CN105165845B - 基于三氟丁烯基化合物的、并表现出杀线虫及杀昆虫特性的活性物质的结合物 - Google Patents
基于三氟丁烯基化合物的、并表现出杀线虫及杀昆虫特性的活性物质的结合物 Download PDFInfo
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- CN105165845B CN105165845B CN201510657093.XA CN201510657093A CN105165845B CN 105165845 B CN105165845 B CN 105165845B CN 201510657093 A CN201510657093 A CN 201510657093A CN 105165845 B CN105165845 B CN 105165845B
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- fluorine
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Classifications
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- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
-
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
- A01N43/38—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings condensed with carbocyclic rings
-
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
-
- 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
- A01N47/02—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 no bond to a nitrogen atom
-
- 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
- A01N47/02—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 no bond to a nitrogen atom
- A01N47/06—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 no bond to a nitrogen atom containing —O—CO—O— groups; Thio analogues thereof
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- 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
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- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
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Abstract
本发明涉及由式(Ⅰ)的杂环三氟丁烯基化合物及已知的杀昆虫物质组成的新型活性物质的结合物,其中X为卤素并且n为0、1或2。所述新型活性物质结合物适于防治如昆虫及线虫等害虫。
Description
本申请为2004年4月20日提交的名称为“基于三氟丁烯基化合物的、并表现出杀线虫及杀昆虫特性的活性物质的结合物”的发明专利申请200480018510.6的分案申请。
技术领域
本发明涉及新型活性化合物的结合物(combination),包括,第一,已知的杂环三氟丁烯基化合物,以及,第二,已知的杀昆虫活性化合物,所述结合物非常适于防治动物病虫害,例如昆虫及线虫。
背景技术
已知某些杂环三氟丁烯基化合物具有杀线虫特性(WO 01/02378 A1)。尚未报道这些化合物具有杀昆虫活性。现已发现某些杂环三氟丁烯基化合物也具有杀昆虫活性。该活性尚好,但并非完全令人满意。
也已知有多种磷酸酯、氨基甲酸酯、杂环、有机锡化合物、苯甲酰脲及拟除虫菊酯具有杀昆虫及杀螨虫特性(参见,例如US 2,758,115、US 3,309,266、GB 1,181,657、WO 93/22297 A1、WO 93/10083 A1、DE 26 41 343 A1、EP 347 488 A1、EP 210 487 A1、US 3,264,177及EP 234 045 A2)。然而,这些化合物的活性同样不是完全令人满意。
发明内容
现已发现新型活性化合物结合物具有非常好的杀线虫、杀昆虫及杀螨虫特性,所述结合物包括至少一种式(Ⅰ)的化合物,
其中
X代表卤素,并且
n代表0、1或2,
(“第1组活性化合物”)
以及
至少一种选自以下活性化合物的活性化合物:
齐墩螨素(abamectin)、ABG-9008、高灭磷(acephate)、灭螨醌(acequinocyl)、吡虫清(acetamiprid)、acetoprole、氟酯菊酯(acrinathrin)、AKD-1022、AKD-3059、AKD-3088、棉铃威(alanycarb)、砜灭威(aldoxycarb)、丙烯除虫菊(allethrin)、丙烯除虫菊1R异构体、甲体氯氰菊酯(alpha-cypermethrin,alphamethrin)、amidoflumet、灭害威(aminocarb)、虫螨脒(amitraz)、阿维菌素(avermectin)、AZ-60541、艾扎丁(azadirachtin)、唑啶磷(azamethiphos)、谷硫磷(azinphos-methyl)、乙基谷硫磷(azinphos-ethyl)、唑环锡(azocyclotin)、波林杆菌芽孢(Bacillus popilliae)、球形芽孢杆菌(Bacillus sphaericus)、柯敌克菌(Bacillus subtilis)、苏云金杆菌(Bacillusthuringiensis)、苏云金杆菌株EG-2348、苏云金杆菌株GC-91、苏云金杆菌株NCTC-11821、杆状病毒(baculoviruses)、巴西安白僵菌(Beauveria bassiana)、纤细白僵菌(Beauveriatenella)、benclothiaz、噁虫威(bendiocarb)、丙硫克百威(benfuracarb)、杀虫磺(bensultap)、苯螨特(benzoximate)、β-氟氯氰菊酯(beta-cyfluthrin)、乙体氯氰菊酯(beta-cypermethrin)、联苯肼酯(bifenazate)、氟氯菊酯(bifenthrin)、乐杀螨(binapacryl)、反丙烯除虫菊(bioallethrin)、反丙烯除虫菊-S-环戊基异构体、bioethanomethrin、生物氯菊酯(biopermethrin)、右旋反灭虫菊酯(bioresmethrin)、双三氟虫脲(bistrifluron)、BPMC、brofenprox、乙基溴硫磷(bromophos-ethyl)、溴螨酯(bromopropylate)、溴苯烯磷(-甲基)(bromfenvinfos(-methyl))、BTG-504、BTG-505、合杀威(bufencarb)、噻嗪酮(buprofezin)、特嘧硫磷(butathiofos)、丁叉威(butocarboxim)、氧丁叉威(butoxycarboxim)、丁基哒螨酮(butylpyridaben)、西维因(carbaryl)、虫螨威(carbofuran)、三硫磷(carbophenothion)、丁硫克百威(carbosulfan)、巴丹(cartap)、CGA-50439、灭螨猛(chinomethionat)、氯丹(chlordane)、chloethocarb、壤虫氯磷(chlorethoxyfos)、氟唑虫清(chlorfenapyr)、毒虫畏(chlorfenvinphos)、定虫隆(chlorfluazuron)、氯甲磷(chlormephos)、乙酯杀螨醇(chlorobenzilate)、chlorproxyfen、chlovaporthrin、环虫酰肼(chromafenozide)、顺-氯氰菊酯、顺-灭虫菊(cis-resmethrin)、顺-氯菊酯(cis-permethrin)、功夫菊酯(clocythrin)、除线威(cloethocarb)、四螨嗪(clofentezine)、噻虫胺(clothianidin)、clothiazoben、十二碳二烯醇(codlemone)、苯腈磷(cyanofenphos)、杀螟腈(cyanophos)、cycloprene、乙氰菊酯(cycloprothrin)、苹果蠹蛾颗粒体病毒(Cydia pomonella granuloviruses)、氟氯氰菊酯(cyfluthrin)、(RS)氯氟氰菊酯(cyhalothrin)、三环锡(cyhexatin)、氯氰菊酯(cypermethrin)、苯醚氯菊酯(1R-反式异构体)(cyphenothrin(1R-trans isomer))、灭蝇胺(cyromazine)、溴氰菊酯(deltamethrin)、甲基一○五九(demeton-S-methyl)、磺吸磷(demeton-S-methylsulfone)、杀螨硫隆(diafenthiuron)、氯亚磷(dialiphos)、二嗪农(diazinon)、除线磷(dichlofenthion)、敌敌畏(dichlorvos)、开乐散(dicofol)、百治磷(dicrotophos)、地昔尼尔(dicyclanil)、氟脲杀(diflubenzuron)、四氟甲醚菊酯(dimefluthrin)、乐果(dimethoate)、甲基毒虫畏(dimethylvinphos)、敌螨通(dinobuton)、敌螨普(dinocap)、呋虫胺(dinotefuran)、噁茂醚(diofenolan)、乙拌磷(disulfoton)、碘酰丁二辛(docusat-sodium)、苯氧炔螨(dofenapyn)、DOWCO-439、eflusilanate、埃玛菌素(emamectin)、埃玛菌素苯甲酸盐(emamectin-benzoate)、烯炔菊酯(1R异构体)(empenthrin(1R isomer))、虫霉属种(entomopthora spp.)