BR112012013846B1 - A COMPOSITION RELATED TO HETEROCYCLIC NICOTINE LINKED BY OXYGEN BRIDGE OR AN OPTICAL ISOTHERM OR AGROCHEMICLY ACCEPTABLE SALT THEREOF, AGROCHEMICAL COMPOSITION, (*) APPLICATION OF AGROCHEMICAL COMPOSITION OF THE SAME AND METHOD FOR CONTROLLING PESTS - Google Patents
A COMPOSITION RELATED TO HETEROCYCLIC NICOTINE LINKED BY OXYGEN BRIDGE OR AN OPTICAL ISOTHERM OR AGROCHEMICLY ACCEPTABLE SALT THEREOF, AGROCHEMICAL COMPOSITION, (*) APPLICATION OF AGROCHEMICAL COMPOSITION OF THE SAME AND METHOD FOR CONTROLLING PESTS Download PDFInfo
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- BR112012013846B1 BR112012013846B1 BR112012013846B1 BR 112012013846 B1 BR112012013846 B1 BR 112012013846B1 BR 112012013846 B1 BR112012013846 B1 BR 112012013846B1
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Description
"COMPOSTO RELACIONADO À NICOTINA HETEROCÍCLICO LIGADO POR PONTE DE OXIGÊNIO, COMPOSIÇÃO AGROQUÍMICA, MÉTODO PARA PREPARAR O COMPOSTO RELACIONADO À NICOTINA HETEROCÍCLICO LIGADO POR PONTE DE OXIGÊNIO OU SAL AGROQUIMICAMENTE ACEITÁVEL DO MESMO E MÉTODO NÃO TERAPÊUTICO PARA CONTROLAR PRAGAS" Campo técnico [0001] A presente invenção refere-se a um novo inseticida relacionado à nicotina, e a métodos de preparação e aplicações do mesmo. Em particular, a presente invenção refere-se a análogos de nitrometileno de imidacloprido e compostos relacionados à nicotina heterociclicos ligados por ponte de oxigênio e bivalentes (ou compostos neonicotinóides) construídos por dialdeídos, e a métodos de preparação dos mesmos."HYPEROCYCLIC NICOTINE-RELATED COMPOUND OXYGEN BRIDGE, AGROCHEMICAL COMPOSITION, METHOD FOR PREPARING HYPEROCYCLIC NICOTINE-RELATED COMPOUND OF THE MATERIALLY EAGLE-PROTEXLY ACEQUATIC THERAPEUTICAL PROJECTS The invention relates to a novel nicotine-related insecticide, and to methods of preparation and applications thereof. In particular, the present invention relates to imidaclopride nitromethylene analogs and bivalent oxygen-linked heterocyclic nicotine-related compounds (or neonicotinoid compounds) constructed by dialdehydes, and methods of preparing them.
Histórico da técnica [0002] Novos pesticidas relacionados à nicotina, tal como representado por imidacloprido, têm elevada atividade inseticida, um amplo espectro inseticida, e baixa toxicidade para mamíferos e animais aquáticos, propriedades sistemáticas favoráveis e apropriada estabilidade no campo bem como benignidade ambiental; portanto, tornou-se uma área com bastante atividade para novas descobertas agroquímicas. Subseqüentemente, descobriu-se, em seqüência, uma série de compostos relacionados à nicotina, tais como tiacloprido, clotianidina, tiametoxam, acetamiprido, nitenpiram, e dinotefuran (vide patentes européias 247477, 296453, 685477, 235725, 315826, 192060, 244777, 0386565, 580553, e 1031556, e patentes japonesas 62292765, 8259568, 8291171, e 7242633).Background Art New nicotine-related pesticides, as represented by imidacloprid, have high insecticidal activity, a broad insecticide spectrum, and low toxicity to mammals and aquatic animals, favorable systemic properties and appropriate field stability as well as environmental benignity; therefore it has become a busy area for new agrochemical discoveries. Subsequently, a series of nicotine-related compounds, such as thiacloprid, clotianidine, thiametoxam, acetamipride, nitenpiram, and dinotefuran, were subsequently discovered (see European patents 247477, 296453, 685477, 235725, 315826, 192060, 244777, 0386565 , 580553, and 1031556, and Japanese patents 62292765, 8259568, 8291171, and 7242633).
[0003] Entretanto, o uso freqüente e excessivo de imidacloprido tem causado problemas de resistência e a semelhança estrutural de compostos relacionados à nicotina tem provocado resistência cruzada entre eles, a aplicação desta classe de compostos tem sido restringida a uma determinada extensão e limitou o desenvolvimento de novos compostos desta classe. Nesse meio tempo, compostos relacionados à nicotina são principalmente inseticidas contra homópteros e coleópteros, e seu espectro inseticida relativamente estrito tem também restringido sua aplicação no controle de pragas.However, frequent and excessive use of imidaclopride has caused resistance problems and the structural similarity of nicotine-related compounds has caused cross-resistance among them, the application of this class of compounds has been restricted to a certain extent and has limited development. of new compounds of this class. In the meantime, nicotine-related compounds are primarily insecticides against homopterans and beetles, and their relatively strict insecticide spectrum has also restricted their application in pest control.
[0004] Portanto, é urgente na técnica modificar estruturalmente compostos de nitrometileno elevada atividade para produzir um novo e ainda mais eficaz inseticida, resolvendo os problemas de resistência de inseticidas relacionados à nicotina, ampliando o espectro inseticida, e aplicando o mesmo em composições inseticidas.Therefore, it is urgent in the art to structurally modify high activity nitromethylene compounds to produce a new and even more effective insecticide, solving nicotine-related insecticide resistance problems, broadening the insecticide spectrum, and applying it to insecticide compositions.
Divulgação da invenção [0005] A presente invenção provê um novo e mais eficaz inseticida, resolvendo, assim, os problemas de resistência de inseticidas relacionados à nicotina, ampliando o espectro inseticida, e resolvendo os problemas existentes na técnica.Disclosure of the Invention The present invention provides a new and more effective insecticide, thereby solving nicotine-related insecticide resistance problems, broadening the insecticide spectrum, and solving problems existing in the art.
[0006] Um objetivo da presente invenção é prover um composto que é muito eficaz no controle de pragas, e o método de preparação do mesmo.[0006] An object of the present invention is to provide a compound which is very effective in pest control, and the method of preparation thereof.
[0007] Outro objetivo da presente invenção é prover proteção para prevenir plantações durante o período de crescimento e colheita da safra de serem atacadas e invadidas por insetos.[0007] Another object of the present invention is to provide protection to prevent crops during the growing and harvesting period from being attacked and invaded by insects.
[0008] Num aspecto, a presente invenção provê um composto relacionado à nicotina heterocíclico ligado por ponte de oxigênio ou ura isômero óptico ou sal agroquimicamente aceitável do mesmo selecionado dos compostos de fórmula (A) ou (B) : nas quais: Ri é um heterociclo de cinco ou seis membros contendo nitrogênio, oxigênio e/ou enxofre; heterociclo de cinco ou seis membros contendo nitrogênio, oxigênio e/ou enxofre halogenado; ou fenila substituído ou não-substituído sendo que os substituintes são selecionados de um ou mais dos seguintes grupos: halogênio, alquila halogenado de C1-4, ou alcoxi clorado de C1-4; cada um de R3 e R.< é selecionado, independentemente de: hidrogênio; alquila de Ci e; alila; benzila; alcoxi de Cj-4-alqui la de C1-4; (alcoxi de Ci-4) carboni la; fenoxicarbonila; alquinila de Ca-g-carbonila; alquenila de Ca-j-carbonila; cicloalquila de Cs-é-carbonila; benzoila; ou benzoil, furanil carbonila, ou N,W~dímetil carbonila substituído por um ou mais substituintes selecionados de um átomo de halogênio·, alquila de C3.h, haloalquila de C1 - 4, alcoxi de C1-4, e (alquila de Ci- 4} carbonila; ou R3 e R,·, juntos formam -CHj-CHj-, -CH2-CH2-CH2-, ou -CH;;;-XR-CH2-/ sendo que X é um heteroátomo e R é um substituinte no heteroátomo selecionado de: hidrogênio; alquila de C:-$; alila; benzila; fenila; alcoxi de Ci-4-alquila de Ci-4; alcoxi de Ci_4-carbonila; fenoxicarbonila; alquinila de C2-6-carbonila; alquenila de C2-3-carbonila; cicloalquila de C3carbonila; benzoila; ou benzoil, furanil carbonila, ou Ν,Ν-dimetil carbonila substituído por um ou mais substituintes selecionados de ora átomo de halogênio, haloalquila de C1-4, alcoxi ou alquila de Ci_a saturado ou insaturado, e alquila de Ci-4-carbonila; Rs/ Re/ R··/ Rs/ e R? são hidrogênio, alquila de C1-4 saturado ou insaturado, halogênio, alcoxi de C] § saturado ou insaturado, alcoxi de C1-4 saturado ou insaturado halogenado, alquila de Cí-4— carbonila, éster de alquila de Ci-g, éster de alquila de C1-4 de ácido sulfônico, fenila, ou benzila; e Y é nitro, triflúor-metila, triflúor-acetila ou triflúor-metano sulfonila.In one aspect, the present invention provides an oxygen-bridged heterocyclic nicotine-related compound or an agrochemically acceptable salt or optical isomer thereof selected from the compounds of formula (A) or (B): wherein: R1 is a five- or six-membered heterocycle containing nitrogen, oxygen and / or sulfur; five or six membered heterocycle containing nitrogen, oxygen and / or halogenated sulfur; or substituted or unsubstituted phenyl wherein the substituents are selected from one or more of the following groups: halogen, halogenated C1-4 alkyl, or chlorinated C1-4 alkoxy; each of R 3 and R 2 is independently selected from: hydrogen; C1-6 alkyl; allyl; benzyl; C 1-4 alkoxyC 1-4 alkyl; (C1-4 alkoxy) carbonyl; phenoxycarbonyl; Ca-g-carbonyl alkynyl; Ca-carbonyl alkenyl; C5 -C6 cycloalkyl; benzoyl; or benzoyl, furanyl carbonyl, or N, W-dimethyl carbonyl substituted by one or more substituents selected from a halogen atom, C1-4 alkyl, C1-4 haloalkyl, C1-4 alkoxy, and (C1-4 alkyl) Carbonyl, or R 3 and R 2 together form -CH 2 -CH 2 -, -CH 2 -CH 2 -CH 2 -, or -CH 3; wherein X is a heteroatom and R is a heteroatom substituent selected from: hydrogen; C1-6 alkyl; allyl; benzyl; phenyl; C1-4 alkoxy C1-4 alkoxy; C1-4 alkoxycarbonyl; phenoxycarbonyl; C2-6 carbonyl alkynyl; alkenyl C3-3-carbonyl; C3-carbonyl cycloalkyl; benzoyl; or benzoyl, furanyl carbonyl, or Î ± -dimethylcarbonyl substituted with one or more substituents selected from now halogen atom, C1-4 haloalkyl, C1-4 alkoxy or alkyl saturated or unsaturated, and C1-4 carbonyl alkyl; Rs / Re / R ·· / Rs / and R 'are hydrogen, saturated or unsaturated C1-4 alkyl, halogen, saturated or unsaturated C1-4 alkoxy, alkoxy in Halogenated saturated or unsaturated C1-4 alkyl, C1-4 alkylcarbonyl, C1-4 alkyl ester, C1-4 alkyl ester of sulfonic acid, phenyl, or benzyl; and Y is nitro, trifluoromethyl, trifluoroacetyl or trifluoromethane sulfonyl.
