BR112021001633A2 - formulações de liberação controlada com lignina para agroquímicos - Google Patents
formulações de liberação controlada com lignina para agroquímicos Download PDFInfo
- Publication number
- BR112021001633A2 BR112021001633A2 BR112021001633-3A BR112021001633A BR112021001633A2 BR 112021001633 A2 BR112021001633 A2 BR 112021001633A2 BR 112021001633 A BR112021001633 A BR 112021001633A BR 112021001633 A2 BR112021001633 A2 BR 112021001633A2
- Authority
- BR
- Brazil
- Prior art keywords
- lignin
- methyl
- active ingredient
- active
- present
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 125
- 229920005610 lignin Polymers 0.000 title claims abstract description 95
- 238000009472 formulation Methods 0.000 title claims abstract description 78
- 238000013270 controlled release Methods 0.000 title claims abstract description 20
- 239000003905 agrochemical Substances 0.000 title claims description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 97
- 239000004480 active ingredient Substances 0.000 claims abstract description 63
- 230000000694 effects Effects 0.000 claims abstract description 22
- -1 isoxaflutol (IFT) Chemical compound 0.000 claims description 88
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- 239000002689 soil Substances 0.000 claims description 33
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- 238000000576 coating method Methods 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 19
- 239000011248 coating agent Substances 0.000 claims description 18
- BNXZHVUCNYMNOS-UHFFFAOYSA-N 1-butylpyrrolidin-2-one Chemical compound CCCCN1CCCC1=O BNXZHVUCNYMNOS-UHFFFAOYSA-N 0.000 claims description 17
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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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/32—Ingredients for reducing the noxious effect of the active substances to organisms other than pests, e.g. toxicity reducing compositions, self-destructing compositions
-
- 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
-
- 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
- A01N25/10—Macromolecular compounds
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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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/12—Powders or granules
- A01N25/14—Powders or granules wettable
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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
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Abstract
FORMULAÇÕES DE LIBERAÇÃO CONTROLADA COM LIGNINA PARA AGROQUÍMICOS.
A presente invenção refere-se a formulações de liberação controlada, baseadas em lignina para compostos ativos (ativos / ingrediente ativos / AI) efeitos negativos eliminados na planta (fitotoxicidade), resultando em compatibilidade biológica intensificada, enquanto a eficácia contra pestes é mantida.
Description
Relatório Descritivo da Patente de Invenção para "FORMULAÇÕES DE LIBERAÇÃO CONTROLADA COM LIGNINA PARA AGROQUÍMICOS". Sumário
[001] A presente invenção refere-se às formulações de liberação controlada, baseadas em lignina para compostos ativos (ativos / ingredientes ativos / AI), com efeitos negativos reduzidos ou eliminados na planta (fitotoxicidade), resultando em compatibilidade biológica intensificada, enquanto a eficácia contra pestes é mantida. Além disso, as formulações de liberação controlada mostram lixiviação de compostos reduzida, por exemplo quando aplicadas no solo, isto é, mobilidade dos compostos ativos mediante irrigação, alagamento ou similares é reduzida. Antecedentes da Invenção
[002] Ingredientes ativos podem ser formulados de várias maneiras, em que as propriedades dos ativos e o processo de formulação podem levantar problemas a respeito da processabilidade, estabilidade, usabilidade e eficácia das formulações, como também efeitos negativos dos próprios ingredientes ativos sobre a planta.
[003] Além do mais, algumas formulações são vantajosas sobre outras, por motivos ecológicos e / ou motivos econômicos.
[004] Como mostrado acima, algumas atividades úteis mostram efeitos indesejáveis sobre as plantas quando aplicadas, como fitotoxicidade levando ao dano grave da planta, deixando necroses (também observado o efeito auréola), emergência tardia (impedimento), rendimento reduzido etc. principais.
[005] Para alguns ativos a gravidade do efeito colateral é quase independente da concentração aplicada, isto é, a despeito de uma significativa diminuição da concentração ativa, o efeito colateral é visto em uma gravidade inalterável. Por exemplo, uma fitotoxidade pronunciada (a.k.a. Halo) pode ser observada para sementes de soja Fluopyram, tratadas nos estágios de emergência iniciais, mesmo se não há mais efeitos nematicidas ou fungicidas nesta concentração diminuída. Um efeito colateral negativo similar é visto para um número de dicotileidôneos, incluindo, mas não limitado a rebentos de soja, tomates, pepinos, pimentas / pimentão quando, por exemplo, fluopiram é spray aplicado ao solo. Exemplos adicionais incluem efeitos fitotóxicos de herbicidas, incluindo, mas não limitado a, por exemplo, pulverização de diflufenicano e/ou isoxaflutol aplicado ao solo para o tratamento de grãos de soja e milho.
[006] Além do mais, alguns ativos mostram uma boa mobilidade no solo, muitas vezes combinada com boa ou alta solubilidade na água, que leva à perda de ativos devido à irrigação, chuva, inundação ou similares. Esta perda de ingrediente ativo, que não está mais disponível para proteger as plantas ou atuar como herbicida, reduz a eficácia e requer tratamentos mais e mais frequentes.
[007] Além disso, ativos solúveis na água também mostram lavagem de folhas, que reduz o ativo disponível, leva à concentrações mais altas de ativos no solo e subsequentemente a água.
[008] O desafio para fabricar uma formulação de liberação controlada, é ainda mais exigente para formas de aplicação pulverizável, isto é, aplicar restrições do tamanho de partícula, e concentrações de ativos muito altas são requeridas (em contraste ao estado da técnica farmacêutica de aplicações de liberação controlada).
[009] Para superar esses efeitos colaterais, é geralmente sabido controlar a liberação dos ativos, desse modo concentrações mais baixas podem levar à menos efeitos não desejados. Entretanto, lado a lado a liberação controlada de ativo, muitas vezes uma redução ou perda total da eficácia contra a peste, está sendo observada.
[0010] Em consequência, é um objetivo da invenção do momento fornecer formulações de liberação controlada para tratamento de semente, aplicações no solo e foliar também, que retem os ativos por um tempo prolongado, enquanto a eficácia desejada dos ativos é ainda mantida em um nível apropriado.
[0011] Para esse fim, é outro objetivo da presente invenção que a formulação de liberação controlada imobilize o ingrediente ativo no solo.
[0012] Como mostrado acima, outro objetivo da presente invenção, é fornecer formulações de liberação controlada pulverizáveis.
[0013] Além do mais, é desejável usar compostos "verdes" nas composições, isto é, compostos que são renováveis e/ou facilmente biodegradáveis. Além disso, esses conceitos de formulação verde sustentável, devem ser simples de fabricar e fortes na aplicação.
[0014] Além do mais, a formulação deverá fornecer inibição da cristalização de ativos novos e pouco solúveis na dita formulação, em cargas desejadas (isto é, pelo menos um nível mínimo de % em AI para ser eficaz), como também a inibição da cristalização de ativos novos e pouco solúveis na formulação, em caldo de pulverização (spray) aquosa.
[0015] Além disso, embora o desempenho biológico de tais sistemas tem que ser garantido, preferivelmente redução da complexidade, por exemplo número de inertes em tais sistemas é requerido.
[0016] Outro aspecto de formulações agroquímicas é que elas são seguras para manusear, enquanto mantém a eficácia e a consistência do uso em um ambiente agrícola desafiador, isto é, o solo.
[0017] Os limites descritos anteriormente requerem uma liberação controlada por excelência, para manufaturar formulações agroquímicas de liberação controlada, que realizem uma redução ou eliminação significativa de efeitos colaterais negativos, tais como fitotoxidade, enquanto mantêm a eficácia como também minimizam a lixiviação do composto.
[0018] Materiais poliméricos encapsulando compostos são descritos em WO2010039865A2. WO2007091494A1 descreve preparações de pesticidas que contêm resina contendo pesticida, com propriedades de liberação controlada. WO200007443A1 divulga grânulos controlados, com um ativo contendo casca sobre um veículo sólido. US4285720A divulga substâncias orgânicas imiscíveis na água, que são encapsuladas com poliureia. Descrição da invenção
[0019] Estes problemas são solucionados, através de modalidades para li-beração controlada com lignina, contendo formulações da presente invenção como descrito abaixo, como também com formulações contendo os ditos ativos de lignina associados, e seus usos para aplicações agroquímicas.
[0020] Em particular, redução significativa, ou em algumas modalidades total eliminação de efeitos colaterais fitotóxicos, foi surpreendentemente realizado em culturas (safras) que estão mostrando uma sensibilidade muito alta para fototoxicidade para respectivos pesticidas, enquanto ingredientes "verdes" foram usados para as formulações.
[0021] As formulações de liberação controlada divulgadas aqui no presente são aplicáveis para Sementes, Solo ou Folha por pulverização / revestimento / regar / granular / no sulco / viveiro / campo de arroz e aplicação foliar, e aplicações comuns para o campo, como também aplicações de silvicultura (por exemplo, eucalipto).
[0022] Além disso, a formulação de liberação controlada melhora a compatibilidade física, química, biológica (fitotoxicidade), ou estabilidade ou longevidade dos respectivos ativos, e/ou minimiza /
elimina efeitos negativos na planta nas aplicações mencionadas acima.
[0023] Além do mais, as formulações de acordo com a invenção do momento, reduzirão a lixiviação no solo arenoso com propriedades de retenção de água baixa em solos ricos em húmus, com propriedades de retenção de água mais alta ou alta.
[0024] Em uma modalidade preferida a redução de fitotoxicidade do ingrediente ativo é mais de 50 %, mais preferido mais do que 80 %, e o preferido é mais do que 90 % por cento, enquanto a eficácia contra as pestes é mantida. Mantida como usada aqui no presente, significa que a eficácia é pelo menos a 50% ou mais da referência não encapsulada.
[0025] As referências testadas dizem respeito às mesmas formulações compreendendo os mesmos ingredientes, que a formulação de acordo com a invenção, exceto que o ativo não é associado com lignina (na referência).
[0026] Em uma modalidade alternativa, os problemas são resolvidos por um kit de peças para uma aplicação de mistura no tanque, compreendendo lignina dissolvida e uma formulação de ingrediente ativo, que são misturados quando a mistura do tanque pronto para aplicar é preparada.
[0027] Solventes apropriados de acordo com a presente invenção são solventes, em que pelo menos 5 % em peso de lignina são solúveis a 20°C.
[0028] Em uma modalidade preferida, os solventes a ser usados para solver lignina são solventes solúveis na água, mais preferivelmente selecionados do grupo consistindo de mono-álcoois (C1-C4-álcoois, mais preferivelmente C1-C3-álcoois), propileno glicol, N-Butilpirrolidona (NBP) e Metil-5-(dimetilamino)-2-metil-5- oxopentanoato (por exemplo Rhodiasolv® Polarclean, tamb´pem conhecido como ácido Pentanoico, 5-(dimetilamino)-2-metil-5-oxo-, metil éster), N,N-dimetil lactamida (CAS Nr: 35123-06-9), Dimetil isosorbida (CAS Nr. 5306-85-4), monobutiléter de dietileno glicol (Cas Nr. 107-98-2), citrato de trietil (CAS Nr. 77-93-0), triacetato de glicerol (CAS Nr: 102-76-1), 1-metil-2-pirrolidona (CAS Nr. 872-50-4) e diacetato de propileno glicol (CAS Nr: 623-84-7).
[0029] Mono-álcoois preferidos são etanol, propanol e isopropanol.
[0030] Mais preferido, o solvente é selecionado do grupo de etanol, propanol e isopropanol, propileno glicol, NBP, e Metil-5- (dimetilamino)-2-metil-5-oxopentanoato.
[0031] Em uma modalidade o solvente é selecionado do grupo de etanol, propanol e isopropanol.
[0032] Em outra modalidade o solvente é selecionado do grupo de NBP e Metil-5-(dimetilamino)-2-metil-5-oxopentanoato.
[0033] Além disso, através da seleção de solventes preferidos, preferivelmente etanol, propanol e isopropanol, para ambos dissolverem ativo e propriedades de precipitação de direção mediante diluição em caldo de pulverização, o tamanho do ingrediente ativo / composto de lignina (ingrediente ativo associado com lignina) pode ser controlado para dar um caldo homogêneo com boas propriedades de aplicação (sem sedimentação, aglomeração significativa).
[0034] Em outra modalidade os problemas delineados acima são solucionados pela formulação SC, com lignina de papel grosso (kraft) insolúvel na água, como inibidor de cristalização e matriz de associação.
[0035] "Pestes" como usado na presente invenção, se refere à insetos, nematoides, fungos, bactérias, vírus e ervas daninhas.
[0036] "Ativos" como usado na presente invenção incluem fungicidas, herbicidas, inseticidas, nematicidas, indutores de defesa do hospedeiro, agentes biológicos e bactericidas.
[0037] Em uma modalidade ativos significa fungicidas.
[0038] Em outra modalidade ativos significa nematicidas.
[0039] Em outra modalidade ativos significa herbicidas.
[0040] Em outra modalidade ativos significa inseticidas.
[0041] Em outra modalidade ativos significa indutores de defesa do hospedeiro.
[0042] Em outra modalidade ativos significa agentes biológicos.
[0043] Em outra modalidade ativos significa bactericidas.
[0044] Em uma modalidade preferida o ativo é um herbicida, mais preferido selecionado do grupo de diflufenicano (DFF), isoxaflutol (IFT) e indaziflam (IAF).
[0045] Em outra modalidade preferida o ativo é um nematicida, mais preferido é fluopiram (FLU).
[0046] Em uma modalidade alternativa o ativo é um fungicida.
[0047] Preferivelmente, "insolúvel" na invenção do momento significa, que 80% em peso do respectivo composto (determinado a 20° C) não são dissolvidos no solvente. Isto pode ser determinado através, por exemplo, de HPLC da amostra filtrada com Padrão interno. "Tratamento da Semente" como usado na presente invenção, significa aplicar pelo menos um ingrediente ativo diretamente ou na forma de um revestimento diretamente em uma semente, antes de colocar a dita semente sobre o campo. Para fins de esclarecimento, aplicações foliar, em aplicação de sulco, aplicações de caixa de viveiro e aplicações no solo não são aplicações de tratamento de semente.
[0048] "Ingredientes ativos associados" como usado aqui no presente, se refere à ativos que são associados / acoplados com Lignina, de acordo com a invenção do momento como descrito abaixo.
[0049] Os termos "compostos ativos", "ativos", "ingredientes ativos", "compostos agroquímicos" e "AIs" podem ser usados aqui no presente intercambiavelmente.
[0050] Nas formulações da presente invenção preferivelmente pelo menos um ativo é associado com lignina, enquanto ativos adicionais podem estar presentes em forma livre na formulação.
[0051] A presente invenção ainda fornece formulações, e formas de aplicação preparadas para elas, como agentes de proteção da colheita e/ou agentes pesticidas, tais como substâncias líquidas de regar, gotejar e borrifar, compreendendo pelo menos um dos compostos ativos da invenção. As formas de aplicação podem compreender agentes adicionais de proteção da colheita e/ou agentes pesticidas, e/ou adjuvantes de intensificação da atividade tais como penetrantes, e/ou espalhadores e/ou promotores de retenção e/ou umectantes e/ou fertilizantes, e ou outros adjuvantes comumente usados por exemplo.
[0052] Exemplos de formulações típicas incluem concentrados emulsificantes (EC), emulsões na água (EW), concentrados de suspensão (SC, SE, FS, OD), grânulos dispersáveis na água (WG), grânulos (GR) e concentrados de cápsulas (CS); estes e outros tipos de possíveis formulações são descritos, por exemplo, por Crop Life International e em Pesticide Specifications, Manual sobre desenvolvimento e uso de relatórios descritivos FAO e WHO para pesticidas, FAO Plant Production and Protection Papers – 173, preparado pela FAO/WHO Joint Meeting on Pesticide Specifications, 2004, ISBN: 9251048576. As formulações podem compreender compostos agroquímicos ativos, em vez de um ou mais compostos ativos da invenção.
[0053] As formulações ou formas de aplicação em questão, preferivelmente compreendem auxiliares, tais como diluentes, solventes, promotores de espontaneidade, veículos, emulsificadores, dispersantes, protetores de geada, biocidas, agentes de espessamento e/ou outros auxiliares, tais como adjuvantes, por exemplo. Um adjuvante, neste contexto, é um componente que intensifica o efeito biológico da formulação, sem o próprio componente tendo um efeito biológico. Exemplos de adjuvantes são agentes que promovem a retenção, disseminação, acoplamento à superfície da folha, ou penetração.
[0054] Essas formulações são produzidas de uma maneira conhecida, por exemplo misturando os compostos ativos com auxiliares tais como, por exemplo, diluentes, solventes e/ou veículos sólidos e/ou auxiliares, tais como, por exemplo, tensoativos. As formulações são preparadas em plantas apropriadas, ou então antes ou depois da aplicação.
[0055] Apropriadas para uso como auxiliares são substâncias que são apropriadas para conferir para a formulação do composto ativo, ou as formas de aplicação preparadas a partir dessas formulações (tais como, por exemplo, agentes de proteção da colheita usáveis, tais como substância líquida de pulverização ou fertilizantes de semente), propriedades particulares tais como certas propriedades física, técnica e/ou biológica.
[0056] Solventes apropriados são descritos acima, em que preferivelmente usados são etanol, propanol, isopropanol, como também NBP e Metil-5-(dimetilamino)-2-metil-5-oxopentanoato.
[0057] Todos os veículos apropriados podem, em princípio, ser usados. Veículos apropriados são, em particular, sais de amônio e minerais naturais do solo tais como caolins, argilas, talco, giz, quartzo, atapulgita, montmorilonita ou terra diatomácea, e minerais sintéticos do solo, tais como sílica finamente dividida, alumina e silicatos naturais ou sintéticos, resinas, ceras e/ou fertilizantes sólidos. Misturas de tais veículos podem da mesma maneira ser usadas. Veículos apropriados para grânulos incluem os seguintes: por exemplo, minerais naturais esmagados e fracionados tais como calcita, mármore, pedra-pome, sepiolita, dolomita e também grânulos sintéticos de farinhas de milho inorgânica e orgânica, e também grânulos de materiais orgânicos tais como serradura, papel, cascas de coco, espigas de milho e caules de tabaco.
