KR100613690B1 - 4-quinolinone derivative and fungicidal composition for agriculture and horticulture comprising same - Google Patents
4-quinolinone derivative and fungicidal composition for agriculture and horticulture comprising same Download PDFInfo
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- KR100613690B1 KR100613690B1 KR1020040060083A KR20040060083A KR100613690B1 KR 100613690 B1 KR100613690 B1 KR 100613690B1 KR 1020040060083 A KR1020040060083 A KR 1020040060083A KR 20040060083 A KR20040060083 A KR 20040060083A KR 100613690 B1 KR100613690 B1 KR 100613690B1
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- 0 *c(c(*)c12)c(*)c(*)c1NC(*)=C(C(S)=O)C2=O Chemical compound *c(c(*)c12)c(*)c(*)c1NC(*)=C(C(S)=O)C2=O 0.000 description 1
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- C07—ORGANIC CHEMISTRY
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- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/20—Oxygen atoms
- C07D215/22—Oxygen atoms attached in position 2 or 4
- C07D215/233—Oxygen atoms attached in position 2 or 4 only one oxygen atom which is attached in position 4
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- 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
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
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Abstract
본 발명은 농원예용 살균제로 유용한 하기 화학식 1의 신규한 4-퀴놀린온 유도체에 관한 것으로, 이 화합물은 광범위한 식물 병원균에 대해 선택적으로 높은 살균 효과를 나타낸다. 또한, 유효성분으로서 상기 화합물 및 약학적으로 허용되는 담체를 포함하는 농원예용 살균제 조성물이 광범위한 식물 병원균에 대해 사용될 수 있다.The present invention relates to a novel 4-quinolinone derivative of formula (I), which is useful as an agricultural horticultural fungicide, which selectively shows a high bactericidal effect against a wide range of plant pathogens. In addition, agricultural and horticultural fungicide compositions comprising the compound as a active ingredient and a pharmaceutically acceptable carrier can be used against a wide range of plant pathogens.
상기 식에서,Where
R1 내지 R4는 수소, 할로겐, C1-10의 선형 또는 분지형 알킬기, C1-6 의 선형 또는 분지형 할로알킬기, C1-10의 선형 또는 분지형 알콕시기, 페닐기, 페녹시기, 벤질기, 니트로기 또는 사이아노기이고(단, R1 내지 R4 가 모두 수소인 경우는 제외됨); R 1 to R 4 are hydrogen, halogen, C 1-10 linear or branched alkyl group, C 1-6 linear or branched haloalkyl group, C 1-10 linear or branched alkoxy group, phenyl group, phenoxy group, Benzyl, nitro or cyano groups (except where R 1 to R 4 are all hydrogen);
R5는 C1-6의 선형 또는 분지형 알킬기이고;R 5 is a C 1-6 linear or branched alkyl group;
X는 NHR6,, NHZAr 또는 이고;X is NHR 6 , , NHZAr or ego;
R6는 치환되거나 치환되지 않은 C1-15의 선형 또는 분지형 알킬기, 치환되거나 치환되지 않은 C3-10의 사이클로알킬기, 피페리딘기, 피페라진기 또는 아릴기이고;R 6 is a substituted or unsubstituted C 1-15 linear or branched alkyl group, a substituted or unsubstituted C 3-10 cycloalkyl group, piperidine group, piperazine group or aryl group;
Y는 (CH-R7)n 또는 산소 원자로서, 이때 n은 0 또는 1이며, n이 1일 경우, R7는 피페리딘기이고;Y is (CH-R 7 ) n or an oxygen atom, where n is 0 or 1 and when n is 1, R 7 is a piperidine group;
Z는 치환되거나 치환되지 않은 C1-6의 선형 또는 분지형 알킬기이며;Z is a substituted or unsubstituted C 1-6 linear or branched alkyl group;
Ar은 아릴기, 헤테로아릴기 또는 피롤리딘기이다.Ar is an aryl group, a heteroaryl group, or a pyrrolidine group.
Description
본 발명은 식물 병원균에 대해 우수한 살균 효과를 갖는, 신규한 4-퀴놀린온 유도체 및 이를 포함하는 농원예용 살균제 조성물에 관한 것이다.The present invention relates to a novel 4-quinolinone derivative having a good bactericidal effect against plant pathogens and agrohorticultural fungicide composition comprising the same.
식물 병해를 방지하기 위한 농원예용 살균제로서 여러 가지 화학구조를 갖는 합성 화합물들이 사용되어 농업 발전에 크게 기여해 왔다. 그러나, 기존 살균제 화합물 중 일부는 약해 또는 환경 오염으로 인해 그 사용이 제한되고 있거나, 활성 및 안정성의 조절이 결코 만족스럽지 못하였으며, 특히 지금까지 알려진 살균제들에 있어서는 그 내성이 생겨남에 따라 새로운 구조의 살균제 개발이 요구되고 있다. As a horticultural fungicide for preventing plant diseases, synthetic compounds having various chemical structures have been used, which has contributed greatly to the development of agriculture. However, some of the existing fungicide compounds have been limited in their use due to weakness or environmental pollution, or they have never been satisfactory in the control of activity and stability, especially in the fungicides known to date, as their resistance has developed. The development of fungicides is required.
따라서, 본 발명의 목적은 환경 오염의 우려없이, 종래에 비하여 보다 강력 한 살균 또는 살충력을 갖는 새로운 구조의 4-퀴놀린온 유도체 화합물을 제공하기 위한 것이다.
Accordingly, it is an object of the present invention to provide a 4-quinolinone derivative compound of a novel structure which has stronger sterilization or insecticidal properties than the conventional one, without fear of environmental pollution.
상기 목적을 달성하기 위하여 본 발명에서는, 농원예용 살균제 또는 살충제로서 유용한 하기 화학식 1의 신규한 4-퀴놀린온 유도체를 제공한다:In order to achieve the above object, the present invention provides a novel 4-quinolinone derivative of the formula (1) useful as an agricultural or horticultural fungicide or insecticide:
화학식 1Formula 1
상기 식에서,Where
R1 내지 R4는 수소, 할로겐, C1-10의 선형 또는 분지형 알킬기, C1-6 의 선형 또는 분지형 할로알킬기, C1-10의 선형 또는 분지형 알콕시기, 페닐기, 페녹시기, 벤질기, 니트로기 또는 사이아노기이고(단, R1 내지 R4 가 모두 수소인 경우는 제외됨); R 1 to R 4 are hydrogen, halogen, C 1-10 linear or branched alkyl group, C 1-6 linear or branched haloalkyl group, C 1-10 linear or branched alkoxy group, phenyl group, phenoxy group, Benzyl, nitro or cyano groups (except where R 1 to R 4 are all hydrogen);
R5는 C1-6의 선형 또는 분지형 알킬기이고;R 5 is a C 1-6 linear or branched alkyl group;
X는 NHR6,, NHZAr 또는 이고;X is NHR 6 , , NHZAr or ego;
R6는 치환되거나 치환되지 않은 C1-15의 선형 또는 분지형 알킬기, 치환되거나 치환되지 않은 C3-10의 사이클로알킬기, 피페리딘기, 피페라진기 또는 아릴기이고;R 6 is a substituted or unsubstituted C 1-15 linear or branched alkyl group, a substituted or unsubstituted C 3-10 cycloalkyl group, piperidine group, piperazine group or aryl group;
Y는 (CH-R7)n 또는 산소 원자로서, 이때 n은 0 또는 1이며, n이 1일 경우, R7는 피페리딘기이고;Y is (CH-R 7 ) n or an oxygen atom, where n is 0 or 1 and when n is 1, R 7 is a piperidine group;
Z는 치환되거나 치환되지 않은 C1-6의 선형 또는 분지형 알킬기이며;Z is a substituted or unsubstituted C 1-6 linear or branched alkyl group;
Ar은 아릴기, 헤테로아릴기 또는 피롤리딘기이다.Ar is an aryl group, a heteroaryl group, or a pyrrolidine group.
또한, 본 발명에서는 유효성분으로서 상기 화학식 1의 퀴놀린온 유도체 및 약학적으로 허용되는 담체를 포함하는 농원예용 살균제 또는 살충제 조성물을 제공한다.In addition, the present invention provides a horticultural fungicide or insecticide composition comprising a quinolinone derivative of Formula 1 and a pharmaceutically acceptable carrier as an active ingredient.
이하 본 발명에 대하여 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명에 따른 4-퀴놀린온 유도체에서, R6의 바람직한 예는 할로겐, C1-3 알콕시기, C1-3 알콕시카르보닐기 또는 C3-6 사이클로알킬기로 치환되거나 치환되지 않은 선형 또는 분지형 알킬기; C1-3 알킬기 또는 페닐기로 치환되거나 치환되지 않은 C3-6 사이클로알킬기; C1-3 알킬기 또는 에톡시카르보닐기로 하나 이상 치환되거나 치환되지 않은 피페리딘기; C1-3 알킬기로 치환된 피페라진기; 할로겐, C1-4의 선형 또는 분지형 알킬, 알콕시 또는 할로알킬기, 또는 사이아노기로 하나 이상 치환되거나 치환되지 않은 페닐기이다.In the 4-quinolinone derivatives according to the invention, preferred examples of R 6 are linear or branched alkyl groups which may or may not be substituted with halogen, C 1-3 alkoxy groups, C 1-3 alkoxycarbonyl groups or C 3-6 cycloalkyl groups ; C 3-6 cycloalkyl group unsubstituted or substituted with a C 1-3 alkyl group or a phenyl group; A piperidine group unsubstituted or substituted with one or more C 1-3 alkyl groups or ethoxycarbonyl groups; Piperazine group substituted with a C 1-3 alkyl group; Halogen, a C 1-4 linear or branched alkyl, alkoxy or haloalkyl group, or a phenyl group, substituted or unsubstituted by one or more cyano groups.
