KR100613688B1 - 2-amino-4-quinolinone derivative and fungicidal composition for agriculture and horticulture comprising same - Google Patents

2-amino-4-quinolinone derivative and fungicidal composition for agriculture and horticulture comprising same Download PDF

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KR100613688B1
KR100613688B1 KR1020040068396A KR20040068396A KR100613688B1 KR 100613688 B1 KR100613688 B1 KR 100613688B1 KR 1020040068396 A KR1020040068396 A KR 1020040068396A KR 20040068396 A KR20040068396 A KR 20040068396A KR 100613688 B1 KR100613688 B1 KR 100613688B1
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branched alkyl
hydrogen
quinolinone
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KR20060019749A (en
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박창식
최은복
연규환
이현규
양희철
최경자
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한국화학연구원
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • 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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • 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
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
    • A01N43/32—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms six-membered rings

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Abstract

본 발명은 농원예용 살균제로 유용한 하기 화학식 1의 신규한 2-아미노-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 2-amino-4-quinolinone derivative of formula (I), which is useful as an agricultural horticultural fungicide, which selectively shows 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.

<화학식 1><Formula 1>

Figure 112004038983111-pat00001
Figure 112004038983111-pat00001

상기 식에서, Where

R1 내지 R4는 각각 수소, 할로겐, C1-10의 선형 또는 분지형 알킬기, C 1-6의 선형 또는 분지형 할로알킬기, C1-10의 선형 또는 분지형 알콕시기, 페닐기, 페녹시기, 벤질기, 니트로기 또는 사이아노기이고;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 group, nitro group or cyano group;

R5는 C1-6의 선형 또는 분지형 알킬기, C3-6의 사이클로알킬기, 페닐기, 페녹시기 또는 벤질기이고;R 5 is a C 1-6 linear or branched alkyl group, a C 3-6 cycloalkyl group, a phenyl group, a phenoxy group or a benzyl group;

R6는 수소 또는 포화되거나 불포화된 C1-5의 선형 또는 분지형 알킬기이고;R 6 is hydrogen or a saturated or unsaturated C 1-5 linear or branched alkyl group;

R7은 수소,

Figure 112004038983111-pat00002
R 7 is hydrogen,
Figure 112004038983111-pat00002

Figure 112004038983111-pat00003
또는 -CH2CN 이며, 여기에서
Figure 112004038983111-pat00003
Or -CH 2 CN, where

R8 내지 R16은 각각 수소, 할로겐, 포화되거나 불포화된 C1-6의 선형 또는 분지형 알킬기, 치환되거나 치환되지 않은 페닐기, 알콕시알킬기 또는 (R19)3Si(이때, R19는 C1-5의 선형 또는 분지형 알킬기임)이고,R 8 to R 16 are each hydrogen, halogen, saturated or unsaturated C 1-6 linear or branched alkyl group, substituted or unsubstituted phenyl group, alkoxyalkyl group or (R 19 ) 3 Si, wherein R 19 is C 1 -5 linear or branched alkyl groups;

R17 및 R18은 각각 수소, 또는 C1-5의 선형 또는 분지형 알킬기이고,R 17 and R 18 are each hydrogen or a C 1-5 linear or branched alkyl group,

X 및 X'는 각각 C1-3의 알콕시, C1-3의 티오알콕시이거나, 함께 -O-(CH2)r-O-, -S-(CH2)r-S- 를 형성하고,X and X 'are each C 1-3 alkoxy, C 1-3 thioalkoxy, or together form -O- (CH 2 ) rO-, -S- (CH 2 ) rS-,

Y는 O, S 또는 S=O 이고,Y is O, S or S = O,

Z는 헤테로사이클릭기이고,Z is a heterocyclic group,

m는 0 내지 4의 정수이며, m is an integer from 0 to 4,

n, p, q, r은 각각 1 내지 4의 정수이다.n, p, q, and r are integers of 1-4, respectively.

Description

2-아미노-4-퀴놀린온 유도체 및 이를 포함하는 농원예용 살균제 조성물 {2-AMINO-4-QUINOLINONE DERIVATIVE AND FUNGICIDAL COMPOSITION FOR AGRICULTURE AND HORTICULTURE COMPRISING SAME}2-amino-4-quinolinone derivative and agricultural horticultural fungicide composition comprising the same {2-AMINO-4-QUINOLINONE DERIVATIVE AND FUNGICIDAL COMPOSITION FOR AGRICULTURE AND HORTICULTURE COMPRISING SAME}

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.

최근 기존의 살균제들 보다 강력하고 내성이 없는 화합물로서 환경에도 안전한 새로운 화합물을 합성하기 위한 연구가 활발히 진행되고 있으며, 예컨대, 본 발명자들의 대한민국 특허출원 제2004-35181호 및 제 2004-60083호에는 기존의 살균제와는 구조가 다르면서 우수한 살균 또는 살충 효과를 갖는 4-퀴놀린온 유도체가 게시되어 있다. 그러나, 이들 화합물은 일부 병원균에 대해서는 충분한 살균 또는 살충 효과를 만족시키지 못하였다.Recently, research is being actively conducted to synthesize new compounds that are safer and more environmentally safe than existing fungicides. For example, Korean Patent Application Nos. 2004-35181 and 2004-60083 of the present inventors 4-quinolinone derivatives having a different structure from the fungicide of and having excellent bactericidal or insecticidal effects have been published. However, these compounds did not satisfy sufficient bactericidal or pesticidal effects against some pathogens.

이에, 본 발명자들은 좀더 지속적인 연구를 거듭한 결과, 퀴놀린온 유도체의 2 위치가 불포화기 또는 헤테로 원자 함유기를 갖는 아민기로 치환되는 경우 더 강력하고 광범위한 살균 또는 살충 효과 뿐만 아니라 제초 효과도 나타냄을 발견하고 본 발명을 완성하게 되었다.Accordingly, the present inventors conducted a more continuous study, and found that when the 2-position of the quinolinone derivative is substituted with an amine group having an unsaturated group or a hetero atom-containing group, it exhibits a stronger and broader bactericidal or insecticidal effect as well as a herbicidal effect. The present invention has been completed.

따라서, 본 발명의 목적은 종래에 비하여 현저하게 탁월한 살균, 살충 및 제초 효과를 가지면서 환경에도 안전한 신규의 2-아미노-4-퀴놀린온 유도체를 제공하는 것이다.
Accordingly, it is an object of the present invention to provide novel 2-amino-4-quinolinone derivatives which are environmentally safe with remarkably superior bactericidal, insecticidal and herbicidal effects as compared with the prior art.