[0058] Exemplos de emulsificantes e/ou formadores de espuma, dispersantes ou agentes de umidificação que têm propriedades iônicas ou não iônicas, ou misturas dessas substâncias de superfície ativa, são sais de ácido poliacrílico, sais de ácido lignossulfônico, sais de ácido fenolsulfônico ou ácido naftalenossulfônico, policondensados de óxido de etileno com álcoois graxos, ou com ácidos graxos ou com aminas gordurosas, com fenóis substituídos (preferivelmente alquilfenóis ou arilfenóis), sais de ésteres sulfossuccínicos, derivados de taurina (preferivelmente alquiltauratos), ésteres fosfóricos de álcoois polietoxilados ou fenóis, ésteres de ácido graxo de polióis, e derivados dos compostos contendo sulfatos, sulfonatos e fosfatos, exemplos sendo ésteres de poliglicol de alquilarila, aquilsulfonatos, sulfatos de alquila, arilsulfonatos, hidrolisatos de proteína, substância líquida de resíduos de lignina-sulfito e metilcelulose. A presença de uma substância de superfície ativa é vantajosa, se um dos compostos ativos e/ou um dos veículos inertes não é solúvel na água, e se a aplicação tem lugar na água.
[0059] Tensoativos apropriados ou auxiliares de dispersão, por exemplo, são todas as substâncias deste tipo, que podem habitualmente ser empregadas em agentes agroquímicos, tais como tensoativos não iônicos ou aniônicos. Tensoativos não iônicos preferidos são ésteres de polietileno glicol de álcoois ramificados ou lineares, produtos de reação de ácidos graxos ou álcoois de ácidos graxos, com óxido de etileno e/ou óxido de propileno, além disso álcool de polivinil, derivados de polioxialquilenamina,
polivinilpirrolidona, copolímeros de álcool de polivinil e polivinilpirrolidona, e copolímeros de ácido (met)acrílico e ésteres de ácido (met)acrílico, etoxilatos de acetileno diol, além disso etoxilatos de alquila ramificada ou linear e etoxilatos de alquilarila, em que ésteres de ácido graxo de óxido de polietileno sorbitano, podem ser mencionados a título de exemplo. Fora dos exemplos mencionados acima, classes selecionadas podem ser opcionalmente fosfato, sulfonado ou sulfatado e neutralizado com bases.
[0060] Tensoativos aniônicos possíveis são todas as substâncias deste tipo, que podem habitualmente ser empregadas em agentes agroquímicos. Metal de álcali, metal alcalino terroso e sais de amônio de ácidos alquilsulfônicos ou alquilfosfóricos, como também ácidos alquilarilsulfônicos ou alquilarilfosfórico são preferidos. Um grupo ainda preferido de tensoativos aniônicos ou auxiliares dispersantes são metal de álcali, metal alcalino terroso e sais de amônio de ácidos poliestirenossulfônico, sais de ácidos polivinilsulfônico, sais de ácidos de alquilnaftaleno sulfônico, sais de ácidos naftaleno sulfônico de produtos de condensação de ácido-formaldeído, sais de produtos de condensação de ácido naftalenossulfônico, ácido de fenolsulfônico e formaldeído e sais de ácido lignosulfônico, como também ácido policarboxílico, sódio e sais de potássio.
[0061] Tensoativos não iônicos preferidos são por exemplo: Etoxilatos de tristirilfenol compreendendo uma média de 5- 60 EO unidades; etoxilatos de óleo de mamona compreendendo uma média de 5-40 EO unidades (por exemplo, Berol® faixa, Emulsogen® EL faixa); etoxilatos de álcool graxo compreendendo álcoois ramificados ou lineares, com 8-18 átomos de carbono e uma média de 2-30 EO unidades;
copolímero em bloco de óxido de polietileno e ácido polihidroxiesteárico; copolímeros de enxerto de polimetacrilato etoxilado; polímeros baseados em polivinilpirrolidona; polímeros baseados em polivinilacetato; etoxilatos de diacetileno-dióis etoxilados (por exemplo, Surfynol® 4xx-faixa); tensoativos de citrato de éter de alquila (por exemplo, Adsee® faixa CE, Akzo Nobel); polissacarídeos / poliglicosídeos de alquila (por exemplo, Agnique® PG8107, PG8105, Atplus® 438, AL-2559, AL-2575); mono- ou diésteres etoxilados de glicerina, compreendendo ácidos graxos com 8 – 18 átomos de carbono e uma média de 10 - 40 EO unidades (por exemplo, faixa de Crovol®); copolímero em bloco de óxido de polietileno e óxido de polibutileno. polissiloxanos organomodificados, por exemplo BreakThru® OE444, BreakThru® S240, Silwett® L77, Silwett® 408, Silwet® 806. tensoativos aniônicos preferidos e polímeros são por exemplo: condensado de formaldeído de naftaleno sulfonado, sal de sódio; diisopropilnaftalenossulfonato de sódio; sal de dioctilsulfossuccinato de sódio; sulfato de etoxilato de tristirilfenol e amônio e sais de potássio dos mesmos; fosfato de etoxilato de tristirilfenol e sais de amônio e potássio dos mesmos; ácido ligninsulfônico, sal de sódio; polímeros de estireno acrílico;
ácidos policarboxílicos, sais de sódio e potássio.
[0062] Tensoativos mais preferidos são copolímeros de enxerto de polimetacrilato etoxilado, ácidos policarboxílicos, sais de sódio e potássio, sulfato de tristirilfenol etoxilado e amônio e sais de potássio dos mesmos, condensado de formaldeído de naftaleno sulfonado, sal de sódio e diacetileno-dióis etoxilados.
[0063] Auxiliares adicionais que podem estar presentes nas formulações e nas formas de aplicação derivadas deles, incluem corantes tais como pigmentos inorgânicos, exemplos sendo óxido de ferro, óxido de titânio, Prussian Blue, e corantes orgânicos, tais como corantes de alizarina, corantes de azo e corantes de ftalocianina de metal, e nutrientes e nutrientes residuais, tais como sais de ferro, manganês, boro, cobre, cobalto, molibdênio e zinco.
[0064] Estabilizadores, tais como estabilizadores de temperatura baixa, conservantes, antioxidantes, estabilizadores de luz, ou outros agentes que melhoram a estabilidade química e/ou física, podem também estar presentes. Adicionalmente, presentes podem ser formadores de espuma ou desespumantes.
[0065] Além disso, as formulações e as formas de aplicação derivadas delas podem também compreender, como auxiliares adicionais, adesivos tais como carboximetilcelulose, polímeros natural e sintético em pó, forma de grânulo ou látex, tais como goma arábica, polivinil álcool, acetato de polivinil e também fosfolipídeos naturais, tais como cefalinas e lecitinas, e fosfolipídeos sintéticos. Auxiliares ainda possíveis incluem óleos mineral e vegetal.
[0066] Pode ainda ser possível auxiliares adicionais presentes nas formulações, e nas formas de aplicação derivadas deles. Exemplos de tais aditivos incluem fragrâncias, coloides protetores, aglutinantes, adesivos, agentes de espessamento, substâncias tixotrópicas, penetrantes, promotores de retenção, estabilizadores, sequestrantes,
agentes de complexidade, humectantes e disseminadores. Falando de um modo geral, os compostos ativos podem ser combinados com qualquer aditivo sólido ou líquido, comumente usados para propósitos de formulação.
[0067] Promotores de retenção apropriados incluem todas essas substâncias que reduzem a tensão da superfície dinâmica, tais como dioctil sulfossuccinato, ou aumentam a viscoelasticidade, tais como polímeros hidroxipropilguar, por exemplo.
[0068] Penetrantes apropriados no presente contexto, incluem todas aquelas substâncias que são tipicamente usadas, a fim de intensificar a penetração compostos agroquímicos ativos nas plantas. Penetrantes neste contexto são definidos pelo fato de que, a partir da aplicação da substância líquida (geralmente aquosa), e/ou do revestimento de pulverização, eles são capazes de penetrar na película da planta, e dessa maneira aumentar a mobilidade dos compostos ativos na película. Esta propriedade pode ser determinada usando o método descrito na literatura (Baur et al., 1997, Pesticide Science 51, 131-152). Exemplos incluem alcoxilatos de álcool tais como etoxilato graxo de coco (10) ou etoxilato de isotridecila (12), ésteres de ácido graxo tais como semente de colza ou ésteres de metil de óleo de soja, alcoxilatos de amina gordurosa tais como etoxilato de amina de gordura (15), ou sais de amônio e/ou de fosfônio tais como sulfato de amônio ou fosfato de hidrogênio de diamônio, por exemplo.
[0069] Em uma modalidade da invenção do momento, a formulação do ingrediente ativo é uma composição de lignina de um ingrediente ativo, caracterizada pelo fato de que a) o ingrediente ativo é selecionado do grupo de fungicidas, herbicidas, inseticidas, nematicidas, indutores de defesa do hospedeiro, b) uma lignina c) o solvente é um solvente solúvel na água, preferivelmente selecionado do grupo consistindo em mono-álcoois (C1-C4-álcoois, mais preferivelmente C1-C3-álcoois), propileno glicol, N- Butilpirrolidona (NBP) e Metil-5-(dimetilamino)-2-metil-5-oxopentanoato (por exemplo, Rhodiasolv® Polarclean, talbém conhecido como ácido Pentanoico, 5-(dimetilamino)-2-metil-5-oxo-, metil éster), N,N-dimetil lactamida (CAS Nr: 35123-06-9), Dimetil isossorbida (CAS Nr. 5306- 85-4), monobutiléter de dietileno glicol (Cas Nr. 107-98-2), citrato de trietila (CAS Nr. 77-93-0), triacetato de glicerol (CAS Nr: 102-76-1), 1- metil-2-pirrolidona (CAS Nr. 872-50-4) e diacetato de propileno glicol (CAS Nr: 623-84-7), d) auxiliares e / ou adjuvantes ainda opcionais, e e) água opcional.
[0070] A proporção de b / c é preferível de 1:4 para 1:40, mais preferivelmente de 1:5 para 1:20, ainda preferido de 1:5 para 1:15, ainda mais preferido mais preferivelmente de 1:7 para 1:12, e mais preferivelmente de 1:8 para 1:10.
[0071] Em uma modalidade preferida, a proporção de ativo a) para lignina b) é 1:0.1 para 1:5, preferivelmente de 1:0,5 para 1:20, mais preferido de 1: 2 para – 1: 18 e o mais preferido de 1: 4 para 1:15.
[0072] Em uma modalidade preferida o ingrediente ativo é um herbicida, preferivelmente selecionado do grupo de diflufenicano (DFF), isoxaflutol (IFT), e indaziflam (IAF), enquanto IFT é particularmente preferido.
[0073] Em outra modalidade preferida, o ativo é um nematicida, preferivelmente fluopiram (FLU).
[0074] Ainda preferido, o componente b) é selecionado do grupo de etanol, propanol e isopropanol, NBP, e Metil-5-(dimetilamino)-2- metil-5-oxopentanoato.
[0075] Em ainda uma modalidade preferida, lignina b) é lignina de papel grosso (kraft).
[0076] Em outra modalidade a lignina é uma lignina insolúvel na água, preferivelmente Lignina de papel grosso insolúvel na água.
[0077] Em outra modalidade a composição compreende pelo menos um composto do grupo d).
[0078] Em outra modalidade, a composição compreende água e).
[0079] Em outra modalidade preferida os compostos b) e c) são pré-misturados como aditivos de mistura de tanque, que é adicionada para o tanque junto com a formulação do respectivo ingrediente ativo ou ingredientes ativos. Ambos, em combinação, formam um kit de peças.
[0080] Ainda outra modalidade é o uso de lignina, preferivelmente lignina de papel grosso, em formulações agroquímicas, preferivelmente com os ingredientes ativos como mostrado acima, para reduzir efeitos indesejáveis (fitotoxicidade) em plantas úteis (plantas de colheita), preferivelmente em soja ou milho, como também o uso da dita lignina para formulações de liberação controlada. A formulação do ingrediente ativo, para mistura no tanque, é preferivelmente um SC, WG ou WP.
[0081] Insolúvel na água, no contexto da presente invenção, se refere a uma solubilidade a 20°C de menos do que 1,0 g/L.
[0082] Além do mais, em todas as aplicações, formulações, compostos da invenção do momento, o ingrediente ativo a) e lignina b) não estão simultaneamente presentes dissolvidos em uma fase, isto é, em um solvente.
[0083] O termo "composto de lignina" na presente invenção refere- se a uma formulação ou composto sólido, em que os ingredientes ativos são associados com lignina por absorção, encapsulação, adsorção, ou outros processos químicos ou físicos.
[0084] Processo para sementes de revestimento e materiais de veículos e preparação de composto de lignina:
[0085] Em uma modalidade preferida, o processo para preparar uma formulação compreende: a) dissolver lignina em um, preferivelmente volátil, solvente, mais preferivelmente etanol, propanol ou isopropanol ou misturas dos mesmos. b) aplicar a solução em um veículo ou em uma semente, junto com o ingrediente ativo formulado, em que no presente a etapa b) pode ser uma única etapa, ou um processo de duas etapas descrito como a seguir: b1) processo de etapa única: a solução de Lignina é misturada com SC, WP, ou WG de ingrediente ativo em proporções apropriadas, e a mistura resultante é aplicada. b2) processo de duas etapas: a solução de lignina é, primeiro, aplicada em uma semente ou material de veículo, e o ingrediente ativo formulado é aplicado subsequencialmente.
[0086] Em outra modalidade a solução alcóolica de lignina é combinada com uma SC baseada na água, do ingrediente ativo, para obter uma formulação.
[0087] Uma modalidade preferida compreende o processo para revestir uma semente ou material de veículo (preferivelmente uma semente), compreendendo as etapas de: a) Dissolver lignina em um solvente, b) Misturar uma dispersão aquosa de um ativo ou uma dispersão aquosa de SC,WG, ou WP com a Lignina dissolvida a), c) Aplicar a mistura resultante da etapa b) para uma semente ou um material de veículo d) Remover o solvente.
[0088] Em uma modalidade alternativa, o processo compreende as etapas de:
a) Dissolver lignina em um solvente, b) Aplicar a solução da etapa a) a uma semente or a material de veículo c) Remover o solvente d) Aplicar uma dispersão aquosa do ativo, ou uma dispersão aquosa de SC, WG, ou WP ou um WG aquoso, ou uma solução de SGs para a semente revestida de lignina, ou o material de veículo.
[0089] Uma modalidade alternativa adicional se refere ao processo para aplicação no solo, compreendendo as etapas: a) Dissolver lignina em um solvente solúvel na água, b) Misturar uma dispersão aquosa de um ativo, ou uma dispersão aquosa de SC,WG, ou WP com a lignina dissolvida a), c) Aplicar a mistura resultante da etapa b) para um substrato do solo.
[0090] Outra modalidade alternativa é direcionada para um processo para aplicação foliar, compreendendo as etapas de: a) Dissolver lignina em um solvente solúvel na água, b) Misturar uma dispersão aquosa de um ativo, ou uma dispersão aquosa de SC, WG, ou WP com a lignina dissolvida a), c) Aplicar a mistura resultante da etapa b) a uma colheita através de aplicação foliar.
[0091] Aparte da modalidade alternativa para revestimento de semente, as etapas a) e b) nos processos descritos acima são intercambiáveis. Para todos aqueles acima, as etapas a seguir podem ser levadas também: a) Fornecer água, b) Adicionar SC, WG, ou WP do ingrediente ativo, e c) Adicionar lignina, em que no presente a ordem das etapas b e c pode ser trocada, se necessário.
[0092] Também divulgado na presente invenção está, para esse fim, o uso da mistura da etapa b) (aparte da modalidade alternativa para revestimento de semente), para aplicação de proteção da colheita no solo ou foliar, como também a mistura da própria.
[0093] Em relação à remoção do solvente, métodos como remoção sob pressão reduzida, aquecimento (em temperaturas aceitáveis para não danificar as sementes) ou uma combinação de ambos, são conhecidos do artesão versado na técnica.
[0094] O solvente é preferivelmente selecionado do grupo consistindo em mono-álcoois (C1-C4-álcoois, mais preferivelmente C1- C3-álcoois), propileno glicol, N-Butilpirrolidona (NBP) e Metil-5- (dimetilamino)-2-metil-5-oxopentanoato (por exemplo Rhodiasolv® Polarclean, também conhecido como ácido Pentanoico, 5- (dimetilamino)-2-metil-5-oxo-, metil éster), N,N-dimetil lactamida (CAS Nr: 35123-06-9), Dimetil isosorbida (CAS Nr. 5306-85-4), monobutiléter de dietileno glicol (Cas Nr. 107-98-2), citrato de Trietil (CAS Nr. 77-93- 0), triacetato de glicerol (CAS Nr: 102-76-1), 1-metil-2-pirrolidona (CAS Nr. 872-50-4) e diacetato de propileno glicol (CAS Nr: 623-84-7).
[0095] Mais preferido, o solvente é selecionado do grupo de etanol, propanol e isopropanol, propileno glicol, NBP, e Metil-5- (dimetilamino)-2-metil-5-oxopentanoato, e mais preferido de etanol, propanol e isopropanol.
[0096] Em particular os álcoois ou solventes com um baixo ponto de poiling são preferidos, se o solvente tem que ser removido.
[0097] A proporção de lignina, que é preferivelmente Lignina de papel grosso, para o solvente, é preferível de 1:4 para 1:40, mais preferivelmente de 1:5 para 1:20, ainda preferido de 1:5 para 1:15, ainda mais preferido de 1:7 para 1: 12, e mais preferivelmente de 1:8 para 1:10.
[0098] A proporção de ativo da proporção a) para lignina b) é de
1:0.1 para 1:5, preferivelmente de 1:0,5 para 1:20, mais preferido de 1: 2 para– 1: 18 e o mais preferido de 1: 4 para 1:15.
[0099] Em uma modalidade preferida o ingrediente ativo é um herbicida, preferivelmente selecionado do grupo de diflufenicano (DFF), isoxaflutol (IFT), e indaziflam (IAF), enquanto IFT é particularmente preferido.
[00100] Em outra modalidade preferida, o ativo é nematicida, preferivelmente nematicida fluopiram (FLU).