본 발명에 따른 4-퀴놀린온 유도체에서, Z의 바람직한 예는 C1-3의 선형 또는 분지형 알킬기, 히드록시메틸기, 또는 페닐기 또는 치환된 페닐기로 치환되거나 치환되지 않은 C1-3 선형 또는 분지형 알킬기이다.In the 4-quinolinone derivative of the present invention, a preferable example of Z is a linear or branched alkyl group, hydroxymethyl group, or a phenyl group or substituted phenyl group substituted or unsubstituted C 1-3 linear or have a C 1-3 of It is a topographic alkyl group.
본 발명에 따른 4-퀴놀린온 유도체에서, Ar의 바람직한 예는 할로겐, C1-4의 선형 또는 분지형 알킬, 알콕시 또는 할로알킬기, 니트로기, 아미노기, 아미노설폰기로 하나 이상 치환되거나 치환되지 않은 페닐기; C1-3의 선형 또는 분지형 알킬기로 치환되거나 치환되지 않은 피롤리딘기; 또는 C1-3의 선형 또는 분지형 알킬기로 치환되거나 치환되지 않은 피리딘기이다.In the 4-quinolinone derivatives according to the invention, preferred examples of Ar are halogen, C 1-4 linear or branched alkyl, alkoxy or haloalkyl groups, nitro groups, amino groups, phenyl groups unsubstituted or substituted with one or more groups ; A pyrrolidine group substituted or unsubstituted with a C 1-3 linear or branched alkyl group; Or a pyridine group unsubstituted or substituted with a C 1-3 linear or branched alkyl group.
본 발명에 따른 상기 화학식 1의 4-퀴놀린온 유도체는, 하기 반응식 1에서 볼 수 있듯이, 하기 구조식(II)의 2-알킬설폭시-4-퀴놀린온과 하기 구조식(III)의 화합물을 반응시켜 제조할 수 있다:4-quinolinone derivatives of the general formula (1) according to the present invention, as can be seen in the following reaction formula 1, by reacting a compound of formula (III) with 2-alkyl sulfoxy-4-quinolinone of formula (II) Can be manufactured:
상기 식에서, R1, R2, R3, R4, R5 및 X는 화학식 1에서 정의한 바와 같으며, R8는 C1-3의 알킬기이다.Wherein R 1 , R 2 , R 3 , R 4 , R 5 and X are as defined in Formula 1, and R 8 is an alkyl group of C 1-3 .
상기 반응은 불활성 용매, 예컨대 디에틸에테르, 아이소프로필 에테르, 테트 라하이드로퓨란, 다이옥산, 다이페닐에테르 등의 에테르류 ; 벤젠, 톨루엔, 자일렌, 리그로인 등의 탄화수소류; 다이클로로에탄, 클로로폼, 사염화탄소 등의 할로겐화 탄화수소류 ; 아세트산에틸, 프로피온산 에틸 등과 같은 에스터류 ; 모노클로로벤젠, 다이클로로벤젠 등과 같은 클로로벤젠류 ; N,N-다이메틸폼 아미드, 다이에틸설폭사이드 등과 같은 비양자성 극성 용매류하에서 이루어질 수 있다. 또한, 피리딘 또는 트라이알킬아민을 염기 및 용매로서 반응에 사용할 수 있다. The reaction is an inert solvent such as ethers such as diethyl ether, isopropyl ether, tetrahydrofuran, dioxane and diphenyl ether; Hydrocarbons such as benzene, toluene, xylene, ligroin; Halogenated hydrocarbons such as dichloroethane, chloroform and carbon tetrachloride; Esters such as ethyl acetate, ethyl propionate and the like; Chlorobenzenes such as monochlorobenzene and dichlorobenzene; And aprotic polar solvents such as N, N-dimethylform amide, diethylsulfoxide and the like. In addition, pyridine or trialkylamine can be used in the reaction as a base and a solvent.
상기 반응은 0 내지 260℃에서 수행될 수 있으나, 바람직하게는 상온 내지 용매의 끓는점에서 수행하는 것이 유리하며, 반응 시간은 반응 온도에 따라 좌우되나, 0.5 내지 8시간이 바람직하다.The reaction may be carried out at 0 to 260 ° C, but is preferably carried out at room temperature to the boiling point of the solvent, the reaction time depends on the reaction temperature, 0.5 to 8 hours is preferred.
상기 구조식(II)의 화합물은 공지된 방법(문헌[R. C. Anand & A. K. Sinha, India Journal of Chemistry, 1991, 30B, 560; 및 한국 특허 제295819호] 참조)에 의해 합성된 설파이드를 과산화수소, 과산화아세트산 또는 m-클로로과산화벤조산 등의 산화제로 산화시켜 얻을 수 있다.Compounds of the above formula (II) may be prepared by hydrogen peroxide, acetic acid, or the like, and the sulfide synthesized by a known method (see RC Anand & AK Sinha, India Journal of Chemistry, 1991, 30B, 560; and Korean Patent No. 295819). Or oxidizing agents such as m-chloroperoxide.
한편, 상기 구조식(III)의 아민화합물은 산부가염의 형태로 사용되는 경우에는 산제거를 위해 트라이알킬아민, 탄산칼륨, 수산화나트륨 등과 같은 무기 염기를 1 내지 2 당량으로 처리된 후에 사용된다.On the other hand, when the amine compound of the formula (III) is used in the form of an acid addition salt, it is used after being treated with 1 to 2 equivalents of an inorganic base such as trialkylamine, potassium carbonate, sodium hydroxide and the like for acid removal.
상기 반응의 종료 후, 상기 화학식(III)의 아민화합물을 산부가염이 아닌 형태로 사용한 경우에는 용매를 감압증류함으로써 직접 조생성물을 얻을 수 있고, 산부가염의 형태로 사용한 경우에는 용매를 감압증류한 다음, 물을 가하여 생성된 염을 녹여내고, 메틸렌클로라이드, 클로로폼 또는 에틸아세테이트와 같은 유기용매로 추출한 후 다시 용매를 감압증류하여 조생성물을 얻는다.After the completion of the reaction, when the amine compound of the formula (III) is used in a form other than an acid addition salt, the crude product can be directly obtained by distilling the solvent under reduced pressure, and in the case of using the acid addition salt, the solvent is distilled under reduced pressure. Next, water is added to dissolve the resulting salt, extracted with an organic solvent such as methylene chloride, chloroform or ethyl acetate, and then the solvent is distilled under reduced pressure to obtain a crude product.
수득된 조생성물은 메탄올 또는 에탄올와 같은 알콜; 에틸아세테이트 또는 메틸아세테이트과 같은 유기산의 에스터; 펜탄 또는 헥산과 같은 하이드로카본; 에틸에테르 또는 테트라하이드로퓨란과 같은 에테르 등의 용매를 단독으로 또는 혼합하여 사용하여 재결정하거나 컬럼크로마토그라피 등의 방법으로 용이하게 분리정제될 수 있다.The crude product obtained is an alcohol such as methanol or ethanol; Esters of organic acids such as ethyl acetate or methyl acetate; Hydrocarbons such as pentane or hexane; Solvents, such as ether, such as ethyl ether or tetrahydrofuran, may be recrystallized by using alone or in combination, or may be easily separated and purified by a method such as column chromatography.
상기와 같은 방법으로 제조된, 본 발명에 따른 화학식 1의 퀴놀린온 유도체는 다양한 식물 병원균에 대해 우수한 살균효과를 가지며, 식물 병원균에 기인하는 질병에 대해 높은 치료 및 예방적 항균 특성을 갖는다. 이러한 병원균의 예로는 벼의 도열병균(Piricularia oryzae), 벼의 잎집무늬 마름병균(Rhizoctonia solani), 오이회색곰팡이병균(Botrytis cinerea), 오이의 흰가루병균(Sphaerotheca fuligiIlea), 오이의 노균병균(Pseudoperonospora cubensis), 포도의 노균병균(Plasmopora viticola), 토마토의 역병균(Phytophthora infestans), 깨씨무늬병균(Cochliobolus miyabeanus), 땅콩의 갈색무늬병균(Cercopora arachidcola), 보리의 흰가루병균(Erysiphe graminis), 밀의 붉은 녹병균(Puccinia recondita) 및 밀의 줄기 녹병균(Puccinis graminis) 등이 있다.The quinolinone derivatives of the formula (1) according to the present invention, prepared by the above method, have excellent bactericidal effects against various plant pathogens, and have high therapeutic and prophylactic antibacterial properties against diseases caused by plant pathogens. An example of such a pathogen is rice blast fungus in rice (Piricularia oryzae), sheath blight fungus of rice (Rhizoctonia solani), cucumber gray mold pathogen (Botrytis cinerea), powdery mildew of cucumber fungus (Sphaerotheca fuligiIlea), downy mildew fungus of cucumber (Pseudoperonospora cubensis ), downy mildew of grape fungus (Plasmopora viticola), Station pathogens of tomato (Phytophthora infestans), kkaessi pattern germs (Cochliobolus miyabeanus), brown pattern germs of peanut (Cercopora arachidcola), powdery mildew fungus of barley (Erysiphe graminis), wheat red rust ( Puccinia recondita ) and wheat stem rust fungus ( Puccinis graminis ).
