乙基己基)-辛基膦酸酯和双-(丁基)-丁基膦酸酯。
5.根据权利要求4所述的杀虫组合物，其中的膦酸酯是双-(2-乙基己基)-2-乙基己基膦酸酯。
6.根据上述任一权利要求所述的杀虫组合物，其中的杀虫剂选自毒死蜱、丙溴磷、抗蚜威、吡虫啉、啶虫脒、烯啶虫胺、噻虫胺、噻虫啉、噻虫嗪、MTI-446、多杀菌素、齐墩螨素、埃玛菌素、氟虫腈、λ-氯氟氰菊酯、γ-氯氟氰菊酯、茚虫威、唑螨酯、吡螨胺、溴虫腈、虱螨脲、灭蝇胺、杀螨隆和吡蚜酮。
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MXPA04011066A (es) 2005-02-14
IL164836A (en) 2010-05-17
CA2758176A1 (en) 2003-12-04
IL164836A0 (en) 2005-12-18
BR0311245A (pt) 2005-03-15
NZ536491A (en) 2006-09-29
BR0311245B1 (pt) 2013-12-17
KR101023926B1 (ko) 2011-03-22
EP1509085B1 (en) 2009-07-15
AU2003227965A1 (en) 2003-12-12
EA007289B1 (ru) 2006-08-25

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