[0009] Numa incorporação preferida 0 composto relacionado à nicotina heterocíclico ligado por ponte de oxigênio é selecionado dos grupos seguintes: [0010] Noutra incorporação preferida, o composto relacionado à ni lcotina heterocíclico ligado por ponte de oxigênio é seleci A°r»ado dos aruoos seauintes: db), [0011] Noutra ■ - , . , α mcorporaçao preferida, o composto relacionado à ηί Λ . nicotina heterocíclico ligado por ponte de oxigênio é um antagonista de receptores de acetil colina nicotínica de insetos.In a preferred embodiment the oxygen-bridged heterocyclic nicotine-related compound is selected from the following groups: In another preferred embodiment, the oxygen-bridged heterocyclic nicotine-related compound is selected from the above. following aroids: db), In another. Preferred embodiment is the compound related to ηί Λ. Oxygen-bridged heterocyclic nicotine is an insect nicotinic acetylcholine receptor antagonist.
[0012] Noutra incorporação preferida, a atividade dos composto relacionado à nicotina heterocíclico ligado por ponte de oxigênio compostos relacionados à nicotina heterocíclicos ligados por pontes de oxigênio (la) e ílb) contra moscas-brancas ("Bemisia tabaci") e gafanhotos marrons ("Nilaparvata lugens") resistentes a imidacloprido ser de 2 a 30 vezes que a de imidacloprido.In another preferred embodiment, the activity of oxygen-bridged heterocyclic nicotine-related compounds oxygen-bridged heterocyclic (la) and ilb-related compounds against whitefly ("Bemisia tabaci") and brown locusts ( Imidacloprid-resistant "Nilaparvata lugens") is 2 to 30 times that of imidacloprid.
[0013] Noutro aspecto, a presente invenção provê uma composição agroquímica compreendendo: (a) de 0,001 a 99,99% em peso do composto relacionado à nicotina heterocíclico ligado· por ponte de oxigênio, ou um isômero óptico ou sal agroquimicamente aceitável supramencionado; e (b) um transportador (veículo) e/ou excipiente agroquiin.icam.ente aceitável.In another aspect, the present invention provides an agrochemical composition comprising: (a) from 0.001 to 99.99% by weight of the oxygen bridged heterocyclic nicotine-related compound, or an above-mentioned agrochemically acceptable salt or optical isomer; and (b) an agriculturally acceptable carrier (vehicle) and / or excipient.
[0014] Noutro aspecto, a presente invenção refere-se ao uso da dita composição agroquímica para exterminar ou evitar pragas agrícolas, pragas sanitárias, e pragas que põem em perigo· a saúde de animais, ou como uma composição inseticida para pragas agrícolas, pragas sanitárias, e pragas que põem em perigo a saúde de animais.In another aspect, the present invention relates to the use of said agrochemical composition to exterminate or prevent agricultural pests, sanitary pests, and pests that endanger the health of animals, or as an insecticidal composition for agricultural pests, pests. sanitary, and pests that endanger the health of animals.
[0015] Noutro aspecto, a presente invenção provê um método para exterminar e/ou impedir pragas, o método compreendendo aplicar a dita composição agroquímica em plantas atacadas por pestes ou com probabilidades de serem atacas por pragas, e no solo circundante ou no ambiente das mesmas.In another aspect, the present invention provides a method for exterminating and / or preventing pests, the method comprising applying said agrochemical composition to pest attacked or likely to be attacked by pests, and to surrounding soil or the environment of the pests. same.
[0016] Noutro aspecto, a presente invenção refere-se ao uso do dito composto, isômero óptico ou sal agroquimicamente aceitável do mesmo, ou a combinação do mesmo na preparação de uma composição inseticida.In another aspect, the present invention relates to the use of said compound, optical isomer or agrochemically acceptable salt thereof, or the combination thereof in the preparation of an insecticidal composition.
[0017] Noutro aspecto ainda, a presente invenção provê um método para preparar o composto, isômero óptico ou sal agroquimicamente aceitável do mesmo, o método compreendendo a etapa de: preparar os compostos tendo as fórmulas (A) e (B) reagindo o composto tendo a fórmula (a) com o composto tendo a fórmula (b) ou (c) em temperatura ambiente na presença de uma quantidade catalítica de ácido, nas quais Ri, R2, R3, R^, R5, R6, R7, Re, Rg e Y são tais como definidos acima.In yet another aspect, the present invention provides a method for preparing the compound, optical isomer or agrochemically acceptable salt thereof, the method comprising the step of: preparing the compounds having formulas (A) and (B) by reacting the compound. having formula (a) with the compound having formula (b) or (c) at room temperature in the presence of a catalytic amount of acid, wherein R 1, R 2, R 3, R 4, R 5, R 6, R 7, Re, Rg and Y are as defined above.
[0018] Numa incorporação preferida, o dito método compreende as seguintes etapas: obter o composto de fórmula (la) executando a reação seguinte durante 2 a 24 horas em acetonitrila em temperatura ambiente na presença de uma quantidade catalítica de ácido: obter o composto de fórmula {lb) executa ndo a reação seguinte durante 2 a 24 horas em acetonitrila temperatura ambiente na presença de uma quantidade catalítiCa MeCN/HCI, temperatura ambiente obter o composto de fórmula {lc) executsr,^ αηαο a reaçao seguinte durante 2 a 24 horas em acetonitrila em +- ^ , , 11 temperatura ambiente na presença de uma quantidade catalítica de ácido* M*CN/HCI r temperatura ambiente obter o composto de fórmula <ld) executando a reação seguinte durante 2 a o a u 4,-4,-1 24 horas em acetonitrila em temperatura ambiente na presença — -----*■ * Jade catalítica de ácido: MtCNJNCI, tempera- tura obter O COni|D ambiente Po§to de fórmula (le) executando a reação seguinte durante 2 a 34 horas em acetonitrila em temperatura ambiente na presençs uma quantidade catalítica de ácido: MeCWHCI tempera- tura ambiente Obter o Cçw. B°sto de fórmula (2a) executando a reação seguinte durante 2 a 24 horas em aeetonitrila em temperatura ambiente na presença de uma quantidade catalítica de ácido: obter o composto de fórmula {2b) executando a reação seguinte durante 2 a 24 horas em aeetonitrila em temperatura ambiente na presença de uma quantidade catalítica de ácido: obter o composto de fórmula (2o) executando a reação seguinte durante 2 a 24 horas em aeetonitrila em temperatura ambiente na presença de uma quantidade catalítíCa ácido- Obter o composto de fórmula {2d) exgCl , ul-ândo a reação seguinte durante 2 a 24 horas em acetonitriia temperatura ambiente na presença de uma quantidade catalí+-i *1» Cl Λ i"·] ΐ Π 1 /4 * e obter o composto de fórmula Oki ' executando a reação seguinte durante 2 a 24 horas em acet-r, u°hitrila em temperatura ambiente na presença de uma quantidade ΟΛ l-jsl it -í fa He Á c ldO : Incorporações específicas [0019] Através de pesquisa ampla e intensa, baseada na estrutura de nitrometileno imidacloprido de inseticidas existentes relacionados à nicotina nitrometileno imidacloprido, os inventores da presente invenção, reagindo um dialdeído com um composto de nitrometileno imidacloprido sintetizaram um novo composto relativo à nicotina que tem uma atividade inseticida notadamente melhorada e possui um espectro inseticida mais amplo. Os presentes inventores executaram a presente invenção com base no exposto acima. Definições de grupos funcionais [0020] Quando aqui usado, o termo "alquila de Ci_6" refere-se a um grupo alquila linear ou ramificado de um a seis átomos de carbono, tais como metila, etila, propila, isopropila, butila, isobutila, secbutila, terciobutila, ou grupos análogos.In a preferred embodiment, said method comprises the following steps: obtaining the compound of formula (1a) by performing the following reaction for 2 to 24 hours in acetonitrile at room temperature in the presence of a catalytic amount of acid: obtaining the compound of (lb) Carrying out the following reaction for 2 to 24 hours in acetonitrile at room temperature in the presence of a catalytic amount MeCN / HCl at room temperature to obtain the compound of formula (lc) performing the following reaction for 2 to 24 hours in acetonitrile at + - ^ .11 at room temperature in the presence of a catalytic amount of acid (M * CN / HCl at room temperature give the compound of formula (1d) by performing the following reaction for 2 to 4, -4, -1 24 hours in acetonitrile at room temperature in the presence - ----- * ■ * Acid catalytic jade: MtCNJNCI, tempera- ture Obtain the ambient COni | D Formula (le) by performing the following reaction during 2 to 34 hours in acetonitrile at room temperature in the presence of a catalytic acid: MeCWHCI room temperature Obtain Cçw. Step 2 of formula (2a) performing the following reaction for 2 to 24 hours in aeetonitrile at room temperature in the presence of a catalytic amount of acid: obtain compound of formula (2b) by performing the following reaction for 2 to 24 hours in aeetonitrile at room temperature in the presence of a catalytic amount of acid: obtain the compound of formula (2o) by performing the following reaction for 2 to 24 hours in aeetonitrile at room temperature in the presence of a catalytic amount of acid- Obtain the compound of formula (2d) The following reaction was carried out for 2 to 24 hours in acetonitrile at room temperature in the presence of a catalytic amount and obtain the compound of formula Oki by performing the next reaction for 2 to 24 hours in acetyl-r, β-hitril at room temperature in the presence of an amount: Specific Incorporations Through broad and intimate research sa, based on the nitromethylene imidaclopride structure of existing nicotine-related insecticides nitromethylene imidaclopride, the inventors of the present invention reacting a dialdehyde with a nitromethylene imidaclopride compound have synthesized a new nicotine-related compound that has a markedly improved insecticidal activity and has a spectrum wider insecticide. The present inventors have performed the present invention based on the above. Definitions of functional groups When used herein, the term "C1-6 alkyl" refers to a straight or branched alkyl group of one to six carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secbutyl, terciobutyl, or the like groups.
[0021] O termo "alcoxi de Ci_4" refere-se a um grupo alcoxi linear ou ramificado tendo de um a quatro átomos de carbono, tais como metoxi, etoxi, propoxi, isopropoxi, butoxi, secbutoxi, terciobutoxi, ou grupos análogos.The term "C1-4 alkoxy" refers to a straight or branched alkoxy group having from one to four carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, secbutoxy, tertiary butoxy, or similar groups.
[0022] O termo "halogênio" refere-se a flúor, cloro, bromo, ou iodo. O termo "halogenado" refere-se a um grupo substituído com um ou mais átomos de halogênios idênticos ou diferentes ditos acima, tais como triflúor metila, pentaflúor etila, ou grupos análogos.The term "halogen" refers to fluorine, chlorine, bromine, or iodine. The term "halogenated" refers to a group substituted with one or more identical or different halogen atoms mentioned above, such as trifluoromethyl, pentafluorethyl, or analogous groups.
[0023] O termo "heterociclo de cinco ou seis membros" refere-se a um anel de cinco ou seis membros contendo um ou mais heteroátomos selecionados de nitrogênio, oxigênio, ou enxofre, tais como piridila, tiazolila, pirimidila, tetraidrofuranila, oxazolila, etc. Método para preparar o· composto da presente invenção [0024] o composto da presente invenção pode ser sintetizado através das etapas de reação descritas acima.The term "five or six membered heterocycle" refers to a five or six membered ring containing one or more heteroatoms selected from nitrogen, oxygen, or sulfur, such as pyridyl, thiazolyl, pyrimidyl, tetrahydrofuranyl, oxazolyl, etc. Method for preparing the compound of the present invention The compound of the present invention may be synthesized by the reaction steps described above.