또한, 본 발명에 따른 화학식 1의 퀴놀린온 유도체는 파리, 모기 및 바퀴와 같은 위생해충, 농경해충, 예를들면 애멸구(Laodelphax striatellus Fallen), 배멸구(Nilapanata lugens stal), 흰등멸구(Sogatella furcifera Horvath), 끝동매미충(Nephotettix cincticeps Uhler), 트리알레우로우즈 바포라리오룸(Trialeurodes vaporariorum) 및 북숭아 흑진딧물(Myzus persicae Sulzer)와 같은 노린재목 해충, 필로노릭터 린고닐라(Phyllonorycter ringoneella Matsumura), 배추좀나방(Plutella xylostella Curtis), 멸강나방(Pseudaletia separata Walker), 도둑나방(Hamestra brassicae Linne), 담배거세미나방(Spodoptera litura Fablicus) 및 배추흰나비(Pieris rapacerucivora Boisduval)와 같은 나비목 해충, 오울레마 오리자에(Oulema oryzae Kuwayama) 및 벼뿌리 바구미(Echirnocnemus squameus Billberg)같은 딱정벌레목 해충, 흰개미 및 나비좀과 같은 가내 해충에 대해 효과적이며, 특히 배추좀나방과 점박이응애와 같은 나비목 해충에 대해 뛰어난 살충 효과를 나타낸다.In addition, the quinolinone derivatives of the formula (1) according to the present invention are sanitary pests such as flies, mosquitoes, and wheels, agricultural pests, for example, Laodelphax striatellus Fallen , Nilapanata lugens stal , and Sogatella furcifera Horvath. ), Stink bugs such as Nephotettix cincticeps Uhler , Trialeurodes vaporariorum , and Pygmy Black Aphid ( Myzus persicae Sulzer ), Phyllonorycter ringoneella Matsumura , Chinese Cabbage Lepidoptera pests such as moth ( Plutella xylostella Curtis ), moth ( Pseudaletia separata Walker ), thief moth ( Hamestra brassicae Linne ), tobacco moth ( Spodoptera litura Fablicus ) and cabbage butterfly ( Pieris rapacerucivora Boisduval ) (Oulema oryzae Kuwayama) and rice weevil roots Coleoptera pests, such as termites and bow a little and home (Echirnocnemus squameus Billberg) Are effective for the charge, in particular it shows an excellent insecticidal effect against Lepidoptera insects such as moths and some T. urticae cabbage.
본 발명에 따르면, 본 발명의 화학식 1의 화합물은 조성물 중량을 기준으로 약 0.01 내지 90 중량%, 바람직하게는 약 0.01 내지 40 중량%를 활성성분으로 하여, 적당한 고체 또는 액체 담체 및 표면활성제, 희석제, 전착제, 상승제, 접착제, 분산제 등과 같은 기타 적당한 보조제와 혼합함으로써 농업용 조성물로 제제화시켜 사용할 수 있으며, 이러한 조성물은 유제, 수화제, 분제, 입제, 분문제 등으로 제조될 수 있다.According to the present invention, the compound of formula 1 of the present invention contains about 0.01 to 90% by weight, preferably about 0.01 to 40% by weight, based on the weight of the composition, as an active ingredient, suitable solid or liquid carriers and surfactants, diluents It can be formulated into agricultural compositions by mixing with other suitable auxiliaries such as electrodeposition agents, synergists, adhesives, dispersants and the like, which can be prepared as emulsions, wetting agents, powders, granules, powders and the like.
본 발명에서 사용될 수 있는 고체 담체로는 활석, 점토, 벤토나이트, 피로필라이트, 카올린, 규조토, 실리카등이 있고; 액체 담체는 물, 메탄올, 에탄올, 아세톤, 다이에틸폼아미드, 에테르, 벤젠, 자일렌, 톨루엔, 나프타 등이 있고; 표면활성제로는 폴리옥시에틸렌 알킬페닐에테르 및 폴리옥시에틸렌 지방산 에스터와 같은 비이온성 표면활성제, 알킬벤젠설폰산염, 리그닌설폰산염 및 다이나프틸메탄설폰산 염과 같은 음이온성 표면활성제 등이 있으며; 접착제로는 폴리바이닐알콜, CMC, 아라비아 고무 등이 있다.Solid carriers that can be used in the present invention include talc, clay, bentonite, pyrophyllite, kaolin, diatomaceous earth, silica and the like; Liquid carriers include water, methanol, ethanol, acetone, diethylformamide, ether, benzene, xylene, toluene, naphtha and the like; Surfactants include nonionic surfactants such as polyoxyethylene alkylphenyl ethers and polyoxyethylene fatty acid esters, anionic surfactants such as alkylbenzenesulfonates, lignin sulfonates and dynaphthylmethanesulfonic acid salts; Adhesives include polyvinyl alcohol, CMC, gum arabic, and the like.
추가로, 본 발명에 따른 조성물은 기타 살충제, 살균제, 제초제, 식물성장 조절제, 살응애제 등과 같은 농화학물질이나 영양물질과 배합하여 사용할 수 있다.In addition, the composition according to the present invention can be used in combination with other pesticides, fungicides, herbicides, plant growth regulators, acaricides and the like or agrochemicals and nutritional substances.
본 발명에 따른 화학식 1의 4-퀴놀린온 유도체의 구체적인 예를 들어보면 하기 표 1과 같다:Specific examples of 4-quinolinone derivatives of formula 1 according to the present invention are shown in Table 1 below:
이하, 본 발명을 하기 실시예에 의거하여 좀더 상세하게 설명하고자 한다. 단, 하기 실시예는 본 발명을 예시하기 위한 것일 뿐 한정하지는 않는다.Hereinafter, the present invention will be described in more detail based on the following examples. However, the following examples are not intended to limit the invention only.
실시예 1: 3-아세틸-6-클로로-8-트라이플루오르메틸-2-(2-페닐에틸아미노)-4-퀴놀린온(화합물 1)의 합성Example 1: Synthesis of 3-acetyl-6-chloro-8-trifluoromethyl-2- (2-phenylethylamino) -4-quinolinone (Compound 1)
3-아세틸-6-클로로-8-트라이플루오르메틸-4-메틸 설폭시-2-퀴놀린온(3.5g, 0.01몰)과 2-페닐에틸아민(1.21g, 0.01몰)을 테트라하이드로퓨란 50ml 용매중에서 4시간 동안 가열 환류시켰다. 반응이 완료되면 용매를 감압증류하여 제거하고, 남은 고체를 에틸아세테이트 10ml에 가열하면서 녹인 후 헥산 30ml를 가하여 재결정시킴으로써 표제 생성물을 2.57g(63%)의 수율로 수득하였다.50 ml of tetrahydrofuran solvent of 3-acetyl-6-chloro-8-trifluoromethyl-4-methyl sulfoxy-2-quinolinone (3.5 g, 0.01 mol) and 2-phenylethylamine (1.21 g, 0.01 mol) Heated to reflux for 4 h. After completion of the reaction, the solvent was distilled off under reduced pressure, and the remaining solid was dissolved in 10 ml of ethyl acetate while heating. Then, 30 ml of hexane was added and recrystallized to obtain the title product in a yield of 2.57 g (63%).
1H NMR(CDCl3) : δ 11.78(brs, 1H), 8.47(d, J=2.0, 1H), 7.75(d, J=2.0, 1H), 7.75(brs, 1H), 7.33(s, 5H), 3.55(m, 2H), 3.08(m, 2H), 2.7(s, 3H) 1 H NMR (CDCl 3 ): δ 11.78 (brs, 1H), 8.47 (d, J = 2.0, 1H), 7.75 (d, J = 2.0, 1H), 7.75 (brs, 1H), 7.33 (s, 5H ), 3.55 (m, 2H), 3.08 (m, 2H), 2.7 (s, 3H)
실시예 2: 3-아세틸-6-클로로-8-트라이플루오르메틸-2-아이소프로필아미노-4-퀴놀린온(화합물 2)의 합성Example 2: Synthesis of 3-acetyl-6-chloro-8-trifluoromethyl-2-isopropylamino-4-quinolinone (Compound 2)
3-아세틸-6-클로로-8-트라이플루오르에틸-4-메틸설폭시-2-퀴놀린온(3.5g, 0.01몰)과 아이소프로필아민(0.6g, 0.01몰)으로부터 실시예 1과 같은 반응을 실시하여 표제 생성물을 2.52g(73%)의 수율로 수득하였다.The same reaction as in Example 1 was carried out from 3-acetyl-6-chloro-8-trifluoroethyl-4-methyl sulfoxy-2-quinolinone (3.5 g, 0.01 mol) and isopropylamine (0.6 g, 0.01 mol). The title product was obtained in 2.52 g (73%) yield.
1H NMR(CDCl3) : δ 11.7(s, 1H), 8.58(m, 1H), 7.87(m, 1H), 3.77(m, J=6.5, 1H), 2.93(s, 3H), 1.47(d, J=6.5, 6H) 1 H NMR (CDCl 3 ): δ 11.7 (s, 1H), 8.58 (m, 1H), 7.87 (m, 1H), 3.77 (m, J = 6.5, 1H), 2.93 (s, 3H), 1.47 ( d, J = 6.5, 6H)
실시예 3: 3-아세틸-6-클로로-8-트라이플루오르에틸-2-사이클로펜틸아미노-4-퀴놀린온(화합물 5)의 합성Example 3: Synthesis of 3-acetyl-6-chloro-8-trifluoroethyl-2-cyclopentylamino-4-quinolinone (Compound 5)
3-아세틸-6-클로로-8-트라이플루오르메틸-2-메틸설폭시-4-퀴놀린온(3,5g, 0.01몰)과 사이클로펜틸아민(0.86g, 0.01몰)으로부터 실시예 1과 같은 반응을 실시하여 표제 생성물을 2.5g(67%)의 수율로 수득하였다.The same reaction as in Example 1 from 3-acetyl-6-chloro-8-trifluoromethyl-2-methylsuloxy-4-quinolinone (3,5 g, 0.01 mol) and cyclopentylamine (0.86 g, 0.01 mol) The title product was obtained in 2.5 g (67%) yield.
1H NMR(CDCl3) : δ 11.8(brs, 1H), 8.47(m, 1H), 7.83(brs, 1H), 7.77(m, 1H), 3.85(brs, 1H), 2.73(s, 3H), 2.47∼1.38(m, 8H) 1 H NMR (CDCl 3 ): δ 11.8 (brs, 1H), 8.47 (m, 1H), 7.83 (brs, 1H), 7.77 (m, 1H), 3.85 (brs, 1H), 2.73 (s, 3H) , 2.47 to 1.38 (m, 8H)
실시예 4: 3-프로피오닐-8-클로로-2-아이소프로필아미노-4-퀴놀린온(화합물 7)의 합성Example 4: Synthesis of 3-propionyl-8-chloro-2-isopropylamino-4-quinolinone (Compound 7)
3-프로피오닐-8-클로로-2-에틸설폭시-4-퀴놀린온(2.97g, 0.01몰)과 아이소프로필아민(0.6g, 0.01몰)으로부터 실시예 1과 같은 반응을 실시하여 표제 생성물을 2.93g(71%)의 수율로 수득하였다.The title product was obtained by the same reaction as in Example 1 from 3-propionyl-8-chloro-2-ethyl sulfoxy-4-quinolinone (2.97 g, 0.01 mol) and isopropylamine (0.6 g, 0.01 mol). Obtained in a yield of 2.93 g (71%).