상기 목적을 달성하기 위하여 본 발명에서는, 농원예용 살균, 살충 또는 제초제로서 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 horticultural bactericidal, insecticide or herbicide:

Figure 112004038983111-pat00004
Figure 112004038983111-pat00004

상기 식에서, Where

R1 내지 R4는 각각 수소, 할로겐, C1-10의 선형 또는 분지형 알킬기, C 1-6의 선형 또는 분지형 할로알킬기, C1-10의 선형 또는 분지형 알콕시기, 페닐기, 페녹시기, 벤질기, 니트로기 또는 사이아노기이고;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 group, nitro group or cyano group;

R5는 C1-6의 선형 또는 분지형 알킬기, C3-6의 사이클로알킬기, 페닐기, 페녹시기 또는 벤질기이고;R 5 is a C 1-6 linear or branched alkyl group, a C 3-6 cycloalkyl group, a phenyl group, a phenoxy group or a benzyl group;

R6는 수소 또는 포화되거나 불포화된 C1-5의 선형 또는 분지형 알킬기이고;R 6 is hydrogen or a saturated or unsaturated C 1-5 linear or branched alkyl group;

R7은 수소,

Figure 112004038983111-pat00005
R 7 is hydrogen,
Figure 112004038983111-pat00005

Figure 112004038983111-pat00006
또는 -CH2CN 이며, 여기에서
Figure 112004038983111-pat00006
Or -CH 2 CN, where

R8 내지 R16은 각각 수소, 할로겐, 포화되거나 불포화된 C1-6의 선형 또는 분지형 알킬기, 치환되거나 치환되지 않은 페닐기, 알콕시알킬기 또는 (R19)3Si(이때, R19는 C1-5의 선형 또는 분지형 알킬기임)이고,R 8 to R 16 are each hydrogen, halogen, saturated or unsaturated C 1-6 linear or branched alkyl group, substituted or unsubstituted phenyl group, alkoxyalkyl group or (R 19 ) 3 Si, wherein R 19 is C 1 -5 linear or branched alkyl groups;

R17 및 R18은 각각 수소, 또는 C1-5의 선형 또는 분지형 알킬기이고,R 17 and R 18 are each hydrogen or a C 1-5 linear or branched alkyl group,

X 및 X'는 각각 C1-3의 알콕시, C1-3의 티오알콕시이거나, 함께 -O-(CH2)r-O-, -S-(CH2)r-S- 를 형성하고,X and X 'are each C 1-3 alkoxy, C 1-3 thioalkoxy, or together form -O- (CH 2 ) rO-, -S- (CH 2 ) rS-,

Y는 O, S 또는 S=O 이고,Y is O, S or S = O,

Z는 헤테로사이클릭기이고,Z is a heterocyclic group,

m는 0 내지 4의 정수이며,m is an integer from 0 to 4,

n, p, q, r은 각각 1 내지 4의 정수이다.n, p, q, and r are integers of 1-4, respectively.

이하, 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.

본 발명에 따른 2-아미노-4-퀴놀린온 유도체의 바람직한 예는 R7이 알켄, 아세틸렌, 알렌 등의 불포화기를 갖는 화합물이다.Preferred examples of 2-amino-4-quinolinone derivatives according to the present invention are compounds in which R 7 has an unsaturated group such as alkene, acetylene, allene and the like.

본 발명에 따른 상기 화학식 1의 2-아미노-4-퀴놀린온 유도체는, 하기 반응식 1에서 볼 수 있듯이, 하기 구조식(II)의 2-알킬설폭시-4-퀴놀린온과 하기 구조식(III)의 아민 화합물을 반응시켜 제조할 수 있다:2-amino-4-quinolinone derivatives of the general formula (1) according to the present invention, as can be seen in the following scheme 1, of the 2-alkyl sulfoxy-4-quinolinone of the formula (II) It can be prepared by reacting an amine compound:

Figure 112004038983111-pat00007
Figure 112004038983111-pat00007

상기 식에서, R1 내지 R7은 화학식 1에서 정의한 바와 같으며, R21은 C 1-3의 알킬기이다.Wherein R 1 to R 7 are as defined in Formula 1, and R 21 is an alkyl group of C 1-3 .

상기 반응은 불활성 용매, 예컨대 다이에틸에테르, 아아이소프로필 에테르, 테트라하이드로퓨란, 다이옥산, 다이페닐에테르 등의 에테르류 ; 벤젠, 톨루엔, 자 일렌, 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 and 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 48시간이 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, but 0.5 to 48 hours is preferred.

상기 구조식(II)의 화합물은 공지된 방법(문헌[R. C. Anand & A. K. Sinha, India Journal of Chemistry, 30B, 560-562(1991); 및 한국 특허 제295819호] 참조)에 의해 합성된 설파이드를 과산화수소, 과산화아세트산 또는 m-클로로과산화벤조산 등의 산화제로 산화시켜 얻을 수 있다.The compound of formula II is hydrogen peroxide synthesized by a known method (see RC Anand & AK Sinha, India Journal of Chemistry, 30B , 560-562 (1991); and Korean Patent No. 295819). And oxidizing agents such as acetic acid peroxide or 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 목적 생성물을 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 목적 생성물을 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 target 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 the desired product.

또한, 본 발명에 따른 상기 화학식 1의 화합물의 일종인 화합물(Ib)는 하기 반응식 2에서와 같이, 화합물(Ia)를 산가수분해시켜 얻을 수 있다:In addition, Compound (Ib), which is a kind of the compound of Formula 1 according to the present invention, may be obtained by acid hydrolysis of Compound (Ia) as in Scheme 2 below:

Figure 112004038983111-pat00008
Figure 112004038983111-pat00008

상기 식에서, R1 내지 R6은 화학식 1에서 정의한 바와 같으며, R20은 C 1-3의 알킬기이다.Wherein R 1 to R 6 are as defined in Formula 1, and R 20 is an alkyl group of C 1-3 .

상기 산가수분해 반응은 5 내지 70％의 산 수용액에서 진행되고, 이때 사용가능한 산은 염산, 황산 등과 같은 무기산 또는 아세트산, 프로피온산 등과 같은 유기산이며, 반응 온도는 상온 내지 끓는점의 온도가 가능하다.The acid hydrolysis reaction is carried out in an acid solution of 5 to 70%, wherein the usable acid is an inorganic acid such as hydrochloric acid, sulfuric acid or the like or an organic acid such as acetic acid or propionic acid, and the reaction temperature may be from room temperature to boiling point.

수득된 목적 생성물은 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 desired 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.

본 발명의 화합물은 넓은 스펙트럼의 식물 병원균에 대해 높은 치료 및 예방적 항균 특성을 나타낸다. 이러한 병원균의 예로는 벼의 도열병균(Pyricularia oryzae), 벼의 잎집무늬 마름병균(Rhizoctonia solani), 오이회색 곰팡이병균(Botrytis cinerea), 오이의 흰가루병균(Sphaerotheca fuliginea), 오이의 노균병균(Pseudoperonospora cubensis), 포도의 노균병균(Plasmopora viticola), 토마토의 역병균(Phytophthora infestans), 깨씨무늬병균(Cochliobolus miyabeanus), 땅콩의 갈색무늬병균(Cercopora arachidicola), 보리의 흰가루병균(Erysiphe graminis), 밀의 붉은 녹병균(Puccinia recondita) 및 밀의 줄기 녹병균(Puccinis graminis)이 있으며, 본 발명에 따른 화합물은 특히 벼도열병과 밀녹병에 탁월한 효과를 나타낸다.The compounds of the present invention exhibit high therapeutic and prophylactic antimicrobial properties against a broad spectrum of plant pathogens. Examples of such pathogens include Pyricularia oryzae of rice, Rhizoctonia solani of rice, Botrytis cinerea of cucumber, Sphaerotheca fuliginea of cucumber, and Pseudoperonospora cube of cucumber. ), downy mildew of grape fungus (Plasmopora viticola), Station pathogens of tomato (Phytophthora infestans), kkaessi pattern germs (Cochliobolus miyabeanus), brown pattern germs of peanut (Cercopora arachidicola), powdery mildew fungus of barley (Erysiphe graminis), wheat red rust ( Puccinia recondita ) and Puccinis graminis of wheat, and the compounds according to the invention show excellent effects, in particular against rice fever and wheat rust.