[0025] Numa incorporação especifica da presente invenção, o método para sintetizar o composto de fórmula (la) é como se segue: ambiente [0026] Numa incorporação específica da presente invenção, o método para sintetizar o composto de fórmula (lb) é como se segue: MeCWHCI·· Temperatura ambiente [0027] Numa incorporação específica da presente invenção, o método para sintetizar o composto de fórmula n,i a ™»nr» *e segue: MftCN/HCIIn a specific embodiment of the present invention, the method for synthesizing the compound of formula (1a) is as follows: environment In a specific embodiment of the present invention, the method for synthesizing the compound of formula (1b) is as follows: MeCWHCI ·· Room Temperature In a specific embodiment of the present invention, the method for synthesizing the compound of the formula is as follows: MftCN / HCl
Temperatur; ambiente [0028] Numa incorporação específica hs „ Λ Presente invenção, o método para sintetizar o composto de fArm, . , “Nia (ld) e como se seque: M6CN/HCITemperatures; In a specific embodiment, the method for synthesizing the compound of fArm. , “Nia (ld) and as follows: M6CN / HCI
Temperatura ambiente [0029] Numa incor rPoração específica da presente invenção, o método para sintet· tlzar o composto de fórmula (2a) é como se segue: [0030] Numa incorporação especifica da presente invenção, o método para sintetizar o composto de fórmula (2b) é como se segue: (2b).Room temperature In a specific embodiment of the present invention, the method for synthesizing the compound of formula (2a) is as follows: In a specific embodiment of the present invention, the method for synthesizing the compound of formula (2a) 2b) is as follows: (2b).
[0031] Numa incorporação especifica da presente invenção, o método para sintetizar o composto de fórmula {2c) é como se segue: [0032] Numa incorporação especifica da presente invenção, o método para sintetizar o composto de fórmula (2d) é como se segue: [0033] Numa incorporação especifica da presente invenção, o método para sintetizar o composto de fórmula {le) é como se segue: [0034] Numa incorporação específica da presente invenção, o método para sintetizar o composto de fórmula (2e) é como se segue: McCN/HCI .In a specific embodiment of the present invention, the method for synthesizing the compound of formula (2c) is as follows: In a specific embodiment of the present invention, the method for synthesizing the compound of formula (2d) is as follows: In a specific embodiment of the present invention, the method for synthesizing the compound of formula (le) is as follows: In a specific embodiment of the present invention, the method for synthesizing the compound of formula (2e) is as follows: McCN / HCI.
Temperatura ambiente [0035] Numa incorporação da presente invenção, os compostos de fórmulas (la) a (le) podem ser preparados pelas seguintes reações: [0036] Uma solução de 2,5-dietoxi tetraidrofurano (2 g, 12,5 mmol) e ácido clorídrico aquoso (0,1 M, 10 mL) é aquecida a 90°C e reage por uma hora, sendo depois, resfriada até temperatura ambiente. Adiciona-se acetonitrila (40 mL) e um análogo de nitrometí leno de imidacloprido (10 mL) na reação, e se agita o sistema em temperatura ambiente.Room temperature In an embodiment of the present invention, the compounds of formulas (la) to (le) may be prepared by the following reactions: A solution of 2,5-diethoxy tetrahydrofuran (2 g, 12.5 mmol) and aqueous hydrochloric acid (0.1 M, 10 mL) is heated to 90 ° C and reacted for one hour, then cooled to room temperature. Acetonitrile (40 mL) and an imidacloprid nitromethylene analog (10 mL) are added to the reaction, and the system is stirred at room temperature.
Monitora-se a reação por TLC, e apt»s o término da reação, ela é neutralizada por bicarbonato de sódio aquoso saturado. O sistema é extraído, o solvente é removido sob pressão reduzida, e se executa separação por cromatografia de coluna (eluente: diclorometano/acetona= 3/1 (v/v)) para obter um pó amarelo claro, isto é, o produto.The reaction is monitored by TLC, and until the end of the reaction, it is neutralized by saturated aqueous sodium bicarbonate. The system is extracted, the solvent is removed under reduced pressure, and separation is performed by column chromatography (eluent: dichloromethane / acetone = 3/1 (v / v)) to obtain a light yellow powder, i.e. the product.
[0037] Noutra incorporação, os compostos de fórmulas (2a) a (2e) podem ser preparados pelas seguintes reações: [0038] Coloca-se um análogo de nitrometileno de imidacloprido (5 mmol), 30 mL de acetonitrila anidra, 3 mL de glutaraldeído aquoso a 25%, e uma quantidade catalítica de HC1 num balão de fundo redondo de 50 mL. Em temperatura ambiente, a reação é agitada e monitorada por TLC. Após o término da reação, o sistema é neutralizado por bicarbonato de sódio aquoso saturado e extraído. O solvente é removido sob pressão reduzida, e se executa separação por cromatografia de coluna (eluente: diclorometano/acetona= 3/1 (v/v)) para obter um pó amarelo claro, isto é, o produto.In another embodiment, the compounds of formulas (2a) to (2e) may be prepared by the following reactions: An imidacloprid nitromethylene analogue (5 mmol), 30 mL of anhydrous acetonitrile, 3 mL of 25% aqueous glutaraldehyde, and a catalytic amount of HCl in a 50 mL round bottom flask. At room temperature, the reaction is stirred and monitored by TLC. Upon completion of the reaction, the system is neutralized by saturated aqueous sodium bicarbonate and extracted. The solvent is removed under reduced pressure, and separation is performed by column chromatography (eluent: dichloromethane / acetone = 3/1 (v / v)) to obtain a light yellow powder, i.e. the product.
[0039] Atividade inseticida da substância ativa da presente invenção [0040] O termo "substância ativa da presente invenção" ou "composto ativo da presente invenção" refere-se ao composto da presente invenção, ou ao isômero óptico ou sal agroquimicamente aceitável do mesmo possuindo atividade inseticida nitidamente melhorada e um espectro inseticida mais amplo.Insecticidal activity of the active substance of the present invention The term "active substance of the present invention" or "active compound of the present invention" refers to the compound of the present invention or the optical isomer or agrochemically acceptable salt thereof. having sharply improved insecticidal activity and a broader insecticidal spectrum.
[0041] O termo "sal agroquimicamente aceitável" significa que o ânion de tal sal formador dos sais agroquimicamente aceitáveis de inseticida é conhecido ou aceitável. Preferivelmente, tal sal é solúvel em água. Os sais de adição de ácidos apropriados formados a partir dos compostos de fórmulas (A) e (B) incluem sais formados por ácidos inorgânicos, tais como cloretos, fosfatos, sulfatos, e nitratos; e os sais formados por ácidos orgânicos, tais como acetatos ou benzoatos. A substância ativa da presente invenção pode ser usada para controlar e exterminar várias das pragas de agricultura e silvicultura, pragas de cereais armazenados, pragas sanitárias, e pragas que põem em perigo a saúde de animais, e similares. No presente relatório, um "inseticida" representa qualquer substância que possui o efeito de impedir ou controlar todas as pragas supramencionadas. Exemplos de pragas incluem, mas não se limitam insetos coleópteros: Sitophilus zeamais, Tribolium castaneum, Henosepilachna vigintioctomaculata, Henosepilachna sparsa, Agriotes fuscicollis, Anômala cupripes, Popillia quadriguttata, Monolepta hieroglyphica, Monochamus alternatus, Echinocnemus squameus, Basiprionota bisignata, Anoplophora chinensis, Apriona germari, Scolytus schevy, ou Agriotes fuscicollis; insetos lepidópteros: Lymantria dispar;The term "agrochemically acceptable salt" means that the anion of such salt forming the agrochemically acceptable insecticide salts is known or acceptable. Preferably, such a salt is water soluble. Suitable acid addition salts formed from the compounds of formulas (A) and (B) include salts formed by inorganic acids, such as chlorides, phosphates, sulfates, and nitrates; and salts formed by organic acids, such as acetates or benzoates. The active substance of the present invention may be used to control and exterminate various agricultural and forestry pests, stored cereal pests, sanitary pests, and animal health endangers, and the like. In this report an "insecticide" represents any substance that has the effect of preventing or controlling all the above mentioned pests. Examples of pests include, but are not limited to, Coleoptera insects: Sitophilus zeamais, Tribolium castaneum, Henosepilachna vigintioctomaculata, Henosepilachna sparsa, Agriotes fuscicollis, Anomalous cupripes, Popillia quadriguttata, Monolepta hieroglyphus, Anoplomota bisocompromis, Monocephaenocomusata, Pemophagous bipolar insects. , Scolytus schevy, or Agriotes fuscicollis; lepidopteran insects: Lymantria dispar;
Malacosoma neustria testacea, Diaphania perspectalis, Clania variegata, Cnidocampa flavescens, Dendrolimus punctatus, Orgyia gonostigma, Paranthrene tabaniformis, Spodoptera litura, Chilo suppressalis, Ostrinia nubilalis, Ephestia cautella, Adoxophyes orana, Laspeyresia splendana, Agrotis fucosa, Galleria mellonella, Plutella xylostella, Phyllocnistis citrella, Mythimna separata; insetos homópteros: Nephotettix cincticeps, Nilaparvata lugens, Pseudococcus comstocki, Unaspis yanonensis, Myzus persicae, Aphis gossypii, Lipaphis erysimi pseduobrassicae, Stephanitis nashi, ou Bemisia tabaci; insetos ortópteros: Blattella germanica, Periplaneta americana, Gryllotalpa africana, ou Locus migratória; ou insetos isópteros: Solenopsis invicta, ou Coptotermes formasanus; insetos dipteros: Musca domestica, Aedes aegypti, Delia platura, Culex sp., ou Anopheles sinensis. Pragas que afetam a saúde de animais compreendem Boophilus microplus, Haemaphysalis longicornis, Hyalomma anatolicum, Hypoderma spp., Fasciola hepatica, Moniezia benedeni, Ostertagia spp., Trypanosoma evansi, Babesia bigemina, e similares.Malacosoma neustria testacea, Diaphania perspectalis, Clania variegata, Cnidocampa flavescens, Dendrolimus punctatus, Orgyia gonostigma, Paranthrene tabaniformis, Spodoptera litura, Chrys suppressalis, Ostrinia nubilalis, Ephestia cautella, Phylaenaella pella, Orellia plains, Orellia pella citrella, Mythimna separata; homopterous insects: Nephotettix cincticeps, Nilaparvata lugens, Pseudococcus comstocki, Unaspis yanonensis, Myzus persicae, Aphis gossypii, Lipaphis erysimi pseduobrassicae, Stephanitis nashi, or Bemisia tabaci; orthoptera insects: Blattella germanica, Periplaneta americana, Gryllotalpa africana, or Locus migratory; or isopteran insects: Solenopsis invicta, or Coptotermes formsanus; dipteran insects: Musca domestica, Aedes aegypti, Delia platura, Culex sp., or Anopheles sinensis. Pests affecting animal health include Boophilus microplus, Haemaphysalis longicornis, Hyalomma anatolicum, Hypoderma spp., Fasciola hepatica, Moniezia benedeni, Ostertagia spp., Trypanosoma evansi, Babesia bigemina, and the like.
[0042] O composto da presente invenção é especialmente eficaz contra insetos de agricultura e silvicultura tendo aparelhos bucais sugadores de perfuração ou sugadores de raspagem, tais como afídeos (pulgões), mosca-branca, gafanhoto marrom, cigarrinha verde, fulgorideos, tripídeos comuns, lagartas das espigas, lagarta do repolho, traça da couve, lagarta da folha de algodoeiro, lagarta de cereais e similares.[0042] The compound of the present invention is especially effective against agricultural and forestry insects by having perforating or scraping sucking mouth braces such as aphids (aphids), whitefly, brown grasshopper, green leafhopper, fulgorids, common tripids, spikes caterpillars, cabbage caterpillar, cabbage moth, cotton leaf caterpillar, cereals caterpillar and the like.