、EPN、高氰戊菊酯(esfenvalerate)、苯虫威(ethiofencarb)、乙虫清(ethiprole)、乙硫磷(ethion)、灭克磷(ethoprophos)、醚菊酯(etofenprox)、特苯噁唑(etoxazole)、氧嘧啶磷(etrimfos)、氨磺磷(famphur)、克线磷(fenamiphos)、喹螨醚(fenazaquin)、杀螨锡(fenbutatin oxide)、五氟苯菊酯(fenfluthrin)、杀螟松(fenitrothion)、丁苯威(fenobucarb)、苯硫威(fenothiocarb)、fenoxacrim、双氧威(fenoxycarb)、甲氰菊酯(fenpropathrin)、必螨立克(fenpyrad)、吡氯氰菊酯(fenpyrithrin)、唑螨酯(fenpyroximate)、丰索磷(fensulfothion)、倍硫磷(fenthion)、氟硝二苯胺(fentrifanil)、灭杀菊酯(fenvalerate)、锐劲特(fipronil)、氟啶虫酰胺(flonicamid)、fluarcypyrim、氟啶蜱脲(fluazuron)、噻唑螨(flubenzimine)、溴氟菊酯(flubrocythrinate)、氟螨脲(flucycloxuron)、氟氰戊菊酯(flucythrinate)、flufenerim、氟虫脲(flufenoxuron)、氟丙苄醚(flufenprox)、氟氯苯菊酯(flumethrin)、吡氟硫磷(flupyrazofos)、氟替阿嗪(flutenzin)(氟螨嗪(flufenzine))、氟胺氰菊酯(fluvalinate)、地虫磷(fonofos)、伐虫脒(formetanate)、安果(formothion)、丁苯硫磷(fosmethilan)、噻唑酮磷(fosthiazate)、fubfenprox(苄螨醚(fluproxyfen))、呋线威(furathiocarb)、精高效氯氟氰菊酯(gamma-cyhalothrin)、林丹(gamma-HCH)、诱虫十六酯(gossyplure)、诱杀烯混剂(grandlure)、颗粒体病毒(granuloviruses)、卤醚菊酯(halfenprox)、特丁苯酰肼(halofenozide)、HCH、HCN-801、庚虫磷(heptenophos)、氟铃脲(hexaflumuron)、噻螨酮(hexythiazox)、灭蚁腙(hydramethylnon)、蒙五一二(hydroprene)、IKA-2002、吡虫磷(imidacloprid)、炔咪菊酯(imiprothrin)、噁二唑虫(indoxacarb)、碘硫磷(iodofenphos)、异稻瘟净(iprobenfos)、氟唑磷(isazofos)、丙胺磷(isofenphos)、异丙威(isoprocarb)、异噁唑啉(isoxathion)、伊维菌素(ivermectin)、japonilure、噻嗯菊酯(kadethrin)、核多角体病毒(nuclearpolyhedrosis viruses)、蒙七七七(kinoprene)、氯氟氰菊酯(lamda-cyhalothrin)、林丹(lindane)、氟丙氧脲(lufenuron)、马拉松(malathion)、灭蚜磷(mecarbam)、甲亚砜磷(mesulfenfos)、蜗牛敌(metaldehyde)、威百亩(metam-sodium)、虫螨畏(methacrifos)、绿僵菌(Metharhizium anisopliae)、黄绿绿僵菌(Metharhiziumflavoviride)、灭虫威(methiocarb)、灭多虫(methomyl)、蒙五一五(methoprene)、甲氧滴滴涕(methoxychlor)、甲氧苯酰肼(methoxyfenozide)、甲氧苄氟菊酯(metofluthrin)、速灭威(metolcarb)、恶虫酮(metoxadiazone)、速灭磷(mevinphos)、米尔螨素(milbemectin)、米尔倍霉素(milbemycin)、MKI-245、MON-45700、莫昔克丁(moxidectin)、MTI-800、二溴磷(naled)、NC-104、NC-170、NC-184、NC-194、NC-196、贝螺杀(niclosamide)、烟碱(nicotine)、硝胺烯啶(nitenpyram)、硝虫噻嗪(nithiazine)、NNI-0001、NNI-0101、NNI-0250、NNI-9768、双苯氟脲(novaluron)、多氟脲(noviflumuron)、OK-5101、OK-5201、OK-9601、OK-9602、OK-9701、OK-9802、氧化乐果(omethoate)、甲氨叉威(oxamyl)、砜吸磷(oxydemeton-methyl)、玫烟色拟青霉(Paecilomyces fumosoroseus)、甲基一六○五(parathion methyl)、一六○五(-乙基)、氯菊酯(顺-、反-)、石油、PH-6045、苯醚菊酯(1R反式异构体)(phenothrin(1R trans isomer)、稻丰散(phenthoate)、三九一一(phorate)、伏杀磷(phosalone)、亚胺硫磷(phosmet)、乙丙磷威(phosphocarb)、腈肟磷(phoxim)、胡椒基丁醚(piperonyl butoxide)、抗蚜威(pirimicarb)、虫螨磷(pirimiphos methyl)、乙基虫螨磷(pirimiphos ethyl)、炔酮菊酯(prallethrin)、丙溴磷(profenofos)、丙氟菊酯(profluthrin)、猛杀威(promecarb)、丙虫磷(propaphos)、克螨特(propargite)、烯虫磷(propetamphos)、残杀威(propoxur)、丙硫磷(prothiofos)、发果(prothoate)、protrifenbute、拒嗪酮(pymetrozine)、吡唑硫磷(pyraclofos)、反灭虫菊(pyresmethrin)、除虫菊(pyrethrum)、哒螨酮(pyridaben)、啶虫丙醚(pyridalyl)、打杀磷(pyridaphenthion)、pyridathion、嘧胺苯醚(pyrimidifen)、蚊蝇醚(pyriproxyfen)、喹噁磷(quinalphos)、灭虫菊、RH-5849、利巴韦林(ribavirin)、RU-12457、RU-15525、S-421、S-1833、杀抗松(salithion)、SI-0009、灭虫硅醚(silafluofen)、艾克敌105(spinosad)、螺螨酯(spirodiclofen)、螺甲螨酯(spiromesifen)、氟虫胺(sulfluramid)、硫特普(sulfotep)、乙丙硫磷(sulprofos)、SZI-121、氟胺氰菊酯(tau-fluvalinate)、双苯酰肼(tebufenozide)、吡螨胺(tebufenpyrad)、嘧丙磷(tebupirimphos)、伏虫磷(teflubenzuron)、七氟菊酯(tefluthrin)、双硫磷(temephos)、灭虫畏(temivinphos)、叔丁威(terbam)、特丁磷(terbufos)、杀虫畏(tetrachlorvinphos)、三氯杀螨砜(tetradifon)、胺菊酯(tetramethrin)、胺菊酯(1R异构体)、杀螨好(tetrasul)、辛体氯氰菊酯(theta-cypermethrin)、噻虫啉(thiacloprid)、噻虫嗪(thiamethoxam)、蛾蝇腈(thiapronil)、thiatriphos、硫环杀(thiocyclam hydrogen oxalate)、硫双灭多威(thiodicarb)、特氨叉威(thiofanox)、甲基乙拌磷(thiometon)、杀虫双(thiosultap-sodium)、敌贝特(thuringiensin)、tolfenpyrad、氟溴氰菊酯(tralocythrin)、四溴菊酯(tralomethrin)、四氟菊酯(transfluthrin)、苯赛螨(thiarathene)、唑蚜威(triazamate)、triazuron、trichlophenidine、敌百虫(trichlorfon)、杀虫隆(triflumuron)、混杀威(trimethacarb)、蚜灭多(vamidothion)、氟吡唑虫(vaniliprole)、verbutin、蜡蚧轮枝菌(Verticillium lecanii)、WL-108477、WL-40027、YI-5201、YI-5301、YI-5302、XMC、灭杀威(xylylcarb)、ZA-3274、己体氯氰菊酯(zeta-cypermethrin)、zolaprofos、ZXI-8901、化合物3-甲基苯基氨基甲酸丙酯(速灭威Z(tsumacide Z))、化合物3-(5-氯-3-吡啶基)-8-(2,2,2-三氟乙基)-8-氮杂双环[3.2.1]辛烷-3-腈(CAS注册号185982-80-3)及相应的3-内型异构体(CAS注册号185984-60-5)(参见WO-96/37494、WO-98/25923)及式(ⅡA)的化合物
(羧酸,3-(2,5-二甲基苯基)-8-甲氧基-2-氧-1-氮杂螺[4.5]癸-3-烯-4-基乙酯,(9Cl))
(“第2组活性化合物”)。
出人意料的是,本发明活性化合物结合物的杀线虫、杀昆虫和/或杀螨虫活性显著高于单独活性化合物的活性总和。因此,存在非可预见的协同效应,而并不仅仅是活性的叠加。
具体实施方式
除至少一种式(Ⅰ)的活性化合物之外,本发明的活性化合物结合物还包括至少一种第2组活性化合物。
第2组活性化合物可划分为以下不同种类的物质,例如:
苯并异噻唑类,例如7-氯-1,2-苯并异噻唑(benclothiaz);苯甲酰脲类,例如双三氟虫脲、定虫隆、氟脲杀、DOWCO-439、氟啶蜱脲、氟螨脲、氟虫脲、氟铃脲、氟丙氧脲、双苯氟脲、多氟脲、伏虫磷、杀虫隆;生物杀昆虫剂,例如ABG-9008、波林杆菌芽孢、球形芽孢杆菌、柯敌克菌、苏云金杆菌、苏云金杆菌株EG-2348、苏云金杆菌株