1H NMR(CDCl3) : δ 11.78(br, 1H), 8.4∼6.97(m, 4H), 3.87(m, J=7.0, 1H), 3.27(q, J=8.0, 2H), 1.65(d, J=7.0, 6H), 1.17(t, J=8.0, 3H) 1 H NMR (CDCl 3 ): δ 11.78 (br, 1H), 8.4 to 6.97 (m, 4H), 3.87 (m, J = 7.0, 1H), 3.27 (q, J = 8.0, 2H), 1.65 (d , J = 7.0, 6H), 1.17 (t, J = 8.0, 3H)
실시예 5: 3-아세틸-8-메틸-2-아이소프로필아미노-4-퀴놀린온(화합물 8)의 합성Example 5: Synthesis of 3-acetyl-8-methyl-2-isopropylamino-4-quinolinone (Compound 8)
3-아세틸-8-메틸-2-메틸설폭시-4-퀴놀린온(2.63g, 0.01몰)과 아이소프로필아민(0.6g, 0.01몰)으로부터 실시예 1과 같은 반응을 실시하여 표제 생성물을 2.59g(68%)의 수율로 수득하였다.The title product was obtained in the same manner as in Example 1 from 3-acetyl-8-methyl-2-methylsuloxy-4-quinolinone (2.63 g, 0.01 mol) and isopropylamine (0.6 g, 0.01 mol) to give the title product 2.59. Obtained in g (68%).
1H NMR(DMSO-d6) : δ 11.5(br.d, 1H), 8.33∼7.23(m, 4H), 3.8(m, J=7.0, 1H), 2.77(s, 3H), 2.4(s, 3H), 1.45(d, J=7.0, 6H) 1 H NMR (DMSO-d 6 ): δ 11.5 (br.d, 1H), 8.33 to 7.33 (m, 4H), 3.8 (m, J = 7.0, 1H), 2.77 (s, 3H), 2.4 (s , 3H), 1.45 (d, J = 7.0, 6H)
실시예 6: 3-아세틸-6-클로로-8-트라이플루오르메틸-2-(p-플루오르펜에틸아미노)-4-퀴놀린온(화합물 25)합성Example 6: 3-acetyl-6-chloro-8-trifluoromethyl-2- (p-fluorophenethylamino) -4-quinolinone (Compound 25) Synthesis
3-아세틸-6-클로로-8-트라이플루오르메틸-2-메틸설폭시-4-퀴놀린온(3.5g, 0.01몰)과 p-플루오르펜에틸아민 염산염(1.76g, 0.01몰) 및 트라이에틸아민(1.1g, 0.01몰)으로부터 실시예 1과 같은 반응을 실시한 후, 용매를 감압증류하여 제거하였다. 남은 고체를 에틸아세테이트 50ml에 녹인 다음 물 50ml로 씻어내고, 무수황산마그네슘으로 건조한 후 용매를 감압증류하여 제거한다. 다시, 남은 고체를 10ml의 에틸아세테이트에 녹인 후 헥산 30ml를 가하여 재결정시킴으로써 표제 생성물을 2.25g(53%)의 수율로 수득하였다.3-acetyl-6-chloro-8-trifluoromethyl-2-methylsulfoxy-4-quinolinone (3.5 g, 0.01 mol) with p-fluorophenethylamine hydrochloride (1.76 g, 0.01 mol) and triethylamine After carrying out the same reaction as in Example 1 from (1.1 g, 0.01 mol), the solvent was distilled off under reduced pressure. The remaining solid was dissolved in 50 ml of ethyl acetate, washed with 50 ml of water, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. Again, the remaining solid was dissolved in 10 ml of ethyl acetate and recrystallized by adding 30 ml of hexane to give the title product in a yield of 2.25 g (53%).
1H NMR(CDCl3) : δ 2.7(s, 3H), 2.97∼3.16(t, J=6.4, 2H), 3.47∼3.77(m, 2H), 6.93∼8.47(m, 7H), 11.73(s, 1H) 1 H NMR (CDCl 3 ): δ 2.7 (s, 3H), 2.97 to 3.16 (t, J = 6.4, 2H), 3.47 to 3.77 (m, 2H), 6.93 to 8.47 (m, 7H), 11.73 (s , 1H)
실시예 7: 3-아세틸-8-플루오르-2-(1-메톡시-2-프로필아미노)-4-퀴놀린온(화합물 27)의 합성Example 7: Synthesis of 3-acetyl-8-fluoro-2- (1-methoxy-2-propylamino) -4-quinolinone (Compound 27)
3-아세틸-8-플루오르-2-메틸설폭시-4-퀴놀린온(2.67g, 0.01몰)과 1-메톡시-2-프로필아민(0.88g, 0.01몰)으로부터 실시예 1과 같은 반응을 실시하여 표제 생성 물을 2.53g(87%)의 수율로 수득하였다.The same reaction as in Example 1 was carried out from 3-acetyl-8-fluoro-2-methylsuloxy-4-quinolinone (2.67 g, 0.01 mol) and 1-methoxy-2-propylamine (0.88 g, 0.01 mol). The title product was obtained in 2.53 g (87%) yield.
1H NMR(CDCl3) : δ 1.5(d, 3H), 2.8(s, 3H), 3.7∼3.9(m, 3H), 3.6(s, 3H), 7.2∼8.3(m, 4H) 1 H NMR (CDCl 3 ): δ 1.5 (d, 3H), 2.8 (s, 3H), 3.7-3.9 (m, 3H), 3.6 (s, 3H), 7.2-8.3 (m, 4H)
실시예 8: 3-아세틸-6-클로로-8-트라이플루오르메틸-2-에틸아미노-4-퀴놀린온(화합물 29)의 합성Example 8: Synthesis of 3-acetyl-6-chloro-8-trifluoromethyl-2-ethylamino-4-quinolinone (Compound 29)
3-아세틸-6-클로로-8-트라이플루오르메틸-2-메틸설폭시-4-퀴놀린온(3.5g, 0.01몰)과 에틸아민(70 중량% 수용액: 0.65g, 0.01몰)으로부터 실시예 1과 같은 반응을 실시하여 표제 생성물을 2.52g(76%)의 수율로 수득하였다.Example 1 from 3-acetyl-6-chloro-8-trifluoromethyl-2-methylsulfoxy-4-quinolinone (3.5 g, 0.01 mol) and ethylamine (70 wt% aqueous solution: 0.65 g, 0.01 mol) The reaction was carried out to give the title product in a yield of 2.52 g (76%).
1H NMR(CDCl3) : δ 1.37∼1.6(t, j=8, 3H), 2.73(s, 3H), 3.23∼3.67(m, 2H), 7.77∼8.47(m, 3H), 11.57(s, 1H) 1 H NMR (CDCl 3 ): δ 1.37-1.6 (t, j = 8, 3H), 2.73 (s, 3H), 3.23-3.67 (m, 2H), 7.77-8.47 (m, 3H), 11.57 (s , 1H)
실시예 9: 3-아세틸-8-플루오르-2-(2-메틸사이클로헥실아미노)-4-퀴놀린온(화합물 34)의 합성Example 9: Synthesis of 3-acetyl-8-fluoro-2- (2-methylcyclohexylamino) -4-quinolinone (Compound 34)
3-아세틸-8-플루오르-2-메틸설폭시-4-퀴놀린온(2.67g, 0.01몰)과 2-메틸사이클로헥실아민(1.13g, 0.01몰)으로부터 실시예 1과 같은 반응을 실시하여 표제 생성물을 2.1g(66%)의 수율로 수득하였다.The same reaction as in Example 1 was carried out from 3-acetyl-8-fluoro-2-methylsuloxy-4-quinolinone (2.67 g, 0.01 mole) and 2-methylcyclohexylamine (1.13 g, 0.01 mole). The product was obtained in a yield of 2.1 g (66%).
1H NMR(CDCl3) : δ 1.0∼1.5(m, 12H), 2.6(s, 3H), 3.9(m, 1H), 7.l∼ 8.4(m, 3H) 1 H NMR (CDCl 3 ): δ 1.0 to 1.5 (m, 12H), 2.6 (s, 3H), 3.9 (m, 1H), 7.l to 8.4 (m, 3H)
실시예 10: 3-아세틸-8-트라이플루오르메틸-2-(α-메틸벤질아미노)-4-퀴놀리온(화합물 38)의 합성Example 10 Synthesis of 3-acetyl-8-trifluoromethyl-2- (α-methylbenzylamino) -4-quinolinone (Compound 38)
3-아세틸-8-트라이플루오르메틸-4-에틸설폭시-2-퀴놀린온(3.17g, 0.01몰)과 α-메틸벤질아민(1.21g, 0.01몰)으로부터 실시예 1과 같은 반응을 실시하여 표제 생성물을 2.43g(65%)의 수율로 수득하였다.The same reaction as in Example 1 was carried out from 3-acetyl-8-trifluoromethyl-4-ethyl sulfoxy-2-quinolinone (3.17 g, 0.01 mol) and α-methylbenzylamine (1.21 g, 0.01 mol). The title product was obtained in a yield of 2.43 g (65%).
1H NMR(CDCl3) : δ 1.63∼1.83(d, J=7, 3H), 2.8(s, 3H), 4.57∼4.77(m, lH), 7.23∼8.6(m, 9H), 12.2(s, 1H) 1 H NMR (CDCl 3 ): δ 1.63-1.83 (d, J = 7, 3H), 2.8 (s, 3H), 4.57-4.77 (m, lH), 7.23-8.6 (m, 9H), 12.2 (s , 1H)
실시예 11: 3-아세틸-5-니트로-8-클로로-2-(p-클로로벤질아미노)-4-퀴놀린온(화합물 86)의 합성Example 11: Synthesis of 3-acetyl-5-nitro-8-chloro-2- (p-chlorobenzylamino) -4-quinolinone (Compound 86)
3-아세틸-5-니트로-8-클로로-2-메틸설폭시-4-퀴놀린온(3.28g, 0.01몰)과 p-클로로벤질아민(1.42g, 0.01몰)으로부터 실시예 1과 같은 반응을 실시하여 표제 생성물을 2.32g(57%)의 수율로 수득하였다.The same reaction as in Example 1 was carried out from 3-acetyl-5-nitro-8-chloro-2-methylsuloxy-4-quinolinone (3.28 g, 0.01 mol) and p-chlorobenzylamine (1.42 g, 0.01 mol). The title product was obtained in 2.32 g (57%) yield.