Composições inseticidas contendo a substância ativa da presente invenção [0043] Pode-se usar um método convencional para preparar uma composição inseticida a partir das substâncias ativas da presente invenção. Tais compostos ativos podem ser preparados numa formulação convencional, tais como soluções, emulsões, suspensões, pós, espumas, pastas, grânulos, aerossóis, materiais naturais ou sintéticos impregnados com a substância ativa, micro-cápsulas num polímero, complexo de revestimento para sementes, uma preparação para ser usada juntamente com um dispositivo de combustão, tal como um cartucho defumador, vaso defumador ou placa defumadora, e preparações de misturas quentes ou misturas frias de ULV.Insecticidal Compositions Containing the Active Substance of the Present Invention A conventional method for preparing an insecticidal composition from the active substances of the present invention can be used. Such active compounds may be prepared in a conventional formulation, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, natural or synthetic materials impregnated with the active substance, microcapsules in a polymer, seed coating complex, a preparation for use in conjunction with a combustion device, such as a smoker cartridge, smoker vessel or smoker plate, and hot mix or cold ULV mix preparations.
[0044] Esta formulação pode ser produzida usando um método conhecido, por exemplo, misturando os compostos ativos e extensores que são diluentes ou transportadores (veículos) na forma de um líquido, gás liquefeito, ou sólido, opcionalmente com um tensoativo, isto é, um agente emulsificante e/ou um agente dispersante e/ou um agente formador de espuma. Por exemplo, quando se usa água como um extensor, pode-se usar também um solvente orgânico como solvente auxiliar.This formulation may be produced using a known method, for example by mixing the active compounds and extenders which are diluents or carriers (vehicles) in the form of a liquid, liquefied gas, or solid, optionally with a surfactant, i.e. an emulsifying agent and / or a dispersing agent and / or a foaming agent. For example, when using water as an extender, an organic solvent may also be used as an auxiliary solvent.
[0045] Geralmente, é apropriado usar solventes líquidos como um diluente ou transportador (veículo), por exemplo: hidrocarbonetos aromáticos, tais como xileno, tolueno, ou alquil naftalenos; hidrocarbonetos aromáticos clorados ou alifáticos clorados, tais como cloro-benzeno, cloreto de vinila, ou diclorometano; hidrocarbonetos alifáticos, tal como ciclo-hexano ou uma parafina tal como uma fração de óleo mineral; álcoois, tais como etanol, etileno glicol, e éteres e ésteres dos mesmos; ou cetonas, tais como acetona, metil etil cetona, metil isobutil cetona, ou ciclo-hexanona; ou solventes polares comumente menos usados, tais como dimetil formamida, sulfóxido de dimetila, e água. Um diluente ou transportador na forma de um gás liquefeito refere-se a um líquido que em temperatura normal e sob pressão atmosférica é gasoso, por exemplo, propelentes em aerossol, tais como hidrocarbonetos halogenados bem como butano, propano, nitrogênio gasoso, e dióxido de carbono.Generally, it is appropriate to use liquid solvents as a diluent or carrier (carrier), for example: aromatic hydrocarbons, such as xylene, toluene, or alkyl naphthalenes; chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzene, vinyl chloride, or dichloromethane; aliphatic hydrocarbons, such as cyclohexane or a paraffin such as a mineral oil fraction; alcohols, such as ethanol, ethylene glycol, and ethers and esters thereof; or ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone; or less commonly used polar solvents such as dimethyl formamide, dimethyl sulfoxide, and water. A diluent or carrier in the form of a liquefied gas refers to a liquid which at normal temperature and under atmospheric pressure is gaseous, for example aerosol propellants such as halogenated hydrocarbons as well as butane, propane, nitrogen gas, and carbon dioxide. carbon.
[0046] Transportadores sólidos incluem minerais naturais moídos, tais como: caulim, argila, talco, quartzo, argila ativada, montmorilonita ou terra diatomácea; ou minerais sintéticos moídos, tais como, ácido silícico muito dispersado, alumina, e silicatos. Um transportador sólido para grânulos é zircônio natural triturado e selecionado, tal como calcita, mármore, pedra-pomes, sepiolita, e dolomita, bem como grânulos sintetizados de pó grosso inorgânico ou orgânico, e materiais orgânicos tais como grânulos de serragem, cascas de coco, espigas de milho, ou talos de tabaco, e similares.Solid carriers include ground natural minerals such as: kaolin, clay, talc, quartz, activated clay, montmorillonite or diatomaceous earth; or ground synthetic minerals such as widely dispersed silicic acid, alumina, and silicates. A solid granule carrier is ground and selected natural zirconium, such as calcite, marble, pumice, sepiolite, and dolomite, as well as synthesized granules of inorganic or organic coarse powder, and organic materials such as sawdust granules, coconut shells. , corncobs, or tobacco stalks, and the like.
[0047] Podem ser usados emulsificantes não-iônicos e aniônicos como agentes emulsificantes e/ou formadores de espuma. Exemplos incluem: ésteres de ácidos graxos/polioxietileno e éteres de ácidos graxos/polioxietileno, tais como alquil aril polietileno glicol éteres, alquil ésteres de ácidos sulfônicos, alquil ésteres de ácido sulfúrico, aril ésteres de ácidos sulfônicos, e produtos de hidrólise de albumina. Agentes de dispersão incluem, por exemplo, sobras de lignina/sulfito e metil celulose.Nonionic and anionic emulsifiers may be used as emulsifying and / or foaming agents. Examples include: fatty acid / polyoxyethylene esters and fatty acid / polyoxyethylene ethers, such as alkyl aryl polyethylene glycol ethers, alkyl sulfonic acid esters, alkyl sulfuric acid esters, aryl sulfonic acid esters, and albumin hydrolysis products. Dispersing agents include, for example, lignin / sulfite and methyl cellulose leftovers.
[0048] Nas formulações, é possível usar um adesivo, tal como carboximetil celulose e um polímero natural ou sintético (por exemplo, goma arábica, poli(álcool vinílico), e poli (acetato de vinila)), na forma de pós, grânulos, ou emulsões. 0 agente colorante também pode ser usado, tal como um corante inorgânico (por exemplo, óxido de ferro, óxido de cobalto, ou azul da Prússia) ; ou um corante orgânico (tal como um azo corante ou corante de ftalocianina metálica); e traços de nutrientes, tais como sais de ferro, manganês, boro, cobre, cobalto, alumínio e zinco, e similares.In the formulations, an adhesive such as carboxymethyl cellulose and a natural or synthetic polymer (e.g. gum arabic, polyvinyl alcohol) and polyvinyl acetate) may be used in the form of powders, granules , or emulsions. The coloring agent may also be used, such as an inorganic dye (e.g. iron oxide, cobalt oxide, or Prussian blue); or an organic dye (such as a metal dye or metal phthalocyanine dye); and nutrient traces such as iron, manganese, boron, copper, cobalt, aluminum and zinc salts, and the like.
[0049] Estes compostos ativos da presente invenção podem, juntamente com outros compostos ativos, ser preparados numa mistura presente numa formulação comercial ou numa forma de dosagem preparada da formulação comercial; os ditos outros compostos ativos incluem, mas não se limitam a, inseticidas, iscas, bactericidas, acaricidas, nematacidas, fungicidas, agentes controladores de crescimento, e similares. Os inseticidas compreendem, por exemplo, ésteres fosfatos, ésteres carbâmicos, ésteres piretróides, hidrocarbonetos clorados, benzoil uréia, toxinas nereis, e substâncias produzidas por microorganismos, tal como abamectina.These active compounds of the present invention may, together with other active compounds, be prepared in a mixture present in a commercial formulation or in a prepared dosage form of the commercial formulation; said other active compounds include, but are not limited to, insecticides, baits, bactericides, acaricides, nematacides, fungicides, growth control agents, and the like. Insecticides include, for example, phosphate esters, carbamic esters, pyrethroid esters, chlorinated hydrocarbons, benzoyl urea, toxic toxins, and substances produced by microorganisms such as abamectin.
[0050] Além disso, estes compostos ativos da presente invenção também podem, juntamente com um sinergista, ser preparados numa mistura presente numa formulação comercial ou numa forma de dosagem preparada destas formulações comerciais. Sinergista é um composto que melhora os efeitos dos compostos ativos; o sinergista não é necessário, uma vez que os compostos ativos são inerentemente ativos.Furthermore, these active compounds of the present invention may also, together with a synergist, be prepared in a mixture present in a commercial formulation or in a prepared dosage form of these commercial formulations. Synergist is a compound that enhances the effects of active compounds; The synergist is not necessary since the active compounds are inherently active.
[0051] Geralmente, as formulações contêm de 0,001 a 99,99% em peso dos compostos ativos da presente invenção, preferivelmente de 0,01 a 99,9% em peso, mais preferivelmente de 0,05 a 90% em peso da dita composição inseticida. A concentração de componentes ativos numa forma de dosagem preparada de uma composição comercial pode variar dentro dos limites de uma ampla faixa. A concentração de componentes ativos numa forma de dosagem preparada de uma composição comercial pode estar entre 0,0000001 e 100% (g/v), preferivelmente entre 0,0001 e 1%.Generally, the formulations contain from 0.001 to 99.99 wt.% Of the active compounds of the present invention, preferably from 0.01 to 99.9 wt.%, More preferably from 0.05 to 90 wt.% Thereof. insecticidal composition. The concentration of active components in a prepared dosage form of a commercial composition may vary within the range of a wide range. The concentration of active components in a prepared dosage form of a commercial composition may be between 0.0000001 and 100% (g / v), preferably between 0.0001 and 1%.
Exemplos [0052] A invenção será adicionalmente ilustrada abaixo com referência aos exemplos seguintes. Deve-se entender que estes exemplos são meramente ilustrativos da presente invenção. Os métodos experimentais descritos nos exemplos seguintes sem quaisquer condições específicas são geralmente executados em condições convencionais, ou de acordo com as instruções do fabricante. Salvo se especificado diferentemente, todas as porcentagens e partes são calculadas em peso. Aqui, "r.t." significa temperatura ambiente.Examples The invention will be further illustrated below with reference to the following examples. It is to be understood that these examples are merely illustrative of the present invention. The experimental methods described in the following examples without any specific conditions are generally performed under conventional conditions, or according to the manufacturer's instructions. Unless otherwise specified, all percentages and parts are calculated by weight. Here, "r.t." means room temperature.