NCTC-11821、苏云金杆菌株GC-91、杆状病毒、巴西安白僵菌、纤细白僵菌、苹果蠹蛾颗粒体病毒(CpGV)、虫霉属种、颗粒体病毒、核多角体病毒、绿僵菌、黄绿绿僵菌、玫烟色拟青霉、蜡蚧轮枝菌;氨基甲酸酯类,例如棉铃威、砜灭威、灭害威、噁虫威、丙硫克百威、BPMC、合杀威、丁叉威、西维因、虫螨威、丁硫克百威、除线威、苯虫威、丁苯威、双氧威、呋线威、异丙威、威百亩、灭虫威、灭多虫、速灭威、速灭威、甲氨叉威、乙丙磷威、抗蚜威、猛杀威、残杀威、硫双灭多威、特氨叉威、混杀威、XMC、灭杀威;二硝基苯酚类,例如乐杀螨、敌螨通、敌螨普;二苯醚类,例如苯虫醚(difenolan)、苯氧炔螨、蚊蝇醚;酯类,例如cycloprene、诱虫十六酯、蒙五一二、蒙七七七、蒙五一五、碘酰丁二辛、螺螨酯、螺螨甲酯;茚并氧杂二嗪酰胺类,例如噁二唑虫;大环内酯类,例如齐墩螨素、阿维菌素、埃玛菌素、埃玛菌素苯甲酸盐、伊维菌素、米尔螨素、米尔倍霉素、莫昔克丁、艾克敌105、敌贝特;新烟碱类(neonicotinoid),例如吡虫清、AKD 1022、噻虫胺、呋虫胺、吡虫磷、硝胺烯啶、噻虫啉、噻虫嗪;磷酸酯类,例如溴苯烯磷(-甲基)、毒虫畏、敌敌畏、百治磷、甲基毒虫畏、庚虫磷、速灭磷、二溴磷、丙虫磷、灭虫畏、杀虫畏;氨基磷酸酯类,例如克线磷、丙胺磷;氨基磷酸硫酯类(phosphoramidothioate),例如高灭磷、烯虫磷;邻苯二酰胺类,例如N2-[1,1-二甲基-2-(甲磺酰基)乙基]-3-碘-N1-[2-甲基-4-[1,2,2,2-四氟-1-(三氟甲基)乙基]苯基-1,2-苯二酰胺(CAS注册号272451-65-7,参见EP 0 919 542A2),吡唑类,例如acetoprole、乙虫清、唑螨酯、锐劲特、氟吡唑虫;吡唑羧胺类,例如必螨立克、吡螨胺、tolfenpyrad;拟除虫菊酯及拟除虫菊酯类似物,例如灭虫菊、氟酯菊酯、丙烯除虫菊(1R异构体)、甲体氯氰菊酯、β-氟氯氰菊酯、乙体氯氰菊酯、氟氯菊酯、反丙烯除虫菊、反丙烯除虫菊(S-环戊基异构体)、bioethanomethrin、生物氯菊酯、右旋反灭虫菊酯、brofenprox、chloethocarb、chlovaporthrin、顺-氯氰菊酯、顺-灭虫菊、功夫菊酯、乙氰菊酯、氟氯氰菊酯、(RS)氯氟氰菊酯、氯氰菊酯、苯醚氯菊酯(1R-反式异构体)、溴氰菊酯、四氟甲醚菊酯、eflusilanate、烯炔菊酯(1R异构体)、高氰戊菊酯、醚菊酯、五氟苯菊酯、甲氰菊酯、吡氯氰菊酯、灭杀菊酯、溴氟菊酯、溴氟菊酯、氟氰戊菊酯、氟丙苄醚、氟丙苄醚、氟氯苯菊酯、氟胺氰菊酯、fubfenprox、精高效氯氟氰菊酯、卤醚菊酯、炔咪菊酯、噻嗯菊酯、氯氟氰菊酯、甲氧苄氟菊酯、MIT-800、氯菊酯、苯醚菊酯(1R-反式异构体)、炔酮菊酯、丙氟菊酯、protrifenbute、反灭虫菊、除虫菊、RU-12457、RU-15525、灭虫硅醚、氟胺氰菊酯、七氟菊酯、胺菊酯(1R异构体)、辛体氯氰菊酯、氟溴氰菊酯、四溴菊酯、四氟菊酯、己体氯氰菊酯;哒嗪酮类,例如丁基哒螨酮、NC-170、NC-184、NC-194、NC-196、哒螨酮、打杀磷、pyridathion;吡咯类,例如氟唑虫清;喹唑啉类,例如喹螨醚;硫代磷酸酯类及二硫代磷酸酯类,例如唑啶磷、乙基谷硫磷、谷硫磷、乙基溴硫磷、特嘧硫磷、三硫磷、壤虫氯磷、氯甲磷、杀螟腈、一○五九、甲基一○五九、磺吸磷、氯亚磷、二嗪农、除线磷、乐果、乙拌磷、乙硫磷、灭克磷、氧嘧啶磷、杀螟松、丰索磷、倍硫磷、吡氟硫磷、地虫磷、安果、丁苯硫磷、碘硫磷、异稻瘟净、氟唑磷、异噁唑啉、马拉松、灭蚜磷、甲亚砜磷、虫螨畏、氧化乐果、砜吸磷、一六○五、稻丰散、三九一一、伏杀磷、亚胺硫磷、乙丙磷威、腈肟磷、乙基虫螨磷、虫螨磷、丙溴磷、丙硫磷、发果、吡唑硫磷、打杀磷、pyridathion、喹噁磷、硫特普、乙丙硫磷、嘧丙磷、双硫磷、特丁磷、thiatriphos、甲基乙拌磷、蚜灭多;硫代膦酸酯类,例如苯腈磷、EPN、噻唑酮磷;硫代磺酸酯类,例如杀虫磺、杀虫双;硫脲类,例如杀螨硫隆;三嗪类,例如灭蝇胺、拒嗪酮;三唑羧胺类,例如唑蚜威、triazuron。
本发明中,发现包括第1组活性化合物及一种或多种选自上述物质种类之一的活性化合物的本发明结合物,较单独使用的活性化合物具有协同增强的活性。
因此,本发明特别提供活性化合物结合物,所述结合物包括至少一种第1组活性化合物及至少一种选自一类或多类以上定义的氨基甲酸酯类、新烟碱类、吡唑类、大环内酯类、硫代磷酸酯类或二硫代磷酸酯类、或拟除虫菊酯或拟除虫菊酯类似物的物质种类的活性化合物。
某些物质种类还具有相同的作用机理或相同的作用位点:
“氨基甲酸酯类”及“硫代磷酸酯类”通过抑制乙酰胆碱酯酶发挥其神经毒害作用,所述乙酰胆碱酯酶在神经冲动的传导中起极为重要的作用:乙酰胆碱酯酶以很高的反应速率破坏在神经元之间传递冲动的信使乙酰胆碱。若抑制此酶,则乙酰胆碱积累,整个神经系统达到过度兴奋的状态。
“新烟碱类”可停靠(dock)于神经系统中的受体分子,该受体分子通常接受乙酰胆碱,即在神经元之间传递冲动的信使。活性化合物不可逆地阻断乙酰胆碱受体并由此而彻底扰乱昆虫体内的生理过程。
“拟除虫菊酯”或“拟除虫菊酯类似物”延迟神经细胞的质膜上钠通道的关闭。从而抑制复极化的生理过程及充分负静息膜电位(sufficiently negative resting membranepotential)的建立。而且,它们还通过抑制钙、镁依赖性ATP酶及钙结合性蛋白钙调蛋白引起突触前神经元中钙浓度的升高。从而导致释放更多的神经递质以及增强突触后膜的去极化。最终,拟除虫菊酯会抑制GABA诱导的氯内流。使用环戊二烯类杀昆虫剂也能观察到后一种现象。
“吡唑类”有时亦被称为“fibroles”,其通过防止氯离子的通过作用于昆虫的GABA(γ-氨基丁酸)受体,从而引起中枢神经系统的崩溃。这种作用模式也与环戊二烯相对应。
“苯甲酰脲类”通过在大多数昆虫的幼虫阶段扰乱几丁质的生物合成而产生作用。通常的结果是,例如,使外皮发生毁坏或畸变。
进一步优选包括至少一种式(I)化合物的上述活性化合物结合物,其中
X代表氟、氯或溴,并且
n代表0或2。
进一步特别优选包括至少一种式(I)化合物的上述活性化合物结合物,其中
X代表氟或氯,并且
n代表2。
尤其优选上述活性化合物结合物包括式(IA)的化合物
以及第2组的活性化合物,
优选地
选自棉铃威、砜灭威、灭害威、噁虫威、丙硫克百威、BPMC、合杀威、丁叉威、西维因、虫螨威、丁硫克百威、除线威、苯虫威、丁苯威、双氧威、呋线威、异丙威、威百亩、灭虫威、灭多虫、速灭威、速灭威、甲氨叉威、乙丙磷威、抗蚜威、猛杀威、残杀威、硫双灭多威、特氨叉威、混杀威、XMC、灭杀威(“氨基甲酸酯类”)的活性化合物,或
选自噻虫胺、吡虫清、AKD 1022、呋虫胺、吡虫磷、硝胺烯啶、噻虫啉、噻虫嗪(“新烟碱类”)的活性化合物,或
选自锐劲特、acetoprole、乙虫清、唑螨酯、氟吡唑虫(“吡唑类”)的活性化合物,或
选自艾克敌105、齐墩螨素、阿维菌素、埃玛菌素、埃玛菌素苯甲酸盐、伊维菌素、米尔螨素、米尔倍霉素、莫昔克丁、敌贝特(“大环内酯类”)的活性化合物,或
选自嘧丙磷、唑啶磷、乙基谷硫磷、谷硫磷、乙基溴硫磷、特嘧硫磷、三硫磷、壤虫氯磷、杀螟腈、一○五九、甲基一○五九、磺吸磷、氯亚磷、二嗪农、除线磷、乐果、乙拌磷、乙硫磷、灭克磷、氧嘧啶磷、杀螟松、丰索磷、倍硫磷、吡氟硫磷、地虫磷、安果、丁苯硫磷、碘硫磷、异稻瘟净、氟唑磷、异噁唑啉、马拉松、灭蚜磷、甲亚砜磷、虫螨畏、氧化乐果、砜吸磷、甲基一六○五、稻丰散、三九一一、伏杀磷、亚胺硫磷、乙丙磷威、腈肟磷、乙基虫螨磷、虫螨磷、丙溴磷、丙硫磷、发果、吡唑硫磷、打杀磷、pyridathion、喹噁磷、硫特普、乙丙硫磷、双硫磷、特丁磷、thiatriphos、甲基乙拌磷、蚜灭多(“硫代磷酸酯类”或“二硫代磷酸酯类”)的活性化合物,或
选自七氟菊酯、灭虫菊、氟酯菊酯、丙烯除虫菊(1R异构体)、甲体氯氰菊酯、β-氟氯氰菊酯、乙体氯氰菊酯、氟氯菊酯、反丙烯除虫菊、反丙烯除虫菊(S-环戊基异构体)、bioethanomethrin、生物氯菊酯、右旋反灭虫菊酯、brofenprox、chloethocarb、chlovaporthrin、顺-氯氰菊酯、顺-灭虫菊、功夫菊酯、乙氰菊酯、氟氯氰菊酯、(RS)氯氟氰菊酯、氯氰菊酯、苯醚氯菊酯(1R-反式异构体)、溴氰菊酯、四氟甲醚菊酯、eflusilanate、烯炔菊酯(1R异构体)、高氰戊菊酯、醚菊酯、五氟苯菊酯、甲氰菊酯、吡氯氰菊酯、灭杀菊酯、溴氟菊酯、溴氟菊酯、氟氰戊菊酯、氟丙苄醚、氟丙苄醚、氟氯苯菊酯、氟胺氰菊酯、fubfenprox、精高效氯氟氰菊酯、卤醚菊酯、炔咪菊酯、噻嗯菊酯、氯氟氰菊酯、甲氧苄氟菊酯、MIT-800、氯菊酯、苯醚菊酯(1R-反式异构体)、炔酮菊酯、丙氟菊酯、protrifenbute、反灭虫菊、除虫菊、RU-12457、RU-15525、灭虫硅醚、氟胺氰菊酯、胺菊酯(1R异构体)、辛体氯氰菊酯、氟溴氰菊酯、四溴菊酯、四氟菊酯、己体氯氰菊酯(“拟除虫菊酯”及“拟除虫菊酯类似物”)的活性化合物。
尤其优选上述活性化合物结合物包括式(IB)的化合物
以及第2组活性化合物,
优选地
选自棉铃威、砜灭威、灭害威、噁虫威、丙硫克百威、BPMC、合杀威、丁叉威、西维因、虫螨威、丁硫克百威、除线威、苯虫威、丁苯威、双氧威、呋线威、异丙威、威百亩、灭虫威、灭多虫、速灭威、速灭威、甲氨叉威、乙丙磷威、抗蚜威、猛杀威、残杀威、硫双灭多威、特氨叉威、混杀威、XMC、灭杀威(“氨基甲酸酯类”)的活性化合物,或
选自吡虫清、AKD 1022、噻虫胺、呋虫胺、吡虫磷、硝胺烯啶、噻虫啉、噻虫嗪(“新烟碱类”)的活性化合物,或
选自acetoprole、乙虫清、唑螨酯、锐劲特、氟吡唑虫(“吡唑类”)的活性化合物,或
选自齐墩螨素、阿维菌素、埃玛菌素、埃玛菌素苯甲酸盐、伊维菌素、米尔螨素、米尔倍霉素、莫昔克丁、艾克敌105、敌贝特(“大环内酯类”)的活性化合物,或
选自唑啶磷、乙基谷硫磷、谷硫磷、乙基溴硫磷、特嘧硫磷、三硫磷、壤虫氯磷、杀螟腈、一○五九、甲基一○五九、磺吸磷、氯亚磷、二嗪农、除线磷、乐果、乙拌磷、乙硫磷、灭克磷、氧嘧啶磷、杀螟松、丰索磷、倍硫磷、吡氟硫磷、地虫磷、安果、丁苯硫磷、碘硫磷、异稻瘟净、氟唑磷、异噁唑啉、马拉松、灭蚜磷、甲亚砜磷、虫螨畏、氧化乐果、砜吸磷、甲基一六○五、稻丰散、三九一一、伏杀磷、亚胺硫磷、乙丙磷威、腈肟磷、乙基虫螨磷、虫螨磷、丙溴磷、丙硫磷、发果、吡唑硫磷、打杀磷、pyridathion、喹噁磷、硫特普、乙丙硫磷、嘧丙磷、双硫磷、特丁磷、thiatriphos、甲基乙拌磷、蚜灭多(“硫代磷酸酯类”或“二硫代磷酸酯类”)的活性化合物,或