1H NMR(DMSO-d6) : δ 11.9(m, 1H), 8.43(brs, 1H), 7.8(d, J=9.0, 1H), 7.5(s, 4H), 7.3(d, J=9.0, 1H), 4.9(d, J=6.0, 2H), 2.7(s, 3H) 1 H NMR (DMSO-d 6 ): δ 11.9 (m, 1H), 8.43 (brs, 1H), 7.8 (d, J = 9.0, 1H), 7.5 (s, 4H), 7.3 (d, J = 9.0 , 1H), 4.9 (d, J = 6.0, 2H), 2.7 (s, 3H)
실시예 12: 3-아세틸-6,8-다이클로로-2-(2-메틸사이클로렉실아미노)-4-퀴놀 린온(화합물 89)의 합성Example 12 Synthesis of 3-acetyl-6,8-dichloro-2- (2-methylcyclolexylamino) -4-quinolinone (Compound 89)
3-아세틸-6,8-다이클로로-2-메틸설폭시-4-퀴놀린온(3.18g, 0.01몰)과 2-메틸사이클로헥실아민(1.13g, 0.01몰)으로부터 실시예 1과 같은 반응을 실시하여 표제 생성물을 2.68g(73%)의 수율로 수득하였다.The same reaction as in Example 1 was carried out from 3-acetyl-6,8-dichloro-2-methylsuloxy-4-quinolinone (3.18 g, 0.01 mol) and 2-methylcyclohexylamine (1.13 g, 0.01 mol). The title product was obtained in 2.68 g (73%) yield.
1H NMR(CDCl3) : δ 12.0(m, 1H), 8.2(d, J=2.0, lH), 7.9(brs, 1H), 7.6(d, J=2.0, 1H), 3.0(m, 1H), 2.8(s, 3H), 1.0∼2.5(m, 9H), 1.0∼1.2(m, 3H) 1 H NMR (CDCl 3 ): δ 12.0 (m, 1H), 8.2 (d, J = 2.0, lH), 7.9 (brs, 1H), 7.6 (d, J = 2.0, 1H), 3.0 (m, 1H ), 2.8 (s, 3H), 1.0 to 2.5 (m, 9H), 1.0 to 1.2 (m, 3H)
실시예 13: 3-아세틸-7-t-부틸-2-사이클로부틸아미노-4-퀴놀린온(화합물 155)의 합성Example 13: Synthesis of 3-acetyl-7-t-butyl-2-cyclobutylamino-4-quinolinone (Compound 155)
3-아세틸-7-t-부틸-2-메틸설폭시-4-퀴놀린온(3.05g, 0.01몰)과 사이클로부틸아민(0.71g, 0.01몰)으로부터 실시예 1과 같은 반응을 실시하여 표제 생성물을 2.6g(83%)의 수율로 수득하였다.The title product was subjected to the same reaction as in Example 1 from 3-acetyl-7-t-butyl-2-methylsuloxy-4-quinolinone (3.05 g, 0.01 mol) and cyclobutylamine (0.71 g, 0.01 mol). Was obtained in a yield of 2.6 g (83%).
1H NMR(CDCl3) : δ 11.4(m, 1H), 8.3∼8.4(d, 1H), 7.2∼7.7(m, 2H), 2.9(s, 3H), 1.5∼2.9(m, 4H), 1.2(s, 9H), 0.9∼1.1(m, 2H) 1 H NMR (CDCl 3 ): δ 11.4 (m, 1H), 8.3 to 8.4 (d, 1H), 7.2 to 7.7 (m, 2H), 2.9 (s, 3H), 1.5 to 2.9 (m, 4H), 1.2 (s, 9H), 0.9 to 1.1 (m, 2H)
실시예 14: 3-아세틸-8-에틸-2-사이클로펜틸아미노-4-퀴놀린온(화합물 178)의 합성Example 14 Synthesis of 3-acetyl-8-ethyl-2-cyclopentylamino-4-quinolinone (Compound 178)
3-아세틸-8-에틸-2-메틸설폭시-4-퀴놀린온(2.77g, 0.01몰)과 사이클로펜틸아민(0.86g, 0.01몰)으로부터 실시예 1과 같은 반응을 실시하여 표제 생성물을 2.15g(72%)의 수율로 수득하였다.The title product was obtained in the same manner as in Example 1 from 3-acetyl-8-ethyl-2-methylsuloxy-4-quinolinone (2.77 g, 0.01 mol) and cyclopentylamine (0.86 g, 0.01 mol) to give the title product 2.15. Obtained in g (72%).
1H NMR(CDCl3) : δ 11.6(m, 1H), 8.1(d, J=6.0, 1H), 7.4∼7.1(m, 3H), 3.8(m, 1H), 2.8(s, 3H), 2.7(m, 2H), 2.1∼1.5(m, 8H), 1.4(t, J=6.0, 3H) 1 H NMR (CDCl 3 ): δ 11.6 (m, 1H), 8.1 (d, J = 6.0, 1H), 7.4-7.1 (m, 3H), 3.8 (m, 1H), 2.8 (s, 3H), 2.7 (m, 2H), 2.1 to 1.5 (m, 8H), 1.4 (t, J = 6.0, 3H)
실시예 15: 3-아세틸-6-클로로-8-메틸-2-(p-플루오르펜에틸아미노)-4-퀴놀린온(화합물 198)의 합성Example 15 Synthesis of 3-acetyl-6-chloro-8-methyl-2- (p-fluorophenethylamino) -4-quinolinone (Compound 198)
3-아세틸-6-클로로-8-메틸-2-메틸설폭시-4-퀴놀린온(2.98g, 0.01몰)과 p-플루오르펜에틸아민 염산염(1.76g, 0.01몰) 및 트라이에틸아민(1.1g, 0.01몰)으로부터 실시예 6과 같은 반응을 실시하여 표제 생성물을 2.9g(71%)의 수율로 수득하였다.3-acetyl-6-chloro-8-methyl-2-methylsuloxy-4-quinolinone (2.98 g, 0.01 mole) with p-fluorophenethylamine hydrochloride (1.76 g, 0.01 mole) and triethylamine (1.1 g, 0.01 mol) to give the title product in the yield of 2.9 g (71%).
1H NMR(DMSO-d6) : δ 11.5(m, 1H), 8.3(s, 1H), 7.9(s, 1H), 7.6-6.8(m, 5H), 3.77(m, 2H), 3.0(t, J=7.0, 2H), 2.6(s, 3H), 2.4(s, 3H) 1 H NMR (DMSO-d 6 ): δ 11.5 (m, 1H), 8.3 (s, 1H), 7.9 (s, 1H), 7.6-6.8 (m, 5H), 3.77 (m, 2H), 3.0 ( t, J = 7.0, 2H), 2.6 (s, 3H), 2.4 (s, 3H)
실시예 16: 3-아세틸-5,8-다이클로로-2-(N-모폴리노)-4-퀴놀린온(화합물 289)의 합성Example 16: Synthesis of 3-acetyl-5,8-dichloro-2- (N-morpholino) -4-quinolinone (Compound 289)
3-아세틸-5,8-다이클로로-4-메틸설폭시-4-퀴놀린온(3.18g, 0.01몰)과 모폴린(0.87g, 0.01몰)으로부터 실시예 1과 같이 반응을 실시하여 표제 생성물을 2.56g(75 %)의 수율로 수득하였다.The reaction was carried out in the same manner as in Example 1 from 3-acetyl-5,8-dichloro-4-methylsuloxy-4-quinolinone (3.18 g, 0.01 mol) and morpholine (0.87 g, 0.01 mol) to give the title product. Was obtained in a yield of 2.56 g (75%).
1H NMR(DMSO-d6) : δ 6.7∼7.3(m, 3H), 2.9∼3.3(m, 8H), 2.3(s, 3H) 1 H NMR (DMSO-d 6 ): δ 6.7-7.3 (m, 3H), 2.9-3.3 (m, 8H), 2.3 (s, 3H)
실시예 17: 3-아세틸-5,7-다이메틸-2-(β-메틸펜에틸아미노)-4-퀴놀린온(화합물 308)의 합성Example 17 Synthesis of 3-acetyl-5,7-dimethyl-2- (β-methylphenethylamino) -4-quinolinone (Compound 308)
3-아세틸-5,7-다이에틸-2-메틸설폭시-4-퀴놀린온(2.77g, 0.01몰)과 β-메틸펜에틸아민(1.35g, 0.01몰)으로부터 실시예 1과 같이 반응을 실시하여 표제 생성물을 2.96g(85%)의 수율로 수득하였다.Reaction was carried out as in Example 1 from 3-acetyl-5,7-diethyl-2-methylsuloxy-4-quinolinone (2.77 g, 0.01 mol) and β-methylphenethylamine (1.35 g, 0.01 mol). The title product was obtained in 2.96 g (85%) yield.
1H NMR(DMSO-d6) : δ 11.6(m, 1H), 7.2(s, 5H), 6.7∼7.1(d, 2H), 3.5(m, 2H), 3.2(m, 1H), 2.7(s, 3H), 2.6(s, 3H), 2.2(s, 3H), 1.3(d, 3H) 1 H NMR (DMSO-d 6 ): δ 11.6 (m, 1H), 7.2 (s, 5H), 6.7-7.1 (d, 2H), 3.5 (m, 2H), 3.2 (m, 1H), 2.7 ( s, 3H), 2.6 (s, 3H), 2.2 (s, 3H), 1.3 (d, 3H)
실시예 18: 3-아세틸-8-아이소프로필-2-sec-부틸아미노-4-퀴놀린온(화합물 316)의 합성Example 18 Synthesis of 3-acetyl-8-isopropyl-2-sec-butylamino-4-quinolinone (Compound 316)
3-아세틸-8-아이소프로필-2-메틸설폭시-4-퀴놀린온(2.91g, 0.01몰)과 sec-부틸아민(0.73g, 0.01몰)으로부터 실시예 1과 같은 반응을 실시하여 표제 생성물을 2.7g(90%)의 수율로 수득하였다.The title product was subjected to the same reaction as in Example 1 from 3-acetyl-8-isopropyl-2-methylsuloxy-4-quinolinone (2.91 g, 0.01 mol) and sec-butylamine (0.73 g, 0.01 mol). Was obtained in a yield of 2.7 g (90%).