[00101] Em uma modalidade adicional, a formulação da presente invenção é preparada misturando uma solução de lignina em NBP ou Metil-5-(dimetilamino)-2-metil-5-oxopentanoato, com uma formulação com ativo sólido, em que no presente a formulação com ativo sólido é preferivelmente uma formulação SC, WP ou WG.
[00102] Além disso, outra modalidade é o uso de lignina em uma composição, ou um processo de acordo com a presente invenção, para tratamento de semente preferivelmente lignina de papel grosso, preferivelmente com os ingredientes ativos como mostrado acima, para reduzir efeitos indesejáveis (fitotoxicidade) em plantas úteis (plantas de colheita), preferivelmente em soja, milho e arroz.
[00103] Outra modalidade é o uso de uma formulação da presente invenção, obtida misturando uma solução de lignina em NBP ou Metil- 5-(dimetilamino)-2-metil-5-oxopentanoato com uma formulação com ativo sólido, em que no presente a formulação com ativo sólido é preferivelmente uma formulação de SC, WP ou WG, para aplicações folares. As formulações finais preferivelmente compreendem entre 0,1% e 70% em peso de composto ativo ou, com particular preferência, entre 1% e 65% em peso de composto ativo, mais preferivelmente entre 5% e 60% em peso de composto ativo, e mais preferido entre 5% e 50% em peso de composto ativo, com base no peso da formulação.
[00104] O conteúdo de composto ativo das formas de aplicação para herbicidas (incluindo, mas não limitado a, o Diflufenican Indaziflam e Isoxaflutol), preparados a partir de formulações pode variar dentro de amplas faixas. As formas de concentração de composto ativo da aplicação, podem ser situadas tipicamente entre
0.00001% e 50% em peso de composto ativo, preferivelmente entre
0.001% e 5% em peso, com base no peso da forma de aplicação. A aplicação tem lugar de uma maneira usual, adaptada para as formas de aplicação.
[00105] O conteúdo de composto das formas de aplicação para nematicidas/fungicidas (incluindo, mas não limitado à Fluopiram), preparadas a partir das formulações, podem variar dentro das faixas. A concentração do composto ativo das formas de aplicação, pode ser situada tipicamente entre 0.00001% e 50% em peso do composto ativo, preferivelmente entre 0.001% e 10% em peso, com base no peso da forma de aplicação. A aplicação tem lugar de uma maneira habitual, adaptada para as formas de aplicação.
[00106] Em uma modalidade, a presente invenção é dirigida para composições de ingrediente ativo com lignina, o método da produção deles, as formulações compreendendo o ingrediente ativo com lignina, e um método e uso para tratamento de semente com as composições de ingrediente ativo com lignina, ou as formulações correspondentes.
[00107] Em uma modalidade, a presente invenção é dirigida para composições de ingrediente ativo com lignina, o método da produção deles, formulações compreendendo o ingrediente ativo com lignina, e um método e o uso na aplicação em sulco, com os ingredientes ativos com lignina ou as formulações correspondentes.
[00108] Em uma modalidade a presente invenção é dirigida para composições de ingrediente ativo com lignina, o método da produção delas, formulações compreendendo os ingredientes ativos com lignina,
e um método e o uso para aplicação foliar com o composto de ingredientes ativos com lignina ou as formulações correspondentes.
[00109] Em uma modalidade a presente invenção é dirigida para composições de ingredientes ativos com lignina, o método da produção delas, formulações compreendendo ingredientes ativos com lignina, e um método e uso para aplicação no solo, com os ingredientes ativos com lignina, ou as formulações correspondentes. Ativos apropriados da presente invenção são, preferivelmente, aqueles que são conhecidos para mostrar efeitos indesejáveis quando aplicados para plantas.
[00110] Ativos para a presente invenção são preferivelmente selecionados do grupo compreendendo herbicidas, inseticidas, nematicidas, fungicidas, indutor de defesa do hospedeiro, agentes de controle biológico.
[00111] Os ditos ativos podem também ser usados como parceiros de misturas para ativos encapsulados. Em uma modalidade o mesmo ativo está presente encapsulado e em forma livre, que leva a uma absorção inicial rápida e libração contínua, e absorção do mesmo ativo por um tempo prolongado. Herbicidas
[00112] Componentes que podem ser usados como herbicida para encapsulação, ou em combinação com os compostos ativos de acordo com a invenção, preferivelmente em formulações misturadas ou em misturas de tanque são, por exemplo, compostos ativos conhecidos como eles são descritos em, por exemplo, Weed Research 26, 441- 445 (1986), ou "The Pesticide Manual", 15ª edição, The British Crop Protection Council and the Royal Soc. of Chemistry, 2006, e a literatura citada aqui no presente, e que por exemplo atua como inibidor de sintase de acetolactato, acetil-CoA-carboxilase, celulose- sintase, enolpiruvilshikimat-3-fosfato-sintase, glutamina-sintetase, p-
hidroxifenilpiruvat-dioxigenase, fitoendessaturase, fotossistema I, fotossistema II e/ou protoporfirinogen-oxidase.
[00113] Exemplos de compostos ativos que podem ser mencionados como herbicidas, ou reguladores do crescimento de planta, que são conhecidos a partir da literatura, são os a seguir (compostos são descritos pelo "nome comum" de acordo com a International Organization for Standardization (ISO), ou pelo nome químico ou pelo número de código habitual), e sempre compreendem todas as formas aplicáveis tais como ácidos, sais, éster, ou modificações tais como isômeros, como estereoisômeros e isômeros ópticos. Como um exemplo, pelo menos um aplicável a partir de e/ou modificações, podem ser mencionados.:
[00114] Exemplos para herbicidas são:
[00115] Acetoclor, acifluorfeno, acifluorfeno-sódio, aclonifeno, alaclor, alidoclor, aloxidim, aloxidim-sódio, ametrin, amicarbazona, amidoclor, amidossulfurona, aminociclopiraclor, aminociclopiraclor- potássio, aminociclopiraclor-metila, aminopiralida, amitrol, amoniossulfamato, anilofos, asulam, atrazina, azafenidina, azinsulfurona, beflubutamida, benazolina, benazolin-etil, benfluralina, benfuressato, bensulfurona, bensulfuron-metila, bensulida, bentazona, benzobiciclon, benzofenap, biciclopirona, bifenox, bilanafos, bilanafos- sódio, bispiribac, bispiribac-sódio, bromacil, bromobutida, bromofenoxim, bromoxinil, bromoxinil-butirato, -potássio, -heptanoato, e -octanoato, busoxinona, butaclor, butafenacil, butamifos, butenaclor, butralin, butroxidim, butilato, cafenstrol, carbetamida, carfentrazona, carfentrazona-etil, cloramben, clorbromurona, clorfenac, clorfenac- sódio, clorfenprop, clorflurenol, clorflurenol-metila, cloridazona, clorimuron, clorimuron-etil, cloroftalim, clorotolurona, clortal-dimetil, 3- [5-cloro-4-(trifluormetil)piridina-2-il]-4-hidróxi-1-metilimidazolidin-2-on, clorsulfurona, cinidon, cinidon-etil, cinmetilina, cinosulfurona, clacifos,
cletodim, clodinafop, clodinafop-propargil, clomazona, clomeprop, clopiralida, cloransulam, cloransulam-metila, cumilurona, cianamida, cianazina, cicloato, ciclopiranil, ciclopirimorato, ciclosulfamurona, cicloxidim, cialofop, cialofop-butil, ciprazina, 2,4-D, 2,4-D-butotil, -butil, -dimetilamônio, -diolamin, -etil, -2-etilexil, -isobutil, -isooctil, -isopropil- amônio, -potássio, -triisopropanolamônio, e -trolamina, 2,4-DB, 2,4-DB- butil, -dimetilamônio, -isooctil, -potássio, e -sódio, daimurona (dimrona), dalapone, dazomete, n-decanol, desmedifam, detosil- pirazolato (DTP), dicamba, diclobenil, 2-(2,4-diclorobenzil)-4,4-dimetil- 1,2-oxazolidin-3-ona, 2-(2,5-diclorobenzil)-4,4-dimetil-1,2-oxazolidin-3- ona, diclorprop, diclorprop-P, diclofop, diclofop-metila, diclofop-P- metila, diclosulam, difenzoquate, diflufenicano, diflufenzopir, diflufenzopir-sódio, dimefurona, dimepiperato, dimetaclor, dimetametrina, dimetenamida, dimetenamida-P, dimetrassulfurona, dinitramina, dinoterbe, difenamida, diquat, diquat-dibromide, ditiopir, diuron, DNOC, endotal, EPTC, esprocarbe, etalfluralina, etametsulfurona, etametsulfuron-metila, etiozina, etofumesato, etoxifeno, etoxifen-etil, etoxissulfurona, etobenzanide, F-5231, isto é, N-{2-cloro-4-fluor-5-[4-(3-fluoropropil)-5-oxo-4,5-diidro-1H-tetrazol-1- il]fenil}etanossulfonamida, F-7967, isto é 3-[7-cloro-5-fluor-2- (trifluorometil)-1H-benzimidazol-4-il]-1-metil-6-(trifluorometil)pirimidina- 2,4(1H,3H)-diona, fenoxaprop, fenoxaprop-P, fenoxaprop-etil, fenoxa- prop-P-etil, fenoxassulfona, fenquinotriona, fentrazamida, flamprop, flamprop-M-isopropil, flamprop-M-metil, flazasulfurona, florasulam, fluazifop, fluazifop-P, fluazifop-butil, fluazifop-P-butil, flucarbazona, flucarbazona-sódio, flucetosulfurona, flucloralina, flufenacete, flufenpir, flufenpir-etil, flumetsulam, flumiclorac, flumiclorac-pentil, flumioxazina, fluometurona, flurenol, flurenol-butil, -dimetilamônio e -metil, fluoroglicofeno, fluoroglicofen-etil, flupropanato, flupirsulfurona, flupirsulfuron-metil-sódio, fluridona, flurocloridona, fluroxipir, fluroxipir-
meptil, flurtamona, flutiaceta, flutiacet-metila, fomesafeno, fomesafen- sódio, foramsulfurona, fosamina, glufosinato, glufosinato-amônio, glufosinato-P-sódio, glufosinato-P-amônio, glufosinato-P-sódio, glifosato, glifosato-amônio, -isopropilamônio, -diamônio, -dimetilamônio, -potássio, -sódio, e -trimesium, H-9201, isto é, O-(2,4- dimetil-6-nitrofenil) O-etil isopropilfosforamidotioato, halauxifeno, halauxifen-metil, halosafeno, halossulfurona, halossulfuron-metil, haloxifop, haloxifop-P, haloxifop-etoxietil, haloxifop-P-etoxietil, haloxifop-metil, haloxifop-P-metil, hexazinona, HW-02, isto é, 1- (dimetoxifosforil) etil-(2,4-diclorofhenóxi)acetato, 4-hidróxi-1-metóxi-5- metil-3-[4-(trifluormetil)piridina-2-il]imidazolidina-2-ona, 4-hidróxi-1- metil-3-[4-(trifluormetil)piridina-2-il]imidazolidina-2-ona, imazametabenz, imazametabenz-metil, imazamox, imazamox-amônio, imazapic, imazapic-amônio, imazapir, imazapir-isopropilamônio, imazaquina, imazaquin-amônio, imazetapir, imazetapir-imônio, imazossulfurona, indanofano, indaziflam, iodossulfurona, iodosulfuron- metil-sódio, ioxinil, ioxinil-octanoato, -potássio e -sódio, ipfencarbazona, isoproturona, isourona, isoxabeno, isoxaflutol, carbutilato, KUH-043, isto é, 3-({[5-(difluorometil)-1-metil-3- (trifluorometil)-1H-pirazol-4-il]metil}sulfonil)-5,5-dimetil-4,5-diidro-1,2- oxazol, cetospiradox, lactofeno, lenacil, linurona, MCPA, MCPA-butotil, -dimetilamônio, -2-etilexil, -isopropilamônio, -potássio, e -sódio, MCPB, MCPB-metil, -eti,l and -sódio, mecoprop, mecoprop-sódio, e -butotil, mecoprop-P, mecoprop-P-butotil, -dimetilamônio, -2-etilexil, e - potássio, mefenacete, mefluidida, mesossulfurona, mesossulfurona- metil, mesotriona, metabenztiazurona, metam, metamifop, metamitrona, metazaclor, metazossulfurona, metabenztiazurona, metiopirsulfurona, metiozolina, metil isotiocianato, metobromurona, metolaclor, S-metolaclor, metosulam, metoxurona, metribuzine, metsulfurona, metsulfurona-metil, molinat, monolinurona,
monossulfurona, monossulfuron-éster, MT-5950, isto é, N-(3-cloro-4- isopropilfenil)-2-metilpentano amida, NGGC-011, napropamida, NC- 310, isto é, [5-(benzilóxi)-1-metil-1H-pirazol-4-il](2,4-diclorofenil)- metanona, neburona, nicossulfurona, ácido nonanoico (ácido pelargônico), norflurazona, ácido oleico (ácidos graxos), orbencarbe, ortossulfamurona, orizalina, oxadiargil, oxadiazona, oxassulfurons, oxaziclomefona, oxifluorfeno, paraquat, dicloreto de paraquat, pebulato, pendimetalina, penoxsulam, pentaclorfenol, pentoxazona, petoxamida, óleos de petróleo, fenmedifam, picloram, picolinafeno, pinoxadeno, piperofos, pretilaclor, primissulfurona, primissulfurona- metil, prodiamina, profoxidim, prometon, prometrina, propalor, propanil, propaquizafop, propazina, profam, propissoclor, propoxicarbazona, propoxicarbazona-sódio, propirissulfurona, propizamida, prossulfocarbe, prossulfurona, piraclonil, piraflufeno, piraflufen-etil, pirassulfotol, pirazolinato (pirazolato), pirazossulfurona, pirazossulfuron-etil, pirazoxifeno, piribambenzo, piribambenzo- isopropil, piribambenzo-propil, piribenzoxim, piributicarb, piridafol, piridato, piriftalida, piriminobac, piriminobac-metil, pirimissulfano, piritiobac, piritiobac-sódio, piroxassulfona, piroxsulam, quinclorac, quinmerac, quinoclamina, quizalofop, quizalofop-etil, quizalofop-P, quizalofop-P-etil, quizalofop-P-tefurila, rinsulfurona, saflufenacil, setoxidim, sidurona, simazina, simetrina, SL-261, sulcotriona, sulfentrazona, sulfometurona, sulfometurona-metil, sulfossulfurona, SYN-523, SYP-249, isto é, 1-etóxi-3-metil-1-oxobut-3-en-2-il 5-[2-cloro- 4-(trifluorometil)fenóxi]-2-nitrobenzoato, SYP-300, isto é, 1-[7-fluor-3- oxo-4-(prop-2-in-1-il)-3,4-diidro-2H-1,4-benzoxazin-6-il]-3-propil-2- tioxoimidazolidin-4,5-diona, 2,3,6-TBA, TCA (ácido tricloroacético), TCA-sódio, tebutiurona, tefuriltriona, tembotriona, tepraloxidim, terbacil, terbucarb, terbumetona, terbutilazina, terbutrina, tenilclor, tiazopir, tiencarbazona, tiencarbazona-metil, tifensulfurona,
tifensulfurona-metil, tiobencarb, tiafenacil, tolpiralato, topramezona, tralcoxidim, triafamona, tri-alato, triassulfurona, triaziflam, tribenurona, tribenurona-metil, triclopir, trietazina, trifloxissulfurona, trifloxissulfurona-sódio, trifludimoxazina, trifluralina, triflussulfurons, triflussulfurons-metil, tritossulfurona, sulfato de ureia, vernolato, ZJ- 0862, isto é, 3,4-dicloro-N-{2-[(4,6-dimetoxipirimidin-2- il)óxi]benzil}anilina, e os compostos a seguir:
[00116] Exemplos para reguladores do crescimento da planta são:
[00117] Acibenzolar, acibenzolar-S-metil, ácido 5-aminolevulinico, ancimidol, 6-benzilaminopurina, Brassinolide, catequina, cloreto de clormequate, cloprop, ciclanilida, 3-(cicloprop-1-enil) ácido propiônico, daminozida, dazomete, n-decanol, diquegulac, diquegulac-sódio, endotal, endotal-dipotássio, -dissódio, e -mono(N,N- dimetilalquilamônio), etefon, flumetralina, flurenol, flurenol-butila, flurprimidol, forclorofenurona, ácido giberelico, inabenfida, ácido indol- 3-acético (IAA), ácido 4-indol-3-ilbutirico, isoprotiolano, probenazol, ácido jasmônico, hidrazida maleico, cloreto de mepiquato, 1- metilciclopropeno, jasmonato de metila, 2-(1-naftil)acetamida, ácido 1- naftilacético, ácido 2- naftiloxiacético, nitrofenolato-mistura, paclobutrazol, N-(2-feniletil)-beta-alanina, ácido N-fenilftalâmico, proexadiona, proexadiona-cálcio, prohidrojasmona, ácido salicílico,
estrigolactona, tecnazeno, tidiazurona, triacontanol, trinexapac, trinexapac-etil, tsitodef, uniconazol, uniconazol-P. Fungicidas
[00118] Exemplos de compostos ativos que podem ser mencionados como fungicidas, que são conhecidos a partir da literatura, são os a seguir (compostos são descritos por "nome comum" de acordo com a International Organization for Standardization (ISO), ou pelo nome químico ou por um número de código habitual), e sempre compreendem todas as formas aplicáveis tais como ácidos, sais, éster, ou modificações tais como isômeros, como estereoisômeros e isômeros ópticos. Como um exemplo de pelo menos uma forma aplicável e/ou modificações pode ser mencionada.:
[00119] Os ingredientes ativos especificados aqui no presente por seus Nomes Comuns são conhecidos e descritos, por exemplo, no The Pesticide Manual (16ª Ed. British Crop Protection Council), ou podem ser pesquisados na internet (por exemplo, www.alanwood.net/pesticides).
[00120] Onde um composto (A) ou um composto (B) pode estar presente em forma tautomérica, tal composto é entendido aqui no presente acima, e aqui no presente abaixo também para incluir, onde aplicável, formas tautoméricas correspondentes, mesmo quando essas não estão especificamente mencionadas em cada caso.