Exemplo 1; Síntese de 9-U6-cloropirid-3-il)metil)-4-nitro-8-oxa-10, 1.1-diidroimidazo-[2,3-a]- biciclo-[3,2,1]-oct-3-eno {o composto la) [0053] Uma solução de 2,5-dietoxi tetraidrofurano (2 g, 12,5 mmol) e ácido clorídrico aquoso [0,1 M, 10 mL) foi aquecida a 90 °C e reagiu por uma hora, sendo depois, resfriada até temperatura ambiente. Adicionou-se na reação acetonitrila (40 mL) e 2-cloro-5-(2-nitrometileno-imidazolidin-l-il metil)-piridina (2,54 g, 10 mmol), e o sistema foi agita do em temperatura ambiente. Monitora-se a reação por TLC, e após o término da reação, o sistema foi neutralizado por bicarbonato de sódio aquoso saturado. O sistema foi extraído, o solvente foi removido sob pressão reduzida, e se executou separação por cromatografia de coluna (eluente: diclorometano/acetona= 3/1 (v/v)) para obter um pó amarelo claro. Rendimento: 53%; mp (ponto de fusão)= 149,0-150,00C; NMR de lH (400 Mz, DMSG-df:) : δ 8,35 (d, J - 2,4 Hz, 1H) , 7,81 (dd, Ji = 2,4 Hz, J,2 = 8,4 Hz, 1H) , 7,51 {d, J = 8,4 Hz, 1H), 5, 36-5, 39 (s, 2H), 5,00 (d, J = 15, 6 Hz, 1H) , 4,68 (d, J= 15,6 Hz, 1H) , 3, 57-3, 73 (m, 4H) , 1, 94-2, 04 (m, 4H) ppm; NMR de UC (100 Mz, DMSO-cfe) : δ 155, 6, 149, 7, 149, 6, 139,7, 132,6, 124,5, 109,6, 87,0, 75,1, 51, 2, 50, 3, 46, 6, 31,9, 31,7 ppm; HRMS (ES +) valor calculado: CuHigN^Oj^Cl (M+H)*, 323,0911; valor medido 323, 0912. Valor calculado: C:,iHi6N.10.337Cl (M+H)’, 325,0811; valor medido 325, 0895. Valor calculado: C^HisN^Oa^ClPa (M+Na) *, 345, 0730, valor calculado 345,0722. Valor calculado: C;4HiSN40337ClNa (M+Na)\ 347,0701; valor calculado 347,0692.Example 1; Synthesis of 9-U6-chloropyrid-3-yl) methyl) -4-nitro-8-oxa-10,1-dihydroimidazo [2,3-a] bicyclo [3,2,1] -oct-3 -ene (compound 1a) A solution of 2,5-diethoxy tetrahydrofuran (2 g, 12.5 mmol) and aqueous hydrochloric acid [0.1 M, 10 mL) was heated to 90 ° C and reacted by one hour, then cooled to room temperature. Acetonitrile (40 mL) and 2-chloro-5- (2-nitromethylene-imidazolidin-1-yl methyl) -pyridine (2.54 g, 10 mmol) were added in the reaction, and the system was stirred at room temperature. . The reaction is monitored by TLC, and after completion of the reaction, the system was neutralized by saturated aqueous sodium bicarbonate. The system was extracted, the solvent was removed under reduced pressure, and separation was performed by column chromatography (eluent: dichloromethane / acetone = 3/1 (v / v)) to obtain a light yellow powder. Yield: 53%; mp (melting point) = 149.0-150.00 ° C; 1 H NMR (400Mz, DMSG-d 6): δ 8.35 (d, J = 2.4Hz, 1H), 7.81 (dd, Ji = 2.4Hz, J, 2 = 8.4 Hz, 1H), 7.51 (d, J = 8.4 Hz, 1H), 5.36-5.39 (s, 2H), 5.00 (d, J = 15.6 Hz, 1H), 4.68 (d, J = 15.6 Hz, 1H); 3.57-3.73 (m, 4H), 1.94-2.04 (m, 4H) ppm; UC NMR (100 MHz, DMSO-cfe): δ 155, 6, 149, 7, 149, 6, 139.7, 132.6, 124.5, 109.6, 87.0, 75.1, 51 2.50, 3.46, 6, 31.9, 31.7 ppm; HRMS (ES +) calculated value: CuHigN2 O4 Cl (M + H) *, 323.0911; measured value 323.0912. Calculated value: C13 H16 N.10.337Cl (M + H) ', 325.0811; measured value 325.0895. Calculated value: C ^ HisHNN ^Oa ^ClPa (M + Na) *, 345.0730, calculated value 345.0722. Calculated value: C 14 H 14 N 4 O 433 7 ClNa (M + Na) δ 347.0701; calculated value 347.0692.
Exemplo 2: Síntese de 9-((2-clorotiazol-5-il) metil)-4-nitro-8-oxa-l0,11-diidroimidazo-[2,3-a]- biciclo-[3,2,1]-oct-3-eno (o composto lb) Mocn;hci_ temperatura ambiente [0054] 0 método de preparação é semelhante ao método acima. 0 solvente foi removido sob pressão reduzida, e se executou separação por cromatografia de coluna (eluente: diclorometano/acetona= 3/1 (v/v)) para obter um pó amarelo claro. Rendimento: 56%; mp (ponto de fusão)= 136,5-138,0°C; NMR de (400 Mz, DMSO-dg) : δ 7,47 (s, 1H) , 5,61 (d, J = 5,2 Hz, 1H), 5,28 (d, J= 15,4 Hz, 1H), 5,16 (d, J = 5,00 Hz, 1Η)f 4f70 (áf J = 15,4 Hz, JtH) , 3, 66-3,82 (mr 3H)f 3f 54-3r 61 {ιγλ ψ 1. H J ψ «2, , ^ ^ ^ , 2 9 (, iti , 1H) , 5*, «L , */* 1> | i^rt, 2 9 ^ ^ 1 ^ 9 9 <2*, 0 ^ {rn , 1H) ppm; NMR de nC (100 Mz, DMSO-ofe) : δ 154, 6, 154,3, 140,6, 135,1, 110,4, 87, 4, 75, 4, 49, 6, 47,9, 46,5, 31, 8, 31,8 ppm; HRMS (ΕΞ +) valor calculado: C,sHiíN^OjS^CI (M+H) 4, 329,0475, valor calculado 329, 0475. Valor calculado: CiaHuN^OsS^Cl (M+H)% 331,0446, valor calculado 331,0461.Example 2: Synthesis of 9 - ((2-chlorothiazol-5-yl) methyl) -4-nitro-8-oxa-10,11-dihydroimidazo [2,3-a] bicyclo [3,2,1 ] -oct-3-ene (compound 1b) Mocn; hci at room temperature The preparation method is similar to the above method. The solvent was removed under reduced pressure, and separation was performed by column chromatography (eluent: dichloromethane / acetone = 3/1 (v / v)) to obtain a light yellow powder. Yield: 56%; mp (melting point) = 136.5-138.0 ° C; (400Mz, DMSO-dg) NMR: δ 7.47 (s, 1H), 5.61 (d, J = 5.2 Hz, 1H), 5.28 (d, J = 15.4 Hz, 1H), 5.16 (d, J = 5.00 Hz, 1Η) f 4f70 (f J = 15.4 Hz, JtH), 3.66-3.82 (mr 3H) f 3f 54-3r 61 { ιγλ ψ 1. HJ ψ «2,, ^ ^ ^, 2 9 (, iti, 1H), 5 *,« L, * / * 1> | t, 299 ^ 2 1 ^ 9 9 (2 *, 0 ^ (rn, 1H) ppm; NC NMR (100 MHz, DMSO-op): δ 154.6, 154.3, 140.6, 135.1, 110.4, 87, 4, 75, 4, 49, 6, 47.9, 46 5.31.8.8 31.8 ppm; HRMS (ΕΞ +) calculated value: C, sHiNN4 O3 S4 CI (M + H) 4, 329.0475, calculated value 329.0475. Calculated value: CiaHuN2 OsS3 Cl (M + H)% 331.0446, calculated value 331.0461.
Exemplos 3: Sintese de 9-benzil-4-nitro-8-oxa-10,11- diidroimidazo-[2,3-a]-biciclo-[3,2,1]-oct-3-eno (o composto lc) McCWÍHCli . er,í-'e z a l u i d imfc íentc- [0055] O método de preparação é semelhante ao método acima. O solvente foi removido sob pressão reduzida, e se executou separação por cromatografia de coluna (eluente: diclorometano/acetona= 3/1 (v/v)) para obter um pó amarelo claro. Rendimento: 58%; mp (ponto de fusão)= 149,0-149,8°C; NMR de lH (400 Mz, DMSG-dé) : δ 7,28-7,39 (m, 5H) , 5,66 (d, J = 4,3 Hz, 1H) , 5,14 (d, J = 4,5 Hz, 1H) , 4,92-5,01 (m, 2H) , 3,57-3,74 (m, 3H) , 3,4 7-3,53 (m, 1H) , 2,30-2,34 (m, IH), 2,13-2,22 (m, 2H), 2,00-2,07 (m, 1H) ppm; NMR de nC (100 Mz, DMSO-d6) : δ 155, 5, 135,9, 128,9, 128,2, 128, 1, 87,7, 75,6, 54,4, 48,9, 47,2, 31,8, 31,6 ppm; HRMS (ES+) valor calculado: Ci5H17N3O3 (M+H)% 287, 1270; valor calculado 287,1272.Examples 3: Synthesis of 9-benzyl-4-nitro-8-oxa-10,11-dihydroimidazo [2,3-a] bicyclo [3,2,1] -oct-3-ene (compound 1c ) McCWIHCl. [0055] The preparation method is similar to the above method. The solvent was removed under reduced pressure, and separation was performed by column chromatography (eluent: dichloromethane / acetone = 3/1 (v / v)) to obtain a light yellow powder. Yield: 58%; mp (melting point) = 149.0-149.8 ° C; 1 H NMR (400Mz, DMSG-d 6): δ 7.28-7.39 (m, 5H), 5.66 (d, J = 4.3 Hz, 1H), 5.14 (d, J = 4.5 Hz, 1H), 4.92-5.01 (m, 2H), 3.57-3.74 (m, 3H), 3.4 7-3.53 (m, 1H), 2, 30-2.34 (m, 1H), 2.13-2.22 (m, 2H), 2.00-2.07 (m, 1H) ppm; NC NMR (100 MHz, DMSO-d 6): δ 155.5, 135.9, 128.9, 128.2, 128.1, 87.7, 75.6, 54.4, 48.9, 47 , 2, 31.8, 31.6 ppm; HRMS (ES +) calculated value: C 15 H 17 N 3 O 3 (M + H)% 287, 1270; calculated value 287.1272.