또한, 본 발명에 따른 화합물은 파리, 모기 및 바퀴와 같은 위생해충, 농경해충, 예를 들면 애멸구(Lodelphax striztellus Fallen), 벼멸구(Nilaparvata lugens stal), 흰등멸구(Sogatella furcifera Horvath), 끝동매미충(Nephotettix cincticeps Uhler), 트라이알레우로우즈 바포라리오룸(Trialeurodes vaporariorum) 및 복숭아 흑진딧물(Myzus persicae Sulzer)과 같은 노린재목 해충, 필로노릭터 린고닐라(Phyllonorycter ringonella Matsumura), 배추좀나방(Plutella zylostella Curtis), 멸강나방(Pseudaletia separata Walker), 도둑나방(Hamestra brassicae Linne), 담배거세미나방(Spodoptera litura Fablicius), 배추흰나비(Pieris rapaecrucivora Boisdubal), 점박이 응애(Tetranychus urticae koch)와 같은 나비목 해충, 오울레마 오리자에(Oulema oryzae Kuwayama) 및 벼뿌리 바구미(Echinocnemus squameus Billberg) 같은 딱정벌레목해충, 희니개비 및 나비좀과 같은 가내 해충에 대해 효과적이며, 특히 배추좀나방과 점박이응애와 같은 나비목 해 충에 대해서 뛰어난 효과를 나타낸다.In addition, the compounds according to the invention are sanitary pests, such as flies, mosquitoes and wheels, agricultural pests, for example, Lodelphax striztellus Fallen , Nilaparvata lugens stal , Sogatella furcifera Horvath , Nephetettix cincticeps Uhler ), stink bugs such as Trialeurodes vaporariorum and Myzus persicae Sulzer , Phyllonorycter ringonella Matsumura , Plutella zylostella Curtis , Lepidoptera pests such as Pseudaletia separata Walker , Thief moth ( Hamestra brassicae Linne ), Tobacco macromoth ( Spodoptera litura Fablicius ), Chinese cabbage butterfly ( Pieris rapaecrucivora Boisdubal ) and Tetranychus urticae koch the Coleoptera pests such as (Oulema oryzae Kuwayama) and rice root weevil (Echinocnemus squameus Billberg), huini cigarettes and bow And are effective against pests such as home, especially to some Lepidoptera such as cabbage moth and T. urticae shows an excellent effect with respect to the charge.

추가로, 본 발명에 따른 화합물은 발아후 제초제로 사용하여 여러 가지 잡초, 예를 들면 개밀(Agropyron smit hii), 바랭이(Digitaria sangulanis (L.) Scop.), 미국 개기장(Panicum dichotomiflorum Michx.), 까마중(Solanum nigrum L.), 자귀풀(Aeschynomene indica L.), 어저귀(Abutilon avicennae Gaertn), 도꼬마리(Xanthium strumarium L.), 메꽃(Calystegia japonica Choisy)에 유효하며, 특히, 까마중과 자귀풀에 대한 제초효과가 두드러진다.In addition, the compounds according to the invention can be used as herbicides after germination, for example, in various weeds, for example, wheatgrass ( Agropyron smit hii ), dianthus (Digitaria sangulanis (L.) Scop. ), And US panicum dichotomiflorum Michx. It is effective for Solanum nigrum L. , Aeschynomene indica L. , Abutilon avicennae Gaertn , Xanthium strumarium L. and Calystegia japonica Choisy . The effect is noticeable.

또한, 본 발명에 따른 화합물은 논조건에서의 벼 제초제로 사용하여 여러 가지 논 잡초들, 예를 들면 논피(E.oryzieola), 올챙이고리(S. juncoides), 물 달개비(M. vaginalis), 너도 방동사니(Cyperus serotinus), 올미(Sagittaria pygmaea)등에 제초효과를 나타내며, 특히, 논피, 물 달개비, 너도 방동사니 및 올미에 좋은 효과를 보인다.In addition, the compounds according to the present invention various non weeds using herbicides in rice plants in paddy conditions, for example barnyard grass (E.oryzieola), ladle ring (S. juncoides), water Tradescantia (M. vaginalis), beech It exhibits herbicidal effect on Cyperus serotinus and Sagittaria pygmaea . Especially, it shows good effect on paddy grass, water stilt, and you.

본 발명에 따르면, 본 발명의 화학식 1의 화합물은 조성물 중량을 기준으로 약 0.01 내지 90 중량％, 바람직하게는 약 1 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 (I) of the present invention contains about 0.01 to 90% by weight, preferably about 1 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, 실리카 등이 있고; 액체 담체는 물, 메탄올, 에탄올, 아 세톤, 다이에틸폼아미드, 에테르, 벤젠, 자일렌, 톨루엔, 나프타 등이 있고; 표면활성제로는 폴리옥시에틸렌 알킬페닐에테르 및 폴리옥시에틸렌 지방산 에스터와 같은 비이온성 표면활성제, 알킬벤젠설폰산염, 리그닌설폰산염 및 다이나프틸메탄설폰산염과 같은 음이온성 표면활성제 등이 있으며; 접착제로는 폴리바이닐알콜, 카복시메틸 셀룰로오스(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 dynaphthylmethanesulfonates; Adhesives include polyvinyl alcohol, carboxymethyl cellulose (CMC), gum arabic and the like.

또한, 본 발명에 따른 조성물은 토양 뿐만 아니라 농업 생산물, 묘종, 종자 등을 살균하는데 사용될 수 있으며, 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 to sterilize agricultural products, seedlings, seeds, as well as soil, and used in combination with other agrochemicals or nutrients such as insecticides, fungicides, herbicides, plant growth regulators, acaricides and the like. Can be.