选自灭虫菊、氟酯菊酯、丙烯除虫菊(1R异构体)、甲体氯氰菊酯、β-氟氯氰菊酯、乙体氯氰菊酯、氟氯菊酯、反丙烯除虫菊、反丙烯除虫菊(S-环戊基异构体)、bioethanomethrin、生物氯菊酯、右旋反灭虫菊酯、brofenprox、chloethocarb、chlovaporthrin、顺-氯氰菊酯、顺-灭虫菊、功夫菊酯、乙氰菊酯、氟氯氰菊酯、(RS)氯氟氰菊酯、氯氰菊酯、苯醚氯菊酯(1R-反式异构体)、溴氰菊酯、四氟甲醚菊酯、eflusilanate、烯炔菊酯(1R异构体)、高氰戊菊酯、醚菊酯、五氟苯菊酯、甲氰菊酯、吡氯氰菊酯、灭杀菊酯、溴氟菊酯、溴氟菊酯、氟氰戊菊酯、氟丙苄醚、精高效氯氟氰菊酯、氟丙苄醚、氟氯苯菊酯、氟胺氰菊酯、fubfenprox、卤醚菊酯、炔咪菊酯、噻嗯菊酯、氯氟氰菊酯、甲氧苄氟菊酯、MIT-800、氯菊酯、苯醚菊酯(1R-反式异构体)、炔酮菊酯、丙氟菊酯、protrifenbute、反灭虫菊、除虫菊、RU-12457、RU-15525、灭虫硅醚、氟胺氰菊酯、七氟菊酯、胺菊酯(1R异构体)、辛体氯氰菊酯、氟溴氰菊酯、四溴菊酯、四氟菊酯、己体氯氰菊酯(“拟除虫菊酯”及“拟除虫菊酯类似物”)的活性化合物。
尤其优选上述活性化合物结合物包括式(IC)的化合物
以及第2组活性化合物,
优选地
选自棉铃威、砜灭威、灭害威、噁虫威、丙硫克百威、BPMC、合杀威、丁叉威、西维因、虫螨威、丁硫克百威、除线威、苯虫威、丁苯威、双氧威、呋线威、异丙威、威百亩、灭虫威、灭多虫、速灭威、速灭威、甲氨叉威、乙丙磷威、抗蚜威、猛杀威、残杀威、硫双灭多威、特氨叉威、混杀威、XMC、灭杀威(“氨基甲酸酯类”)的活性化合物,或
选自吡虫清、AKD 1022、噻虫胺、呋虫胺、吡虫磷、硝胺烯啶、噻虫啉、噻虫嗪(“新烟碱类”)的活性化合物,或
选自acetoprole、乙虫清、唑螨酯、锐劲特、氟吡唑虫(“吡唑类”)的活性化合物,或
选自齐墩螨素、阿维菌素、埃玛菌素、埃玛菌素苯甲酸盐、伊维菌素、米尔螨素、米尔倍霉素、莫昔克丁、艾克敌105、敌贝特(“大环内酯类”)的活性化合物,或
选自唑啶磷、乙基谷硫磷、谷硫磷、乙基溴硫磷、特嘧硫磷、三硫磷、壤虫氯磷、杀螟腈、一○五九、甲基一○五九、磺吸磷、氯亚磷、二嗪农、除线磷、乐果、乙拌磷、乙硫磷、灭克磷、氧嘧啶磷、杀螟松、丰索磷、倍硫磷、吡氟硫磷、地虫磷、安果、丁苯硫磷、碘硫磷、异稻瘟净、氟唑磷、异噁唑磷、马拉松、灭蚜磷、甲亚砜磷、虫螨畏、氧化乐果、砜吸磷、甲基一六○五、稻丰散、三九一一、伏杀磷、亚胺硫磷、乙丙磷威、腈肟磷、乙基虫螨磷、虫螨磷、丙溴磷、丙硫磷、发果、吡唑硫磷、打杀磷、pyridathion、喹噁磷、硫特普、乙丙硫磷、嘧丙磷、双硫磷、特丁磷、thiatriphos、甲基乙拌磷、蚜灭多(“硫代磷酸酯类”或“二硫代磷酸酯类”)的活性化合物,或
选自灭虫菊、氟酯菊酯、丙烯除虫菊(1R异构体)、甲体氯氰菊酯、β-氟氯氰菊酯、乙体氯氰菊酯、氟氯菊酯、反丙烯除虫菊、反丙烯除虫菊(S-环戊基异构体)、bioethanomethrin、生物氯菊酯、右旋反灭虫菊酯、brofenprox、chloethocarb、chlovaporthrin、顺-氯氰菊酯、顺-灭虫菊、功夫菊酯、乙氰菊酯、氟氯氰菊酯、(RS)氯氟氰菊酯、氯氰菊酯、苯醚氯菊酯(1R-反式异构体)、溴氰菊酯、四氟甲醚菊酯、eflusilanate、烯炔菊酯(1R异构体)、高氰戊菊酯、醚菊酯、五氟苯菊酯、甲氰菊酯、吡氯氰菊酯、灭杀菊酯、溴氟菊酯、溴氟菊酯、氟氰戊菊酯、氟丙苄醚、氟丙苄醚、氟氯苯菊酯、氟胺氰菊酯、fubfenprox、精高效氯氟氰菊酯、卤醚菊酯、炔咪菊酯、噻嗯菊酯、氯氟氰菊酯、甲氧苄氟菊酯、MIT-800、氯菊酯、苯醚菊酯(1R-反式异构体)、炔酮菊酯、丙氟菊酯、protrifenbute、反灭虫菊、除虫菊、RU-12457、RU-15525、灭虫硅醚、氟胺氰菊酯、七氟菊酯、胺菊酯(1R异构体)、辛体氯氰菊酯、氟溴氰菊酯、四溴菊酯、四氟菊酯、己体氯氰菊酯(“拟除虫菊酯”及“拟除虫菊酯类似物”)的活性化合物。
下表示出特别优选的本发明的结合物。
表1
此外,活性化合物结合物还可包括其它可混合的杀真菌、杀螨虫或杀昆虫的活性组分。
若本发明的活性化合物结合物中活性化合物以某些重量比存在,则协同效应特别显著。然而,活性化合物结合物中活性化合物的重量比可在相对宽的范围内改变。一般而言,本发明的结合物包括下表给出的优选混合比的式(Ⅰ)活性化合物及共存组分,所述混合比基于重量比。该比例的含义应理解为式(Ⅰ)的活性化合物:共存组分
表2
优选混合比 |
2:1至1:1000 |
10:1至1:10 |
20:1至1:5 |
50:1至1:5 |
100:1至1:5 |
1000:1至1:2 |
本发明的活性化合物结合物适于防治动物病虫害,优选节肢动物及线虫,特别是在农业、动物健康、森林、贮存产品及材料保护及卫生部门发现的线虫及昆虫。所述结合物对于通常敏感和抗性物种、及全部或单个的发育阶段具有活性。上述害虫包括:
等足目(Isopoda),例如,栉水虱(Oniscus asellus)、鼠妇(Armadilliudiumvulgare)、球鼠妇(Porcellio scaber)。
倍足目(Diplopoda),例如,Blaniulus guttulatus。
唇足目(Chilopoda),例如,Geophilus carpophagus、Scutigera spp.。
综合目(Symphyla),例如,Scutigerella immaculata。
缨尾目(Thysanura),例如,衣鱼(Lepisma saccharina)。
弹尾目(Collembola),例如,武装棘跳虫(Onychiurus armatus)。
直翅目(Orthoptera),例如,家蟋(Acheta domesticus)、蝼蛄属(Gryllotalpaspp.)、非洲飞蝗(Locusta migratoria migratorioides)、黑蝗属(Melanoplus spp.)、沙漠蝗(Schistocerca gregaria)。
蜚蠊目(Blattaria),例如,东方蜚蠊(Blatta orientalis)、美洲大蠊(Periplaneta americana)、马德拉蜚蠊(Leucophaea maderae)、德国蠊(Blattellagermanica)。
革翅目(Dermaptera),例如,欧洲球螋(Forficula auricularia)。
等翅目(Isoptera),例如,散白蚁属(Reticulitermes spp.)。
虱目(Phthiraptera),例如,体虱(Pediculus humanus corporis)、血虱属(Haematopinus spp.)、毛虱属(Linognathus spp.)、嚼虱属(Trichodectes spp.)、畜虱属(Damalinia spp.)。
缨翅目(Thysanoptera),例如,温室条篱蓟马(Hercinothrips femoralis)、烟蓟马(Thrips tabaci)、棕榈蓟马(Thrips palmi)、苜蓿蓟马(Frankliniellaoccidentalis)。
异翅目(Heteroptera),例如,扁盾蝽属(Eurygaster spp.)、Dysdercusintermedius、方背皮蝽(Piesma quadrata)、温带臭虫(Cimex lectularius)、长红猎蝽(Rhodnius prolixus)、锥猎蝽属(Triatoma spp.)。
同翅目(Homoptera),例如,甘蓝粉虱(Aleurodes brassicae)、木薯粉虱(Bemisiatabaci)、温室粉虱(Trialeurodes vaporariorum)、棉蚜(Aphis gossypii)、甘蓝蚜(Brevicoryne brassicae)、茶藨隐瘤蚜(Cryptomyzus ribis)、甜菜蚜(Aphis fabae)、苹果蚜(Aphis pomi)、苹果绵蚜(Eriosoma lanigerum)、梅大尾蚜(Hyalopterusarundinis)、葡萄根瘤蚜(Phylloxera vastatrix)、瘿绵蚜属(Pemphigus spp.)、麦长管蚜(Macrosiphum avenae)、瘤蚜属(Myzus spp.)、忽布疣蚜(Phorodon humuli)、禾谷缢管蚜(Rhopalosiphum padi)、小绿叶蝉属(Empoasca spp.)、Euscelis bilobatus、黑尾叶蝉(Nephotettix cincticeps)、水木坚蚧(Lecanium corni)、乌盔蚧(Saissetia oleae)、灰飞虱(Laodelphax striatellus)、褐飞虱(Nilaparvata lugens)、红肾圆盾蚧(Aonidiellaaurantii)、常春藤圆盾蚧(Aspidiotus hederae)、粉蚧属(Pseudococcus spp.)、木虱属(Psylla spp.)。
鳞翅目(Lepidoptera),例如,红铃麦蛾(Pectinophora gossypiella)、松尺蠖(Bupalus piniarius)、冬尺蛾(Cheimatobia brumata)、苹细蛾(Lithocolletisblancardella)、苹果巢蛾(Hyponomeuta padella)、菜蛾(Plutella xylostella)、黄褐天幕毛虫(Malacosoma neustria)、黄毒蛾(Euproctis chrysorrhoea、毒蛾属(Lymantriaspp.)、棉潜蛾(Bucculatrix thurberiella)、桔潜蛾(Phyllocnistis citrella)、地老虎属(Agrotis spp.)、切根虫属(Euxoa spp.)、脏切夜蛾属(Feltia spp.)、埃及金刚钻(Earias insulana)、实夜蛾属(Heliothis spp.)、甘蓝夜蛾(Mamestra brassicae)、小眼夜蛾(Panolis flammea)、灰翅夜蛾属(Spodoptera spp.)、粉纹夜蛾(Trichoplusia ni)、苹果小卷蛾(Carpocapsa pomonella)、菜粉蝶属(Pieris spp.)、禾草螟属(Chilo spp.)、玉米螟(Pyrausta nubilalis)、地中海粉斑螟(Ephestia kuehniella)、大蜡螟(Galleriamellonella)、幕谷蛾(Tineola bisselliella)、袋谷蛾(Tinea pellionella)、褐织蛾(Hofmannophila pseudospretella)、亚麻黄卷蛾(Cacoecia podana)、Capua reticulana、枞色卷蛾(Choristoneura fumiferana)、葡萄果蠹蛾(Clysia ambiguella)、茶长卷蛾(Homona magnanima)、栎绿卷蛾(Tortrix viridana)、Cnaphalocerus spp.、水稻负泥虫(Oulema oryzae)。