1H NMR(CDCl3) : δ 11.6(m, 1H), 8.2(d, J=8.0, 1H), 7.7-7.1(m, 3H), 3.5(m, 1H), 2.9(m, 1H), 2.8(s, 3H), 1.7(m, 2H), 1.4(m, 9H), 1.1(t, J=6.0, 3H) 1 H NMR (CDCl 3 ): δ 11.6 (m, 1H), 8.2 (d, J = 8.0, 1H), 7.7-7.1 (m, 3H), 3.5 (m, 1H), 2.9 (m, 1H), 2.8 (s, 3H), 1.7 (m, 2H), 1.4 (m, 9H), 1.1 (t, J = 6.0, 3H)
실시예 19: 3-아세틸-8-페닐-2-(β-메틸펜에틸아미노)-4-퀴놀린온(화합물 337)의 합성Example 19 Synthesis of 3-acetyl-8-phenyl-2- (β-methylphenethylamino) -4-quinolinone (Compound 337)
3-아세틸-8-페닐-2-메틸설폭시-4-퀴놀린온(3.25, 0.01몰)과 β-메틸펜에틸아민(1.35g, 0.01몰)으로부터 실시예 1과 같은 반응을 실시하여 표제 생성물을 3.29 g(83%)의 수율로 수득하였다.The title product was subjected to the same reaction as in Example 1 from 3-acetyl-8-phenyl-2-methylsuloxy-4-quinolinone (3.25, 0.01 mol) and β-methylphenethylamine (1.35 g, 0.01 mol). Was obtained in a yield of 3.29 g (83%).
1H NMR(DMSO-d6) : δ 11.3(m, 1H), 8.3(brs, 1H), 8.3∼8.0(m, 1H), 7.8∼6. 9(m, 12H), 3.3(m, 2H), 3.03(m, 1H), 2.6(s, 3H), 1.23(d, J=7-0, 3H) 1 H NMR (DMSO-d 6 ): δ 11.3 (m, 1H), 8.3 (brs, 1H), 8.3 to 8.0 (m, 1H), 7.8 to 6. 9 (m, 12H), 3.3 (m, 2H), 3.03 (m, 1H), 2.6 (s, 3H), 1.23 (d, J = 7-0, 3H)
실시예 20: 3-아세틸-5-메틸-8-클로로-2-(p-클로로펜에틸아미노)-4-퀴놀린온(화합물 434)의 합성Example 20 Synthesis of 3-acetyl-5-methyl-8-chloro-2- (p-chlorophenethylamino) -4-quinolinone (Compound 434)
3-아세틸-5-메틸-8-클로로-2-메틸설폭시-4-퀴놀린온(2.97g, 0.01몰)과 p-클로로펜에틸아민(1.56g, 0.01몰)으로부터 실시예 1과 같은 반응을 실시하여 표제 생성물을 3.11g(80%)의 수율로 수득하였다.Reaction as in Example 1 from 3-acetyl-5-methyl-8-chloro-2-methylsuloxy-4-quinolinone (2.97 g, 0.01 mol) and p-chlorophenethylamine (1.56 g, 0.01 mol) To give the title product in 3.11 g (80%) yield.
1H NMR(DMSO-d6) : δ 1l.6(m, 1H), 8.7(s, 1H), 7.7(s, 4H), 7.1∼7.9(m, 2H), 3.9(q, 2H), 3.2(t, 2H), 2.9(s, 3H), 2.7(s, 3H) 1 H NMR (DMSO-d 6 ): δ 1 l.6 (m, 1H), 8.7 (s, 1H), 7.7 (s, 4H), 7.1 to 7.9 (m, 2H), 3.9 (q, 2H), 3.2 (t, 2H), 2.9 (s, 3H), 2.7 (s, 3H)
실시예 21: 3-아세틸-6-플루오르-8-클로로-2-아이소아밀아미노-4-퀴놀린온(화합물 437)의 합성Example 21 Synthesis of 3-acetyl-6-fluoro-8-chloro-2-isoamylamino-4-quinolinone (Compound 437)
3-아세틸-6-플루오르-8-클로로-2-메틸설폭시-4-퀴놀린온(3.02g, 0.01몰)과 아이소아밀아민(0.87g, 0.01몰)으로부터 실시예 1과 같은 반응을 실시하여 표제 생성물을 2.79g(86%)의 수율로 수득하였다.The same reaction as in Example 1 was carried out from 3-acetyl-6-fluoro-8-chloro-2-methylsuloxy-4-quinolinone (3.02 g, 0.01 mol) and isoamylamine (0.87 g, 0.01 mol). The title product was obtained in a yield of 2.79 g (86%).
1H NMR(CDCl3) : δ 11.6(m, 1H), 8.0∼7.8(m, 2H), 7.4(dd, J=8.0, 2.0, 1H), 3.4(m, 2H), 2.8(s, 3H), 1.7(m, 3H), 0.9(d, J=6.0, 6H) 1 H NMR (CDCl 3 ): δ 11.6 (m, 1H), 8.0-7.8 (m, 2H), 7.4 (dd, J = 8.0, 2.0, 1H), 3.4 (m, 2H), 2.8 (s, 3H ), 1.7 (m, 3H), 0.9 (d, J = 6.0, 6H)
실시예 22: 3-아세틸-5-트라이플루오르메틸-8-메톡시-2-아이소부틸아미노-4-퀴놀린온(화합물 446)의 합성Example 22 Synthesis of 3-acetyl-5-trifluoromethyl-8-methoxy-2-isobutylamino-4-quinolinone (Compound 446)
3-아세틸-5-트라이플루오르메틸-8-메톡시-2-메틸설폭시-4-퀴놀린온(3.47g, 0.01몰)과 아이소부틸아민(0.73g, 0.01몰)으로부터 실시예 1과 같은 반응을 실시하여 표제 생성물을 2.46g(69%)의 수율로 수득하였다.The same reaction as in Example 1 from 3-acetyl-5-trifluoromethyl-8-methoxy-2-methylsuloxy-4-quinolinone (3.47 g, 0.01 mol) and isobutylamine (0.73 g, 0.01 mol) To give the title product in 2.46 g (69%) yield.
1H NMR(DMSO-d6) : δ 11.1(m, 1H), 8.5(brs, 1H), 7.2∼7.7(m, 2H), 4.2(s, 3H), 3.0∼3.6(m, 2H), 2.6(s, 3H), 1.8∼2.3(m, 1H), 1.1(d, J=6.0, 6H) 1 H NMR (DMSO-d 6 ): δ 11.1 (m, 1H), 8.5 (brs, 1H), 7.2 to 7.7 (m, 2H), 4.2 (s, 3H), 3.0 to 3.6 (m, 2H), 2.6 (s, 3H), 1.8 to 2.3 (m, 1H), 1.1 (d, J = 6.0, 6H)
살균 효과 시험예Sterilization Effect Test Example
식물 병원균에 대한 예방효과를 조사하기 위하여, 시험 화합물 25mg을 10ml의 아세톤에 용해시키고, 이 용액에 트윈(Tween) 20의 250ppm 수용액 90ml를 첨가하여 그 농도가 250ppm이 되게 조정한 후, 이를 일정 크기의 기주 식물에 50ml씩 엽면 살포하였다. 약제가 살포된 식물을 실내온도에서 24시간 동안 방치하여 용매 및 물을 휘산시켰다. 이와 같이 살균제 조성물로 처리된 식물체(시험군)와 처리되 지 않은 식물체(대조군)에, 각기 하기 시험예와 같이 특정 식물 병원균을 접종하여 동일한 조건(습도 및 온도)하에서 동일한 기간동안 방치한 후, 각 잎의 병반면적율(측정된 병반면적이 잎집면적에 대해 차지하는 비율을 기준으로 하여 작성한 이병면적율 대비표로 구함)을 구해 하기 수학식 1과 같이 방제가(Control Value, %)를 산출하였다. 모든 실험은 2회 반복하였으며, 방제가가 높을수록 살균 효과는 우수한 것이다.To investigate the protective effect against plant pathogens, 25 mg of test compound was dissolved in 10 ml of acetone, 90 ml of 250 ppm aqueous solution of Tween 20 was added to the solution, and the concentration was adjusted to 250 ppm. 50 ml of foliar spray was applied to host plants. The sprayed plants were left at room temperature for 24 hours to volatilize the solvent and water. Thus, plants (test group) and untreated plants (control group) treated with the fungicide composition were inoculated with specific plant pathogens as shown in the following test examples, and left for the same period under the same conditions (humidity and temperature), The control area (Control Value,%) was calculated as shown in Equation 1 by obtaining the disease area ratio of each leaf (obtained from the ratio of disease area ratio prepared based on the ratio of the measured disease area to the leaf area). All experiments were repeated twice, and the higher the control value, the better the sterilization effect.