본 발명에 따른 화학식 1의 2-아미노-4-퀴놀린온 유도체의 구체적인 예를 들어보면 하기 표 1과 같다:Specific examples of 2-amino-4-quinolinone derivatives of formula 1 according to the present invention are shown in Table 1 below:

Figure 112004038983111-pat00009
Figure 112004038983111-pat00009

Figure 112004038983111-pat00010
Figure 112004038983111-pat00010

Figure 112004038983111-pat00011
Figure 112004038983111-pat00011

Figure 112004038983111-pat00012
Figure 112004038983111-pat00012

Figure 112004038983111-pat00013
Figure 112004038983111-pat00013

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: 6-클로로-3-사이크로프로판카보닐-2-(2,2-다이메톡시에틸아미노)-8-트라이플루오르메틸-4-퀴놀린온(화합물 9)의 합성Example 1 Synthesis of 6-Chloro-3-cyclopropanecarbonyl-2- (2,2-dimethoxyethylamino) -8-trifluoromethyl-4-quinolinone (Compound 9)

6-클로로-3-사이클로프로판카보닐-2-메틸설폭시-8-트라이플루오르메틸-4-퀴놀린온(377mg, 1mmol)과 2,2-다이메톡시에틸아민(105mg, 1mmol)을 테트라하이드로퓨란 2ml에 가하고 24시간 동안 상온에서 교반하였다. 반응이 완료되면 용매를 감압증류하여 제거하고 남은 고체를 에탄올에서 재결정하여 표제 생성물 335mg(수율 80％)을 수득하였다.6-Chloro-3-cyclopropanecarbonyl-2-methylsuloxy-8-trifluoromethyl-4-quinolinone (377 mg, 1 mmol) and 2,2-dimethoxyethylamine (105 mg, 1 mmol) It was added to 2 ml of furan and stirred at room temperature for 24 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and the remaining solid was recrystallized in ethanol to obtain 335 mg (yield 80%) of the title product.

1H NMR(CDCI3): δ 0.7-1.2(m, 4H), 3.4(s, 6H), 3.6-3.8(m, 1H), 4.4(t, 1H), 4.5-4.9(m, 2H), 7.7(d, 1H), 8.8(d, 1H), 9.5(br, 1H), 11.6(br, 1H) 1 H NMR (CDCI 3 ): δ 0.7-1.2 (m, 4H), 3.4 (s, 6H), 3.6-3.8 (m, 1H), 4.4 (t, 1H), 4.5-4.9 (m, 2H), 7.7 (d, 1H), 8.8 (d, 1H), 9.5 (br, 1H), 11.6 (br, 1H)

실시예 2: 6-클로로-2-(2,2-다이메톡시에틸아미노)-3-아이소부티릴-8-트라이플루오르메틸-4-퀴놀린온(화합물 10)의 합성Example 2: Synthesis of 6-chloro-2- (2,2-dimethoxyethylamino) -3-isobutyryl-8-trifluoromethyl-4-quinolinone (Compound 10)

6-클로로-3-아이소부티릴-2-메틸설폭시-8-트라이플루오르메틸-4-퀴놀린온(379mg, 1mmol)과 2,2-다이메톡시에틸아민(105mg, 1mmol)으로부터 실시예 1과 같은 반응을 실시하여 표제 생성물 307mg(수율 73％)을 수득하였다.Example 1 from 6-chloro-3-isobutyryl-2-methylsuloxy-8-trifluoromethyl-4-quinolinone (379 mg, 1 mmol) and 2,2-dimethoxyethylamine (105 mg, 1 mmol) The reaction was carried out to give 307 mg (73% yield) of the title product.

1H NMR(CDCI3): δ 1.5(d, 6H), 3.6-3.8(m, 1H), 3.8(s, 6H), 4.4(t, 1H), 4.5-4.9(m, 2H), 8.1(d, 1H), 8.8(d, 1H), 9.9(br, 1H), 12.2(br, 1H) 1 H NMR (CDCI 3 ): δ 1.5 (d, 6H), 3.6-3.8 (m, 1H), 3.8 (s, 6H), 4.4 (t, 1H), 4.5-4.9 (m, 2H), 8.1 ( d, 1H), 8.8 (d, 1H), 9.9 (br, 1H), 12.2 (br, 1H)

실시예 3: 3-아세틸-6-클로로-2-(N-메틸-N'-프로파질아미노)-8-트라이플루오르메틸-4-퀴놀린온(화합물 13)의 합성Example 3: Synthesis of 3-acetyl-6-chloro-2- (N-methyl-N'-propazylamino) -8-trifluoromethyl-4-quinolinone (Compound 13)

3-아세틸-6-클로로-2-메틸설폭시-8-트라이플루오르메틸-4-퀴놀린온(351mg, 1mmol)과 N-메틸-N'-프로파질아민(69mg, 1mmol)으로부터 실시예 1과 같은 반응을 실시하여 표제 생성물 235mg(수율 66％)을 수득하였다.Example 1 from 3-acetyl-6-chloro-2-methylsulfoxy-8-trifluoromethyl-4-quinolinone (351 mg, 1 mmol) and N-methyl-N'-propazylamine (69 mg, 1 mmol) The same reaction was carried out to give 235 mg (66% yield) of the title product.

1H NMR(CDCI3): δ 2.6(t, 1H), 3.0(s, 3H), 3.4(m, 3H), 4.6(d, 2H), 8.2(d, 1H), 8.6(d, 1H), 14.0(br, 1H) 1 H NMR (CDCI 3 ): δ 2.6 (t, 1H), 3.0 (s, 3H), 3.4 (m, 3H), 4.6 (d, 2H), 8.2 (d, 1H), 8.6 (d, 1H) , 14.0 (br, 1H)

실시예 4: 3-아세틸-2-(N-메틸-N'-프로파질아미노)-8-트라이플루오르메틸-4-퀴놀린온(화합물 16)의 합성Example 4: Synthesis of 3-acetyl-2- (N-methyl-N'-propazylamino) -8-trifluoromethyl-4-quinolinone (Compound 16)

3-아세틸-2-메틸설폭시-8-트라이플루오르메틸-4-퀴놀린온(317mg, 1mmol)과 N-메틸-N'-프로파질아민(69mg, 1mmol)으로부터 실시예 1과 같은 반응을 실시하여 표제 생성물 235mg(수율 66％)을 수득하였다.The same reaction as in Example 1 was carried out from 3-acetyl-2-methylsulfoxy-8-trifluoromethyl-4-quinolinone (317 mg, 1 mmol) and N-methyl-N'-propazylamine (69 mg, 1 mmol). This gave 235 mg (66% yield) of the title product.

1H NMR(CDCI3): δ 2.5(t, 1H), 2.9(s, 3H), 3.3(s, 3H), 4.5(d, 2H), 7.4(t, 1H), 8.2(d, 1H), 9.6(br, 1H) 1 H NMR (CDCI 3 ): δ 2.5 (t, 1H), 2.9 (s, 3H), 3.3 (s, 3H), 4.5 (d, 2H), 7.4 (t, 1H), 8.2 (d, 1H) , 9.6 (br, 1H)

실시예 5: 6-클로로-3-사이클로프로판카보닐-2-프로파질아미노-8-트라이플루오르메틸-4-퀴놀린온(화합물 22)의 합성Example 5 Synthesis of 6-Chloro-3-cyclopropanecarbonyl-2-propazylamino-8-trifluoromethyl-4-quinolinone (Compound 22)

6-클로로-3-사이클로프로판카보닐-2-메틸설폭시-8-트라이플루오르메틸-4-퀴놀린온(377mg, 1mmol)과 프로파질아민(55mg, 1mmol)으로부터 실시예 1과 같은 반응을 실시하여 표제 생성물 265mg(수율 72％)을 수득하였다.The same reaction as in Example 1 was carried out from 6-chloro-3-cyclopropanecarbonyl-2-methylsuloxy-8-trifluoromethyl-4-quinolinone (377 mg, 1 mmol) and propazylamine (55 mg, 1 mmol). This gave 265 mg (72% yield) of the title product.