Exemplo 4: Sintese de 9-(4-cloro-benzil)-4-nitro-8-oxa-10,11-diidroimidazo-[2,3-a]-biciclo-[3,2,1]-oct-3-eno (o composto ld) MêCMÍHCI temperatura ambiente [0056] O método de preparação é semelhante ao método acima. O solvente foi removido sob pressão reduzida, e se executou separação por cromatografia de coluna {eluente: diclorometano/acetona= 3/1 (v/v) ) para obter um pó' amarelo claro. Rendimento: 38%; mp (ponto de fusão)= 140,0-140, 9 0 C; MMR de (400 Mz, DMSO-d*) : õ 7,27-7,34 <m, 4H) , 5,63 (d, J = 5,4 Hz, 1H) , 5,14 (d, J = 5,2 Hz, 1H) , 5,04 (d, J = 15,1 Hz, 1H), 4,78 (d, J= 15, 1 Hz, 1H) , 3, 62-3, 73 (m, 3H) , 3,45-3,51 (m, 1H) , 2,26-2,31 (m, 1H) , 2, 11-2,21 (m, 2H) , 1,98-2,07 (m, 1H) ppm; NMR de 13C (100 Mz, DMSO-ds) : Ô 155, 3, 134,4, 133,9, 129,6, 129,0, 110,2, 87,6, 75, 5, 53, 9, 49, 2, 47, 0, 31,8, 31,7 ppm; HRM5 (ES+) valor calculado: Ci5H-;?N 5θ3,:>€1 (M+H)*, 322,0958; valor calculado: 322,0972. Valor calculado: Cí5H17N3033íC1 (M+H)+, 324,0929; valor calculado 324,0938. Exemplo 5: Síntese de 9-({tetraidrofuran-3-il) metil)-4- nitro-8-oxa-lO, 11-diidroimidazo-[2,3-a]-biciclo-[3,2,1]-oct-3-eno (o composto le) MeCNÍHCI temperatura ambiente [0057] O método de preparação é semelhante ao método acima. O solvente foi removido sob pressão reduzida, e se executou separação por cromatografia de coluna (eluente: diclorometano/acetona= 3/1 (v/v)) para obter um pó amarelo claro. Rendimento: 57%; mp (ponto de fusão)= 126,3-127,9°C; NMR de JH (400 Mz, DMSO-ds) : õ 5,11 (s, 1H), 5,00-5,03 (m, 1H) , 4,18 (d, J= 3,2 Hz, 2H), 4, 05-4,25 (m, 2H) , 3,85-3,96 <m, 4 Η), 2,25 (m, 1H), 1,66-1,81 (m, 4H), 2,35-2,40 <m, 1H), 2,17-2,21 (m, 2H) , 1,93-2,01 (m, 1H) ppm; NMR de 13C (100 Mz, DMSO-d6) : δ 81,9, 81, 6, 77, 9, 68,2, 53, 1, 49, 9, 48, 0, 44, 1, 36, 4, 33, 9, 29, 5, 23,2, 19, 8, ppm; HRMS (EI + ) valor calculado: C13H19N3O4 (M+) , 281.1376; valor medido 281, 1365. Exemplo 6: Síntese de 10-((6-cloropirid-3-il) metil)-4-nitro-8-oxa-ll,12-diidroimidazo-[2,3-a]-biciclo-[3, 2,1]-non-3-eno (o· composto 2a) MeCN/HCI temperatura ambiente [0058] Colocaram-se 1,27 de 2-cloro-5-(2-nitrometileno-imidazolidin-1-il metil)-piridina (0,005 mol), 30 mL de acetonitrila anidra, 3 mL de glutaraldeído aquoso a 25%', e uma quantidade catalítica de HCl num balão de fundo redondo de 50 mL. 0 sistema foi agitado em temperatura ambiente. Monitorou-se a reação por TLC. Após o término da reação, o sistema foi neutralizado por bicarbonato de sódio aquoso saturado, e extraído. O solvente foi removido sob pressão reduzida, e se executou separação por cromatografia de coluna (eluente: diclorometano/acetona- 3/1 (v/v)) para obter um pó amarelo claro. Rendimento: 76%; mp (ponto de fusão)= 174,7-175,4 °C; NMR de 3H (400 Mz, DMS0-df:) : δ 8,38 (dd, Ji = 0,6 Hz, J2 = 2,4 Hz, 1HJ, 7,84 (dd, Ji = 2,4 Hz, J2 = 8,4 Hz, 1H) , 7,52 (dd, Jj= 0,6 Hz, J2 = 8,4 Hz, 1H), 5,12 (s, 1H) , 5,04-5,05 (m, 1H), 4,97 (d, J = 15,6 Hz, 1H>, 4,71 (d, J = 15,6 Hz, 1H), 3, 62-3, 74 <m, 4H), 1,66-1,81 (m, 4H) , 1,51-1,55 (m, 1H), 1,32-1,44 (m, 1H) ppm; NMR de UC (100 Mz, DMSO-d*) : δ 156,6, 149, 7, 149, 6, 139, 7, 132, 9, 124,5, 105, 8, 81,7, 68, 9, 51, 7, 50,0, 46,3, 28,8, 27,2, 14,8 ppm; HRMS (EI+) valor calculado: Ci5Hl7N^033Xl ÍM+) , 336,0989; valor calculado 336,0988, Valor calculado: CisH17N40337C1 (M+>, 338, 0960; valor calculado 338,0968.Example 4: Synthesis of 9- (4-chloro-benzyl) -4-nitro-8-oxa-10,11-dihydroimidazo [2,3-a] -bicyclo [3,2,1] -oct-3 -ene (compound 1d) MECHCl at room temperature The preparation method is similar to the above method. The solvent was removed under reduced pressure, and column chromatography (eluent: dichloromethane / acetone = 3/1 (v / v)) was performed to obtain a light yellow powder. Yield: 38%; mp (melting point) = 140.0-140.9 ° C; MMR (400Mz, DMSO-d *): δ 7.27-7.34 (m, 4H), 5.63 (d, J = 5.4 Hz, 1H), 5.14 (d, J = 5.2 Hz, 1H), 5.04 (d, J = 15.1 Hz, 1H), 4.78 (d, J = 15.1 Hz, 1H), 3.62-3.73 (m, 3H), 3.45-3.51 (m, 1H), 2.26-2.31 (m, 1H), 2.11-2.21 (m, 2H), 1.98-2.07 ( m, 1H) ppm; 13 C NMR (100 MHz, DMSO-d 6): δ 155, 3, 134.4, 133.9, 129.6, 129.0, 110.2, 87.6, 75, 5, 53, 9, 49 2.47.0.0 31.8, 31.7 ppm; HRM5 (ES +) calculated value: C15 H -? N 5θ 3,:> 1 (M + H) *, 322.0958; calculated value: 322.0972. Calculated: C15 H17 N3033 Cl (M + H) +, 324.0929; calculated value 324.0938. Example 5: Synthesis of 9 - ({Tetrahydrofuran-3-yl) methyl) -4-nitro-8-oxa-10,11-dihydroimidazo [2,3-a] bicyclo [3,2,1] - oct-3-ene (compound 1e) MeCNHCl at room temperature The preparation method is similar to the above method. The solvent was removed under reduced pressure, and separation was performed by column chromatography (eluent: dichloromethane / acetone = 3/1 (v / v)) to obtain a light yellow powder. Yield: 57%; mp (melting point) = 126.3-127.9 ° C; 1 H NMR (400Mz, DMSO-d 6): δ 5.11 (s, 1H), 5.00-5.03 (m, 1H), 4.18 (d, J = 3.2Hz, 2H) 4.05-4.25 (m, 2H), 3.85-3.96 (m, 4 Η), 2.25 (m, 1H), 1.66-1.81 (m, 4H), 2.35-2.40 (m, 1H), 2.17-2.21 (m, 2H), 1.93-2.01 (m, 1H) ppm; 13 C NMR (100 MHz, DMSO-d 6): δ 81.9, 81, 6, 77, 9, 68.2, 53, 1, 49, 9, 48, 0, 44, 1, 36, 4, 33 , 9.29, 5, 23.2, 19.8, ppm; HRMS (EI +) calculated value: C13H19N3O4 (M +), 281.1376; 281, 1365. Example 6: Synthesis of 10 - ((6-chloropyrid-3-yl) methyl) -4-nitro-8-oxa-11,12-dihydroimidazo [2,3-a] bicyclo [3,1,1] non-3-ene (the compound 2a) MeCN / HCl at room temperature 1.27 µl of 2-chloro-5- (2-nitromethylene-imidazolidin-1-yl) methyl) pyridine (0.005 mol), 30 mL of anhydrous acetonitrile, 3 mL of 25% aqueous glutaraldehyde, and a catalytic amount of HCl in a 50 mL round bottom flask. The system was stirred at room temperature. The reaction was monitored by TLC. After completion of the reaction, the system was neutralized by saturated aqueous sodium bicarbonate and extracted. The solvent was removed under reduced pressure, and separation was performed by column chromatography (eluent: dichloromethane / acetone-3/1 (v / v)) to obtain a light yellow powder. Yield: 76%; mp (melting point) = 174.7-175.4 ° C; 3 H NMR (400Mz, DMSO-d 6): δ 8.38 (dd, J1 = 0.6Hz, J2 = 2.4Hz, 1HJ, 7.84 (dd, Ji = 2.4Hz, J2 = 8.4 Hz, 1H), 7.52 (dd, Jj = 0.6 Hz, J2 = 8.4 Hz, 1H), 5.12 (s, 1H), 5.04-5.05 (m , 1H), 4.97 (d, J = 15.6 Hz, 1H>, 4.71 (d, J = 15.6 Hz, 1H), 3.62-3.74 (m, 4H), 1 , 66-1.81 (m, 4H), 1.51-1.55 (m, 1H), 1.32-1.44 (m, 1H) ppm UC NMR (100 MHz, DMSO-d *) ): δ 156.6, 149, 7, 149, 6, 139, 7, 132, 9, 124.5, 105, 8, 81.7, 68, 9, 51, 7, 50.0, 46.3 , 28.8, 27.2, 14.8 ppm, HRMS (EI +) calculated: C15 H17 N4 O33 Xl M +), 336.0989; calculated value 336.0988, Calculated value: C17 H17 N40337 Cl (M +>, 338, 0960; calculated value 338.0968.
Exemplo 7: Síntese de 10-((2-clorotiazol-5-il)metil)-4-nitro-8-oxa-ll,12-diidroimidazo-[2,3-a]-biciclo -[3,2,1]-non-3-eno (o composto 2 b) , M»CMlHCÍ. tempera- tura ambiente [0059] O método de preparaçao é semelhante ao método acima, 0 solvente foi removido sob pressão reduzida, e se executou separação por cromatografia de coluna (eluente: diclorometano/acetona= 3/1 (v/v)) para obter um pó amarelo Claro. Rendimento: 62%; mp [ponto de fusão)= 159,1-160,5 ° C; MMR de !H [400 Mz, DMSO-dí) : δ 7,48 (s, 1H), 5,30 (d, J = 3,2 Hz, 1H) , 5,24 [d, J = 15,4 Hz, 1H), 4,98 (s, 1H), 4,78 [d, J = 15,4 Hz, 1H), 3, 76-3, 87 (m, 1H) , 3,60-3,71 [m, 3H) , 2,12 (d, J = 14,0 Hz, 1H), 1,82-1,96 (m, 2H) , 1,64-1,77 (m, 2H), 1, 48-1,60 [m, 1H) ppm; HMR de 13C [100 Mz, DMSO-cFe) : δ 155, 7, 154,1, 140,5, 135, 6, 107,0, 82,7, 69, 4, 49, 4, 48,3, 46,2, 29,4, 26,5, 14,9 ppm; HRMS (EI+) valor calculado: Ci3H15N403S3jC1 ÍM*) , 342, 0553; valor calculado: 342,0548. Valor calculado CuHisN^QaS^Cl [M')r 344,0524; valor calculado 344,0564.Example 7: Synthesis of 10 - ((2-chlorothiazol-5-yl) methyl) -4-nitro-8-oxa-11,12-dihydroimidazo [2,3-a] bicyclo - [3,2,1 ] -non-3-ene (compound 2b), M, CMHCl. The preparation method is similar to the above method, the solvent was removed under reduced pressure, and column chromatography (eluent: dichloromethane / acetone = 3/1 (v / v)) was performed to get a light yellow powder. Yield: 62%; mp [melting point] = 159.1-160.5 ° C; 1 H MMR [400 Mz, DMSO-d 1): δ 7.48 (s, 1H), 5.30 (d, J = 3.2 Hz, 1H), 5.24 [d, J = 15.4 Hz, 1H), 4.98 (s, 1H), 4.78 [d, J = 15.4 Hz, 1H), 3.76-3.87 (m, 1H), 3.60-3.71 [m, 3H), 2.12 (d, J = 14.0 Hz, 1H), 1.82-1.96 (m, 2H), 1.64-1.77 (m, 2H), 1, 48-1.60 [m, 1H) ppm; 13 C HMR [100 Mz, DMSO-cFe): δ 155.7, 154.1, 140.5, 135.6, 107.0, 82.7, 69.4, 49.4, 48.3, 46 , 2, 29.4, 26.5, 14.9 ppm; HRMS (EI +) calculated value: C13 H15 N403 S3 Cl (M +), 342.0553; calculated value: 342.0548. Calculated value CuH 1 N 4 QaS 2 Cl (M ') r 344.0524; calculated value 344.0564.