[00121] Todos os parceiros de misturas mencionados das classes (1) a (15) podem, se seus grupos funcionais possibilitarem isto, opcionalmente formar sais com bases apropriadas ou ácidos.
[00122] 1) Inibidores da biossíntese de ergosterol, por exemplo (1.001) ciproconazol, (1.002) difenoconazol, (1.003) epoxiconazol, (1.004) fenexamida, (1.005) fenpropidina, (1.006) fenpropimorfo, (1.007) fenpirazamina, (1.008) fluquinconazol, (1.009) flutriafol, (1.010) imazalila, (1.011) sulfato de imazalila, (1.012) ipconazol, (1.013)
metconazol, (1.014) miclobutanil, (1.015) paclobutrazol, (1.016) procloraz, (1.017) propiconazol, (1.018) protioconazol, (1.019) Pirisoxazol, (1.020) espiroxamina, (1.021) tebuconazol, (1.022) tetraconazol, (1.023) triadimenol, (1.024) tridemorfo, (1.025) triticonazol, (1.026) (1R,2S,5S)-5-(4-clorobenzil)-2-(clorometil)-2-metil- 1-(1H-1,2,4-triazol-1-ilmetil)ciclopentanol, (1.027) (1S,2R,5R)-5-(4- clorobenzil)-2-(clorometil)-2-metil-1-(1H-1,2,4-triazol-1- ilmetil)ciclopentanol, (1.028) (2R)-2-(1-clorociclopropil)-4-[(1R)-2,2- diclorociclopropil]-1-(1H-1,2,4-triazol-1-il)butan-2-ol, (1.029) (2R)-2-(1- clorociclopropil)-4-[(1S)-2,2-diclorociclopropil]-1-(1H-1,2,4-triazol-1- il)butan-2-ol, (1.030) (2R)-2-[4-(4-clorofenóxi)-2-(trifluorometil)fenil]-1- (1H-1,2,4-triazol-1-il)propan-2-ol, (1.031) (2S)-2-(1-clorociclopropil)-4- [(1R)-2,2-diclorociclopropil]-1-(1H-1,2,4-triazol-1-il)butan-2-ol, (1.032) (2S)-2-(1-clorociclopropil)-4-[(1S)-2,2-diclorociclopropil]-1-(1H-1,2,4- triazol-1-il)butan-2-ol, (1.033) (2S)-2-[4-(4-clorofenóxi)-2- (trifluorometil)fenil]-1-(1H-1,2,4-triazol-1-il)propan-2-ol, (1.034) (R)-[3- (4-cloro-2-fluorofenil)-5-(2,4-difluorofenil)-1,2-oxazol-4-il](piridin-3- il)metanol, (1.035) (S)-[3-(4-cloro-2-fluorofenil)-5-(2,4-difluorofenil)-1,2- oxazol-4-il](piridin-3-il)metanol, (1.036) [3-(4-cloro-2-fluorofenil)-5-(2,4- difluorofenil)-1,2-oxazol-4-il](piridin-3-il)metanol, (1.037) 1-({(2R,4S)-2- [2-cloro-4-(4-clorofenóxi)fenil]-4-metil-1,3-dioxolan-2-il}metil)-1H-1,2,4- triazol, (1.038) 1-({(2S,4S)-2-[2-cloro-4-(4-clorofenóxi)fenil]-4-metil-1,3- dioxolan-2-il}metil)-1H-1,2,4-triazol, (1.039) 1-{[3-(2-clorofenil)-2-(2,4- difluorofenil)oxiran-2-il]metil}-1H-1,2,4-triazol-5-il tiocianato, (1.040) 1- {[rel(2R,3R)-3-(2-clorofenil)-2-(2,4-difluorofenil)oxiran-2-il]metil}-1H- 1,2,4-triazol-5-il tiocianato, (1.041) 1-{[rel(2R,3S)-3-(2-clorofenil)-2-(2,4- difluorofenil)oxiran-2-il]metil}-1H-1,2,4-triazol-5-il tiocianateo, (1.042) 2- [(2R,4R,5R)-1-(2,4-diclorofenil)-5-hidróxi-2,6,6-trimetileptan-4-il]-2,4- diidro-3H-1,2,4-triazol-3-tiona, (1.043) 2-[(2R,4R,5S)-1-(2,4- diclorofenil)-5-hidróxi-2,6,6-trimetileptan-4-il]-2,4-diidro-3H-1,2,4-triazol-
3-tiona, (1.044) 2-[(2R,4S,5R)-1-(2,4-diclorofenil)-5-hidróxi-2,6,6- trimetileptan-4-il]-2,4-diidro-3H-1,2,4-triazol-3-tiona, (1.045) 2- [(2R,4S,5S)-1-(2,4-diclorofenil)-5-hidróxi-2,6,6-trimetileptan-4-il]-2,4- diidro-3H-1,2,4-triazol-3-tiona, (1.046) 2-[(2S,4R,5R)-1-(2,4- diclorofenil)-5-hidróxi-2,6,6-trimetileptan-4-il]-2,4-diidro-3H-1,2,4-triazol- 3-tiona, (1.047) 2-[(2S,4R,5S)-1-(2,4-diclorofenil)-5-hidróxi-2,6,6- trimetileptan-4-il]-2,4-diidro-3H-1,2,4-triazol-3-tiona, (1.048) 2- [(2S,4S,5R)-1-(2,4-diclorofenil)-5-hidróxi-2,6,6-trimetileptan-4-il]-2,4- diidro-3H-1,2,4-triazol-3-tiona, (1.049) 2-[(2S,4S,5S)-1-(2,4- diclorofenil)-5-hidróxi-2,6,6-trimetileptan-4-il]-2,4-diidro-3H-1,2,4-triazol- 3-tiona, (1.050) 2-[1-(2,4-diclorofenil)-5-hidróxi-2,6,6-trimetileptan-4-il]- 2,4-diidro-3H-1,2,4-triazol-3-tiona, (1.051) 2-[2-cloro-4-(2,4- diclorofenóxi)fenil]-1-(1H-1,2,4-triazol-1-il)propan-2-ol, (1.052) 2-[2- cloro-4-(4-clorofenóxi)fenil]-1-(1H-1,2,4-triazol-1-il)butan-2-ol, (1.053) 2-[4-(4-clorofenóxi)-2-(trifluorometil)fenil]-1-(1H-1,2,4-triazol-1-il)butan- 2-ol, (1.054) 2-[4-(4-clorofenóxi)-2-(trifluorometil)fenil]-1-(1H-1,2,4- triazol-1-il)pentan-2-ol, (1.055) Mefentrifluconazol, (1.056) 2-{[3-(2- clorofenil)-2-(2,4-difluorofenil)oxiran-2-il]metil}-2,4-diidro-3H-1,2,4- triazol-3-tiona, (1.057) 2-{[rel(2R,3R)-3-(2-clorofenil)-2-(2,4- difluorofenil)oxiran-2-il]metil}-2,4-diidro-3H-1,2,4-triazol-3-tiona, (1.058) 2-{[rel(2R,3S)-3-(2-clorofenil)-2-(2,4-difluorofenil)oxiran-2-il]metil}-2,4- diidro-3H-1,2,4-triazol-3-tiona, (1.059) 5-(4-clorobenzil)-2-(clorometil)- 2-metil-1-(1H-1,2,4-triazol-1-ilmetil)ciclopentanol, (1.060) 5-(alilsulfanil)- 1-{[3-(2-clorofenil)-2-(2,4-difluorofenil)oxiran-2-il]metil}-1H-1,2,4-triazol, (1.061) 5-(alilsulfanil)-1-{[rel(2R,3R)-3-(2-clorofenil)-2-(2,4- difluorofenil)oxiran-2-il]metil}-1H-1,2,4-triazol, (1.062) 5-(alilsulfanil)-1- {[rel(2R,3S)-3-(2-clorofenil)-2-(2,4-difluorofenil)oxiran-2-il]metil}-1H- 1,2,4-triazol, (1.063) N'-(2,5-dimetil-4-{[3-(1,1,2,2- tetrafluoroetóxi)fenil]sulfanil}fenil)-N-etil-N-metilimidoformamida, (1.064) N'-(2,5-dimetil-4-{[3-(2,2,2-trifluoroetóxi)fenil]sulfanil}fenil)-N-
etil-N-metilimidoformamida, (1.065) N'-(2,5-dimetil-4-{[3-(2,2,3,3- tetrafluorpropóxi)fenil]sulfanil}fenil)-N-etil-N-metilimidoformamida, (1.066) N'-(2,5-dimetil-4-{[3-(pentafluoroetóxi)fenil]sulfanil}fenil)-N-etil- N-metilimidoformamida, (1.067) N'-(2,5-dimetil-4-{3-[(1,1,2,2- tetrafluoroetil)sulfanil]fenoxi}fenil)-N-etil-N-metilimidoformamida, (1.068) N'-(2,5-dimetil-4-{3-[(2,2,2-trifluoroetil)sulfanil]fenoxi}fenil)-N- etil-N-metilimidoformamida, (1.069) N'-(2,5-dimetil-4-{3-[(2,2,3,3- tetrafluoropropil)sulfanil]fenoxi}fenil)-N-etil-N-metilimidoformamida, (1.070) N'-(2,5-dimetil-4-{3-[(pentafluoroetil)sulfanil]fenoxi}fenil)-N-etil- N-metilimidoformamida, (1.071) N'-(2,5-dimetil-4-fenoxifenil)-N-etil-N- metilimidoformamida, (1.072) N'-(4-{[3-(difluorometóxi)fenil]sulfanil}- 2,5-dimetilfenil)-N-etil-N-metilimidoformamida, (1.073) N'-(4-{3- [(difluorometil)sulfanil]fenoxi}-2,5-dimetilfenil)-N-etil-N- metilimidoformamida, (1.074) N'-[5-bromo-6-(2,3-diidro-1H-inden-2- ilóxi)-2-metilpiridin-3-il]-N-etil-N-metilimidoformamida, (1.075) N'-{4- [(4,5-dicloro-1,3-tiazol-2-il)óxi]-2,5-dimetilfenil}-N-etil-N- metilimidoformamida, (1.076) N'-{5-bromo-6-[(1R)-1-(3,5- difluorofenil)etóxi]-2-metilpiridin-3-il}-N-etil-N-metilimidoformamida, (1.077) N'-{5-bromo-6-[(1S)-1-(3,5-difluorofenil)etóxi]-2-metilpiridin-3-il}- N-etil-N-metilimidoformamida, (1.078) N'-{5-bromo-6-[(cis-4- isopropilciclohexil)óxi]-2-metilpiridin-3-il}-N-etil-N-metilimidoformamida, (1.079) N'-{5-bromo-6-[(trans-4-isopropilciclohexil)óxi]-2-metilpiridin-3- il}-N-etil-N-metilimidoformamida, (1.080) N'-{5-bromo-6-[1-(3,5- difluorofenil)etóxi]-2-metilpiridin-3-il}-N-etil-N-metilimidoformamida, (1.081) Ipfentrifluconazol.
[00123] 2) Inibidores da cadeia respiratória no complexo I ou II, por exemplo (2.001) benzovindiflupir, (2.002) bixafeno, (2.003) boscalide, (2.004) carboxina, (2.005) fluopiram, (2.006) flutolanil, (2.007) fluxapiroxade, (2.008) furametpir, (2.009) Isofetamida, (2.010) isopirazam (enantiômero anti-epimérico 1R,4S,9S), (2.011) isopirazam
(enantiômero anti-epimérico 1S,4R,9R), (2.012) isopirazam (racemato anti-epimérico 1RS,4SR,9SR), (2.013) isopirazam (mistura de racemato sin-epimérico 1RS,4SR,9RS e racemato anti-epimérico 1RS,4SR,9SR), (2.014) isopirazam (enantiômero sin-epimérico 1R,4S,9R), (2.015) isopirazam (enantiômero sin-epimérico 1S,4R,9S), (2.016) isopirazam (racemate sin-epimérico 1RS,4SR,9RS), (2.017) penflufeno, (2.018) pentiopirade, (2.019) pidiflumetofeno, (2.020) Piraziflumide, (2.021) sedaxano, (2.022) 1,3-dimetil-N-(1,1,3-trimetil- 2,3-diidro-1H-inden-4-il)-1H-pirazol-4-carboxamida, (2.023) 1,3-dimetil- N-[(3R)-1,1,3-trimetil-2,3-diidro-1H-inden-4-il]-1H-pirazol-4- carboxamida, (2.024) 1,3-dimetil-N-[(3S)-1,1,3-trimetil-2,3-diidro-1H- inden-4-il]-1H-pirazol-4-carboxamida, (2.025) 1-metil-3-(trifluorometil)- N-[2'-(trifluorometil)bifenil-2-il]-1H-pirazol-4-carboxamida, (2.026) 2- fluoro-6-(trifluorometil)-N-(1,1,3-trimetil-2,3-diidro-1H-inden-4- il)benzamida, (2.027) 3-(difluorometil)-1-metil-N-(1,1,3-trimetil-2,3- diidro-1H-inden-4-il)-1H-pirazol-4-carboxamida, (2.028) 3- (difluorometil)-1-metil-N-[(3R)-1,1,3-trimetil-2,3-diidro-1H-inden-4-il]-1H- pirazol-4-carboxamida, (2.029) 3-(difluorometil)-1-metil-N-[(3S)-1,1,3- trimetil-2,3-diidro-1H-inden-4-il]-1H-pirazol-4-carboxamida, (2.030) Fluindapir, (2.031) 3-(difluorometil)-N-[(3R)-7-fluor-1,1,3-trimetil-2,3- diidro-1H-inden-4-il]-1-metil-1H-pirazol-4-carboxamida, (2.032) 3- (difluorometil)-N-[(3S)-7-fluor-1,1,3-trimetil-2,3-diidro-1H-inden-4-il]-1- metil-1H-pirazol-4-carboxamida, (2.033) 5,8-difluor-N-[2-(2-fluor-4-{[4- (trifluorometil)piridin-2-il]oxi}fenil)etil]quinazolin-4-amina, (2.034) N-(2- ciclopentil-5-fluorbenzil)-N-ciclopropil-3-(difluorometil)-5-fluor-1-metil- 1H-pirazol-4-carboxamida, (2.035) N-(2-tert-butil-5-metilbenzil)-N- ciclopropil-3-(difluorometil)-5-fluoro-1-metil-1H-pirazol-4-carboxamida, (2.036) N-(2-tert-butilbenzil)-N-ciclopropil-3-(difluorometil)-5-fluor-1- metil-1H-pirazol-4-carboxamida, (2.037) N-(5-cloro-2-etilbenzil)-N- ciclopropil-3-(difluorometil)-5-fluor-1-metil-1H-pirazol-4-carboxamida,
(2.038) N-(5-cloro-2-isopropilbenzil)-N-ciclopropil-3-(difluorometil)-5- fluor-1-metil-1H-pirazol-4-carboxamida, (2.039) N-[(1R,4S)-9- (diclorometileno)-1,2,3,4-tetraidro-1,4-metanonaftaleno-5-il]-3- (difluorometil)-1-metil-1H-pirazol-4-carboxamida, (2.040) N-[(1S,4R)-9- (diclorometileno)-1,2,3,4-tetraidro-1,4-metanonaftaleno-5-il]-3- (difluorometil)-1-metil-1H-pirazol-4-carboxamida, (2.041) N-[1-(2,4- diclorofenil)-1-metoxipropan-2-il]-3-(difluorometil)-1-metil-1H-pirazol-4- carboxamida, (2.042) N-[2-cloro-6-(trifluorometil)benzil]-N-ciclopropil-3- (difluorometil)-5-fluoro-1-metil-1H-pirazol-4-carboxamida, (2.043) N-[3- cloro-2-fluoro-6-(trifluorometil)benzil]-N-ciclopropil-3-(difluorometil)-5- flúor-1-metil-1H-pirazol-4-carboxamida, (2.044) N-[5-cloro-2- (trifluorometil)benzil]-N-ciclopropil-3-(difluorometil)-5-flúor-1-metil-1H- pirazol-4-carboxamida, (2.045) N-ciclopropil-3-(difluorometil)-5-flúor-1- metil-N-[5-metil-2-(trifluorometil)benzil]-1H-pirazol-4-carboxamida, (2.046) N-ciclopropil-3-(difluorometil)-5-flúor-N-(2-flúor-6- isopropilbenzil)-1-metil-1H-pirazol-4-carboxamida, (2.047) N- ciclopropil-3-(difluorometil)-5-flúor-N-(2-isopropil-5-metilbenzil)-1-metil- 1H-pirazol-4-carboxamida, (2.048) N-ciclopropil-3-(difluorometil)-5- flúor-N-(2-isopropilbenzil)-1-metil-1H-pirazol-4-carbothioamida, (2.049) N-ciclopropil-3-(difluorometil)-5-flúor-N-(2-isopropilbenzil)-1-metil-1H- pirazol-4-carboxamida, (2.050) N-ciclopropil-3-(difluorometil)-5-flúor-N- (5-flúor-2-isopropilbenzil)-1-metil-1H-pirazol-4-carboxamida, (2.051) N- ciclopropil-3-(difluorometil)-N-(2-etil-4,5-dimetilbenzil)-5-flúor-1-metil- 1H-pirazol-4-carboxamida, (2.052) N-ciclopropil-3-(difluorometil)-N-(2- etil-5-fluorobenzil)-5-flúor-1-metil-1H-pirazol-4-carboxamida, (2.053) N- ciclopropil-3-(difluorometil)-N-(2-etil-5-metilbenzil)-5-flúor-1-metil-1H- pirazol-4-carboxamida, (2.054) N-ciclopropil-N-(2-ciclopropil-5- fluorobenzil)-3-(difluorometil)-5-flúor-1-metil-1H-pirazol-4-carboxamida, (2.055) N-ciclopropil-N-(2-ciclopropil-5-metilbenzil)-3-(difluorometil)-5- fluor-1-metil-1H-pirazol-4-carboxamida, (2.056) N-ciclopropil-N-(2-
ciclopropilbenzil)-3-(difluorometil)-5-flúor-1-metil-1H-pirazol-4- carboxamida, (2.057) pirapropoina.