1H NMR(CDCI3): δ 1.3-1.6(m, 4H), 2.9(t, 1H), 3.9-4.3(m, 1H), 4.6(q, 2H), 8.2(d, 1H), 8.8(d, 2H), 12.4(br, 1H) 1 H NMR (CDCI 3 ): δ 1.3-1.6 (m, 4H), 2.9 (t, 1H), 3.9-4.3 (m, 1H), 4.6 (q, 2H), 8.2 (d, 1H), 8.8 ( d, 2H), 12.4 (br, 1H)

실시예 6: 3-아세틸-6-클로로-2-프로파질아미노-8-트라이플루오르메틸-4-퀴놀린온(화합물 25)의 합성Example 6: Synthesis of 3-acetyl-6-chloro-2-propazylamino-8-trifluoromethyl-4-quinolinone (Compound 25)

3-아세틸-6-클로로-2-메틸설폭시-8-트라이플루오르메틸-4-퀴놀린온(351mg, 1mmol)과 프로파질아민 (55mg, 1mmol)으로부터 실시예 1과 같은 반응을 실시하여 표제 생성물 284mg(수율 83％)을 수득하였다.The title product was subjected to the same reaction as in Example 1 from 3-acetyl-6-chloro-2-methylsuloxy-8-trifluoromethyl-4-quinolinone (351 mg, 1 mmol) and propazylamine (55 mg, 1 mmol). 284 mg (83% yield) were obtained.

1H NMR(CDCI3): δ 2.9(t, 1H), 3.0(s, 3H), 4.54(q, 2H), 8.0(d, 1H), 8.7(d, 2H), 12.3(br, 1H) 1 H NMR (CDCI 3 ): δ 2.9 (t, 1H), 3.0 (s, 3H), 4.54 (q, 2H), 8.0 (d, 1H), 8.7 (d, 2H), 12.3 (br, 1H)

실시예 7: 6-클로로-2-(3,3-다이에톡시프로필아미노)-3-아이소부티릴-8-트라이플루오르메틸-4-퀴놀린온(화합물 33)의 합성Example 7: Synthesis of 6-chloro-2- (3,3-diethoxypropylamino) -3-isobutyryl-8-trifluoromethyl-4-quinolinone (Compound 33)

6-클로로-3-아이소부티릴-2-메틸설폭시-8-트라이플루오르메틸-4-퀴놀린온(379mg, 1mmol)과 3,3-다이에톡시프로필아민(147mg, 1mmol)으로부터 실시예 1과 같은 반응을 실시하여 표제 생성물 335mg(수율 78％)을 수득하였다.Example 1 from 6-chloro-3-isobutyryl-2-methylsuloxy-8-trifluoromethyl-4-quinolinone (379 mg, 1 mmol) and 3,3-diethoxypropylamine (147 mg, 1 mmol) The reaction was carried out to obtain 335 mg (yield 78%) of the title product.

1H NMR(CDCI3): δ 0.7-1.5(m, 12H), 2.0-2.40(m, 2H), 3.2-4.0(m, 6H), 4.2(m, 1H), 4.7(t, 1H), 7.8(d, 1H), 8.0(br, 1H). 11.9(br, 1H) 1 H NMR (CDCI 3 ): δ 0.7-1.5 (m, 12H), 2.0-2.40 (m, 2H), 3.2-4.0 (m, 6H), 4.2 (m, 1H), 4.7 (t, 1H), 7.8 (d, 1 H), 8.0 (br, 1 H). 11.9 (br, 1 H)

실시예 8: 6-클로로-3-아이소부티릴-2-(3-옥소프로필아미노)-8-트라이플루오르메틸-4-퀴놀린온(화합물 34)의 합성Example 8: Synthesis of 6-chloro-3-isobutyryl-2- (3-oxopropylamino) -8-trifluoromethyl-4-quinolinone (Compound 34)

6-클로로-2-(3,3-다이에톡시프로필아미노)-아이소부티릴-8-트라이플루오르메틸-4-퀴놀린온(33)(462mg, 1mmol)에 80％ 아세트산 수용액 20ml를 가한 다음, 70ㅀC에서 2시간 동안 가열하였다. 반응이 완료되면 상온으로 냉각한 뒤 물 20ml 및 에틸아세테이트 30ml를 가하여 추출하고 유기층을 무수황산마그네슘으로 건조시킨 후 용매를 증류하였다. 남은 고체를 n-헥산과 에틸아세테이트의 혼합 용매를 용리액으로 하여 크로마토그래피로 분리정제함으로써 표제 생성물 280mg(수율 72％)을 수득하였다.To 6-chloro-2- (3,3-diethoxypropylamino) -isobutyryl-8-trifluoromethyl-4-quinolinone (33) (462 mg, 1 mmol) was added 20 ml of an aqueous 80% acetic acid solution, Heated at 70 ° C. for 2 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, extracted with 20 ml of water and 30 ml of ethyl acetate, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off. The remaining solid was purified by chromatography using a mixed solvent of n-hexane and ethyl acetate as eluent to obtain 280 mg (72% yield) of the title product.

1H NMR(CDCI3): δ 1.3(d, 6H), 3.1(t, 2H), 3.7(q, 2H), 4.2(m, 1H), 7.8(d, 1H), 8.5(d, 1H), 9.1(br, 1H). 10.0(s, 1H), 11.2(br, 1H) 1 H NMR (CDCI 3 ): δ 1.3 (d, 6H), 3.1 (t, 2H), 3.7 (q, 2H), 4.2 (m, 1H), 7.8 (d, 1H), 8.5 (d, 1H) , 9.1 (br, 1H). 10.0 (s, 1H), 11.2 (br, 1H)

실시예 9: 2-알릴아미노-6-클로로-3-아이소부티릴-8-트라이플루오르메틸-4-퀴놀린온(화합물 37)의 합성Example 9: Synthesis of 2-allylamino-6-chloro-3-isobutyryl-8-trifluoromethyl-4-quinolinone (Compound 37)

6-클로로-3-아이소부티릴-2-메틸설폭시-8-트라이플루오르메틸-4-퀴놀린온(379mg, 1mmol)과 알릴아민(57mg, 1mmol)으로부터 실시예 1과 같은 반응을 실시하여 표제 생성물 279mg(수율 75％)을 수득하였다.The same reaction as in Example 1 was carried out from 6-chloro-3-isobutyryl-2-methylsuloxy-8-trifluoromethyl-4-quinolinone (379 mg, 1 mmol) and allylamine (57 mg, 1 mmol). 279 mg (75% yield) of product were obtained.