鞘翅目(Coleoptera),例如,家具窃蠹(Anobium punctatum)、谷蠹(Rhizoperthadominica)、恶条豆象(Bruchidius obtectus)、菜豆象(Acanthoscelides obtectus)、北美家天牛(Hylotrupes bajulus)、杨树萤叶甲(Agelastica alni)、马铃薯甲虫(Leptinotarsa decemlineata)、辣根猿叶虫(Phaedon cochleariae)、叶甲属(Diabroticaspp.)、油菜金头跳甲(Psylliodes chrysocephala)、墨西哥大豆瓢虫(Epilachnavarivestis)、Atomaria spp.、锯谷盗(Oryzaephilus surinamensis)、花象属(Anthonomusspp.)、谷象属(Sitophilus spp.)、黑葡萄耳象(Otiorrhynchus sulcatus)、香蕉根颈象(Cosmopolites sordidus)、白菜籽龟象(Ceuthorrhynchus assimilis)、紫苜蓿叶象(Hypera postica)、皮蠹属(Dermestes spp.)、斑皮蠹属(Trogoderma spp.)、圆皮蠹属(Anthrenus spp.)、毛皮蠹属(Attagenus spp.)、粉蠹属(Lyctus spp.)、油菜花露尾甲(Meligethes aeneus)、蛛甲属(Ptinus spp.)、黄蛛甲(Niptus hololeucus)、裸蛛甲(Gibbium psylloides)、拟谷盗属(Tribolium spp.)、黄粉虫(Tenebrio molitor)、叩甲属(Agriotes spp.)、宽胸叩头虫属(Conoderus spp.)、西方五月鳃角金龟(Melolonthamelolontha)、马铃薯鳃角金龟(Amphimallon solstitialis)、褐新西兰肋翅鳃角金龟(Costelytra zealandica)、稻根象(Lissorhoptrus oryzophilus)。
膜翅目(Hymenoptera),例如,松叶蜂属(Diprion spp.)、实叶蜂属(Hoplocampaspp.)、毛蚁属(Lasius spp.)、小家蚁(Monomorium pharaonis)、胡蜂属(Vespa spp.)。
双翅目(Diptera),例如,伊蚊属(Aedes spp.)、按蚊属(Anopheles spp.)、库蚊属(Culex spp.)、黑尾果蝇(Drosophila melanogaster)、家蝇属(Musca spp.)、厕蝇属(Fannia spp.)、红头丽蝇(Calliphora erythrocephala)、绿蝇属(Lucilia spp.)、金蝇属(Chrysomyia spp.)、黄蝇属(Cuterebra spp.)、胃蝇属(Gastrophilus spp.)、Hyppoboscaspp.、螫蝇属(Stomoxys spp.)、狂蝇属(Oestrus spp.)、皮蝇属(Hypoderma spp.)、虻属(Tabanus spp.)、Tannia spp.、Bibio hortulanus、瑞典麦秆蝇(Oscinella frit)、草种蝇属(Phorbia spp.)、藜泉蝇(Pegomyia hyoscyami)、地中海蜡实蝇(Ceratitis capitata)、橄榄大实蝇(Dacus oleae)、欧洲大蚊(Tipula paludosa)、黑蝇属(Hylemyia spp.)、斑潜蝇属(Liriomyza spp.)。
蚤目(Siphonaptera),例如,印鼠客蚤(Xenopsylla cheopis)、角叶蚤属(Ceratophyllus spp.)。
蛛形纲(Arachnida),例如,中东金蝎(Scorpio maurus)、黑寡妇蜘蛛(Latrodectus mactans)、粗脚粉螨(Acarus siro)、锐缘蜱属(Argas spp.)、钝缘蜱属(Ornithodoros spp.)、鸡皮刺螨(Dermanyssus gallinae)、茶藨瘿螨(Eriophyes ribis)、桔芸锈螨(Phyllocoptruta oleivora)、牛蜱属(Boophilus spp.)、扇头蜱属(Rhipicephalus spp.)、花蜱属(Amblyomma spp.)、璃眼蜱属(Hyalomma spp.)、硬蜱属(Ixodes spp.)、痒螨属(Psoroptes spp.)、皮螨属(Chorioptes spp.)、疥螨属(Sarcoptesspp.)、跗线螨属(Tarsonemus spp.)、苜蓿苔螨(Bryobia praetiosa)、全爪螨属(Panonychus spp.)、叶螨属(Tetranychus spp.)、半跗线螨属(Hemitarsonemus spp.)、短须螨属(Brevipalpus spp.)。
植物寄生线虫包括,例如,短体线虫属(Pratylenchus spp.)、相似穿孔线虫(Radopholus similis)、起绒草茎线虫(Ditylenchus dipsaci)、半穿刺线虫(Tylenchulussemipenetrans)、异皮线虫属(Heterodera spp.)、球异皮线虫属(Globodera spp.)、根结线虫属(Meloidogyne spp.)、滑刃线虫属(Aphelenchoides spp.)、长针线虫属(Longidorus spp.)、毛刺线虫属(Trichodorus spp.)、伞滑刃线虫属(Bursaphelenchusspp.)。
活性化合物结合物可转化为常规制剂,例如溶液剂、乳剂、可湿性粉剂、悬浮剂、粉剂、粉末剂、膏剂、可溶性粉剂、颗粒剂、悬乳浓缩剂、用活性化合物浸渍过的天然及合成物、及聚合物中的微胶囊。
所述制剂以已知方式制备,例如将活性化合物与填料混合,即与液体溶剂和/或固体载体混合,同时可选择性使用表面活性剂,即乳化剂和/或分散剂、和/或发泡剂。
若使用的填料为水,还可,例如,使用有机溶剂作为助溶剂。以下基本适于用作液体溶剂:芳香族化合物,例如二甲苯、甲苯或烷基萘;氯化芳香族化合物及氯化脂肪烃,例如氯苯、氯乙烯及二氯甲烷;脂肪烃,例如环己烷或石蜡,如矿物油馏分、矿物油及植物油;醇,例如丁醇或乙二醇及其醚及酯;酮,例如丙酮、甲乙酮、甲基异丁基酮或环己酮;强极性溶剂,例如二甲基甲酰胺及二甲基亚砜,或水。
适合的固体载体为:
例如铵盐及粉碎的天然矿物、例如高岭土、粘土、滑石粉、白垩、石英、凹凸棒石、蒙脱石或硅藻土,及粉碎的合成矿物、例如研细的二氧化硅、氧化铝及硅酸盐;适合于颗粒剂的固体载体为:例如粉碎并分级的天然岩石、例如方解石、大理石、浮石、海泡石及白云石,或合成的无机及有机粉颗粒,及有机物颗粒、例如锯木屑、椰壳、玉米穗轴及烟草茎;适合的乳化剂和/或发泡剂为:例如非离子及阴离子乳化剂、例如聚氧乙烯脂肪酸酯、聚氧乙烯脂肪醇醚、例如烷基芳基聚乙二醇醚、烷基磺酸盐、烷基硫酸盐、芳基磺酸盐、或蛋白质水解产物;适合的分散剂为:例如木素亚硫酸盐废液及甲基纤维素。
制剂中可使用增粘剂,例如羧甲基纤维素及粉末、颗粒剂或胶乳形式的天然及合成聚合物、例如阿拉伯树胶、聚乙烯醇及聚乙酸乙烯酯,或天然磷脂、例如脑磷脂及卵磷脂及合成磷脂。其它的添加剂可以是矿物油及植物油。
可使用着色剂,例如无机颜料、例如氧化铁、氧化钛及普鲁士蓝,及有机着色剂、例如茜素着色剂、偶氮着色剂及金属酞菁着色剂,及微量营养物、例如铁盐、镁盐、硼盐、铜盐、钴盐、钼盐及锌盐。
制剂一般包括0.1~95重量%的活性化合物,优选0.5~90%。
本发明的活性化合物结合物可为市售制剂及由所述制剂制备的与其它活性化合物混合的使用形式,所述其它活性化合物例如杀昆虫剂、引诱剂、消毒剂、杀细菌剂、杀螨剂、杀线虫剂、杀真菌剂、生长调节物质或除草剂。杀昆虫剂包括,例如,磷酸酯类、氨基甲酸酯类、羧酸酯类、氯化烃类、苯脲类及微生物制备物。
也可与其它已知活性化合物、例如除草剂、或与肥料及生长调节剂混合。
用作杀昆虫剂时,本发明的活性化合物结合物可进一步为市售制剂及由所述制剂制备的与增效剂混合的使用形式。增效剂为提高活性化合物活性、而其本身不一定具有活性的化合物。
由市售制剂制备的使用形式的活性化合物含量可在较宽的限度内变化。使用形式的活性化合物浓度可为0.0000001至95重量%的活性化合物,优选0.0001至1重量%。
化合物以与使用形式相适应的常规方式使用。
用于卫生害虫(hygiene pest)及贮存产品害虫时,活性化合物结合物在以下两方面表现突出,即木材及粘土上的极好的残留活性、以及对石灰基质上的碱的良好耐受性。
本发明的活性化合物结合物不仅对植物害虫、卫生害虫及贮存产品害虫具有活性,而且在兽医领域对动物寄生虫(体外寄生虫)、例如硬蜱、软蜱、疥螨、秋螨、蝇(叮咬或吸食)、寄生蝇幼虫、虱、毛虱、羽虱及蚤也具有活性。所述寄生虫包括:
虱目(Anoplurida),例如,血虱属、毛虱属、虱属(Pediculus spp.)、Phtirusspp.、管虱属(Solenopotes spp.)。
食毛目(Mallophagida)及钝角亚目(Amblycerina)及细角亚目(Ischnocerina),例如,毛羽虱属(Trimenopon spp.)、禽虱属(Menopon spp.)、巨羽虱属(Trinoton spp.)、牛羽虱属(Bovicola spp.)、Werneckiella spp.、Lepikentron spp.、畜虱属、嚼虱属、猫羽虱属(Felicola spp.)。