[00124] 3) Inibidores da cadeia respiratória no complexo III, por exemplo (3.001) ametoctradina, (3.002) amissulbrom, (3.003) azoxistrobina, (3.004) coumetoxistrobina, (3.005) coumoxistrobina, (3.006) ciazofamida, (3.007) dimoxistrobina, (3.008) enoxastrobina, (3.009) famoxadona, (3.010) fenamidona, (3.011) flufenoxistrobina, (3.012) fluoxastrobina, (3.013) cresoxim-metil, (3.014) metominostrobina, (3.015) orisastrobina, (3.016) picoxistrobina, (3.017) piraclostrobina, (3.018) pirametostrobina, (3.019) piraoxistrobina, (3.020) trifloxistrobina, (3.021) (2E)-2-{2-[({[(1E)-1-(3-{[(E)-1-flúor-2- fenilvinil]oxi}fenil)etilideno]amino}óxi)metil]fenil}-2-(metoxiimino)-N- metilacetamida, (3.022) (2E,3Z)-5-{[1-(4-clorofenil)-1H-pirazol-3-il]oxi}- 2-(metoxiimino)-N,3-dimetilpent-3-enamida, (3.023) (2R)-2-{2-[(2,5- dimetilfenóxi)metil]fenil}-2-metóxi-N-metilacetamida, (3.024) (2S)-2-{2- [(2,5-dimetilfenóxi)metil]fenil}-2-metóxi-N-metilacetamida, (3.025) (3S,6S,7R,8R)-8-benzil-3-[({3-[(isobutirilóxi)metóxi]-4-metoxipiridin-2- il}carbonil)amino]-6-metil-4,9-dioxo-1,5-dioxonan-7-il 2- metilpropanoato, (3.026) mandestrobina, (3.027) N-(3-etil-3,5,5- trimetilcicloexil)-3-formamido-2-hidroxibenzamida, (3.028) (2E,3Z)-5- {[1-(4-cloro-2-fluorofenil)-1H-pirazol-3-il]oxi}-2-(metoxiimino)-N,3- dimetilpent-3-enamida, (3.029) metil {5-[3-(2,4-dimetilfenil)-1H-pirazol- 1-il]-2-metilbenzil}carbamato, (3.030) metiltetraprol, (3.031) florilpicoxamida.
[00125] 4) Inibidores da mitose e divisão de células, por exemplo (4.001) carbendazim, (4.002) dietofencarbe, (4.003) etaboxam, (4.004) fluopicolide, (4.005) pencicurona, (4.006) tiabendazol, (4.007) tiofanato-metil, (4.008) zoxamida, (4.009) 3-cloro-4-(2,6-difluorofenil)-6- metil-5-fenilpiridazina, (4.010) 3-cloro-5-(4-clorofenil)-4-(2,6- difluorofenil)-6-metilpiridazina, (4.011) 3-cloro-5-(6-cloropiridin-3-il)-6-
metil-4-(2,4,6-trifluorofenil)piridazina, (4.012) 4-(2-bromo-4-fluorofenil)- N-(2,6-difluorofenil)-1,3-dimetil-1H-pirazol-5-amina, (4.013) 4-(2- bromo-4-fluorofenil)-N-(2-bromo-6-fluorofenil)-1,3-dimetil-1H-pirazol-5- amina, (4.014) 4-(2-bromo-4-fluorofenil)-N-(2-bromofenil)-1,3-dimetil- 1H-pirazol-5-amina, (4.015) 4-(2-bromo-4-fluorofenil)-N-(2-cloro-6- fluorofenil)-1,3-dimetil-1H-pirazol-5-amina, (4.016) 4-(2-bromo-4- fluorofenil)-N-(2-clorofenil)-1,3-dimetil-1H-pirazol-5-amina, (4.017) 4-(2- bromo-4-fluorofenil)-N-(2-fluorofenil)-1,3-dimetil-1H-pirazol-5-amina, (4.018) 4-(2-cloro-4-fluorofenil)-N-(2,6-difluorofenil)-1,3-dimetil-1H- pirazol-5-amina, (4.019) 4-(2-cloro-4-fluorofenil)-N-(2-cloro-6- fluorofenil)-1,3-dimetil-1H-pirazol-5-amina, (4.020) 4-(2-cloro-4- fluorofenil)-N-(2-clorofenil)-1,3-dimetil-1H-pirazol-5-amina, (4.021) 4-(2- cloro-4-fluorofenil)-N-(2-fluorofenil)-1,3-dimetil-1H-pirazol-5-amina, (4.022) 4-(4-clorofenil)-5-(2,6-difluorofenil)-3,6-dimetilpiridazine, (4.023) N-(2-bromo-6-fluorofenil)-4-(2-cloro-4-fluorofenil)-1,3-dimetil-1H- pirazol-5-amina, (4.024) N-(2-bromofenil)-4-(2-cloro-4-fluorofenil)-1,3- dimetil-1H-pirazol-5-amina, (4.025) N-(4-cloro-2,6-difluorofenil)-4-(2- cloro-4-fluorofenil)-1,3-dimetil-1H-pirazol-5-amina.
[00126] 5) Compostos capazes de ter uma ação de multisítios, por exemplo (5.001) mistura bordeaux, (5.002) captafol, (5.003) captan, (5.004) clorotalonil, (5.005) hidróxido de cobre, (5.006) naftenato de cobre, (5.007) óxido de cobre, (5.008) oxicloreto de cobre, (5.009) sulfato de cobre(2+), (5.010) ditianona, (5.011) dodina, (5.012) folpete, (5.013) mancozebe, (5.014) manebe, (5.015) metiram, (5.016) zinco de metiram, (5.017) oxino-cobre, (5.018) propinebe, (5.019) enxofre e preparações de enxôfre incluindo polissulfeto de cálcio, (5.020) tiram, (5.021) zinebe, (5.022) ziram, (5.023) 6-etil-5,7-dioxo-6,7-diidro-5H- pirrolo[3',4':5,6][1,4]ditiino[2,3-c][1,2]tiazol-3-carbonitrila.
[00127] 6) Compostos capazes de induzir uma defesa do hospedeiro, por exemplo (6.001) acibenzolar-S-metil, (6.002) isotianil,
(6.003) probenazol, (6.004) tiadinil.
[00128] 7) Inibidores da biossíntese de amino ácido e/ou proteína, por exemplo (7.001) ciprodinil, (7.002) casugamicina, (7.003) hidrocloreto de hidrato de casugamicina, (7.004) oxitetraciclina, (7.005) pirimetanil, (7.006) 3-(5-flúor-3,3,4,4-tetrametil-3,4-diidroisoquinolin-1- il)quinolina.
[00129] 8) Inibidores da produção de ATP, por exemplo (8.001) siltiofam.
[00130] 9) Inibidores da síntese da parede da célula, por exemplo (9.001) bentiavalicarbe, (9.002) dimetomoro, (9.003) flumorfo, (9.004) iprovalicarbe, (9.005) mandipropamida, (9.006) pirimorfo, (9.007) valifenalato, (9.008) (2E)-3-(4-terc-butilfenil)-3-(2-cloropiridin-4-il)-1- (morfolin-4-il)prop-2-en-1-ona, (9.009) (2Z)-3-(4-terc-butilfenil)-3-(2- cloropiridin-4-il)-1-(morfolin-4-il)prop-2-en-1-ona.
[00131] 10) Inibidores da síntese de lipídeo e membrana, por exemplo (10.001) propamocarbe, (10.002) cloridrato de propamocarbe, (10.003) tolclofos-metil.
[00132] 11) Inibidores da biossíntese de melanina, por exemplo (11.001) triciclazol, (11.002) 2,2,2-trifluoroetil {3-metil-1-[(4- metilbenzoil)amino]butan-2-il}carbamato.
[00133] 12) Inibidores da síntese de ácido nucleico, por exemplo (12.001) benalaxil, (12.002) benalaxil-M (quiralaxil), (12.003) metalaxil, (12.004) metalaxil-M (mefenoxam).
[00134] 13) Inibidores da transdução de sinal, por exemplo (13.001) fludioxonil, (13.002) iprodiona, (13.003) procimidona, (13.004) proquinazida, (13.005) quinoxifeno, (13.006) vinclozolina.
[00135] 14) Compostos capazes de atuar como um desacoplador, por exemplo (14.001) fluazinam, (14.002) meptildinocape.
[00136] 15) Compostos adicionais, por exemplo (15.001) Ácido abscísico, (15.002) bentiazol, (15.003) betoxazina, (15.004)
capsimicina, (15.005) carvona, (15.006) chinomethioneto, (15.007) cufraneb, (15.008) ciflufenamida, (15.009) cimoxanil, (15.010) ciprossulfamida, (15.011) flutianil, (15.012) fosetil-alumínio, (15.013) fosetil-cálcio, (15.014) fosetil-sódio, (15.015) metil isotiocianato, (15.016) metrafenona, (15.017) mildiomicina, (15.018) natamicina, (15.019) dimetilditiocarbamato de níquel, (15.020) nitrotal-isopropil, (15.021) oxamocarb, (15.022) Oxatiapiprolina, (15.023) oxifentiina, (15.024) pentaclorofenol e sais, (15.025) ácido fosforoso e seus sais, (15.026) propamocarb-fosetilato, (15.027) piriofenona (clazafenona), (15.028) tebufloquina, (15.029) tecloftalam, (15.030) tolnifanida, (15.031) 1-(4-{4-[(5R)-5-(2,6-difluorofenil)-4,5-diidro-1,2-oxazol-3-il]- 1,3-tiazol-2-il}piperidin-1-il)-2-[5-metil-3-(trifluorometil)-1H-pirazol-1- il]etanona, (15.032) 1-(4-{4-[(5S)-5-(2,6-difluorofenil)-4,5-diidro-1,2- oxazol-3-il]-1,3-tiazol-2-il}piperidin-1-il)-2-[5-metil-3-(trifluorometil)-1H- pirazol-1-il]etanona, (15.033) 2-(6-benzilpiridin-2-il)quinazolina, (15.034) dipimetitrona, (15.035) 2-[3,5-bis(difluorometil)-1H-pirazol-1- il]-1-[4-(4-{5-[2-(prop-2-in-1-ilóxi)fenil]-4,5-diidro-1,2-oxazol-3-il}-1,3- tiazol-2-il)piperidin-1-il]etanona, (15.036) 2-[3,5-bis(difluorometil)-1H- pirazol-1-il]-1-[4-(4-{5-[2-cloro-6-(prop-2-in-1-ilóxi)fenil]-4,5-diidro-1,2- oxazol-3-il}-1,3-tiazol-2-il)piperidin-1-il]etanona, (15.037) 2-[3,5- bi(difluorometil)-1H-pirazol-1-il]-1-[4-(4-{5-[2-flúor-6-(prop-2-in-1- ilóxi)fenil]-4,5-diidro-1,2-oxazol-3-il}-1,3-tiazol-2-il)piperidin-1- il]etanona, (15.038) 2-[6-(3-flúor-4-metoxifenil)-5-metilpiridin-2- il]quinazolina, (15.039) 2-{(5R)-3-[2-(1-{[3,5-bi(difluorometil)-1H-pirazol- 1-il]acetil}piperidin-4-il)-1,3-tiazol-4-il]-4,5-diidro-1,2-oxazol-5-il}-3- clorofenil metanossulfonato, (15.040) 2-{(5S)-3-[2-(1-{[3,5- bi(difluorometil)-1H-pirazol-1-il]acetil}piperidin-4-il)-1,3-tiazol-4-il]-4,5- diidro-1,2-oxazol-5-il}-3-clorofenil metanossulfonato, (15.041) Ipflufenoquina, (15.042) 2-{2-flúor-6-[(8-flúoro-2-metilquinolin-3- il)óxi]fenil}propan-2-ol, (15.043) 2-{3-[2-(1-{[3,5-bi(difluorometil)-1H-
pirazol-1-il]acetil}piperidin-4-il)-1,3-tiazol-4-il]-4,5-diidro-1,2-oxazol-5-il}- 3-clorofenil metanossulfonato, (15.044) 2-{3-[2-(1-{[3,5- bi(difluorometil)-1H-pirazol-1-il]acetil}piperidin-4-il)-1,3-tiazol-4-il]-4,5- diidro-1,2-oxazol-5-il}fenil metanossulfonato, (15.045) 2-fenilfenol e sais, (15.046) 3-(4,4,5-triflúor-3,3-dimetil-3,4-diidroisoquinolin-1- il)quinolina, (15.047) quinofumelina, (15.048) 4-amino-5-fluoropirimidin- 2-ol (forma tautomérica: 4-amino-5-fluoropirimidin-2(1H)-ona), (15.049) ácido 4-oxo-4-[(2-feniletil)amino]butanoico, (15.050) 5-amino-1,3,4- tiadiazol-2-tiol, (15.051) 5-cloro-N'-fenil-N'-(prop-2-in-1-il)tiofeno-2- sulfonoidrazida, (15.052) 5-flúor-2-[(4-fluorobenzil)óxi]pirimidin-4- amina, (15.053) 5-flúor-2-[(4-metilbenzil)óxi]pirimidin-4-amina, (15.054) 9-flúor-2,2-dimetil-5-(quinolin-3-il)-2,3-diidro-1,4-benzoxazepina, (15.055) but-3-in-1-il {6-[({[(Z)-(1-metil-1H-tetrazol-5- il)(fenil)metileno]amino}óxi)metil]piridin-2-il}carbamata, (15.056) etil (2Z)-3-amino-2-ciano-3-fenilacrilato, (15.057) ácido fenazina-1- carboxílico, (15.058) propil 3,4,5-trihidroxibenzoato, (15.059) quinolin- 8-ol, (15.060) sulfato de quinolin-8-ol (2:1), (15.061) terc-butil {6-[({[(1- metil-1H-tetrazol-5-il)(fenil)metileno]amino}óxi)metil]piridin-2- il}carbamato, (15.062) 5-flúor-4-imino-3-metil-1-[(4-metilfenil)sulfonil]- 3,4-diidropirimidin-2(1H)-ona, (15.063) aminopirifeno. Protetor:
[00137] Os grupos de compostos a seguir são, por exemplo, para ser considerados como protetores:
[00138] S1) compostos do grupo de derivados de ácido carboxílico heterocíclico:
[00139] S1a) compostos do tipo de ácido diclorofenilpirazolina-3-carboxílico (S1a), preferivelmente compostos tais como ácido 1-(2,4-diclorofenil)-5-(etoxicarbonil)-5-metil-2-pirazolina-3-carboxilico, etil 1-(2,4-diclorofenil)-5-(etoxicarbonil)-5-metil-2-pirazolina-3-
carboxilato (S1-1) ("mefenpir(-dietil)"), e compostos relacionados, como descrito em WO-A-91/07874;
[00140] S1b) derivados de ácido diclorofenilpirazolcarboxilico (S1b), preferivelmente compostos tais como etil 1-(2,4-diclorofenil)- 5-metilpirazol-3-carboxilato (S1-2), etil 1-(2,4-diclorofenil)-5-isopropilpirazol-3-carboxilato (S1-3), etil 1-(2,4-diclorofenil)-5-(1,1-dimetiletil)pirazol-3-carboxilateo (S1-4) e compostos relacionados, como descrito em EP-A-333 131 e EP-A-269 806;
[00141] S1c) derivados de ácido 1,5-difenilpirazol-3-carboxílico (S1c), preferivelmente compostos tais como etil 1-(2,4-diclorofenil)-5-fenilpirazol-3-carboxilato (S1-5), metil 1-(2-clorofenil)-5-fenilpirazol-3-carboxilato (S1-6) e compostos relacionados, como descrito, por exemplo, em EP-A-268554;
[00142] S1d) compostos do tipo de ácidos triazolcarboxílicos (S1d), preferivelmente compostos tais como fenclorazol(-etil), isto é, etil 1-(2,4-diclorofenil)-5-triclorometil-(1H)-1,2,4-triazol-3-carboxilato (S1-7), e compostos relacionados, como descrito em EP-A-174 562 e EP-A-346 620;
[00143] S1e) compostos do tipo de 5-benzil- ou ácido 5-fenil-2-isoxazolina-3-carboxílico ou 5,5-difenil-2-isoxazolina-3- carboxílico (S1e), preferivelmente compostos tais como etil 5-(2,4-diclorobenzil)-2-isoxazoline-3-carboxilato (S1-8) ou etil 5-fenil-2-isoxazolina-3-carboxilato (S1-9) e compostos relacionados, como descrito em WO-A-91/08202, ou ácido 5,5-difenil-2- isoxazolinacarboxílico (S1-10) ou etil 5,5-difenil-2- isoxazolinacarboxilato (S1-11) ("isoxadifen-etil") ou n-propil 5,5-difenil- 2-isoxazolinacarboxilato (S1-12) ou etil 5-(4-fluorofenil)-5-fenil-2- isoxazolina-3-carboxilato (S1-13), como descrito no pedido de patente WO-A-95/07897.
[00144] S2) Compostos do grupo de derivados de 8-quinolinoxi (S2):
[00145] S2a) compostos do tipo de ácido 8-quinolinoxiacético (S2a), preferivelmente 1-metilexil (5-cloro-8-quinolinóxi)acetato (nome comum "cloquintocet-mexil" (S2-1), 1,3-dimetil-but-1-il (5-cloro-8-quinolinóxi)acetato (S2-2), 4-aliloxibutil (5-cloro-8-quinolinóxi)acetato (S2-3), 1-aliloxiprop-2-il (5-cloro-8-quinolinóxi)acetato (S2-4), etil (5-cloro-8-quinolinóxi)acetato (S2-5), metil (5-cloro-8-quinolinóxi)acetato (S2-6), alil (5-cloro-8-quinolinóxi)acetato (S2-7), 2-(2-propilidenoiminóxi)-1-etil (5-cloro-8-quinolinóxi)acetato (S2-8), 2-oxo-prop-1-il (5-cloro-8-quinolinóxi)acetato (S2-9) e compostos relacionados, como descrito em EP-A-86 750, EP-A-94 349 e EP-A-191 736 ou EP-A-0 492 366, e também ácido (5-cloro-8- quinolinóxi)acético (S2-10), seus hidratos e sais, por exemplo seus sais de lítio, sódio, potássio, cálcio, magnésio, alumínio, ferro, amônio, amônio quaternário, sulfônio ou fosfônio, como descrito em WO-A- 2002/34048;
[00146] S2b) compostos do tipo de ácido (5-cloro-8-quinolinóxi)malônico (S2b), preferivelmente compostos tais como dietil (5-cloro-8-quinolinóxi)malonate, dialil (5-cloro-8- quinolinóxi)malonate, metil etil (5-cloro-8-quinolinóxi)malonate e compostos relacionados, as descrito em EP-A-0 582 198.