1H NMR(CDCI3): δ 1.2(d, 6H), 4.0-4.6(m, 3H), 5.3-5.6(m, 3H), 7.8(d, 1H), 8.1(br, 1H), 8.6(d, 1H), 12.1(br, 1H) 1 H NMR (CDCI 3 ): δ 1.2 (d, 6H), 4.0-4.6 (m, 3H), 5.3-5.6 (m, 3H), 7.8 (d, 1H), 8.1 (br, 1H), 8.6 ( d, 1H), 12.1 (br, 1H)

실시예 10: 3-아세틸-6-클로로-8-트라이플루오르메틸-2-(3-트라이메틸실릴프로파질아미노)-4-퀴놀린온(화합물 46)의 합성Example 10 Synthesis of 3-acetyl-6-chloro-8-trifluoromethyl-2- (3-trimethylsilylpropazylamino) -4-quinolinone (Compound 46)

3-아세틸-6-크로로-2-메틸설폭시-8-트라이플루오르메틸-4-퀴놀린온(350mg, 1mmol)과 3-트라이메틸실릴프로파질아민염산염(164mg, 1mmol)을 테트라하이드로퓨란 20ml에 가한 다음 트라이에틸아민을 과량 가한 후 상온에서 24시간 교반하였다. 반응이 완료되면 용매를 감압증류하여 제거하였다. 남은 고체를 다이클로로메탄 20ml에 녹인 다음 물 20ml로 씻어낸 후 무수 황산마그네슘으로 건조하고 용매를 감압증류하여 제거하였다. 다시 남은 고체를 에탄올에서 재결정하여 표제 생성물 330mg(수율 80％)을 수득하였다.20 ml of 3-acetyl-6-chloro-2-methylsuloxy-8-trifluoromethyl-4-quinolinone (350 mg, 1 mmol) and 3-trimethylsilylpropazamineamine hydrochloride (164 mg, 1 mmol) tetrahydrofuran After adding to the triethylamine excess and stirred at room temperature for 24 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure. The remaining solid was dissolved in 20 ml of dichloromethane, washed with 20 ml of water, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The remaining solid was recrystallized in ethanol to give 330 mg (80% yield) of the title product.

1H NMR(CDCI3): δ 0.2(s, 9H), 2.7(s, 3H), 4.3(d, 2H), 6.8(d, 1H), 8.5(br, 1H), 8.6(d, 1H), 12.0(br, 1H) 1 H NMR (CDCI 3 ): δ 0.2 (s, 9H), 2.7 (s, 3H), 4.3 (d, 2H), 6.8 (d, 1H), 8.5 (br, 1H), 8.6 (d, 1H) , 12.0 (br, 1H)

실시예 11: 6-클로로-2-프로파질아미노-3-프로피오닐-8-트라이플루오르메틸-4-퀴놀린온(화합물 48)의 합성Example 11 Synthesis of 6-Chloro-2-propazylamino-3-propionyl-8-trifluoromethyl-4-quinolinone (Compound 48)

6-클로로-2-메틸설폭시-3-프로피오닐-8-트라이플루오르메틸-4-퀴놀린온(365mg, 1mmol)과 프로파질아민(55mg, 1mmol)으로부터 실시예 1과 같은 반응을 실시하여 표제 생성물 310mg(수율 87％)을 수득하였다.The same reaction as in Example 1 was carried out from 6-chloro-2-methylsuloxy-3-propionyl-8-trifluoromethyl-4-quinolinone (365 mg, 1 mmol) and propazylamine (55 mg, 1 mmol). 310 mg (87% yield) of product was obtained.

1H NMR(CDCI3): δ 1.2(t, 3H), 2.7(t, 1H), 3.4(q, 2H), 4.3(d, 2H), 7.9(d, 1H), 8.6(br, 1H), 8.7(d, 1H), 12.2(br, 1H) 1 H NMR (CDCI 3 ): δ 1.2 (t, 3H), 2.7 (t, 1H), 3.4 (q, 2H), 4.3 (d, 2H), 7.9 (d, 1H), 8.6 (br, 1H) , 8.7 (d, 1 H), 12.2 (br, 1 H)

실시예 12: 3-아세틸-6-클로로-2-(1,1-다이메틸프로파질아미노)-8-트라이플루오르메틸-4-퀴놀린온(화합물 55)의 합성Example 12 Synthesis of 3-acetyl-6-chloro-2- (1,1-dimethylpropazylamino) -8-trifluoromethyl-4-quinolinone (Compound 55)

3-아세틸-6-클로로-2-메틸설폭시-8-트라이플루오르메틸-4-퀴놀린온(350mg, 1mmol)과 1,1-다이메틸프로파질아민(83ml, 1mmol)으로부터 실시예 1과 같은 반응을 실시하여 표제 생성물 322mg(수율 87％)을 수득하였다.Same as Example 1 from 3-acetyl-6-chloro-2-methyl sulfoxy-8-trifluoromethyl-4-quinolinone (350 mg, 1 mmol) and 1,1-dimethylpropazamine (83 ml, 1 mmol) The reaction was carried out to give 322 mg (87% yield) of the title product.

1H NMR(CDCI3): δ 1.5(s, 6H), 2.5(t, 1H), 2.6(s, 3H), 7.7(m, 1H), 8.4(m, 1H), 9.1(br, 1H), 12.0(br, 1H) 1 H NMR (CDCI 3 ): δ 1.5 (s, 6H), 2.5 (t, 1H), 2.6 (s, 3H), 7.7 (m, 1H), 8.4 (m, 1H), 9.1 (br, 1H) , 12.0 (br, 1H)

실시예 13: 3-아세틸-6-콜로로-2-(페닐알릴아미노)-8-트라이플루오르메틸-4-퀴놀린온(화합물 66)의 합성Example 13: Synthesis of 3-acetyl-6-cholo-2- (phenylallylamino) -8-trifluoromethyl-4-quinolinone (Compound 66)

3-아세틸-6-클로로-2-메틸설폭시-8-트라이플루오르메틸-4-퀴놀린온(350mg, 1mmol)과 3-페닐알릴아민(133mg, 1mmol)으로부터 실시예 1과 같은 반응을 실시하여 표제 생성물 286mg(수율 68％)을 수득하였다.The same reaction as in Example 1 was carried out from 3-acetyl-6-chloro-2-methylsulfoxy-8-trifluoromethyl-4-quinolinone (350 mg, 1 mmol) and 3-phenylallylamine (133 mg, 1 mmol). 286 mg (68% yield) of the title product were obtained.

1H NMR(CDCI3): δ 2.8(s, 3H), 4.3(t, 2H), 6.0-6.7(m, 2H), 7.4(s, 5H), 7.7(d, 1H), 8.1(br, 1H), 8.5(d, 1H), 12.1(br, 1H) 1 H NMR (CDCI 3 ): δ 2.8 (s, 3H), 4.3 (t, 2H), 6.0-6.7 (m, 2H), 7.4 (s, 5H), 7.7 (d, 1H), 8.1 (br, 1H), 8.5 (d, 1H), 12.1 (br, 1H)

실시예 14: 6-클로로-2-(2-클로로알릴아미노)-3-프로피오닐-8-트라이플루오르메틸-4-퀴놀린온(화합물 80)의 합성Example 14 Synthesis of 6-chloro-2- (2-chloroallylamino) -3-propionyl-8-trifluoromethyl-4-quinolinone (Compound 80)

6-클로로-2-메틸설폭시-3-프로피오닐-8-트라이플루오르메틸-4-퀴놀린온(365mg, 1mmol)과 2-클로로알릴아민(92mg, 1mmol)으로부터 실시예 1과 같은 반응을 실시하여 표제 생성물 279mg(수율 71％)을 수득하였다.The same reaction as in Example 1 was carried out from 6-chloro-2-methyl sulfoxy-3-propionyl-8-trifluoromethyl-4-quinolinone (365 mg, 1 mmol) and 2-chloroallylamine (92 mg, 1 mmol). This gave 279 mg (71% yield) of the title product.