Exemplo 8 : Síntese de 10-benzil-4-nitro-8-oxa-l1, 12- diidroimidazo- [2, 3-a] -biciclo-[3,2,1]-non-3-eno [o composto 2c) HeCMHCI, 'emperatur; ambiente [0060] O método de preparação é semelhante ao método acima. 0 solvente foi removido sob pressão reduzida, e se executou separação por cromatografia de coluna (eluente: diclorometano/acetona= 3/1 (v/v)) para obter um pó amarelo claro·. Rendimento: 7 7%; mp (ponto de fusão) = 180,5-181,2°C; NMR de :iH (400 Mz, DMSÜ-ds) : 7, 29-7,37 (m, 5H) , 5,33 (d, J = 3,1 Hz, 1H}, 5,02 (d, J - 15,0 Hz, 1H) , 4,95 (s, 1H>, 4,85 (d, J = 15, 0 Hz, 1H) , 3, 68-3, 75 (m, 1H) , 3,48-3, 64 (m, 3H) , 2.14 (d, J= 13,1 Hz, 1H) , 1,81-1,93 (m, 2H) , 1,51-1,70 (m, 3H) ppm; NMR de l3C (100 Mz, DM50-dé) ; δ 156,6, 136,4, 128,8, 128,3, 128,0, 10 6, 7, 83, 0, 69,7, 54,8, 48, 6, 46,7, 29,5, 26,5, 15,0 ppm; HRMS (EI + ) valor calculado : €ι6Η19Ν303 (M+) , 301,1426; valor calculado: 301,1429.Example 8: Synthesis of 10-benzyl-4-nitro-8-oxa-1,12-dihydroimidazo [2,3-a] -bicyclo [3,2,1] -non-3-ene [compound 2c ) HeCMHCI, 'emperatur; environment [0060] The preparation method is similar to the above method. The solvent was removed under reduced pressure, and separation was performed by column chromatography (eluent: dichloromethane / acetone = 3/1 (v / v)) to obtain a light yellow powder. Yield: 7 7%; mp (melting point) = 180.5-181.2 ° C; 1 H NMR (400Mz, DMS δ-ds): 7.29-7.37 (m, 5H), 5.33 (d, J = 3.1Hz, 1H), 5.02 (d, J- 15.0 Hz, 1H), 4.95 (s, 1H), 4.85 (d, J = 15.0 Hz, 1H), 3.68-3.75 (m, 1H), 3.48- 3.64 (m, 3H), 2.14 (d, J = 13.1 Hz, 1H), 1.81-1.93 (m, 2H), 1.51-1.70 (m, 3H) ppm; 13 C NMR (100 MHz, DM 50 -d6) δ 156.6, 136.4, 128.8, 128.3, 128.0, 106, 83, 0, 69.7, 54.8, 48.6, 46.7, 29.5, 26.5, 15.0 ppm HRMS (EI +) calculated value: € 61919303 (M +), 301.1426, calculated value: 301.1429.
Exemplo 9: Síntese de 10-(4-clorò-benzil)-4-nitro-8-òxa- 11, 12-diidroimidazo-[2,3-a]-biciclo-[3,2,1]-non-3-eno (o composto 2d) MeCWHCI tempera- tura ambiente [0061] O método de preparação é semelhante ao método acima. O solvente foi removido sob pressão reduzida, e se executou separação por cromatografia de coluna (eluente: diclorometano/acetona= 3/1 (v/v)) para obter um pó amarelo claro. Rendimento: 70%; mp (ponto de fusão)= 156,9-158,3°C; NMR de lH (400 Mz, DMSQ-dg) : δ 7,29-7,34 (m, 4H) , 5,33 (d, J - 4,0 Hz, 1H), 5,05 (d, 15,1 Hz, 1H) , 4,96 (s, 1H) , 4,75 (d, J = 15.1 Hz, 1H) , 3, 66-3, 73 (m, 1H) , 3, 55-3, 60 (m, 3H) , 2.14 (d, J = 13,6 Hz, 1H) , 1,82-1,95 (m, 2H) , 1,51-1,71 (m, 3H) ppm; NMR de l3C (100 Mz, DMSO-de) ; δ 156, 5, 134,9, 133,8, 129,7, 129,0, 106, 8, 83, 0, 69,6, 54, 4, 48, 9, 46, 6, 29, 6, 26,5, 15,0 ppm; HRMS (EI + ) valor calculado: CigHieNsOa^Cl ÍM+) , 335,1037 ; valor calculado 335,1044. Valor calculado: CicHisNuGa3 'Cl (M+) , 337,1007; valor calculado 337,1036.Example 9: Synthesis of 10- (4-chlorobenzyl) -4-nitro-8-oxa-11,12-dihydroimidazo [2,3-a] bicyclo [3,2,1] -non-3 -ene (compound 2d) MeCWHCI room temperature The preparation method is similar to the above method. The solvent was removed under reduced pressure, and separation was performed by column chromatography (eluent: dichloromethane / acetone = 3/1 (v / v)) to obtain a light yellow powder. Yield: 70%; mp (melting point) = 156.9-158.3 ° C; 1H NMR (400Mz, DMSQ-dg): δ 7.29-7.34 (m, 4H), 5.33 (d, J = 4.0 Hz, 1H), 5.05 (d, 15, 1 Hz, 1H), 4.96 (s, 1H), 4.75 (d, J = 15.1 Hz, 1H), 3.66-3.73 (m, 1H), 3.55-3.60 ( m, 3H), 2.14 (d, J = 13.6 Hz, 1H), 1.82-1.95 (m, 2H), 1.51-1.71 (m, 3H) ppm; 13 C NMR (100 MHz, DMSO-d 6); δ 156, 5, 134.9, 133.8, 129.7, 129.0, 106, 8, 83.0, 69.6, 54, 4.48, 9, 46, 6, 29, 6, 26 0.5.0 ppm; HRMS (EI +) calculated value: C18 H17 N5 O4 (Cl (M +)), 335.1037; calculated value 335.1044. Calculated value: C18 H18 N9 O3 Cl (M +), 337.1007; calculated value 337.1036.
Exemplo 10: Síntese de 10-((tetraidrofuran-3-il) metil)-4-nitro-8-oxa-ll, 12-diídroímídazo- [2,3-a]-biciclo-[3, 2,1]-non-3-eno (o composto· 2e) MéCWHCI, temperatura ambiente [0062] Colocaram-se 1,065 g de 1- ( (tetraidrofuran-3-il)metil)-2-{nitrometileno)-1-imidazolina (0,005 mol), 3 mL de glutaraldeído aquoso a 25%, e uma quantidade catalítica de HC1 num balão de fundo redondo de 50 mL. O sistema foi agitado em temperatura ambiente, e se monitorou a reação por TLC. Após o término da reação, o solvente foi removido sob pressão reduzida, e se executou separação por cromatografia para obter um produto puro amarelo· claro· em pó. O rendimento foi de 36%; mp (ponto de fusão) = 115,3-116, 9°C; NMR de ]H (400 Mz, DMSO-ds) : δ 5,11 (s, 1H) , 5,00-5,03 (m, 1H) , 4,18 (d, J = 3,2 Hz, 2H) , 4,05-4,25 <m, 2H), 3,85-3,96 (m, 4H) , 2,25 (m, 1H) , 1,66-1,81 (m, 4H) , 1,63 -1,64 (m, 2H) , 1,57- 1,59 (m, 2H> , 1,51-1,55 (ra, 1H), 1,32-1,44 (m, 1H) ppm; NMR de 13C (100 Mz, DMSO-de) : õ 81,7, 80,6, 78,5, 68,9, 50,0, 49,7, 46, 9, 44,6, 36, 8, 33, 9, 28,8, 27, 2, 17,8, 14, 8 ppm; HRMS (EI + ) valor calculado: C14H21N3O4 (M*), 295, 1532; valor medido· 295, 1598.Example 10: Synthesis of 10 - ((tetrahydrofuran-3-yl) methyl) -4-nitro-8-oxa-11,12-dihydroimidazo [2,3-a] bicyclo [3,1,1] - non-3-ene (the compound · 2e) MetHCHCl, room temperature 1.065 g of 1- ((tetrahydrofuran-3-yl) methyl) -2- (nitromethylene) -1-imidazoline (0.005 mol) 3 mL of 25% aqueous glutaraldehyde, and a catalytic amount of HCl in a 50 mL round bottom flask. The system was stirred at room temperature and the reaction monitored by TLC. After completion of the reaction, the solvent was removed under reduced pressure, and chromatographic separation was performed to obtain a pure light yellow · powdered product. The yield was 36%; mp (melting point) = 115.3-116.9 ° C; 1 H NMR (400Mz, DMSO-d 6): δ 5.11 (s, 1H), 5.00-5.03 (m, 1H), 4.18 (d, J = 3.2Hz, 2H ), 4.05-4.25 (m, 2H), 3.85-3.96 (m, 4H), 2.25 (m, 1H), 1.66-1.81 (m, 4H), 1.63 -1.64 (m, 2H), 1.57-1.59 (m, 2H, 1.51-1.55 (ra, 1H), 1.32-1.44 (m, 1H 13 C NMR (100 MHz, DMSO-d 6): δ 81.7, 80.6, 78.5, 68.9, 50.0, 49.7, 46.9, 44.6, 36, 8.33, 9, 28.8, 27, 2, 17.8, 14.8 ppm HRMS (EI +) calculated value: C 14 H 21 N 3 O 4 (M *), 295, 1532, measured value 295, 1598.
Exemplo 11: Mensuração da atividade inseticida dos compostos da presente invenção (1) Atividade inseticida contra afideos [0063] Os afideos, que pertencem à ordem Homóptera e têm aparelhos bucais sugadores de perfuração, são uma praga comum para culturas agrícolas. Usou-se Aphis craccivora como o objetivo e se empregou um método de imersão para teste. Método de teste: Pesou-se precisamente cada amostra, e se adicionou, respectivamente, 2 mL de DMSO e 18 mL de água; depois foram adicionadas três gotas do agente de emulsão 2001 para formar um líquido de teste; preparou-se também um em branco adicionando-se três gotas de agente de emulsão 2201 a 2 mL de DMSO e 18 mL de água. Folhas largas de feijão com insetos aderidos nelas foram imersas no líquido de teste por três a cinco segundos, depois removidas e secadas em ar; os insetos foram movidos para um recipiente limpo juntamente com alimentação e se colocou o recipiente num espaço de recuperação termostática seca. Após 24 horas, checou-se o número de insetos mortos. A Tabela 1 mostra os resultados. (2) Atividade inseticida contra Nilaparvata lugens [0064] Nilaparvata lugens, que pertence à ordem Homóptera e tem aparelho bucal sugador de perfuração, é uma praga comum para culturas agrícolas. Usou-se Nilaparvata lugens como o objetivo e se empregou um método de mensuração de micro-gotejamento relatado por Nagata para teste.Example 11: Measurement of insecticidal activity of the compounds of the present invention (1) Aphid insecticidal activity The aphids, which belong to the order Homoptera and have perforating sucking mouthpieces, are a common pest for agricultural crops. Aphis craccivora was used as the objective and an immersion method for testing was employed. Test Method: Each sample was precisely weighed and 2 mL DMSO and 18 mL water respectively added; then three drops of emulsifying agent 2001 were added to form a test liquid; One blank was also prepared by adding three drops of emulsifying agent 2201 to 2 mL DMSO and 18 mL water. Broad bean leaves with insects attached to them were immersed in the test liquid for three to five seconds, then removed and air dried; The insects were moved to a clean container along with food and the container was placed in a dry thermostatic recovery space. After 24 hours, the number of dead insects was checked. Table 1 shows the results. (2) Insecticidal activity against Nilaparvata lugens [0064] Nilaparvata lugens, which belongs to the Homoptera order and has a perforating sucking mouthpiece, is a common pest for agricultural crops. Nilaparvata lugens was used as the objective and a micro-drip measurement method reported by Nagata was employed for testing.
Procedimento operacional: Fêmeas aladas não-acasaladas dois a três dias após eclosão foram selecionadas como os objetos de teste; os compostos foram diluídos em acetona numa série de concentrações. Os insetos foram paralisados por dióxido de carbono, e o líquido (0,08 pL) foi gotejado sobre o pronoto dos insetos usando um micro-gotejador manual (Burkard Manufacturing Co., Ltd., Rickmansworth, UK). Usou-se cada uma das concentrações para tratar cerca de 30 insetos em triplicata. Usou-se acetona como o controle. Os insetos adultos tratados foram desenvolvidos em mudas de arroz cultivado sem solo numa incubadora (20 x 20 x 10 cm), onde se controlou a temperatura a (25 ± 1)°C com 16/8 horas de ciclo de luz e escuridão. Os resultados foram checados após 48 horas, e se calculou LD50 usando um método de análise de probabilidade padrão. A Tabela 2 mostra os resultados. (3) Atividade inseticida contra lagartas de cereais [0065] Usaram-se larvas de Pseudaletia separata Walker de segunda fase como os sujeitos e se empregou o método de imersão para teste.Operational procedure: Unmated winged females two to three days after hatching were selected as the test objects; The compounds were diluted in acetone at a number of concentrations. The insects were paralyzed by carbon dioxide, and the liquid (0.08 pL) was dripped onto the insect pronotum using a manual micro-dripper (Burkard Manufacturing Co., Ltd., Rickmansworth, UK). Each concentration was used to treat about 30 insects in triplicate. Acetone was used as the control. The treated adult insects were grown in seedlings of rice grown without soil in an incubator (20 x 20 x 10 cm), where the temperature was controlled at (25 ± 1) ° C with 16/8 hours of light and dark cycle. Results were checked after 48 hours, and LD50 was calculated using a standard probability analysis method. Table 2 shows the results. (3) Insecticidal activity against grainworms Second-phase Pseudaletia separata Walker larvae were used as the subjects and the immersion method for testing was employed.