双翅目及长角亚目(Nematocerina)及短角亚目(Brachycerina),例如,伊蚊属、按蚊属、库蚊属、蚋属(Simulium spp.)、真蚋属(Eusimulium spp.)、白蛉属(Phlebotomusspp.)、罗蛉属(Lutzomyia spp.)、库蠓属(Culicoides spp.)、斑虻属(Chrysops spp.)、瘤虻属(Hybomitra spp.)、黄虻属(Atylotus spp.)、虻属、麻虻属(Haematopota spp.)、Philipomyia spp.、蜂虱蝇属(Braula spp.)、家蝇属、齿股蝇属(Hydrotaea spp.)、螫蝇属、黑角蝇属(Haematobia spp.)、莫蝇属(Morellia spp.)、厕蝇属、舌蝇属(Glossinaspp.)、丽蝇属(Calliphora spp.)、绿蝇属、金蝇属、污蝇属(Wohlfahrtia spp.)、麻蝇属(Sarcophaga spp.)、狂蝇属、皮蝇属、胃蝇属(Gasterophilus spp.)、虱蝇属(Hippoboscaspp.)、羊虱蝇属(Lipoptena spp.)、蜱蝇属(Melophagus spp.)。
蚤目(Siphonapterida),例如,蚤属(Pulex spp.)、栉首蚤属(Ctenocephalidesspp.)、客蚤属(Xenopsylla spp.)、角叶蚤属。
异翅目(Heteropterida),例如,臭虫属(Cimex spp.)、锥猎蝽属、红猎蝽属(Rhodnius spp.)、锥蝽属(Panstrongylus spp.)。
蜚蠊目(Blattarida),例如,东方蜚蠊、美洲大蠊、德国蠊、夏柏拉蟑螂属(Supellaspp.)。
蜱螨亚纲(Acaria或Acarida)及后气门目(Metastigmate)及中气门目(Mesostigmata),例如,锐缘蜱属、钝缘蜱属(Ornithodorus spp.)、残喙蜱属(Otobiusspp.)、硬蜱属、花蜱属、牛蜱属、革蜱属(Dermacentor spp.)、Haemophysalis spp.、璃眼蜱属、扇头蜱属、皮刺螨属(Dermanyssus spp.)、刺利螨属(Raillietia spp.)、肺刺螨属(Pneumonyssus spp.)、胸刺螨属(Sternostoma spp.)、蜂螨属(Varroa spp.)。
轴螨目(Actinedida)(前气门亚目(prostigmata))及粉螨目(Acaridida)(无气门亚目(Astigmata)),例如,蜂盾螨属(Acarapis spp.)、姬螯螨属(Cheyletiella spp.)、禽螯螨属(Ornithocheyletia spp.)、肉螨属(Myobia spp.)、疮螨属(Psorergates spp.)、蠕形螨属(Demodex spp.)、恙螨属(Trombicula spp.)、Listrophorus spp.、粉螨属(Acarusspp.)、食酪螨属(Tyrophagus spp.)、嗜木螨属(Caloglyphus spp.)、颈下螨属(Hypodectes spp.)、翅螨属(Pterolichus spp.)、痒螨属、皮螨属、耳疥螨属(Otodectesspp.)、疥螨属、耳螨属(Notoedres spp.)、疙螨属(Knemidocoptes spp.)、气囊螨属(Cytodites spp.)、鸡雏螨属(Laminosioptes spp.)。
本发明的活性化合物结合物也适用于防治节肢动物,所述节肢动物侵袭农业牲畜,例如黄牛、绵羊、山羊、马、猪、驴、骆驼、水牛、兔、鸡、火鸡、鸭、鹅、蜜蜂,其它家养动物、例如狗、猫、笼鸟、观赏鱼及所谓的试验动物、例如仓鼠、豚鼠、大鼠及小鼠。通过对所述节肢动物进行防治,应减少死亡病例及减产量(肉、奶、毛、皮、蛋、蜜等),从而可通过使用本发明的活性化合物结合物使畜牧更经济、更简便。
本发明的活性化合物结合物以已知方式用于兽医领域中,可通过例如片剂、胶囊剂、口服饮剂、浸剂、颗粒剂、膏剂、丸剂、喂服(feed-through)法、栓剂的方式进行肠内给药,可通过例如注射(肌内、皮下、静脉、腹膜内等)、植入进行肠外给药,可鼻部给药,可通过例如浸泡或浸洗、喷雾、泼浇、点滴、清洗、喷粉,借助于含活性化合物的模型制品、例如项圈、耳标、尾标、肢体缚带(limb band)、笼头、标识器等等进行皮肤给药。
用于牲口、家禽、家畜等时,活性化合物结合物可以包括1至80重量%的活性化合物的制剂(例如粉末、乳剂、胶悬剂)形式直接使用、也可稀释100至10 000倍后使用,或将所述结合物用作化学药浴剂(chemical dip)。
而且,已发现本发明的活性化合物结合物对毁坏工业材料的昆虫表现出杀昆虫活性。
以非限制性的实例的方式可优选提出下述昆虫:
甲虫,例如北美家天牛、Chlorophorus pilosis、家具窃蠹、报死窃蠹(Xestobiumrufovillosum)、梳角细脉窃蠹(Ptilinus pecticornis)、Dendrobium pertinex、松窃蠹(Ernobius mollis)、Priobium carpini、褐粉蠹(Lyctus brunneus)、非洲粉蠹(Lyctusafricanus)、南方粉蠹(Lyctus planicollis)、栎粉蠹(Lyctus linearis)、柔毛粉蠹(Lyctus pubescens)、Trogoxylon aequale、鳞毛粉蠹(Minthes rugicollis)、材小蠹种(Xyleborus spec.)、Tryptodendron spec.、咖啡黑长蠹(Apate monachus)、槲长蠹(Bostrychus capucins)、褐异翅长蠹(Heterobostrychus brunneus)、棘长蠹种(Sinoxylon spec.)、竹长蠹(Dinoderus minutus)。
革翅目昆虫(dermapteran),例如大树蜂(Sirex juvencus)、枞大树蜂(Urocerusgigas)、泰加大树蜂(Urocerus gigas taignus)、Urocerus augur。
白蚁,例如欧洲木白蚁(Kalotermes flavicollis)、麻头堆砂白蚁(Cryptotermesbrevis)、灰点异白蚁(Heterotermes indicola)、欧美散白蚁(Reticulitermesflavipes)、桑特散白蚁(Reticulitermes santonensis)、南欧网纹白蚁(Reticulitermeslucifugus)、达尔文澳白蚁(Mastotermes darwiniensis)、内华达古白蚁(Zootermopsisnevadensis)、家白蚁(Coptotermes formosanus)。
蠹虫,例如衣鱼。
本发明中工业材料的含义应理解为非活体(non-living)材料,例如,优选为聚合物、胶粘剂、胶液、纸张及板材、皮革、木材、木材产品及漆。
待保护以免受昆虫侵袭的材料特别优选为木材及木材产品。
可由本发明的组合物、或包括所述组合物的混合物保护的木材及木材产品的含义应理解为,例如:建筑木材、木梁、铁路枕木、桥梁组件、突堤、木制交通工具、箱、托架、集装箱、电线杆、木制支拱板条(wood lagging)、木制门窗、胶合板、刨花板、细木工制品、或一般用于房屋建造或建筑木工的木材产品。
活性化合物结合物使用时可直接使用,或者以浓缩液、或一般常规制剂形式使用,例如粉末、颗粒剂、溶液剂、悬浮剂、乳剂或膏剂。
上述制剂可以本身已知的方式制备,例如将活性化合物与至少一种溶剂或稀释剂、乳化剂、分散剂和/或粘合剂或固定剂、防水剂混合,需要的话还可与干燥剂及UV稳定剂混合,并且需要的话也可与着色剂及染料及其它处理助剂混合。
用于保护木材及木材产品的杀昆虫组合物或浓缩液,包括浓度为0.0001至95重量%,特别是0.001至60重量%的本发明的活性化合物。
组合物或浓缩液的使用量取决于昆虫的种类、数量以及介质。最优的使用量可在各种情形下通过一系列施用试验而确定。然而,一般而言,基于待保护的原材料,使用0.0001至20重量%,优选0.001至10重量%的活性化合物便足够。
适合的溶剂和/或稀释剂为有机化学溶剂或溶剂混合物和/或低挥发性油状或油型有机化学溶剂或溶剂混合物和/或极性有机化学溶剂或溶剂混合物和/或水以及,适当的话还有乳化剂和/或润湿剂。
优选使用的有机化学溶剂为蒸发值(evaporation number)高于35、闪点高于30℃、优选高于45℃的油状或油型溶剂。使用的所述不溶于水的低挥发性油状及油型溶剂为适合的矿物油或其芳香性馏分或含矿物油的溶剂混合物,优选石油溶剂、石油和/或烷基苯。
有利地使用沸程170至220℃的矿物油、沸程170至220℃的石油溶剂、沸程250至350℃的锭子油、沸程160至280℃的石油及芳香性化合物、松节油等等。
在一个优选实施方案中,使用沸程180至210℃的液态脂肪烃、或沸程180至220℃的芳香烃与脂肪烃的高沸点混合物和/或锭子油和/或一氯代萘,优选α-一氯代萘。
蒸发值高于35、闪点高于30℃、优选高于45℃的低挥发性有机油状或油型溶剂,可以部分地用高挥发性或中等挥发性的有机化学溶剂代替,只要溶剂混合物也具有高于35的蒸发值及高于30℃、优选高于45℃的闪点,并且混合物在该溶剂混合物中可溶或可乳化。
在一个优选实施方案中,有机化学溶剂或溶剂混合物的一部分被脂肪族极性有机化学溶剂或溶剂混合物所代替。优选使用包含羟基和/或酯基和/或醚基的脂肪族有机化学溶剂,例如,乙二醇醚、酯等等。
为本发明的目的而使用的有机化学粘合剂为合成树脂和/或可在水中稀释和/或可在使用的有机化学溶剂中溶解或分散或乳化的本身已知的粘合干性油(binding dryingoil),特别是由以下物质组成、或包括以下物质的粘合剂:丙烯酸树脂,乙烯基树脂、例如聚乙酸乙烯酯,聚酯树脂,缩聚或加聚树脂,聚氨酯树脂,醇酸树脂或改性醇酸树脂,酚树脂,烃类树脂例如茚/苯并呋喃树脂,硅氧烷树脂,干性植物油和/或干性油和/或基于天然和/或合成树脂的物理干性粘合剂。
用作粘合剂的合成树脂使用时可为乳液、分散体或溶液形式。沥青或沥青物质也可用作粘合剂,用量最高为10重量%。此外,可使用着色剂、染料、防水剂、遮味剂、及抑制剂或防蚀剂等等,以上物质本身均为已知。
依据本发明,组合物或浓缩液优选包括至少一种醇酸树脂或改性醇酸树脂和/或干性植物油,作为有机化学粘合剂。依据本发明而优选使用的醇酸树脂为油含量高于45重量%,优选50至68重量%的醇酸树脂。