1H NMR(CDCI3): δ 1.2(t, 2H), 3.3(q, 2H), 4.2(d, 2H), 5.6(s, 2H), 7.8(d, 1H), 8.0(br, 1H), 8.5(d, 1H), 12.3(br, 1H) 1 H NMR (CDCI 3 ): δ 1.2 (t, 2H), 3.3 (q, 2H), 4.2 (d, 2H), 5.6 (s, 2H), 7.8 (d, 1H), 8.0 (br, 1H) , 8.5 (d, 1H), 12.3 (br, 1H)

실시예 15: 6-클로로-2-(N-메틸-N'-프로파질아미노)-3-아이소브티릴-8-트라이플루오르메틸-4-퀴놀린온(화합물 98)의 합성Example 15 Synthesis of 6-Chloro-2- (N-methyl-N'-propazylamino) -3-isobutyryl-8-trifluoromethyl-4-quinolinone (Compound 98)

6-클로로-3-아이소부티릴-2-메틸설폭시-8-트라이플루오르메틸-4-퀴놀린온(379mg, 1mmol)과 N,N'-다이프로파질아민(93mg, 1mmol)으로부터 실시예 1과 같은 반응을 실시하여 표제 생성물 290mg(수율 71％)을 수득하였다.Example 1 from 6-chloro-3-isobutyryl-2-methylsuloxy-8-trifluoromethyl-4-quinolinone (379 mg, 1 mmol) and N, N'-dipropazamine (93 mg, 1 mmol) The reaction was carried out to obtain 290 mg (71% yield) of the title product.

1H NMR(CDCI3): δ1.2(d, 6H), 2.3(t, 2H), 4.0-4.3(m, 1H), 4.3(d, 4H), 8.0(d, 1H), 8.3(d, 1H), 13.1(br, 1H) 1 H NMR (CDCI 3 ): δ1.2 (d, 6H), 2.3 (t, 2H), 4.0-4.3 (m, 1H), 4.3 (d, 4H), 8.0 (d, 1H), 8.3 (d , 1H), 13.1 (br, 1H)

실시예 16: 3-아세틸-6-클로로-2-(3-페닐프로파질아미노)-8-트라이플루오르메틸-4-퀴놀린온(화합물 104)의 합성Example 16: Synthesis of 3-acetyl-6-chloro-2- (3-phenylpropazylamino) -8-trifluoromethyl-4-quinolinone (Compound 104)

3-아세틸-6-클로로-2-메틸설폭시-8-트라이플루오르메틸-4-퀴놀린온(350mg, 1mmol)과 3-페닐프로파질아민 염산염(167mg, 1mmol)으로부터 실시예 1과 같은 반응을 실시하여 표제 생성물 305mg(수율 73％)을 수득하였다.The same reaction as in Example 1 was carried out from 3-acetyl-6-chloro-2-methylsuloxy-8-trifluoromethyl-4-quinolinone (350 mg, 1 mmol) and 3-phenylpropazylamine hydrochloride (167 mg, 1 mmol). This gave 305 mg (73% yield) of the title product.

1H NMR(CDCI3): δ 2.7(t, 1H), 4.5(d, 2H), 7.5(s, 5H), 7.8(d, 1H), 8.6(d, 2H), 12.0(br, 1H) 1 H NMR (CDCI 3 ): δ 2.7 (t, 1H), 4.5 (d, 2H), 7.5 (s, 5H), 7.8 (d, 1H), 8.6 (d, 2H), 12.0 (br, 1H)

실시예 17: 3-아세틸-6-클로로-2-(3-에톡시프로필아미노)-8-트라이플루오르메틸-4-퀴놀린온(화합물 107)의 합성Example 17 Synthesis of 3-acetyl-6-chloro-2- (3-ethoxypropylamino) -8-trifluoromethyl-4-quinolinone (Compound 107)

3-아세틸-6-클로로-2-메틸설폭시-8-트라이플루오르메틸-4-퀴놀린온(350mg, 1mmol)과 3-에톡시프로필아민(103mg, 1mmol)으로부터 실시예 1과 같은 반응을 실시하여 표제 생성물 278mg(수율 71％)을 수득하였다.The same reaction as in Example 1 was carried out from 3-acetyl-6-chloro-2-methylsuloxy-8-trifluoromethyl-4-quinolinone (350 mg, 1 mmol) and 3-ethoxypropylamine (103 mg, 1 mmol). This gave 278 mg (71% yield) of the title product.

1H NMR(CDCI3): δ 1.2(t, 3H), 2.1(q, 2H), 2.7(s, 3H), 3.3-3.8(m, 6H), 7.7(d, 1H) 1 H NMR (CDCI 3 ): δ 1.2 (t, 3H), 2.1 (q, 2H), 2.7 (s, 3H), 3.3-3.8 (m, 6H), 7.7 (d, 1H)

실시예 18: 3-아세틸-6-클로로-2-메틸티오에틸아미노-8-트라이플루오르메틸-4-퀴놀린온(화합물 114)의 합성Example 18 Synthesis of 3-acetyl-6-chloro-2-methylthioethylamino-8-trifluoromethyl-4-quinolinone (Compound 114)

3-아세틸-6-클로로-2-메틸설폭시-8-트라이플루오르메틸-4-퀴놀린온(350mg, 1mmol)과 메틸티오에틸아민(91mg, 1mmol)으로부터 실시예 1과 같은 반응을 실시하여 표제 생성물 287mg(수율 76％)을 수득하였다.The same reaction as in Example 1 was carried out from 3-acetyl-6-chloro-2-methylsuloxy-8-trifluoromethyl-4-quinolinone (350 mg, 1 mmol) and methylthioethylamine (91 mg, 1 mmol). 287 mg (76% yield) of product were obtained.

1H NMR(CDCI3): δ 2.15(s, 3H), 2.7(s, 3H), 2.8(t, 2H), 3.6(q, 2H), 7.7(br, 1H), 8.1(br, 1H), 8.5(br, 1H), 12.0(br, 1H) 1 H NMR (CDCI 3 ): δ 2.15 (s, 3H), 2.7 (s, 3H), 2.8 (t, 2H), 3.6 (q, 2H), 7.7 (br, 1H), 8.1 (br, 1H) , 8.5 (br, 1H), 12.0 (br, 1H)

실시예 19: 3-아세틸-6-클로로-2-[2-(플루오로페닐)-2,3-부타다이에닐아미노]-8-트라이플루오르메틸-4-퀴놀린온(화합물 126)의 합성Example 19 Synthesis of 3-acetyl-6-chloro-2- [2- (fluorophenyl) -2,3-butadienylamino] -8-trifluoromethyl-4-quinolinone (Compound 126)

3-아세틸-6-클로로-2-메틸설폭시-8-트라이플루오르메틸-4-퀴놀린온(350mg, 1mmol)과 2-(4-플루오로페닐)-2,3-부타다이에닐아민(163mg, 1mmol)을 테트라하이드로퓨란 20ml에 가하고 24시간 동안 상온에서 교반하였다. 반응이 완료되면 용매를 감압 증류하여 제거하고 남은 고체를 에타올에 재결정하여 표제 생성물 369mg(수율 82％)을 수득하였다.3-acetyl-6-chloro-2-methylsulfoxy-8-trifluoromethyl-4-quinolinone (350 mg, 1 mmol) and 2- (4-fluorophenyl) -2,3-butadienylamine ( 163 mg, 1 mmol) was added to 20 ml of tetrahydrofuran and stirred at room temperature for 24 hours. After the reaction was completed, the solvent was distilled off under reduced pressure, and the remaining solid was recrystallized in ethanol to obtain 369 mg (yield 82%) of the title product.