[00147] S3) Compostos ativos do tipo de dicloroacetamidas (S3) que são frequentemente usados como protetores de pré-emergência (protetores atuando no solo), tais como, por exemplo, "diclormida" (N,N-diallil-2,2-dicloroacetamida) (S3-1), "R-29148" (3-dicloroacetil-2,2,5-trimetil-1,3-oxazolidina) de Stauffer (S3-2),
"R-28725" (3-dicloroacetil-2,2-dimetil-1,3-oxazolidina) de Stauffer (S3- 3), "benoxacor" (4-dicloroacetil-3,4-diidro-3-metil-2H-1,4-benzoxazina) (S3-4), "PPG-1292" (N-alil-N-[(1,3-dioxolan-2-il)metil]dicloroacetamida) de PPG Industries (S3 5), "DKA-24" (N-alil-N-[(alilaminocarbonil)metil]dicloroacetamida) de Sagro-Chem (S3-6), "AD-67" ou "MON 4660" (3-dicloroacetil-1-oxa-3-aza-spiro[4,5]decano) de Nitrokemia ou Monsanto (S3-7), "TI-35" (1-dicloroacetilazepano) de TRI-Chemical RT (S3-8) "diclonon" (diciclonon) ou "BAS145138" ou "LAB145138" (S3-9) ((RS)-1-dicloroacetil-3,3,8a-trimetilperhidropirrol[1,2-a]pirimidin-6-ona) de BASF, furilazol" ou "MON 13900" ((RS)-3-dicloroacetil-5-(2-furil)-2,2-dimetil- oxazolidina) (S3-10), e também seu (R)-isômero (S3-11).
[00148] S4) Compostos da classe de acilsulfonamidas (S4):
[00149] S4a) N-acilsulfonamidas da fórmula (S4a) e sais dos mesmos, como descrito em WO-A-97/45016 em que
[00150] RA1 é (C1-C6)-alquila, (C3-C6)-cicloalquila, em que os 2 radicais mencionados por último são substituídos pelos substituintes vA do grupo consistindo em halogênio, (C1-C4)-alcóxi, halo-(C1-C6)-alcoxi e (C1-C4)-alquilatio e, no caso de radicais cíclicos, também (C1-C4)- alquila e (C1-C4)-haloalquila;
[00151] RA2 é halogênio, (C1-C4)-alquila, (C1-C4)-alcóxi, CF3 mA é 1 ou 2;
vD é 0, 1, 2 ou 3
[00152] S4b) compostos do tipo de 4-(benzoilsulfamoil)benzamidas da fórmula (S4b) e sais dos mesmos, como descrito em WO-A- 99/16744,
[00153] em que
[00154] a) RB1, RB2 independentemente um do outro são hidrogênio, (C1-C6)-alquila, (C3-C6)-cicloalquila, (C3-C6)-alquenila, (C3- C6)-alquinila,
[00155] RB3 é halogênio, (C1-C4)-alquila, (C1-C4)-haloalquila ou (C1-C4)-alcóxi,
[00156] mB é 1 ou 2;
[00157] por exemplo aqueles em que
[00158] RB1 = ciclopropila, RB2 = hidrogênio e (RB3) = 2-OMe ("ciprossulfamida", S4-1),
[00159] RB1 = ciclopropila, RB2 = hidrogênio e (RB3) = 5-Cl-2-OMe (S4-2),
[00160] RB1 = etila, RB2 = hidrogênio e (RB3) = 2-OMe (S4-3),
[00161] RB1 = isopropila, RB2 = hidrogênio e (RB3) = 5-Cl-2-OMe (S4-4) e
[00162] RB1 = isopropila, RB2 = hidrogênio e (RB3) = 2-OMe (S4-5);
[00163] S4c) compostos da classe de benzoilsulfamoilfenilureas da fórmula (S4c) como descrito em EP-A-365484, 1 RC O O O 3 (RC ) mC N N S N (S4c) 2
RC H O H em que
[00164] RC1, RC2 independentemente um do outro são hidrogênio, (C1-C8)-alquila, (C3-C8)-cicloalquila, (C3-C6)-alquenil, (C3- C6)-alquinila,
[00165] RC3 é halogênio, (C1-C4)-alquila, (C1-C4)-alcóxi, CF3,
[00166] mC é 1 ou 2;
[00167] por exemplo
[00168] 1-[4-(N-2-metoxibenzoilsulphamoil)fenil]-3-metilureia („metcamifeno", S4-6), 1-[4-(N-2-metoxibenzoilsulfamoil)fenil]-3,3-dimetilurea, 1-[4-(N-4,5-dimetilbenzoilsulfamoil)fenil]-3-metilureia;
[00169] S4d) compostos do tipo de N-fenilsulfoniltereftalamidas da fórmula (S4d) e sais dos mesmos, que são conhecidos, por exemplo, de CN 101838227, em que
[00170] RD4 é halogênio, (C1-C4)-alquila, (C1-C4)-alcóxi, CF3;
[00171] mD é 1 ou 2;
[00172] RD5 é hidrogênio, (C1-C6)-alquila, (C3-C6)-cicloalquila, (C2-C6)-alquenila, (C2-C6)-alquinila, (C5-C6)-cicloalquenila.
[00173] S5) Compostos ativos da classe de hidroxiaromáticos e derivados de ácido carboxílico aromátici-alifático (S5), por exemplo etil 3,4,5-triacetoxibenzoato, ácido 3,5-dimetóxi-4-hidroxibenzoico, ácido 3,5-dihidroxibenzoico, ácido 4-hidroxisalicílico, ácido 4- fluorossalicíclico, ácido 2-hidroxicinâmico, ácido 2,4-diclorocinâmico, como descrito em WO-A-2004/084631, WO-A-2005/015994, WO-A- 2005/016001.
[00174] S6) Compostos ativos da classe de 1,2-diidroquinoxalin-
2-onas (S6), por exemplo 1-metil-3-(2-tienil)-1,2-diidroquinoxalin-2-ona, 1-metil-3-(2-tienil)-1,2- diidroquinoxalina-2-tiona, cloridrato de 1-(2-aminoetil)-3-(2-tienil)-1,2- diidroquinoxalin-2-ona, 1-(2-metilsulfonilaminoetil)-3-(2-tienil)-1,2- diidroquinoxalin-2-ona, como descrito em WO-A-2005/112630.
[00175] S7) Compostos da classe de derivados de ácido difenilmetoxiacético (S7), por exemplo metil difenilmetoxiacetato (CAS-Reg.Nr. 41858-19-9) (S7-1), etil difenilmetoxiacetato, ou ácido difenilmetoxiacético, como descrito em WO-A-98/38856.
[00176] S8) Compostos da fórmula (S8), como descrito em WO-A-98/27049, em que os símbolos e índices têm os significados a seguir:
[00177] RD1 é halogênio, (C1-C4)-alquila, (C1-C4)-haloalquila, (C1- C4)-alcóxi, (C1-C4)-haloalcóxi,
[00178] RD2 é hidrogênio ou (C1-C4)-alquila,
[00179] RD3 é hidrogênio, (C1-C8)-alquila, (C2-C4)-alquenila, (C2- C4)-alquinila ou arila, em que cada um dos radicais contendo carbono mencionados acima, é não substituído ou substituído por um ou mais, preferivelmente por até três, radicais idênticos ou diferentes do grupo consistindo em halogênio e alcóxi; ou sais dos mesmos,
[00180] nD é um número inteiro de 0 a 2.
[00181] S9) Compostos ativos da classe de 3-(5- tetrazolilcarbonil)-2-quinolonas (S9), por exemplo 1,2-diidro-4-hidróxi- 1-etil-3-(5-tetrazolilcarbonil)-2-quinolona (CAS Reg. No.: 219479-18-2), 1,2-diidro-4-hidróxi-1-metil-3-(5-tetrazolilcarbonil)-2-quinolona (CAS Reg. No.: 95855-00-8), como descrito em WO-A-1999/000020.
[00182] S10) Compostos da fórmula (S10a) ou (S10b), como descrito em WO-A-2007/023719 e WO-A-2007/023764
[00183] em que
[00184] RE1 é halogênio, (C1-C4)-alquila, metóxi, nitro, ciano, CF3, OCF3
[00185] YE, ZE independentemente um do outro são O ou S,
[00186] nE é um número inteiro de 0 a 4,
[00187] RE2 é (C1-C16)-alquila, (C2-C6)-alquenila, (C3-C6)- cicloalquila, arila; benzila, halobenzila,
[00188] RE3 é hidrogênio ou (C1-C6)-alquila.
[00189] S11) Compostos ativos do tipo de compostos de oxiimino (S11), que são conhecidos como revestimentos de semente, tais como, por exemplo, "oxabetrinila" ((Z)-1,3-dioxolan-2-ilmetoxiimino- (fenil)acetonitrila) (S11-1), que é conhecido como protetor de revestimento de semente para painço (milhete) contra dano de metolaclor, "fluxofenim" (1-(4-clorofenil)-2,2,2-trifluoro-1-etanona O-(1,3-dioxolan- 2-ilmetil)oxima) (S11-2), que é conhecido como protetor de revestimento de semente para painço contra dano de metolaclor, e "ciometrinil" ou "CGA-43089" ((Z)-cianometoxiimino(fenil)acetonitrila) (S11-3), que é conhecido como protetor de revestimento de semente para painço contra dano de metolaclor.
[00190] S12) Compostos ativos da classe de isotiocromanonas (S12), tais como, por exemplo, metil [(3-oxo-1H-2-benzotiopiran-4(3H)-
ilideno)metóxi]acetato (CAS Reg. No.: 205121-04-6) (S12-1) e compostos relacionados de WO-A-1998/13361.
[00191] S13) Um ou mais compostos do grupo (S13): "anidrido naftálico " (anidrido 1,8-naftalenodicarboxílico) (S13-1), que é conhecido como protetor de revestimento de semente para milho contra dano de herbicida de tiocarbamato, "fenclorim" (4,6-dicloro-2-fenilpirimidina) (S13-2), que é conhecido como protetor para pretilaclor em arroz semeado, "flurazol" (benzil 2-cloro-4-trifluorometil-1,3-tiazol-5-carboxilato) (S13-3), que é conhecido as protetor de revestimento de semente para milhete (painço) contra dano (avaria) de alaclor e metolaclor, "CL 304415" (CAS Reg. No.: 31541-57-8) (ácido 4-carbóxi-3,4-diidro-2H-1-benzopiran-4-acético) (S13-4) de American Cyanamid, que é conhecido como protetor para milho contra dano de imidazolinona, "MG 191" (CAS Reg. No.: 96420-72-3) (2-diclorometil-2-metil-1,3- dioxolano) (S13-5) de Nitrokemia, que é conhecido como protetor para milho, "MG 838" (CAS Reg. No.: 133993-74-5) (2-propenil 1-oxa-4-azaspiro[4.5]decano-4-carboditioato) (S13-6) de Nitrokemia, "dissulfoton" (O,O-dietil S-2-etiltioetil fosforoditioato) (S13-7), "dietolato" (O,O-dietil O-fenil fosforotioato) (S13-8), "mefenato" (4-clorofenil metilcarbamato) (S13-9).
[00192] S14) Compostos ativos que, além de um efeito herbicida contra plantas nocivas, têm também um efeito protetor sobre plantas de colheita tais como arroz, tais como, por exemplo, "dimepiperato" ou "MY 93" (S-1-metil-1-feniletil piperidina-1- carbotioato), que é conhecido como protetor para arroz contra o dano de herbicida molinato, "daimuron" ou "SK 23" (1-(1-metil-1-feniletil)-3-p-tolilureia), que é conhecido como protetor para arroz contra dano de herbicida imazossulfurona, "cumiluron" = "JC 940" (3-(2-clorofenilmetil)-1-(1-metil-1-feniletil)ureia, ver JP-A-60087254), que é conhecida as protetora para arroz contra algum dano de herbicida, "metoxifenona" ou "NK 049" (3,3'-dimetil-4-metoxibenzofenona), que é conhecido como protetora para arroz contra algum dano de herbicida, "CSB" (1-bromo-4-(clorometilsulfonil)benzeno) de Kumiai (CAS Reg. No. 54091-06-4), que é conhecido como protetor contra algum dano de herbicida no arroz.
[00193] S15) Compostos da fórmula (S15) ou seus tautômeros,
[00194] como descrito em WO-A-2008/131861 e WO-A- 2008/131860,
[00195] em que
[00196] RH1 é (C1-C6)-haloalquila,
[00197] RH2 é hidrogênio ou halogênio,
[00198] RH3, RH4 independentemente um do outro são hidrogênio, (C1-C16)-alquila, (C2-C16)-alquenila ou (C2-C16)-alquinila, em que cada um dos 3 últimos radicais mencionados é não substituído ou substituído, por um ou mais radicais do grupo que consiste em halogênio, hidróxi, ciano, (C1-C4)-alcóxi, (C1-C4)- haloalcóxi, (C1-C4)-alquilatio, (C1-C4)-alquilamino, di-[(C1-C4)-alquil]- amino, [(C1-C4)-alcóxi]-carbonila, [(C1-C4)-haloalcóxi]-carbonila, (C3-C6)-cicloalquila não substituída ou substituída, fenila não substituída ou substituída, e heterociclila não substituída ou substituída;
ou (C3-C6)-cicloalquila, (C4-C6)-cicloalquenila, (C3-C6)- cicloalquila que está em um sítio do anel condensado, com 4 a 6-membros de anel carboxílico saturados ou não saturados, ou (C4-C6)-cicloalquenila que está em um sítio (site) do anel condensado com 4 a 6-membros de anel carboxílico saturado ou não saturado, em que cada um dos 4 últimos radicais mencionados é não substituído ou substituído por um ou mais radicais do grupo consistindo em halogênio, hidróxi, ciano, (C1-C4)-alquila, (C1-C4)- haloalquila, (C1-C4)-alcóxi, (C1-C4)-haloalcóxi, (C1-C4)-alquilatio, (C1-C4)-alquilamino, di-(C1-C4)-alquila]-amino, [(C1-C4)-alcóxi]- carbonila, [(C1-C4)-haloalcóxi]-carbonila, não substituída ou substituída (C3-C6)-cicloalquila, fenila não substituída ou substituída, e heterociclila não substituída ou substituída; ou
[00199] RH3 é (C1-C4)-alcóxi, (C2-C4)-alquenilóxi, (C2-C6)- alquiniloxi ou (C2-C4)-haloalcóxi, e
[00200] RH4 é hidrogênio ou (C1-C4)-alquila, ou
[00201] RH3 e RH4 juntos com o N-átomo diretamente ligados são um anel heterocíclico de 4 a 8-membros, que pode conter ainda átomos de anel hetero além de N-átomo, preferivelmente até dois átomos de anel hetero adicionais, do grupo consistindo em N, O e S, e que é não substituído ou substituído por um ou mais radicais do grupo consistindo em halogênio, ciano, nitro, (C1-C4)-alquila, (C1-C4)- haloalquila, (C1-C4)-alcóxi, (C1-C4)-haloalcoxi e (C1-C4)-alquiltio.
[00202] S16) Compostos ativos que são principalmente usados como herbicidas, mas também têm efeito protetor sobre plantas de colheita, por exemplo ácido (2,4-diclorofenóxi)acético (2,4-D), ácido (4-clorofenóxi)acético, ácido (R,S)-2-(4-cloro-o-tolilóxi)propiônico (mecoprop), ácido 4-(2,4-diclorofenóxi)butírico (2,4-DB),
ácido (4-cloro-o-tolilóxi)acético (MCPA), ácido 4-(4-cloro-o-tolilóxi)butírico, ácido 4-(4-clorofenóxi)butírico, 3,6-dicloro-2-metoxibenzoico (dicamba), 1-(etoxicarbonil)etil 3,6-dicloro-2-metoxibenzoato (lactidiclor-etila). Agentes de controle biológico:
[00203] Como usado aqui no presente, "controle biológico" é definido como controle de um patógeno e/ou inseto e/ou um acarídeo e/ou a nematóide, através do uso de um segundo organismo. Mecanismos conhecidos de controle biológico incluem bactérias entéricas, que controlam podridão de raiz por fungos competindo de forma clara, por espaço na superfície da raiz. Toxinas bacterianas, tais como antibióticos, têm sido usados para controlar patógenos. A toxina pode ser isolada e aplicada diretamente na planta, ou as espécies bacterianas podem ser administradas de maneira a produzir toxina no local.
[00204] Agentes de controle biológico incluem em particular bactérias, fungos ou leveduras, protozoários, vírus, nematóides entomopatogênicos, Inoculantes e botânicos e/ou mutantes deles, que têm todas as características identificadoras da respectiva cepa, e/ou a metabólito produzido pela respectiva cepa que exibe atividade contra insetos, ácaros, nematóides e/ou fitopatógenos.
[00205] De acordo com a invenção, agentes de controle biológico que são resumidos sob o termo "bactéria" incluem bactérias formando esporos, bactérias colonizando raízes, ou bactérias e seus metabólitos úteis como inseticidas, -nematicidas, miticidas ou -fungicidas biológicos, ou emendas do solo melhorando a saúde e o crescimento da planta.
[00206] Agentes de controle biológico de acordo com a invenção, em combinação com boa tolerância da planta e toxidade favorável para animais de sangue quente, e sendo bem tolerados pelo ambiente, são apropriados para proteger plantas órgão de plantas, para aumentar os rendimentos da colheita, para melhorar a qualidade do material colhido, e para controlar pestes animais, em particular insetos, araquinídeos, helmintos, nematoides e moluscos, que são encontrados na agricultura, na horticultura, em criação de animais domésticos, em florestas, em jardins e instalações de lazer, na proteção de produtos armazenados e de materiais, e no setor de higiene. Eles podem ser preferivelmente empregados como agentes de proteção das plantas. Eles são ativos contra espécies normalmente sensíveis de resistentes, e contra todo ou alguns estágios de desenvolvimento. Agentes de controle biológico incluem, em particular, bactérias, fungos ou leveduras, protozoários, vírus, nematóides entomopatogênicos, produtos produzidos por microorganismos incluindo proteínas ou metabólitos secundários e botânicos, especialmente extratos botânicos.