시험예 1 : 벼도열병에 대한 살균 효과Test Example 1: bactericidal effect on rice fever
병원균(Pyricularia oryzae)의 균주를 쌀겨 한천배지(Rice Polish 20g, 덱스트로즈 10g, 한천 15g, 증류수 1ℓ)에 접종하여 26℃ 배양기에서 2주간 배양하였다. 병원균이 자란 배지의 표면을 고무쓸개로 긁어 기중균사를 제거하고 형광등이 켜진 25 내지 28℃의 선반에서 48시간 동안 포자를 형성시켰다. 병균 접종은 형성된 분생포자를 살균 증류수를 이용하여 일정 농도의 포자 현탁액(106개/㎖의 포자)을 만든 후, 벼 도열병에 감수성인 낙동벼(3-4엽기)에 흘러내릴 정도로 충분히 분무하였다. 병균 접종된 벼를 습실상에서 암상태로 24시간 방치하고, 상대습도 90% 이상 및 26±2℃인 항온항습실에서 5일동안 발병을 유도하여 잎의 병반면적율을 구했다. 이때 3-4엽기 벼의 최상위엽 바로 밑의 완전 전개된 잎에 형성된 병반면 적을 측정하였다.Strains of pathogens ( Pyricularia oryzae ) were inoculated in rice bran agar medium (Rice Polish 20g, dextrose 10g, agar 15g, distilled water 1L) and incubated for 2 weeks in a 26 ℃ incubator. The surface of the medium in which the pathogen was grown was scraped with a rubber gallbladder to remove airborne hyphae, and spores were formed for 48 hours on a shelf of 25 to 28 ° C. in which a fluorescent lamp was turned on. Germ inoculation was sprayed sufficiently to flow into the Nakdong rice (3-4 leaf stage) susceptible to rice blast, after making a spore suspension (10 6 spores / ml of spores) of a certain concentration using sterile distilled water. The inoculated rice was incubated for 24 hours in a dark state, and the disease area ratio of leaves was determined by inducing the disease for 5 days in a constant temperature and humidity chamber at a relative humidity of 90% or higher and 26 ± 2 ° C. At this time, the lesion area formed on the fully developed leaf just below the top leaf of 3-4 leaf rice was measured.
시험예 2 : 벼잎집무늬 마름병에 대한 살균 효과Test Example 2: The bactericidal effect on the rice leaf blight blight
적당한 양의 밀기울을 1ℓ 배양병에 넣고 멸균한 후 감자 한천배지에서 3일간 자란 병원균(Rhizoctonia solani)의 한천조각을 접종하고, 배양된 균사덩어리를 적당히 잘게 마쇄하여 2-3엽기의 낙동벼가 자란 포트(5cm)에 고르게 접종하고 28±1℃ 및 상대습도 80% 이상인 항온항습실에서 5일동안 발병을 유도하여 2-3엽기 유묘의 잎의 병반면적율을 구했다.Put the appropriate amount of wheat bran into 1L culture bottle, sterilize, inoculate agar pieces of pathogen ( Rhizoctonia solani ) grown on potato agar medium for 3 days, and finely crush the cultured mycelium masses. (5cm) and inoculated evenly in a constant temperature and humidity room with 28 ± 1 ℃ and relative humidity of 80% or more for 5 days to determine the lesion area ratio of leaves of 2-3 leaf seedlings.
시험예 3 : 토마토 회색곰팡이병에 대한 살균 효과Test Example 3: bactericidal effect on tomato gray mold
토마토로부터 분리한 균주(Botrytis cinerea)를 감자 한천배지(PDA)에 접종하고 25℃의 배양기에 플레이트를 놓아 광암상태하에서 15일간 배양하여 포자를 형성시켰다. 배지에 형성된 포자를 플레이트당 10㎖의 증류수를 넣은 후 붓으로 포자를 긁어 이를 가아제로 걸러서 포자를 수확하고 포자 농도가 106개/㎖가 되게 만들어 1엽기 오이에 분무접종하였다. 이를 20℃ 습실상에서 3일간 발병을 유도하여 1엽의 병반면적율을 구했다.Strains ( Botrytis cinerea ) isolated from tomatoes were inoculated in potato agar medium (PDA) and plated in an incubator at 25 ° C. to incubate for 15 days under light dark conditions to form spores. The spores formed on the medium were put in 10 ml of distilled water per plate, scraped with a brush, and then spores were filtered with gauze to harvest spores. The spore concentration was 10 6 / ml, and then sprayed on single-leaf cucumbers. This was induced for 3 days in a 20 ℃ wet room to determine the lesion area ratio of one leaf.
시험예 4 : 토마토역병에 대한 살균 효과 Test Example 4: bactericidal effect against tomato late blight
역병균(Phytophthora infestans)을 V-8 쥬스 한천배지(V-8 juice 200㎖, CaCO3 4.5g, 한천 15g, 증류수 800㎖)에 올려놓고 20℃에서 16시간 광처리 및 8시간 암처리하여 14일동안 배양한 후 포자를 수확하였다. 이때, 플레이트에 살균 증류수를 넣고 흔들어서 유주자낭을 균총으로부터 떼어낸 후 4겹 헝겊조각을 사용하여 유주자낭을 걸러냈다. 걸러낸 유주자낭의 농도를 105개/㎖로 조정하고 이 접종원을 토마토 유묘에 분무접종하여 20℃ 습실상에서 1일 동안 습실 처리한 후, 온도 20℃ 및 상대습도 80% 이상의 항온항습실로 옮겨 4일 동안 발병시킨 다음 토마토 1엽과 2엽의 병반면적율을 조사하였다. Phytophthora infestans were placed on V-8 juice agar medium (V-8 juice 200ml, CaCO 3 4.5g, agar 15g, distilled water 800ml) and light treated at 20 ℃ for 16 hours and dark treated for 14 hours. Spores were harvested after incubation. At this time, sterile distilled water was added to the plate and shaken to separate the zygote sac from the flora, and then, the 4-stage piece of cloth was used to filter the stool sac. Adjust the concentration of strained sachets to 10 5 pcs / ml and inoculate the inoculum to tomato seedlings for 1 day in a 20 ° C. chamber, and then transfer to a constant temperature and humidity room with a temperature of 20 ° C. and a relative humidity of 80% or more. After 1 day of onset, the lesion area ratio of one and two leaves of tomato was examined.
시험예 5 : 밀 붉은녹병에 대한 살균 효과Test Example 5: bactericidal effect on wheat rust
병원균(Puccinia recondita)은 실험실에서 식물체에 직접 계대배양하여 사용하였다. 균주의 계대배양 및 약효조사를 위해서 일회용 포트(직경: 6.5cm)에 15립씩의 밀종자(은파)를 파종하여 온실에서 7일간 재배한 1엽기의 밀에 포자를 털어 접종하였다. 접종한 1엽기의 밀을 20℃의 습실상에서 1일간 습실처리한 후, 상대습도 70% 및 20℃의 항온항습실로 옮겨 10일동안 발병을 유도한 다음 잎의 병반면적율을 구했다.The pathogen ( Puccinia recondita ) was used for direct passage to plants in the laboratory. For subculture and pharmacological investigation of strains, 15 seed grains (silver onions) were seeded in a disposable pot (diameter: 6.5 cm), and spores were inoculated by sprinkling the wheat of one leaf grown for 7 days in a greenhouse. The inoculated one-leafed wheat was incubated for one day in a 20 ° C. chamber, then transferred to a constant temperature and humidity chamber of 70% relative humidity and 20 ° C. for 10 days to induce onset, and the leaf area ratio of the leaves was determined.
시험예 6 : 보리 흰가루병에 대한 살균 효과 Test Example 6: bactericidal effect on barley powdery mildew
병원균(Erysiphe graminis f.sp.hordei)은 실험실에서 계대 배양하여 사용하였다. 균주의 계대배양 및 약효조사를 위해서 일회용 포트(직경: 6.5cm)에 15립씩 의 보리종자(동보리 1호)를 파종하여, 온실(25±5 ℃)에서 7일간 재배한 1엽기의 보리에 흰가루병 포자를 털어 접종한 후, 상대습도 50% 및 22 내지 24℃의 항온항습실에 옮겨 7일간 발병을 유도한 다음 잎의 병반면적율을 구했다.The pathogen ( Erysiphe graminis f.sp.hordei ) was used by passage in the laboratory. For subculture and pharmacological investigation of strains, seeded 15 barley seeds (East barley No. 1) in a disposable pot (diameter: 6.5 cm) and seeded on barley plants grown for 7 days in a greenhouse (25 ± 5 ℃). After inoculating the powdery mildew spores, it was transferred to a constant temperature and humidity room of 50% relative humidity and 22 to 24 ° C to induce the onset for 7 days, and then the leaf area ratio of the leaves was determined.
상기 시험예 1 내지 6에서 측정한 처리구 및 대조구 잎의 병반면적율을 대입하여 방제가를 산출하고, 그 결과를 활성지수로서 하기 표 2에 나타내었다.The control value was calculated by substituting the lesion area ratios of the treated and control leaves measured in Test Examples 1 to 6, and the results are shown in Table 2 as the activity index.
살충 효과 시험예Insecticidal Effect Test Example
본 발명에 따른 4-퀴놀린온 유도체의 살충 효과를 조사하기 위해, 시험 화합물 25mg을 5ml의 아세톤에 용해시키고, 이를 계면활성제인 트리톤엑스(Triton-X)-100 의 100ppm 수용액 45ml와 혼합한 다음, 그 농도가 250ppm으로 되도록 조정하여 얻은 시험약물을 각 성충에 살포하였다. 한편, 대조군에 대해서는 시험화합물을 함유하지 않은 아세톤-계면활성제-증류수 용액으로 처리하였다. 이와 같이 시험군 및 대조군을, 각기 하기 시험예와 같이 동일한 조건(습도 및 온도)하에서 동일한 기간 동안 방치한 후, 얻어진 결과로부터 하기 수학식 2와 같이 사충률(%)을 산출 하였으며, 모든 실험은 각각 3회 반복하였다.In order to investigate the insecticidal effect of the 4-quinolinone derivative according to the present invention, 25 mg of the test compound was dissolved in 5 ml of acetone, and then mixed with 45 ml of a 100 ppm aqueous solution of Triton-X-100, a surfactant, The test drug obtained by adjusting the concentration to 250 ppm was sprayed on each adult. On the other hand, the control group was treated with acetone-surfactant-distilled water solution containing no test compound. Thus, after leaving the test group and the control group for the same period of time under the same conditions (humidity and temperature) as in the following test examples, the mortality rate (%) was calculated as shown in Equation 2 from the results obtained, all the experiments Each repeat was repeated three times.