上述粘合剂的一部分或全部可以被固定剂(混合物)或增塑剂(混合物)所取代。所述添加剂用于防止活性化合物挥发,以及结晶或沉淀。所述添加剂优选取代0.01至30%的粘合剂(基于所使用的粘合剂为100%)。
增塑剂来自于以下化学类别:邻苯二甲酸酯、例如邻苯二甲酸二丁酯、邻苯二甲酸二辛酯或邻苯二甲酸苯甲基丁基酯,磷酸酯、例如磷酸三丁酯,己二酸酯、例如己二(2-乙基己基)酸酯,硬脂酸酯、例如硬脂酸丁酯或硬脂酸戊酯,油酸酯、例如油酸丁酯,丙三醇醚或高分子量乙二醇醚、丙三醇酯及对甲苯磺酸酯。
固定剂化学上基于聚乙烯烷基醚、例如聚乙烯甲基醚,或酮、例如二苯甲酮及亚乙基二苯甲酮。
其它适合的溶剂或稀释剂,特别是水,如果适当的话可作为与一种或多种上述有机化学溶剂或稀释剂、乳化剂及分散剂的混合物。
特别有效的木材保护通过工业规模的浸渍工艺而完成,例如真空、双真空或压力工艺。
本发明的活性化合物结合物可同时用于保护与盐水或半咸水接触的物体,例如船体、筛、网、建筑、系留及信号系统,防止其产生污垢。
由固着性的寡毛纲(Oligochaeta)动物、例如龙介虫科(Serpulidae),及由贝壳(shell)及Ledamorpha类(鹅茗荷(goose barnacles))的种、例如不同的茗荷属(Lepas)及铠茗荷属(Scalpellum)种,或由藤壶(Balanomorpha)类(藤壶(acorn barnacles))的种、例如藤壶属(Balanus)或龟足属(Pollicipes)种引起的污垢,提高船只的摩擦阻力,从而导致较高能量消耗及干船坞上附加的频繁滞留产生的运转成本的显著增加。
除藻类,例如水云属(Ectocarpus sp.)及角藻属(Ceramium sp.)引起的污垢之外,由归入总称为蔓足纲(Cirripedia)(cirriped crustaceans)的固着性的Entomostraka类引起的污垢亦特别重要。
出人意料的是,现已发现本发明的活性化合物结合物具有突出的防污活性。
使用本发明的活性化合物结合物,可以免除重金属的使用,例如,在双(三烃基锡)硫化物,三-正丁基锡月桂酸,三-正丁基氯化锡,氧化亚铜(Ⅰ),三乙基氯化锡,三-正丁基(2-苯基-4-氯苯氧基)锡,三丁基氧化锡,二硫化钼、氧化锑、钛酸丁酯聚合物、苯基(双吡啶)三氯化铋,三-正丁基氟化锡、乙烯基双硫代氨基甲酸镁,二甲基二硫代氨基甲酸锌、乙烯基双硫代氨基甲酸锌、2-吡啶硫羟1-氧化物的锌盐及铜盐、双二甲基二硫代氨基甲酰锌的乙烯基双硫代氨基甲酸盐(bisdimethyldithiocarbamoylzinc ethylenebisthiocarbamate)、氧化锌、乙烯基双二硫代氨基甲酸亚铜(Ⅰ)、硫氰酸铜、环烷酸铜及待配制的三丁锡卤化物中免除重金属的使用,或显著降低所述化合物的浓度。
如果适当的话,制成待用(ready-to-use)的防污漆还可另外包括其它活性化合物、优选杀藻剂、杀真菌剂、除草剂、杀软体动物剂,或其它防污活性化合物。
优选适合的与本发明的防污组合物结合的组分为:
杀藻剂,例如
2-叔丁基氨基-4-环丙基氨基-6-甲基硫代-1,3,5-三嗪、二氯芬、敌草隆(diuron)、草藻灭(endothal)、薯瘟锡(fentin acetate)、异丙隆(isoproturon)、噻唑隆(methabenzthiazuron)、氟硝草醚(oxyfluorfen)、灭藻醌(quinoclamine)及去草净(terbutryne);
杀真菌剂,例如
苯并[b]噻吩羧酸环己基酰胺S,S-二氧化物、抑菌灵(dichlofluanid)、fluorfolpet、3-碘-2-丙炔基氨基甲酸丁酯、对甲抑菌灵(tolyfluanid)及吡咯、例如戊环唑(azaconazole)、环唑醇(cyproconazole)、氧唑菌(epoxyconazole)、己唑醇(hexaconazole)、环戊唑菌(metconazole)、丙环唑(propiconazole)及戊唑醇(tebuconazole);
杀软体动物剂,例如
薯瘟锡、蜗牛敌、灭虫威、贝螺杀、硫双灭多威及混杀威;
或常规的防污活性化合物,例如4,5-二氯-2-辛基-4-异噻唑啉-3-酮、diiodomethylparatryl sulfone、2-(N,N-二甲基硫代氨基甲酰基硫)-5-硝基噻唑基、2-吡啶硫羟1-氧化物的钾、铜、钠及锌盐、吡啶-三苯基甲硼烷、四丁基二锡环氧乙烷、2,3,5,6-四氯-4-(甲磺酰基)吡啶、2,4,5,6-四氯间苯二氰、二硫化四甲基秋兰姆及2,4,6-三氯苯基马来酰亚胺。
使用的防污组合物包括0.001至50重量%、特别是0.01至20重量%浓度的本发明的活性化合物结合物。
而且,本发明的防污组合物还包括常规组分,例如Ungerer,Chem.Ind.1985,37,730-732及Williams,Antifouling Marine Coatings,Noyes,Park Ridge,1973中所述的组分。
除本发明的杀藻、杀真菌、杀软体动物活性化合物及杀昆虫活性化合物之外,防污漆还包括,特别是,粘合剂。
公认粘合剂的实例为溶剂体系中的聚氯乙烯,溶剂体系中的氯化橡胶,溶剂体系、特别是水体系中的丙烯酸树脂,水分散体形式或有机溶剂体系形式的氯乙烯/乙烯基乙酸酯共聚物体系,丁二烯/苯乙烯/丙烯腈橡胶,干性油、例如亚麻子油,树脂酯或与焦油或沥青、柏油及环氧化合物结合的改性硬化树脂,少量的氯橡胶(chlorine rubber)、氯化聚丙烯及乙烯树脂。
如果适当的话,漆还包括优选不溶于盐水的无机染料、有机染料或着色剂。漆可进一步包括使活性化合物控释的材料,例如松香。进一步地,漆可包括增塑剂、影响流变学特性的改性剂及其它常规成分。本发明的化合物或上述混合物也可包含于自抛光防污体系中。
活性化合物结合物亦适于防治封闭空间内发现的动物病虫害,特别是昆虫、蜘蛛及螨虫,所述封闭空间例如住所、工厂车间、办公室、交通工具工作间(vehicle hall)等等。所述结合物可用于防治所述害虫的家用杀昆虫产品中。所述结合物对于敏感物种和抗性物种及全部发育阶段均具有活性。所述害虫包括:
蝎目(Scorpionidea),例如,地中海黄蝎(Buthus occitanus)。
蜱螨目(Acarina),例如,波斯锐缘蜱(Argas persicus)、鸽锐缘蜱(Argasreflexus)、苔螨亚种(Bryobia ssp.)、鸡皮刺螨、家嗜甜螨(Glyciphagus domesticus)、非洲钝缘蜱(Ornithodorus moubat)、血红扇头蜱(Rhipicephalus sanguineus)、阿氏真恙螨(Trombicula alfreddugesi)、Neutrombicula autumnalis、特嗜皮螨(Dermatophagoidespteronissimus)、法嗜皮螨(Dermatophagoides forinae)。
蜘蛛目(Araneae),例如,捕鸟蛛(Aviculariidae)、圆蛛(Araneidae)。
盲蛛目(Opiliones),例如,螯蝎(Pseudoscorpiones chelifer)、Pseudoscorpiones cheiridium、长盲蛛(Opiliones phalangium)。
等足目,例如,栉水虱、球鼠妇。
倍足目,例如,Blaniulus guttulatus、山蛩虫(Polydesmus spp.)。
唇足目,例如,地蜈蚣(Geophilus spp.)。
衣鱼目(Zygentoma),例如,栉衣鱼属(Ctenolepisma spp.)、衣鱼、盗火虫(Lepismodes inquilinus)。
蜚蠊目,例如,东方蜚蠊、德国蠊、亚洲蠊(Blattella asahinai)、马德拉蜚蠊、角腹蠊属(Panchlora spp.)、木蠊属(Parcoblatta spp.)、澳洲大蠊(Periplanetaaustralasiae)、美洲大蠊、大褐大蠊(Periplaneta brunnea)、烟色大蠊(Periplanetafuliginosa)、棕带蜚蠊(Supella longipalpa)。
跳跃亚目(Saltatoria),例如,家蟋。
革翅目,例如,欧洲球螋。
等翅目,例如,木白蚁属(Kalotermes spp.)、散白蚁属。
啮虫目(Psocoptera),例如,Lepinatus spp.、粉啮虫属(Liposcelis spp.)。
鞘翅目,例如,圆皮蠹属、毛皮蠹属、皮蠹属、长头谷盗(Latheticus oryzae)、隐跗郭公虫属(Necrobia spp.)、蛛甲属、谷蠹、谷象(Sitophilus granarius)、米象(Sitophilus oryzae)、玉米象(Sitophilus zeamais)、药材甲(Stegobium paniceum)。
双翅目,例如,埃及伊蚊(Aedes aegypti)、白纹伊蚊(Aedes albopictus)、带喙伊蚊(Aedes taeniorhynchus)、按蚊属、红头丽蝇、高额麻虻(Chrysozona pluvialis)、五带淡色库蚊(Culex quinquefasciatus)、尖音库蚊(Culex pipiens)、环喙库蚊(Culextarsalis)、果蝇属(Drosophila spp.)、夏厕蝇(Fannia canicularis)、家蝇(Muscadomestica)、白蛉属、Sarcophaga carnaria、蚋属、厩螫蝇(Stomoxys calcitrans)、欧洲大蚊。
鳞翅目,例如,小蜡螟(Achroia grisella)、大蜡螟、印度谷螟(Plodiainterpunctella)、木塞谷蛾(Tinea cloacella)、袋谷蛾、幕谷蛾。
蚤目,例如,犬栉首蚤(Ctenocephalides canis)、猫栉首蚤(Ctenocephalidesfelis)、人蚤(Pulex irritans)、穿皮潜蚤(Tunga penetrans)、印鼠客蚤。
膜翅目,例如,广布弓背蚁(Camponotus herculeanus)、黑臭蚁(Lasiusfuliginosus)、黑蚁(Lasius niger)、Lasius umbratus、小家蚁、Paravespula spp.、铺道蚁(Tetramorium caespitum)。
虱目(Anoplura),例如,头虱(Pediculus humanus capitis)、体虱、阴虱(Phthirus pubis)。
异翅目,例如,热带臭虫(Cimex hemipterus)、温带臭虫、长红猎蝽、侵扰锥猎蝽(Triatoma infestans)。