[00207] De acordo com a invenção, o agente de controle biológico pode ser empregado ou usado em qualquer estado fisiológico, tais como ativo ou inerte (dormente). Inseticidas/acaricidas/nematicidas:
[00208] Os ingredientes ativos especificados aqui no presente por seu "nome comum" são conhecidos e descritos, por exemplo, no Manual de Pesticida ("The Pesticide Manual", 14ª Ed., British Crop Protection Council 2006), ou pode ser pesquisado na internet (por exemplo http://www.alanwood.net/pesticides).
[00209] (1) Inibidores de acetilcolinesterase (AChE), por exemplo, carbamatos, por exemplo Alanicarb, Aldicarb, Bendiocarb, Benfuracarb, Butocarboxim, Butoxicarboxim, Carbaril, Carbofurano, Carbossulfano, Etiofencarb, Fenobucarb, Formetanato, Furatiocarb, Isoprocarb, Metiocarb, Metomil, Metolcarb, Oxamil, Pirimicarb,
Propoxur, Tiodicarb, Tiofanox, Triazamato, Trimetacarb, XMC e Xililcarb ou organofosfatos, por exemplo, Acefato, Azametifos, Azinfos- etil, Azinfos-metil, Cadusafos, Cloretoxifos, Clorfenvinfos, Clormefos, Clorpirifos, Clorpirifos-metil, Coumafos, Cianofos, Demeton-S-metil, Diazinona, Diclorvos/DDVP, Dicrotofos, Dimetoato, Dimetilvinfos, Dissulfotona, EPN, Etiona, Etoprofos, Famfur, Fenamifos, Fenitrotiona, Fentiona, Fostiazato, Heptenofos, Imiciafos, Isofenfos, Isopropil O- (metoxiaminotio-fosforil)salicilato, Isoxation, Malation, Mecarbam, Metamidofos, Methidathion, Mevinfos, Monocrotofos, Naled, Ometoato, Oxidemeton-metil, Paration, Paration-metil, Fentoato, Forato, Fosalona, Fosmete, Fosfamidona, Foxim, Pirimifos-metil, Profenofos, Propetamfos, Protiofos, Piraclofos, Piridafentiona, Quinalfos, Sulfotep, Tebupirinfos, Temefos, Terbufos, Tetraclorvinfos, Tiometon, Triazofos, Triclorfona e Vamidotiona.
[00210] (2) Antagonistas do canal de cloreto bloqueado por GABA, por exemplo ciclodieno organoclorinas, por exemplo Clordano e Endossulfano, ou fenilpirazóis (fiproles), por exemplo Etiprole e Fipronil.
[00211] (3) Moduladores do canal de sódio / bloqueadores de canal de sódio dependentes da voltagem, por exemplo piretroides, por exemplo Acrinatrina, Aletrina, d-cis-trans Aletrina, d-trans Aletrina, Bifentrina, Bioaletrina, Bioaletrina S-ciclopentenil isômero, Bioresmetrina, Cicloprotrina, Ciflutrina, beta-Ciflutrina, Cialotrina, lambda-Cialotrina, gama-Cialotrina, Cipermetrina, alfa-Cipermetrina, beta-Cipermetrina, teta-Cipermetrina, zeta-Cipermetrina, Cifenotrina [(1R)-trans isômeros], Deltametrina, Empentrina [(EZ)-(1R) isômeros), Esfenvalerato, Etofenprox, Fenpropatrina, Fenvalerato, Flucitrinaato, Flumetrina, tau-Fluvalinato, Halfenprox, Imiprotrina, Kadetrina, Momfluorotrina, Permetrina, Fenotrina [(1R)-trans isômero), Praletrina, Piretrinae (piretrum), Resmetrina, Silafluofeno, Teflutrina, Tetrametrina,
Tetrametrina [(1R) isômeros)], Tralometrina e Transflutrina ou DDT ou Metoxiclor.
[00212] (4) Agonistas receptores de acetilcolina nicotinico (nAChR), por exemplo neonicotinoides, por exemplo Acetamipride, Clotianidine, Dinotefurano, Imidaclopride, Nitenpiram, Tiaclopride e Tiametoxam ou Nicotina ou Sulfoxaflor ou Flupiridafurona.
[00213] (5) Ativadores alostéricos de receptor de acetilcolina nicotínico (nAChR), por exemplo espinosins, por exemplo Spinetoram e Spinosad.
[00214] (6) Ativadores do canal de cloreto, por exemplo avermectinas/milbemicinas, por exemplo Abamectina, Benzoato de Emamectina, Lepimectina e Milbemectina.
[00215] (7) Imitações do hormônio juvenil, por exemplo, análogos do hormônio juvenil, por exemplo Hidropreno, Kinopreno e Metopreno ou Fenoxicarb ou Piriproxifeno.
[00216] (8) Iibidores de miscelânea não específica (multi-sites), por exemplo, haletos de alquila, por exemplo Metil brometo e outros haletos de alquila; ou Cloropicrina ou fuotreto de Sulfurila ou Borax ou Tartar emético.
[00217] (9) Bloqueadores alimentadores de homopteran seletivo, por exemplo Pimetrozina ou Flonicamida.
[00218] (10) Inibidores do crescimento de ácaros, por exemplo Clofentezina, Hexitiazox e Diflovidazina ou Etoxazol.
[00219] (11) Disruptores microbianos de membranas intestinais de inseto, por exemplo, subespécies israelenses de Bacilus turingiensis, Bacillus sphaericus, subespécies de Bacillus turingiensis aizawai, subespécies de Bacillus turingiensis subespecies kurstaki, subespecies Bacillus turingiensis tenebrionis e proteínas de colheita BT: Cry1Ab, Cry1Ac, Cry1Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb, Cry34/35Ab1.
[00220] (12) Inibidores de síntese ATP mitocondrial, por exemplo Diafentiuron ou miticidas organotinas, por exemplo Azociclotin, Ciexatin e óxido de Fenbutatin ou Propargita ou Tetradifon.
[00221] (13) Desacopladores de fosforilação oxidativa através de disrrupção do gradiente de próton, por exemplo Clorfenapir, DNOC e Sulfluramida.
[00222] (14) Bloqueadores de canal receptor de acetilcolina nicotínica (nAChR), por exemplo Bensultap, cloridrato de Cartap, Tiociclam e Tiossultap-sódio.
[00223] (15) Inibidores de biossíntese de quitina, tipo 0, por exemplo Bistrifluron, Clorfluazuron, Diflubenzuron, Flucicloxuron, Flufenoxuron, Hexaflumuron, Lufenuron, Novaluron, Noviflumuron, Teflubenzuron e Triflumuron.
[00224] (16) Inibidores de biossíntese de quitina, tipo 1, por exemplo Buprofezina.
[00225] (17) Disruptores de muda, por exemplo Ciromazina.
[00226] (18) Agonistas receptores de ecdisona, por exemplo Cromafenozida, Halofenozida, Metoxifenozida e Tebufenozida.
[00227] (19) Agonistas receptores de octopamina, por exemplo Amitraz.
[00228] (20) Inibidores do transporte de elétron do complexo mitocondrial III, por exemplo Hidrametilnona ou Acequinocil ou Fluacripirim.
[00229] (21) Inibidores do transporte de elétron do complexo mitocondrial I, por exemplo, acaricidas METI, por exemplo Fenazaquino, Fenpiroximato, Pirimidifeno, Piridabeno, Tebufenpirade e Tolfenpirade ou Rotenona (Derris).
[00230] (22) Bloqueadores do canal de sódio dependentes da voltagem, por exemplo, Indoxacarb ou Metaflumizona.
[00231] (23) Inibidores de acetil CoA carboxilase, por exemplo derivados de ácido tetrônico e tetrâmico, por exemplo, Spirobudiclofeno, Spirodiclofeno, Spiromesifeno e Spirotetramato.
[00232] (24) Inibidores de transporte de elétron do complexo IV mitocondrial, por exemplo fosfinas, por exemplo Fosforeto de alumínio, Fosforeto de cálcio, Fosfina e Fosforeto de Zinco ou Cianida.
[00233] (25) Inibidores do transporte de elétron Mitocondrial de complexo II, por exemplo Cienopirafeno e Ciflumetofeno.
[00234] (28) Moduladores do receptor de Rianodina, por exemplo diamidas, por exemplo, Clorantraniliprol, Ciantraniliprol, Flubendiamida e Tetracloroantraniliprol.
[00235] Ingredientes ativos adicionais com modo de ação desconhecido ou incerto, por exemplo Afidopiropeno, Afoxolaner, Azadiraquitina, Benclotiazol, Benzoximata, Bifenazato, Broflanilida, Bromopropilato, Quinometionato, Criolita, Ciclaniliprol, Cicloxaprida, Cialodiamida Dicloromezotiaz, Dicofol, Diflovidazina, Flometoquina, Fluazaindolizina, Fluensulfona, Flufenerim, Flufenoxistrobina, Flufiprol, Fluexafona, Fluopiram, Fluralaner, Fluxametamida, Fufenozida, Guadipir, Heptaflutrina, Imidaclotiz, Iprodiona, Lotilaner, Meperflutrina, Paicongdinge, Piflubumida, Piridalil, Pirifluquinazona, Piriminostrobina, Sarolaner, Tetrametilflutrina, Tetraniliprol, Tetraclorantraniliprol, Tioxazafeno, Tiofluoximato, Triflumezopirim e Iodometano; além disso, produtos baseados em Bacillus firmus (incluindo mas não limitado à cepa CNCM I-1582, tais como, por exemplo, VOTiVO TM, BioNem) ou um dos compostos ativos conhecidos a seguir: 1-{2-flúor-4-metil-5- [(2,2,2-trifluoretil)sulfinil]fenil}-3-(trifluorometil)-1H-1,2,4-triazol-5-amina (conhecidos de WO2006/043635), {1'-[(2E)-3-(4-clorofenil)prop-2-en-1- il]-5-fluorospiro[indol-3,4'-piperidin]-1(2H)-il}(2-cloropiridin-4- il)metanona (conhecidos de WO2003/106457), 2-cloro-N-[2-{1-[(2E)-3- (4-clorofenil)prop-2-en-1-il]piperidin-4-il}-4- (trifluorometil)fenil]isonicotinamida (conhecidos de WO2006/003494),
3-(2,5-dimetilfenil)-4-hidróxi-8-metóxi-1,8-diazaspiro[4.5]dec-3-en-2- ona (conhecido de WO2009/049851), 3-(2,5-dimetilfenil)-8-metóxi-2- oxo-1,8-diazaspiro[4.5]dec-3-en-4-il etil carbonato (conhecido de WO2009/049851), 4-(but-2-in-1-ilóxi)-6-(3,5-dimetilpiperidin-1-il)-5- fluoropirimidina (conhecido de WO2004/099160), 4-(but-2-in-1-ilóxi)-6- (3-clorofenil)pirimidina (conhecido de WO2003/076415), PF1364 (CAS-Reg.No. 1204776-60-2), metil 2-[2-({[3-bromo-1-(3-cloropiridin-2- il)-1H-pirazol-5-il]carbonil}amino)-5-cloro-3-metilbenzoil]-2- metilidrazinacarboxilato (conhecido de WO2005/085216), metil 2-[2- ({[3-bromo-1-(3-cloropiridin-2-il)-1H-pirazol-5-il]carbonil}amino)-5- ciano-3-metilbenzoil]-2-etilidrazinacarboxilato (conhecido de WO2005/085216), metil 2-[2-({[3-bromo-1-(3-cloropiridin-2-il)-1H- pirazol-5-il]carbonil}amino)-5-ciano-3-metilbenzoil]-2- metilidrazinacarboxilato (conhecido de WO2005/085216), metil 2-[3,5- dibromo-2-({[3-bromo-1-(3-cloropiridin-2-il)-1H-pirazol-5- il]carbonil}amino)benzoil]-2-etilidrazinecarboxilato (conhecido de WO2005/085216), N-[2-(5-amino-1,3,4-tiadiazol-2-il)-4-cloro-6- metilfenil]-3-bromo-1-(3-cloropiridin-2-il)-1H-pirazol-5-carboxamida (conhecido de CN102057925), 8-cloro-N-[(2-cloro-5- metoxifenil)sulfonil]-6-(trifluorometil)imidazo[1,2-a]piridina-2- carboxamida (conhecido de WO2009/080250 ), N-[(2E)-1-[(6- cloropiridin-3-il)metil]piridin-2(1H)-ilideno]-2,2,2-trifluoroacetamida (conhecido de WO2012/029672 ), 1-[(2-cloro-1,3-tiazol-5-il)metil]-4- oxo-3-fenil-4H-pirido[1,2-a]pirimidin-1-ium-2-olato (conhecido de WO2009/099929), 1-[(6-cloropiridin-3-il)metil]-4-oxo-3-fenil-4H- pirido[1,2-a]pirimidin-1-ium-2-olato (conhecido de WO2009/099929 ), 4-(3-{2,6-dicloro-4-[(3,3-dicloroprop-2-en-1-il)óxi]fenoxi}propóxi)-2- metóxi-6-(trifluorometil)pirimidina (conhecido de CN101337940), N-[2- (terc-butilcarbamoil)-4-cloro-6-metilfenil]-1-(3-cloropiridin-2-il)-3- (fluorometóxi)-1H-pirazol-5-carboxamida (conhecido de
WO2008/134969), butil [2-(2,4-diclorofenil)-3-oxo-4-oxaspiro[4.5]dec-1- en-1-il] carbonat(conhecido de CN 102060818), , 3E)-3-[1-[(6-cloro-3- piridil)metil]-2-piridilidene]-1,1,1-trifluoro-propan-2-one (conhecido de WO2013/144213), N-(metilsulfonil)-6-[2-(piridin-3-il)-1,3-thiazol-5- il]piridine-2-carboxamida (conhecido de WO2012/000896), N-[3- (benzilcarbamoil)-4-clorofenil]-1-metil-3-(pentafluoroetil)-4- (trifluorometil)-1H-pirazol-5-carboxamida (conhecido de WO2010/051926), 5-bromo-4-cloro-N-[4-cloro-2-metil-6- (metilcarbamoil)fenil]-2-(3-cloro-2-piridil)pirazol-3-carboxamido (conhecido de CN103232431), ), Tioxazafen, 4-[5-(3,5-diclorofenil)-4,5- diidro-5-(trifluorometil)-3-isoxazolil]-2-metil-N-(cis-1-oxido-3-thietanil)- benzamida, 4-[5-(3,5-diclorofenil)-4,5-diidro-5-(trifluorometil)-3- isoxazolil]-2-metil-N-(trans-1-oxido-3-thietanil)-benzamida e 4-[(5S)-5- (3,5-diclorofenil)-4,5-diidro-5-(trifluorometil)-3-isoxazolil]-2-metil-N-(cis- 1-oxido-3-tietanil)benzamida (conhecido de WO 2013050317 A1), N- [3-cloro-1-(3-piridinil)-1H-pirazol-4-il]-N-etil-3-[(3,3,3- trifluoropropil)sulfinil]-propanamida (+)-N-[3-cloro-1-(3-piridinil)-1H- pirazol-4-il]-N-etil-3-[(3,3,3-trifluoropropil)sulfinilpropanamida eand (-)- N-[3-cloro-1-(3-piridinil)-1H-pirazol-4-il]-N-etil-3-[(3,3,3- trifluoropropil)sulfinil]-propanamida (conhecido de WO 2013162715 A2, WO 2013162716 A2, US 20140213448 A1), 5-[[(2E)-3-cloro-2-propen- 1-il]amino]-1-[2,6-dicloro-4-(trifluorometil)fenil]-4-[(trifluorometil)sulfinil]- 1H-pirazol-3-carbonitrile (conhecido de CN 101337937 A), 3-bromo-N- [4-cloro-2-metil-6-[(metilamino)thioxometil]fenil]-1-(3-cloro-2-piridinil)- 1H-pirazol-5-carboxamida, (Liudaibenjiaxuanan, conhecido de CN 103109816 A); N-[4-cloro-2-[[(1,1-dimetiletil)amino]carbonil]-6- metilfenil]-1-(3-cloro-2-piridinil)-3-(fluorometóxi)-1H-Pirazol-5- carboxamida (conhecido de WO 2012034403 A1), N-[2-(5-amino-1,3,4- thiadiazol-2-il)4-cloro-6-metilfenil]-3-bromo-1-(3-cloro-2-piridinil)-1H- pirazol-5-carboxamida (conhecido de WO 2011085575 A1), 4-[3-[2,6-
dicloro-4-[(3,3-dicloro-2-propen-1-il)óxi]fenóxi]propóxi]-2-metóxi-6- (trifluorometil)-pirimidina (conhecido de CN 101337940 A); (2E)- e 2(Z)-2-[2-(4-cianofenil)-1-[3-(trifluorometil)fenil]etilideno]-N-[4- (difluorometóxi)fenil]-hydrazinecarboxamida (conhecido de CN 101715774 A); éster de ácido 3-(2,2-dicloroetenil)-2,2-dimetil-4- (1H-benzimidazol-2-il)fenil-ciclopropanocarboxílico (conhecido de CN 103524422 A); (4aS)-7-cloro-2,5-diidro-2-[[(metoxicarbonil)[4- [(trifluorometil)tio]fenil]amino]carbonil]-indeno[1,2-e][1,3,4]oxadiazinaa- 4a(3H)-éster de metil ácido carboxílico (conhecido de CN 102391261 A).
[00236] Compostos ativos preferidos são selecionados do grupo compreendendo SDH-Inibidores, nAChR-Agonistas (incluindo neonicotinóides), clorotica incluindo inibidores de PDS (HRAC F1) e inibidores de HPPD (HRAC F2) e carboxamidas de tiadiazol / indutores de defesa do hospedeiro.
[00237] Compostos ativos mais preferidos para encapsulação de acordo com a invenção, são selecionados do grupo compreendendo Fluopiram, Flupiradifurona, Diflufenicano, Isoxaflutol, Imidaclopride e Isotianil.
[00238] Compostos ativos mais preferidos Fluopiram, Diflufenicano, Isoxaflutol.