[0066] Pseudaletia separata Walker, que é uma importante praga de lepidópteros de vários grãos, pode se usada apropriadamente em várias aplicações, por exemplo, no estudo de toxicidade, tais como toxicidade de estômago, envenenamento por contato, efeitos residuais e abrangentes de inseticidas, e outros aspectos de toxicologia de insetos, bem como o teste de investigação para novos compostos. Testou-se a atividade de extermínio de Pseudaletia separata Walker de acordo com um método relatado na literatura.Pseudaletia separata Walker, which is an important multi-grain lepidopteran pest, can be used appropriately in various applications, for example in the study of toxicity such as stomach toxicity, contact poisoning, residual and comprehensive insecticide effects. , and other aspects of insect toxicology, as well as research testing for new compounds. Pseudaletia separata Walker extermination activity was tested according to a method reported in the literature.
Procedimento operacional do método de imersão de folha: [0067] Pesou-se precisamente cada amostra, e se adicionou, respectivamente, 2 mL de DMSO e 18 mL de água; depois foram adicionadas três gotas do agente de emulsão 2001 (adquirido de Shanghai Nongyaochang Co., Ltd.) para formar um liquido de teste. Preparou-se também um em branco adicionando-se três gotas de agente de emulsão 2201 a 2 mL de DMSO e 28 mL de água. Folhas novas de milho foram cortadas em pedaços e imersas por cinco segundos no líquido, depois removidas e secadas em ar e colocadas num recipiente de 100 mL. Cerca de 20 larvas de segunda fase foram introduzidas no recipiente. O recipiente foi fechado usando gaze branca e fita de borracha (elástico)f e as larvas foram alimentadas com milho embebido continuamente com o líquido. Checou-se a taxa de mortalidades das larvas após cinco dias. A temperatura necessária foi de 22°C a 27°C, com umidade relativa de 70% a 80%. Não foi necessário corrigir as taxas de mortalidade para cada tratamento se a taxa de mortalidade do em branco foi menor ou igual a 5%; entretanto, se a taxa de mortalidade de controle foi de 5% a 20% deve-se usar a correção de Abbott para as taxas de mortalidade de cada tratamento. A fórmula de Abbott é: Taxa de mortalidade corrigida=[(taxa de mortalidade tratada -taxa de mortalidade de controle)/(100 - taxa de mortalidade de controle) x 100].Leaf Immersion Method Operating Procedure: Each sample was precisely weighed and 2 mL DMSO and 18 mL water respectively added; Then three drops of emulsion agent 2001 (purchased from Shanghai Nongyaochang Co., Ltd.) were added to form a test liquid. One blank was also prepared by adding three drops of emulsifying agent 2201 to 2 mL DMSO and 28 mL water. New corn leaves were cut into pieces and immersed for five seconds in the liquid, then removed and air dried and placed in a 100 ml container. About 20 second stage larvae were introduced into the container. The container was closed using white gauze and rubber (elastic) tape and the larvae were fed with corn continuously soaked with the liquid. The larval mortality rate was checked after five days. The required temperature was 22 ° C to 27 ° C, with relative humidity of 70% to 80%. Mortality rates need not be corrected for each treatment if the blank mortality rate is less than or equal to 5%; however, if the control mortality rate was 5% to 20%, Abbott's correction should be used for the mortality rates of each treatment. Abbott's formula is: Corrected mortality rate = [(treated mortality rate - control mortality rate) / ((100 - control mortality rate) x 100].
Tabela 1: Atividades inseticidas de compostos-alvos contra afideos e Fseudaletia separata Walker Tabela 2: Atividades de compostos contra Nilaparvata lugens suscetível e resistente [0068] Testaram-se as atividades dos compostos-alvos era afídeos, Pseudaletia separata Walker, e Nilaparvata lugens, e os resultados estão mostrados nas Tabelas 1 e 2. Pode-se observar das Tabelas 1 e 2 que o composto heterocíclico ligado por ponte de oxigênio la possui atividade muito elevada que é muito maior que a de imidacloprido: LC50 contra af ídeos é 1,52 mg. Li1, e LC50 contra Pseudaletia separata Walker é 12,5 mg.L~J. De modo ainda mais importante, a atividade do composto la contra Nilaparvata lugens suscetível é geralmente a mesma que de imidacloprido, e a atividade do mesmo contra Nilaparvata lugens resistente a imidacloprido é 50 vezes aquela de imidacloprido. O composto· la tem atividade relativamente fraca. Interessantemente, as atividades dos compostos heterocíclicos ligados por pontes de oxigênio 2a a 2c, que são construídos a partir de gíutaraldeído, foram muito mais fracos, e alguns compostos foram eficazes somente contra afídeos. Uma análise da estrutura cristalina dos compostos la e 2a mostra que os compostos la e 2a têm diferentes configurações de ligação por ponte de oxigênio, onde as pontes de oxigênio são opostas em orientação; esta diferença pode ser muito claramente observada sobrepondo as duas moléculas. Estas diferenças nas estruturas de pontes de oxigênio podem ser responsáveis pelas atividades notadamente diferentes dos compostos la e 2a.Table 1: Insecticidal activities of target compounds against aphids and Walker Fseudaletia separata Table 2: Activities of compound against susceptible and resistant Nilaparvata lugens [0068] The activities of the aphid target compounds, Pseudaletia separata Walker, and Nilaparvata lugens and the results are shown in Tables 1 and 2. It can be seen from Tables 1 and 2 that the oxygen-bridged heterocyclic compound 1a has very high activity that is much higher than that of imidacloprid: LC50 against aphids is 1, 52 mg. Li1, and LC50 against Pseudaletia separata Walker is 12.5 mg.L-J. Most importantly, the activity of compound la against susceptible Nilaparvata lugens is generally the same as that of imidacloprid, and its activity against imidacloprid resistant Nilaparvata lugens is 50 times that of imidacloprid. Compound · la has relatively weak activity. Interestingly, the activities of oxygen-bridged heterocyclic compounds 2a to 2c, which are constructed from gutaraldehyde, were much weaker, and some compounds were effective only against aphids. An analysis of the crystal structure of compounds 1a and 2a shows that compounds 1a and 2a have different oxygen bridge binding configurations, where oxygen bridges are opposite in orientation; This difference can be very clearly observed by overlapping the two molecules. These differences in oxygen bridge structures may be responsible for the remarkably different activities of compounds 1a and 2a.
Exemplo 12; Pesquisa do mecanismo de ação do composto (la) [0069] Submeteu-se separadamente o composto (la) a teste eletrofisiológico e teste com substituição de marcador isotópico. O composto (la) pode inibir resposta de agonista, o composto (la) não tem nenhuma ação agonistica sobre receptores de acetil colina nicotinica de Periplaneta americana nos receptores NI α 1/β 2 expressos pelos oócitos, e o composto (la) pode inibir a resposta de agonista para acetil colina. Estes experimentos demonstram que o composto é um antagonista do receptor de acetil colina nicotinica (nAChRs).Example 12; Research on the mechanism of action of compound (la) Compound (la) was subjected to electrophysiological testing and isotopic marker replacement testing separately. Compound (la) may inhibit agonist response, compound (la) has no agonistic action on Periplaneta americana nicotinic acetylcholine receptors on oocyte-expressed NI α 1 / β 2 receptors, and compound (la) may inhibit the agonist response to acetyl choline. These experiments demonstrate that the compound is a nicotinic acetylcholine receptor antagonist (nAChRs).
Exemplo 13: Preparação de composições inseticidas contendo os compostos da presente invenção (a) Suspensão oleosa [0070] Prepararam-se os seguintes componentes: 25% em peso de qualquer um dos compostos la a le e 2a a 2e; 5% em peso de sorbitol hexaoleato de polioxietileno; e 70% em peso de um óleo de hidrocarboneto alifático superior. Todos os componentes foram moidos juntos numa areia de moagem até o tamanho de partícula de grânulos sólidos ser reduzido a menos que cerca de cinco microns. A suspensão viscosa resultante pode ser usada diretamente, ou pode ser usada após ser emulsifiçada em água. (b) Suspensão aquosa [0071] Prepararam-se os seguintes componentes: 25% em peso de qualquer um dos compostos la a le e 2a a 2e; 3% em peso de atapulgita hidratada; 10% em peso de lignossulfato de cálcio; 0,5% em peso de diidrogeno fosfato de sódio (NaH2P04) ; e 61,5% em peso de água. Todos os componentes foram moidos juntos numa areia de moagem até o tamanho de partícula de grânulos sólidos ser reduzido a menos que cerca de dez mícrons. A suspensão aquosa pode ser usada diretamente. (c) Isca [0072] Prepararam-se os seguintes componentes: 0,1-10% em peso de qualquer um dos compostos la a le e 2a a 2e; 80% em peso de farinha de trigo; e 19,9-10% em peso de melaço. Estes componentes foram completamente misturados e moldados quando necessário. A isca comestível pode ser distribuída num local infestado por pragas sanitárias, por exemplo, um local doméstico ou industrial, tal como uma cozinha, hospital, loja, ou área externa, controlando assim a praga através de ingestão oral.Example 13: Preparation of Insecticidal Compositions Containing the Compounds of the Present Invention (a) Oily Suspension The following components were prepared: 25% by weight of any of compounds 1a to 1a and 2a to 2e; 5% by weight polyoxyethylene sorbitol hexaoleate; and 70% by weight of a higher aliphatic hydrocarbon oil. All components were ground together in a grinding sand until the particle size of solid granules was reduced to less than about five microns. The resulting viscous suspension may be used directly, or may be used after being emulsified in water. (b) Aqueous suspension The following components were prepared: 25% by weight of any of compounds la to l and 2a to 2e; 3% by weight of hydrated attapulgite; 10% by weight calcium lignosulfate; 0.5% by weight sodium dihydrogen phosphate (NaH2PO4); and 61.5% by weight of water. All components were ground together in a grinding sand until the particle size of solid granules was reduced to less than about ten microns. The aqueous suspension can be used directly. (c) Bait The following components were prepared: 0.1-10% by weight of any of compounds la to l and 2a to 2e; 80% by weight of flour; and 19.9-10% by weight of molasses. These components were thoroughly mixed and molded as needed. Edible bait may be distributed in a sanitary pest-infested location, for example, a domestic or industrial location, such as a kitchen, hospital, shop, or outdoor area, thereby controlling the pest by oral ingestion.
[0073] Todas as referências mencionadas no presente pedido de patente aqui se incorporam por referência, como se individualmente incorporadas por referência. Adicionalmente, deve-se entender que após leitura do ensinamento acima, podem ser feitas muitas variações e modificações pelos especialistas na técnica, e estes equivalentes caem também dentro dos limites da abrangência definida pelas reivindicações anexas.All references mentioned in this patent application are incorporated herein by reference, as if individually incorporated by reference. In addition, it should be understood that upon reading the above teaching, many variations and modifications may be made by those skilled in the art, and these equivalents also fall within the range defined by the appended claims.
REIVINDICAÇÕES
Claims (11)
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