所述结合物用于气雾器、真空喷雾(pressure-free spray)产品、例如泵及喷雾器(atomizer spray)、自动弥雾系统、烟雾发生器、泡沫、凝胶、具有纤维素或聚合物制成的蒸发器片剂(evaporator tablet)的蒸发器产品、液体蒸发器、凝胶及薄膜蒸发器、推进剂推动的蒸发器、无动力(energe-free)、或被动(passive)蒸发系统、捕蛾纸、捕蛾袋及捕蛾胶中,作为颗粒剂或粉剂,用于抛撒的饵料中或用于毒饵站(bait station)中。
所有的植物及植物部位(part)均可依据本发明来处理。本发明中植物的含义应理解为所有的植物及植物种群,例如需要的及不需要的野生植物或农作物植物(包括自然存在的农作物植物)。农作物植物可以是通过常规植物育种及最优方法或通过生物技术及基因工程或通过所述方法的结合而获得的植物,包括转基因植物、也包括受植物种苗权保护或不受其保护的植物品种。植物部位的含义应理解为植物所有的地上及地下部位及植物器官,例如芽、叶、花及根,可提及的实例为叶、针叶(needle)、茎、干、花、子实体、果实、种子、根、块茎及根茎。植物部位还包括采收物及无性与有性繁殖物,例如插条、块茎、根茎、侧枝及种子。
本发明的使用活性化合物对植物及植物部位进行的处理,依据常规处理方法直接进行或使活性化合物作用于其环境、生境或贮存区域,所述常规处理方法例如浸泡、喷雾、蒸发、弥雾(fogging)、撒播、涂抹(painting-on),在繁殖物、特别是种子的情况下,也可涂布一层或多层。
如上所述,可依据本发明处理所有的植物及其部位。在一个优选实施方案中,处理了野生植物种及植物栽培种、或由常规生物育种方法、例如杂交或原生质体融合而获得的植物及其部位。在一个更优选实施方案中,处理了由基因工程、如果适当的话还可与常规方法相结合(遗传修饰的生物(Genetic Modified Organism))而获得的转基因植物及植物栽培种及其部位。术语“部位”或“植物的部位”或“植物部位”解释如上。
特别优选地,各种情形下市售或使用的植物栽培种植物均依据本发明进行处理。
依据植物种或植物栽培种、其种植地点及生长条件(土壤、气候、植物生长期、营养(diet)),本发明的处理也可产生超加和性(superadditive)(“协同的”)效应。由此,例如,可降低施用率和/或加宽活性谱(activity spectrum)和/或提高可按本发明使用的物质或组合物的活性、改善植物生长、提高高温或低温耐受性、提高干旱或水或土壤含盐量耐受性、提高开花品质、使采收更简易、加速成熟、提高采收产量、改善采收产品的质量和/或提高其营养价值、改善采收产品的贮存稳定性和/或其加工性能(processability),这些可超过实际预期的效果。
优选的并由本发明处理的转基因植物或植物栽培种(即由基因工程获得的植物)包括在遗传修饰中接受遗传物质的所有植物,所述遗传物质将特别有利的有用特性(“特征”)赋予所述植物。所述特性的实例为改善植物生长、提高高温或低温耐受性、提高干旱或水或土壤含盐量耐受性、提高开花品质、使采收更简易、加速成熟、提高采收产量、改善采收产品的质量和/或提高其营养价值、改善采收产品的贮存稳定性和/或其加工性能。进一步且特别强调的所述特性的实例为改善植物对动物及微生物害虫的抵抗力,例如对昆虫、螨虫、植物致病真菌、细菌和/或病毒,以及提高植物对某些除草活性化合物的耐受性。可提及的转基因植物的实例为重要的农作物植物,例如谷物(小麦、稻)、玉米、大豆、马铃薯、棉花、油菜(oilseed rape)及果树(果实为苹果、梨、柑橘类果实及葡萄),特别强调的为玉米、大豆、马铃薯、棉花及油菜。特别强调的特征为通过在植物体内形成毒素、特别是由苏云金杆菌的遗传物质(例如基因CryⅠA(a)、CryⅠA(b)、CryⅠA(c)、CryⅡA、CryⅢA、CryⅢB2、Cry9cCry2Ab、Cry3Bb及CryⅠF以及其结合)形成的毒素来提高植物对昆虫的抵抗力(以下简称为“Bt植物”)。进一步特别强调的特征为提高植物对某些除草活性化合物的耐受性,例如咪唑啉酮类、磺酰脲类、草甘磷(glyphosate)或phosphinotricin(例如“PAT”基因)。赋予所述需要特征的基因也可在转基因植物体内相互结合。可提及的“Bt植物”的实例为市售的商标名称为YIELD(例如玉米、棉花、大豆)、(例如玉米)、(例如玉米)、(棉花)、(棉花)及(马铃薯)的玉米栽培种、棉花栽培种、大豆栽培种及土豆栽培种。可提及的具有除草剂耐受性的植物的实例为市售的商标名称为Roundup(具有草甘磷耐受性,例如玉米、棉花、大豆)、Liberty(具有phosphinotricin耐受性,例如油菜)、(具有咪唑啉酮耐受性)及(具有磺酰脲耐受性,例如玉米)的玉米栽培种、棉花栽培种及大豆栽培种。可提及的具有除草剂抗性的植物(以常规的除草剂耐受性方式育种的植物)包括的市售栽培种(例如玉米)。当然,以上叙述也适用于具有所述或待开发的基因特征的植物栽培种,所述植物将在未来进行开发和/或上市。
所列植物可依据本发明通过特别有利的方式用本发明的活性化合物混合物进行处理。上述混合物的优选范围也适用于所述植物的处理。特别强调的为用本发明特别提及的混合物对植物进行处理。
本发明活性化合物结合物的良好的杀昆虫及杀螨虫活性可从以下实施例中看出。单独的活性化合物的活性较弱,而结合物所表现的活性则高于活性的简单叠加。
当活性化合物结合物的活性超过单独使用的活性化合物的活性总和时,总能表现出协同效应。
给定的两种活性化合物的结合物的预期活性可如下计算,采用S.R.Colby,Weeds15(1967),20-22的公式:
若
X为杀灭率,当以施用率m g/ha(公顷)或浓度m ppm使用活性化合物A时,表示为未处理对照品的%,
Y为杀灭率,当以施用率n g/ha或浓度n ppm使用活性化合物B时,表示为未处理对照品的%,
E为杀灭率,当以施用率m及n g/ha或浓度m及n ppm使用活性化合物A及B时,表示为未处理对照品的%,
则
若实际的昆虫杀灭率高于计算值,则结合物的活性具有超加和性,即存在协同效应。此时,实际观测的杀灭率必须高于用于计算预期杀灭率(E)的上式的计算值。
实施例
实施例A
猿叶甲(Phaedon)-幼虫试验
溶剂:7重量份的二甲基甲酰胺
乳化剂:2重量份的烷基芳基聚乙二醇醚
为制备活性化合物的适合制剂,将1重量份的活性化合物与所述量的溶剂及乳化剂混合,用含乳化剂的水稀释浓缩液至所需浓度。
将甘蓝叶(Brassica oleracea)浸渍至所需浓度的活性化合物制剂中进行处理,并在叶子湿润时接入辣根猿叶甲(Phaedon cochleariae)的幼虫。经过所需一段时间后,确定杀灭百分比。100%表示杀灭全部幼虫;0%表示未杀灭幼虫。确定的杀灭率代入Colby公式(见34页)。
本试验中,以下本发明的活性化合物结合物较单独使用的活性化合物表现出协同增强的活性(实测值*=试验中发现的活性;计算值**=Colby公式计算的活性):
表3:(ⅠC)+七氟菊酯
表5:(ⅠC)+噻虫胺
表6:(ⅠC)+吡虫磷
实施例B
菜蛾(Plutella)试验,敏感株
溶剂:7重量份的二甲基甲酰胺
乳化剂:2重量份的烷基芳基聚乙二醇醚
为制备活性化合物的适合制剂,将1重量份的活性化合物与所述量的溶剂及乳化剂混合,用含乳化剂的水稀释浓缩液至所需浓度。
将甘蓝叶(Brassica oleracea)浸渍至所需浓度的活性化合物制剂中,并在叶子湿润时接入菜蛾蠋(Plutella xylostella,敏感株)。经过所需一段时间后,确定杀灭百分比。100%表示杀灭全部的蠋;0%表示未杀死蠋。确定的杀灭率代入Colby公式(见34页)。
本试验中,以下本发明的活性化合物结合物较单独使用的活性化合物表现出协同增强的活性(实测值*=试验中发现的活性;计算值**=Colby公式计算的活性):
表7:(ⅠC)+七氟菊酯
表9:(ⅠC)+吡虫磷
表10:(ⅠC)+嘧丙磷
表11:(ⅠC)+(ⅡA)
实施例C
草地夜蛾(Spodoptera frugiperda)试验
溶剂:7重量份的二甲基甲酰胺
乳化剂:2重量份的烷基芳基聚乙二醇醚
为制备活性化合物的适合制剂,将1重量份的活性化合物与所述量的溶剂及乳化剂混合,用含乳化剂的水稀释浓缩液至所需浓度。
将甘蓝叶(Brassica oleracea)浸渍至所需浓度的活性化合物制剂中,并在叶子湿润时接入草地夜蛾(Spodoptera frugiperda)蠋。经过所需一段时间后,确定杀灭百分比。100%表示杀灭全部的蠋;0%表示未杀灭蠋。确定的杀灭率代入Colby公式(见34页)。
本试验中,以下本申请的活性化合物结合物较单独使用的活性化合物表现出协同增强的活性(实测值*=试验中发现的活性;计算值**=Colby公式计算的活性):
表12:(IC)+七氟菊酯
表13:(IC)+艾克敌105
表14:(IC)+噻虫胺
表15:(IC)+锐劲特
表16:(IC)+嘧丙磷
表17:(ⅠC)+(ⅡA)
实施例D
桃蚜试验
溶剂:7重量份的二甲基甲酰胺
乳化剂:2重量份的烷基芳基聚乙二醇醚
为制备活性化合物的适合制剂,将1重量份的活性化合物与所述量的溶剂及乳化剂混合,用含乳化剂的水稀释浓缩液至所需浓度。
将被桃蚜(Myzus persicae)严重浸染的甘蓝叶(Brassica oleracea)浸渍至所需浓度的活性化合物制剂中。经过所需一段时间后,确定杀灭%。100%表示杀灭全部蚜虫;0%表示未杀灭蚜虫。确定的杀灭率代入Colby公式(见1页)。
本试验中,以下本申请的活性化合物结合物较单独使用的活性化合物表现出协同增强的活性(实测值*=试验中发现的活性;计算值**=Colby公式计算的活性):
表18:(ⅠC)+七氟菊酯
表19:(IC)+嘧丙磷
表20:(IC)+(IIA)
Claims (4)
1.一种协同组合物,其特征在于所述组合物包括一种活性化合物结合物,所述结合物包括
(a)式(ⅠC)的活性化合物
(“第1组活性化合物”)
以及
(b)选自以下种类(b5)的活性化合物:
(b5)嘧丙磷;
(“第2组活性化合物”)
其中,第1组活性化合物和第2组活性化合物的重量比为625:1至5:1。
2.权利要求1的组合物用于防治害虫的用途。
3.一种防治害虫的方法,其特征在于使权利要求1的组合物作用于害虫和/或其生境。
4.一种制备协同组合物的方法,其特征在于将权利要求1的组合物与表面活性剂和/或填料混合。
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