시험예 7: 벼멸구(Nilaparvata lugens stal)에 대한 살충 효과Test Example 7: Insecticidal effect on Nilaparvata lugens stal
실내에서 살충제 살포없이 누대 사육된 감수성 계통의 벼멸구(Nilaparvata lugens stal)를 아크릴 케이지(가로 26cm, 세로 29cm, 높이 20cm)내에서 사육하되 케이지당 최종 성충의 밀도가 약 500마리가 되도록 동일 영기의 약충을 항온실 (온도 27±1℃, 상대습도 50±5%, 광조건 16명 8암)내에서 동진벼를 이용하여 실내 사육하고 부화후 4일째의 암컷 성충을 공시하였다. Raise susceptible Nilaparvata lugens stalls bred indoors without spraying insecticides in an acrylic cage (26 cm wide, 29 cm long and 20 cm high) with the same reproductive nymphs to have a final adult density of approximately 500 per cage. Were bred indoors using Dongjin rice in a constant temperature room (temperature 27 ± 1 ℃, relative humidity 50 ± 5%, light conditions of 16 females, 8 females).
살충 시험을 위해, 먼저, 초장 5-7cm인 수도 유묘(품종: 동진) 6본을 탈지면으로 말아 시험관(직경 31cm, 높이 15cm)에 삽입한 후, 여기에 상기 성충 20마리를 접종한 다음, 시험관의 입구 중앙부에 미량 분무기 (1회 분사량 0.0254±0.0005ml)의 노줄을 위치시켜 미리 제조해둔 시험약물을 2회 분사하였다. 이어서, 시험관을 항온실(온도 25±1℃, 상대습도 50±5%, 광조건 16명 8암)에 보관하면서 24시간 및 48시간 후에 사충률을 조사하였다. 이때, 침으로 자극을 주었을 때 반사작용을 보이지 않는 것을 사망 개체로 간주하였다.For insecticidal testing, first, 6 seedlings (cultivar: Dongjin), 5-7 cm long, are rolled with cotton wool, inserted into a test tube (31 cm in diameter, 15 cm in height), and then inoculated with 20 adult adults. The test drug prepared beforehand was sprayed twice by placing a nozzle of a micro atomizer (a single injection amount of 0.0254 ± 0.0005 ml) in the center of the inlet. Subsequently, the mortality rate was examined after 24 hours and 48 hours while the test tube was kept in a constant temperature room (temperature 25 ± 1 ° C., relative humidity 50 ± 5%, light conditions 16 people 8 cancer). At this time, when the stimulation with saliva did not show a reflex action was considered as a death.
시험예 8: 복숭아 혹진딧물(Myzus persicae sulzer)에 대한 살충 효과Test Example 8: Insecticidal effect on peach aphid ( Myzus persicae sulzer )
실내에서 살충제 살포없이 2년간 누대 사육된 복숭아 혹 진딧물(Myzus persicae sulzer)을 항온실(온도 21±1℃, 상대습도 50±5%, 광조건 16명 8암)내에서 담배(품종: NC-82)를 이용하여 실내 사육하고, 무시자충을 공시하였다.Peach or aphid ( Myzus persicae sulzer ), which was raised for 2 years without spraying pesticides indoors, was smoked in a constant temperature room (temperature 21 ± 1 ℃, relative humidity 50 ± 5%, light conditions 16 people, 8 cancers). Indoor breeding using), and the insects were notified.
살충 시험을 위해, 먼저 농도가 500ppm인 시험약물 50ml에다 직경이 9cm인 원형으로 자른 담배잎(품종:NC-82)을 30초간 침적시키고, 이를 다시 30분 동안 바람에 건조시킨 후 9cm 페트리접시에 넣어두었다. 이어서, 무시자충 20마리를 각각의 약제가 처리된 담배잎에 접종한 후, 항온실 (온도 25±1℃, 상대습도 50±5%, 광조건 16명 8임)에 보관하면서 24시간 및 48시간 후에 사충률을 조사하였다. 가는붓 끝으로 자극을 주었을때 반사작용을 보이지 않는 것을 사망 개체로 간주하였다.For the insecticidal test, first, 50 ml of the test drug with a concentration of 500 ppm and tobacco leaf (variety: NC-82) cut into a circular shape of 9 cm in diameter were immersed for 30 seconds and dried in the wind for 30 minutes, followed by 9 cm petri dish. I put it. Subsequently, 20 worms were inoculated into tobacco leaves treated with the respective drugs, and then stored in a constant temperature room (temperature 25 ± 1 ° C., relative humidity 50 ± 5%, light conditions of 16 people 8 and 24 hours). The mortality rate was later examined. When irritated with a thin brush tip, no reflexes were considered dead.
시험예 9: 배추좀나방(Plutella Xylostella Linnaeus)에 대한 살충 효과Test Example 9: Insecticidal effect on Chinese cabbage moth ( Plutella Xylostella Linnaeus )
항온실(온도 27±1℃, 상대습도 50±5%, 광조건 16명 8암)에서 양배추를 이용하여 살충제 살포없이 누대 사육된 배추좀나방(Plutella Xylostella Linnaeus)에 대하여 사육 상자당 평균 밀도가 500마리 정도 되도록 사육하고, 3령 유충을 공시하였다.The average density per breeding box was 500 for the Chinese cabbage moth ( Plutella Xylostella Linnaeus ), which was raised using a cabbage in a constant temperature room (temperature 27 ± 1 ℃, relative humidity 50 ± 5%, 8 females in the light condition) without using insecticide. As many as three breeding, three larvae were disclosed.
살충 시험을 위해, 먼저, 양배추잎을 직경이 6cm인 원형으로 잘라 농도가 500ppm인 시험약물에 36초 동안 침적시킨 후, 이를 30분 동안 바람에 건조시켰다. 이와같이 처리된 잎을 각각 직경이 6cm인 페트리 접시에 넣은 후, 여기에 3령 유충 10마리를 접종하였다. 이어서, 페트리접시를 뚜껑을 덮어 항온실 (온도 25±1℃, 상대습도 50±5%, 광조건 16명 8암)에 보관하면서 24시간 및 48시간 후에 사충률을 조사하였다. 가는 붓끝으로 자극을 주었을 때 반사작용을 보이지 않는 것을 사망개체로 간주하였다.For the pesticidal test, first, the cabbage leaves were cut into 6 cm diameter circles, soaked in a test drug having a concentration of 500 ppm for 36 seconds, and then dried in the wind for 30 minutes. The leaves thus treated were placed in a Petri dish each 6 cm in diameter, and then 10 larvae of 3 larvae were inoculated. Subsequently, the petri dishes were covered with a lid and stored in a constant temperature room (temperature 25 ± 1 ° C., relative humidity 50 ± 5%, light conditions of 16 patients, 8 cancers), and the mortality rate was examined after 24 and 48 hours. Death was considered to not show reflexes when stimulated with a thin brush tip.
시험예 10: 점박이 응애(Tetranychus urticae koch)에 대한 살충 효과Test Example 10: Insecticidal effect on spotted mite ( Tetranychus urticae koch )
살충제 감수성 계통의 점박이 응애(Tetranychus urticae koch)를 항온실(온도 23±1℃, 상대습도 50±5%, 광조건 16명 8암)내에서 강낭콩잎을 이용하여 실내 사육하고, 그 충성을 공시하였다.The insecticide susceptible mite ( Tetranychus urticae koch ) was bred indoors using kidney beans in a constant temperature room (temperature 23 ± 1 ° C, relative humidity 50 ± 5%, light conditions of 16 people, 8 cancers), and their loyalty was disclosed. .
살충 시험을 위해, 먼저, 끓인 한천액(한천함량 0.5%)을 샤알레에 깊이 1cm 정도가 되게 흘려 넣은 후 식혀서 굳힌 다음, 그 위에다 강낭콩잎을 고정시켰다. 여기에 성충 40마리 접종하고, 미량 분무기를 이용하여 농도가 500ppm인 시험약물 3ml를 살포하였다. 이어서, 샤알레를 항온실(온도 25±1℃, 상대습도 50±5%, 광조건 16명 8암)에 보관하면서 24시간 및 48시간 후에 각각 현미경을 통하여 사충률을 조사하였다. 자극을 주었을 때 반사작용을 보이지 않는 것을 사망개체로 간주하였다.For the insecticidal test, first, the boiled agar solution (agar content of 0.5%) was poured into the chaile to a depth of about 1 cm, cooled and hardened, and then the kidney beans were fixed on it. 40 adults were inoculated and 3 ml of test drug with a concentration of 500 ppm was sprayed using a micro sprayer. Subsequently, the mortality was examined through a microscope after 24 hours and 48 hours, respectively, while keeping the saale in a constant temperature room (temperature 25 ± 1 ° C., relative humidity 50 ± 5%, light conditions of 16 people 8 cancers). Death was considered to show no reflex when stimulated.
상기 시험예 7 내지 10로부터 측정한 사충률을 하기 표 3에 나타내었다.The mortality measured from Test Examples 7 to 10 is shown in Table 3 below.
상기 표 2 및 3의 결과로부터 알 수 있듯이, 본 발명에 따른 4-퀴놀린온 유도체를 포함하는 조성물은 식물 병원균에 대해 광범위한 살균 효과를 가질 뿐만 아니라, 살충 효과, 특히 배추좀나방과 점박이응애에 대해 탁월한 살충 효과를 갖는다. As can be seen from the results of Tables 2 and 3, the composition comprising the 4-quinolinone derivatives according to the present invention not only has a wide range of bactericidal effects against plant pathogens, but also against insecticidal effects, in particular cabbage moth and spotted mite Has excellent pesticidal effect.
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KR101074212B1 (en) * | 2009-05-18 | 2011-10-14 | 한국화학연구원 | An insecticidal composition comprising 4-quinolinone derivative compound for tree insecticide and the method for killing the insect using thereby |
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KR900018036A (en) * | 1988-05-24 | 1990-12-20 | 모토야마 히데요 | 4 (1H) -quinolone derivative |
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KR101074212B1 (en) * | 2009-05-18 | 2011-10-14 | 한국화학연구원 | An insecticidal composition comprising 4-quinolinone derivative compound for tree insecticide and the method for killing the insect using thereby |
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