[00239] Preferivelmente, o ativo é sólido na temperatura ambiente, em que no presente a temperatura ambiente, no pedido do momento, é 20°C se não for de outra maneira definido.
[00240] Além do mais, o ativo é insolúvel na água, em que no presente insolúvel significa uma solubilidade de menos do que 1 g/l, na temperatura ambiente e pH 7.
[00241] Preferivelmente, as composições de ingrediente ativo com Lignina do pedido do momento, ou as formulações correspondentes podem ser usadas em Dicotiledônios, por exemplo Soja (por exemplo
FLU, DFF) tomate (por exemplo FLU), pepino (por exemplo FLU) e pimenta ou Monocotiledônios, como milho (por exemplo, IFT), ou cereais. Exemplos:
[00242] Exemplo 1: (efeitos indesejáveis reduzidos)
[00243] Figura I mostra a área de cotiledônio vs. Composições testadas
[00244] Figura II mostra altura da planta vs. composições testadas
[00245] A Lignina, BiopivaTM 190, foi recebida como um pó e formulada em 15% em p/p de soluções de propileno glicol e etanol. Para cada mistura, os componentes foram combinados de acordo com as proporções descritas na Tabela 1 e permitidos agitar durante a noite. Tabela 1. Composição de soluções de BiopivaTM 190 Massa de Componente (g) Entrada BiopivaTM 190 Propileno glicol Etanol Água 1 15 75 0 10 2 15 0 85 0
[00246] Sementes de soja (17030081) com uma conta de semente média de 6186.4 sementes/kg, foram tratadas com revestimentos de polímeros consecutivos, em uma proporção fixa de aplicação de FLU de 0.075 mg/semente. BiopivaTM 190 aplicada para 200 g de semente de soja como uma solução (Tabela 2, Entradas 5a, 6a, 7a, 8a) e permitida secar completamente (0,15 mg de BiopivaTM 190 sólidos / semente). Subsequentemente, um segundo revestimento consecutivo contendo FLU (Ilevo® FS 600) e água (Tabela 2, Entradas 5b, 6b, 7b, 8b) foram aplicados para as sementes mencionadas acima, usando a mesma técnica de tratamento de jarra de vidro. Tabela 2. Aplicação da formulação e massa de tratamento de semente
Massa de Componente Tratamento Massa (g) (g) Entrad Amostra ID Polím FLU FS Água Total Em 1 kg semente a ero 600 1a Revestimento Principal : 6,35 0,00 0,00 6,35 Dados em BiopivaTM 190 (15% em 200g de propileno glicol/H2O) semente removida 1b Revestimento 0,00 0,97 4,11 5,08 Secundário: Ilevo® FS 600 2a Revestimento Principal: 6,35 0,00 0,00 6,35 BiopivaTM 190 (15% em etanol) 2b Revestimento 0,00 0,97 4,11 5,08 Secundário: Ilevo® FS 600
2.2.1 Plantação e Crescimento
[00247] Avaliações da estufa foram conduzidas usando um solo de barro arenoso pasteurizado, consistindo em menos de 1% de matéria orgânica do solo, e um mínimo de 20 reps para cada tratamento. Três opções de plantação foram usadas com base no espaço da estufa e tamanho do experimento 1) 60 bandejas de células 2) 30 bandejas de células e 6 em potes isolados. Antes da plantação 6 in., os potes foram umedecidos com 150 mL de água por pote, enquanto 30 e 60 bandejas de células foram irrigadas por 10 s com uma fonte de água suspensa. Subsequentemente, um furo de 2 cm foi criado e 1 semente foi plantada por furo e coberta com solo. As plantas foram crescendo por aproximadamente 21 d em uma temperatura, e a estuda regulada na duração do dia. A água foi uniformemente suprida em intervalos regulares, através de todo o período de crescimento. Todas as experiências demonstraram uma taxa de germinação de 90% ou mais.
2.2.2 Análise do Cotiledônio
[00248] Cotiledônios foram colhidos quando as folhas unifoliadas atingiram completo desenvolvimento, e foram analisadas para o efeito halo. Especificamente, os cotiledônio foram removidos e analisados, quando as folhas unifoliadas emergiram totalmente para todas as amostras, e as primeiras folhas trifoliadas estavam presentes, mas não totalmente desenvolvidas. O topo de cada cotiledônio foi escaneado e analisado, usando o software WinFolia que mediu a área total da folha, área da folha saudável, e a área halo. A diferenciação entre área de cotiledônio saudável e halo, foi determinada usando análise de varredura da cor, em que regiões mais escuras significaram área halo, e as regiões verdes significaram tecido da folha saudável.
2.2.3 Análise do Peso
[00249] Alturas das plantas foram tipicamente medidas em aproximadamente 7 DAP, que é quando as folhas unifoliadas primeiro emerges, e começam a se desenvolver e a 14 DAP, ou quando o primeiro trifoliato emergiu completamente. Tabela 3. Resultados de mitigação do halo de biopiva e altura da planta Cotiledônio Folha Área Resultdos 2 (cm ) Entrad Amostra ID Revestim Total Saudá Halo % Planta a ento vel Halo Height (cm) 1 UTC na 1,8112 1,8109 0,0003 0,02 8,09 2 Ilevo® FS 600 na 1,2694 1,1132 0,1563 12,31 8,12 3 BiopivaTM 190 (in Consecuti 1,5175 1,4100 0,0814 5,37 8,53 propileno glicol/H2O) vo & Ilevo® FS 600 (BAYER) 4 BiopivaTM 190 (in Consecuti 1,6467 1,5652 0,1209 7,34 8,53 etanol) & Ilevo® FS vo 600 (BAYER) Exemplo 2: (Teste da Coluna Para Comportamento Molhado)
[00250] Um método baseado na coluna do solo foi usado para caracterizar o comportamento de lixiviação de Isoxaflutol. Para este fim, uma coluna vertical (diâmetro de 11cm, altura 17cm) com uma extremidade do fundo com orifícios, foi parcialmente preenchida com uma camada comprimida de adubo de pinho, com no topo uma camada comprimida de uma mistura de solo (1 parte do solo de argila + 3,7 partes de areia). A coluna com a extremidade do fundo imersa em um banho de água, é deixada durante a noite para umidificar o solo pelas forças capilares. Subsequentemente, caldos de spray foram preparados através da diluição de ForDor® 75 WG (com 75% em peso de Isoxaflutol) e pulverizado no topo da coluna do solo, para obter uma taxa de aplicação de 100 g ai/ha. Nos exemplos de acordo com a invenção, soluções de Lignina de papel grosso foram adicionadas ao caldo de pulverização subsequentemente para a formulação de Isoxaflutol, como mostrado nas tabelas abaixo.
[00251] Consequentemente, depois de um período de 5 horas secando, a coluna do solo tratada foi molhada pela chuva por 20 minutos, com taxa de 20 L H2O/m2. Depois do evento da chuva, as colunas foram viradas para 90 graus para cortar uma fenda horizontal (2,5 cm de largura e 14 cm de comprimento), que possibilitou a semeadura das sementes de grama, e o seu crescimento da extremidade do topo para a extremidade do fundo da coluna do solo. Depois de 3 semanas de incubação sob condições de umidade, o crescimento de ambas, raiz & folha foi quantificado. Não só o peso de secagem do sistema de raiz e folhagem foi medido, mas também o comprimento da zona de inibição da raiz. O comprimento dessa zona de inibição em que o crescimento da raiz é fortemente reduzido, caracteriza a profundida de lixiviação de herbicida durante o evento da chuva. Os experimentos foram realizados em triplicata, os resultados expressos como média do meio.
Tabela 4: Aplica- 1. Isoxaflutol WG 75 dissolvido em caldo e homogeneizado ção
2. Subsequentemente lignina foi adicionada para IFT contendo caldo enquanto agitado.
Aplicação Ref. Ex. 5 Ex. 6 ForDor ® WG 75 x x x Lignina de papel grosso premix B x Lignina de papel grosso premix A x Dados do caldo de pulverização kg /ha % em caldo de pulveri- zação Taxa de IFT 0,10 Lignina de papel grosso premix TK 12,30 1,51 10 ForDor ® WG 75 0,133 0,0164 Volume de pulverização (L/ha) 815 Tabela 5: Amostras Ex. 5 Ex. 6 Lignina de papel grosso premix A B w% w% Biopiva 190 10 10 Rhodiasolv Polarclean (Solvay) 90 Genagen NBP (Clariant) 90 Tabela 6: Resultados
Lignina de Lignina de papel papel Fordor grosso grosso premix A premix B Aplicação não tratado Ref Ex.5 Ex. 6 Zona de inibição funda (cm) 0 8,4 4,13 4,87 Biomassa de rebentos (peso seco, g) 1,05 0,58 0,89 0,89 Biomassa de raiz (peso seco, g) 1,89 0,42 1,74 1,82
[00252] Como pode ser visto na tabela acima como também na Figura 3, a combinação do ativo com Lignina no caldo leva à mobilidade significativamente reduzida, e respectivamente menos lixiviação do ativo no solo, enquanto a eficácia é mantida na área, em que o ativo foi retido.
[00253] Em consequência, a eficácia a longo prazo do ativo no solo é intensificada.
Claims (19)
1. Composição de ingrediente ativo de lignina, caracterizado pelo fato de que compreende a) o ingrediente ativo que é selecionado do grupo de fungicidas, herbicidas, inseticidas, nematicidas, indutores de defesa do hospedeiro, b) uma lignina c) o solvente é selecionado do grupo de solventes solúveis na água. d) auxiliares e / ou adjuvantes adicionais opcionais, e e) água opcional.
2. Composição de Lignina de ingrediente ativo de acordo com reivindicação 1, caracterizada pelo fato de que no presente o solvente b) é selecionado do grupo consistindo em mono-álcoois (C1- C4-álcoois, mais preferivelmente C1-C3-álcoois), propileno glicol, N- Butilpirrolidona (NBP) e Metil-5-(dimetilamino)-2-metil-5-oxopentanoato (por exemplo, Rhodiasolv® Polarclean, também conhecido como ácido pentanoico, 5-(dimetilamino)-2-metil-5-oxo-, metil éster), N,N-dimetil lactamida (CAS Nr: 35123-06-9), Dimetil isosorbide (CAS Nr. 5306-85- 4), monobutiléter de dietileno glicol (Cas Nr. 107-98-2), citrato de Trietil (CAS Nr. 77-93-0), triacetato de glicerol (CAS Nr: 102-76-1), 1-metil-2- pirrolidona (CAS Nr. 872-50-4) e diacetato de propileno glicol (CAS Nr: 623-84-7),3.
3. Composição de lignina de ingrediente ativo, de acordo com qualquer uma das reivindicaçõesprecedentesde acordo com a reivindicação 1 ou 2, caracterizada pelo fato de que o ingrediente ativo é uma herbicida.
4. Composição de lignina de ingrediente ativo de acordo com as reivindicações 1 a 3, caracterizada pelo fato de que no presente o ingrediente ativo é um nematicida.
5. Composição de lignina de ingrediente ativo de acordo com qualquer uma das reivindicações precedentes, caracterizada pelo fato de que no presente o ingrediente ativo é selecionado do grupo de diflufenicano (DFF), isoxaflutol (IFT) e indaziflam (IAF) e fluopiram (FLU).
6. Composição de lignina de ingrediente ativo de acordo com qualquer uma das reivindicações precedentes, caracterizada pelo fato de que no presente a proporção do ativo a) para lignina b) é de 1:0,1 a 1:5, preferivelmente de 1:0,5 a 1:20, mais preferido de 1: 2 a 1: 18 e mais preferido de 1: 4 a 1:15.
7. Composição de lignina de ingrediente ativo de acordo com qualquer uma das reivindicações precedentes, caracterizada pelo fato de que no presente a proporção de b / c é preferível de 1:4 para 1:40, mais preferivelmente de 1:5 para 1:20, ainda preferida de 1:5 para 1:15, ainda mais preferida de 1:7 para 1: 12, e mais preferivelmente de 1:8 para 1:10.
8. Composição de lignina de ingrediente ativo de acordo com qualquer uma das reivindicações precedentes, caracterizada pelo fato de que no presente o componente b) é selecionado do grupo consistindo em etanol, propanol e isopropanol, propileno glicol, NBP e Metil-5-(dimetilamino)-2-metil-5-oxopentanoato.
9. Composição de lignina de ingrediente ativo de acordo com qualquer uma das reivindicações precedentes, caracterizada pelo fato de que no presente pelo menos um composto do grupo d) está presente.
10. Composição de lignina de ingrediente ativo de acordo com qualquer uma das reivindicações precedentes, caracterizada pelo fato de que no presente como composto e) a água está presente.
11. Kit de peças caracterizado pelo fato de que compreende uma formulação de ingrediente ativo, preferivelmente como SC, WG, ou WP e lignina a) dissolvida em um solvente b).
12. Processo para sementes de revestimento e materiais de veículos, caracterizado pelo fato de que compreende as etapas: a) Dissolver lignina em um solvente solúvel na água, b) Misturar uma dispersão aquosa de um ativo, ou uma dispersão aquosa de SC,WG ou WP com a lignina dissolvida a), c) Aplicar a mistura resultante da etapa b) para uma semente ou um material de veículo d) Remover o solvente.
13. Processo para sementes de revestimento e materiais de veículos, caracterizado pelo fato de que compreende as etapas de: a) Dissolver lignina em um solvente solúvel na água, b) Aplicar a solução da etapa a) para uma semente ou um material de veículo c) Remover o solvente d) Aplicar uma dispersão aquosa de um ativo, ou uma dispersão aquosa de um SC, WG ou WP para a semente revestida de lignina, ou material de veículo.
14. Processo para aplicação no solo, caracterizado pelo fato de que compreende as etapas de: a) Dissolver lignina em um solvente solúvel na água, b) Misturar uma dispersão aquosa de um ativo, ou uma dispersão aquosa de SC, WG ou WP com a igina a) dissolida, c) Aplicar a mistura resultante da etapa b) para um substrato do solo.
15. Processo para sementes de revestimento e materiais de veículos de acordo com a reivindicação 12 ou 13, caracterizado pelo fato de que no presente o solvente é selecionado do grupo consistindo em mono-álcoois (C1-C4-álcoois, mais preferivelmente C1-C3-álcoois) e propileno glicol.
16. Processo para sementes de revestimento e materiais de veículos de acordo com a reivindicação 12 ou 13, caracterizado pelo fato de que no presente o ingrediente ativo é selecionado do grupo diflufenicano (DFF), isoxaflutol (IFT), e indaziflam (IAF) e fluopiram (FLU).
17. Processo para sementes de revestimento e materiais de veículos de acordo com a reivindicação 12 ou 13, caracterizado pelo fato de que no presente a proporção de lignin, que é preferivelmente lignina de papel grosso, para o solvente, é preferível de 1:4 para 1:40, mais preferivelmente de 1:5 para 1:20, ainda preferido de 1:5 para 1:15, ainda mais preferido de 1:7 para 1:12, e mais preferivelmente de 1:8 para 1:10.
18. Processo para sementes de revestimento e materiais de veículos de acordo com a reivindicação 10 ou 11, caracterizado pelo fato de que no presente a proporção do ativo a) para lignina b), é de 1:0,1 para 1:5, preferivelmente de 1:0,5 para 1:20, mais preferido de 1: 2 para 1: 18 e mais preferido de 1: 4 para 1:15.
19. Uso de lignina, preferivelmente lignina de papel grosso, em formulações agroquímicas, caracterizado pelo fato de que é para reduzir efeitos indesejáveis, e a intensificação da eficácia a longo prazo em plantas úteis por liberação controlada do ingrediente ativo.
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CN103119036B (zh) | 2010-06-28 | 2018-05-08 | 拜耳知识产权有限责任公司 | 作为杀虫剂的杂环化合物 |
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CN102057925B (zh) | 2011-01-21 | 2013-04-10 | 陕西上格之路生物科学有限公司 | 一种含噻虫酰胺和生物源类杀虫剂的杀虫组合物 |
WO2013050317A1 (en) | 2011-10-03 | 2013-04-11 | Syngenta Limited | Polymorphs of an isoxazoline derivative |
CN102391261A (zh) | 2011-10-14 | 2012-03-28 | 上海交通大学 | 一种n-取代噁二嗪类化合物及其制备方法和应用 |
CN104202981B (zh) | 2012-03-30 | 2018-01-30 | 巴斯夫欧洲公司 | 防治动物害虫的n‑取代的吡啶亚基化合物和衍生物 |
AP2014008072A0 (en) | 2012-04-27 | 2014-11-30 | Dow Agrosciences Llc | Pesticidal compositions and processes related thereto |
US9282739B2 (en) | 2012-04-27 | 2016-03-15 | Dow Agrosciences Llc | Pesticidal compositions and processes related thereto |
CN103109816B (zh) | 2013-01-25 | 2014-09-10 | 青岛科技大学 | 硫代苯甲酰胺类化合物及其应用 |
CN103232431B (zh) | 2013-01-25 | 2014-11-05 | 青岛科技大学 | 一种二卤代吡唑酰胺类化合物及其应用 |
CN103524422B (zh) | 2013-10-11 | 2015-05-27 | 中国农业科学院植物保护研究所 | 苯并咪唑衍生物及其制备方法和用途 |
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2019
- 2019-07-31 BR BR112021001633-3A patent/BR112021001633A2/pt not_active Application Discontinuation
- 2019-07-31 WO PCT/EP2019/070571 patent/WO2020025650A1/en unknown
- 2019-07-31 AU AU2019313545A patent/AU2019313545A1/en active Pending
- 2019-07-31 CA CA3107984A patent/CA3107984A1/en active Pending
- 2019-07-31 US US17/264,199 patent/US20210307322A1/en not_active Abandoned
- 2019-07-31 EP EP19752664.3A patent/EP3829298A1/en active Pending
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2021
- 2021-01-29 CL CL2021000253A patent/CL2021000253A1/es unknown
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CL2021000253A1 (es) | 2021-06-25 |
US20210307322A1 (en) | 2021-10-07 |
WO2020025650A1 (en) | 2020-02-06 |
AU2019313545A1 (en) | 2021-02-25 |
EP3829298A1 (en) | 2021-06-09 |
CA3107984A1 (en) | 2020-02-06 |
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