1H NMR(CDCI3): δ 2.6(s, 3H), 3.6(t, 2H), 5.2(t, 2H), 7.2(m, 4H), 7.8(d, 1H), 8.5(br, 1H), 8.6(d, 1H), 11.8(br, 1H). 1 H NMR (CDCI 3 ): δ 2.6 (s, 3H), 3.6 (t, 2H), 5.2 (t, 2H), 7.2 (m, 4H), 7.8 (d, 1H), 8.5 (br, 1H) , 8.6 (d, 1H), 11.8 (br, 1H).

살균 효과 시험예Sterilization Effect Test Example

식물 병원균에 대한 예방효과를 조사하기 위하여, 시험 화합물 10mg을 10ml의 아세톤에 용해시키고, 이 용액에 트윈(Tween) 20의 100ppm 수용액 90ml를 첨가하여 그 농도가 100ppm이 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, 10 mg of test compound was dissolved in 10 ml of acetone, 90 ml of a 100 ppm aqueous solution of Tween 20 was added to the solution, and the concentration was adjusted to 100 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.

방제가(％) = (1-(처리구의 병반면적율/대조구의 병반면적율))×100Control value (%) = (1- (Length of treatment area / lesion area of control)) × 100

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 5일 동안 발병을 유도하여 잎의 병반면적율을 구했다. 이때 3-4엽기 벼의 최상위엽 바로 밑의 완전 전개된 잎에 형성된 병반 면적을 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 in a wet room, and the disease area ratio of the leaves was obtained by inducing the onset for 5 days in a constant temperature and humidity room with 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 효과 Test 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 10일 동안 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, and then transferred to a constant temperature and humidity chamber at a relative humidity of 70% and 20 ° C. to induce the disease for 10 days, and then calculated the leaf area ratio of the leaves.

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.

Figure 112004038983111-pat00014
Figure 112004038983111-pat00014

Figure 112004038983111-pat00015
Figure 112004038983111-pat00015

살충 효과 시험예Insecticidal Effect Test Example

본 발명에 따른 2-아미노-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 500ppm으로 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 산출하였으며, 모든 실험은 각각 3회 반복하였다.In order to investigate the insecticidal effect of the 2-amino-4-quinolinone derivative according to the present invention, 25 mg of test compound was dissolved in 5 ml of acetone, and 45 ml of 100 ppm aqueous solution of Triton-X-100, a surfactant, was used. After mixing, the test drug obtained by adjusting the concentration to 500 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 example, the mortality rate (%) was calculated as shown in Equation 2 from the results obtained, and all the experiments Each repeat was repeated three times.

사충률(％) = ( 100 - 생존성충수/공시충수 ) × 100Mortality rate (%) = (100-surviving appendix)

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±1ㅀC, 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 습 C, relative humidity 50 ± 5%, 8 females in the light condition), and the adult females were observed 4 days after hatching.

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±1ㅀC, 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 bred for 2 years without spraying insecticide indoors, was smoked in a constant temperature room (temperature 21 ± 1 ㅀ C, relative humidity 50 ± 5%, light conditions 16 persons 8 cancers). 82) was used to breed indoors, 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±1ㅀC, 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. 20 worms were then 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 48 hours. Mortality was examined after time. 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±1ㅀC, 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 cage for the cabbage moth ( Plutella Xylostella Linnaeus ) was raised in a constant temperature room (temperature 27 ± 1 ㅀ C, relative humidity 50 ± 5%, light conditions 16 females, 8 cancers) using a cabbage. About 500 animals were bred and 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±1ㅀC, 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. The petri dishes were then covered with a lid and stored in a constant temperature room (temperature 25 ± 1 ° C., relative humidity 50 ± 5%, 8 females in 16 light conditions), 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±1ㅀC, 상대습도 50±5％, 광조건 16명 8암)내에서 강낭콩잎을 이용하여 실내 사육하고, 그 충성을 공시하였다. Tetranychus urticae koch of the insecticide susceptible strain was bred indoors using a kidney bean leaf in a constant temperature room (temperature 23 ± 1 ㅀ C, relative humidity 50 ± 5%, light conditions of 16 females, 8 cancers). It was.

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±1ㅀC, 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 storing the saale in a constant temperature room (temperature 25 ± 1 ° C, relative humidity 50 ± 5%, light conditions 16 people 8 cancer). 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.

Figure 112004038983111-pat00016
Figure 112004038983111-pat00016

Figure 112004038983111-pat00017
Figure 112004038983111-pat00017

제초 효과 시험예Herbicide effect test example

이번에는 본 발명에 따른 2-아미노-4-퀴놀린온 유도체의 제초 효과를 조사하였다.This time, the herbicidal effects of the 2-amino-4-quinolinone derivatives according to the present invention were investigated.

적정량의 비료가 혼합된 사질토양을 살균한 다음, 시험용 포트(발조건: 348cm2 논조건:115cm2)에 담았으며, 이때 사용된 포트수는 한 화합물당 밭조건에서는 2포트, 논조건에서는 1포트였다. 다음, 밭작물 및 잡초로서 수수, 피, 개밀, 바랭이, 미국 개기장, 까마중, 자귀풀, 어저귀, 도꼬마리, 메꽃 등의 종자 또는 지하경을 밭조건의 포트에; 논작물 및 잡초로서 벼, 논피, 너도 방동사니, 올미, 올챙이 고리, 물 달개비 등의 종자를 논조건의 포트에 각각 파종한 후 곱게 친 흙으 로 부토한 다음 온실에 두었다. 발아전 토양에는 파종후 1일째, 발아후 경엽에는 파종후 9-14일째에, 약량이 4kg/ha의 수준이 되도록 시험 화합물을 조제하여(밭조건 : 14mg/포트, 논조건 : 4mg/포트) 동량의 아세톤에 용해시킨 후 시험 토양에 논조건 및 밭조건에 각각 14ml씩 살포하였다. 약제 처리후 상온에서 2-3주간 키운 다음 제초효과를 형태 및 생리학적 검정기준(0％ 무제초효과; 10-30％ 약간의 제초효과; 40-60％ 중정도 효과; 70-90％ 심한효과; 및 100％ 완전 제초효과)에 의하여 달관으로 평가하였다. 평가된 밭조건 및 논조건에서의 제초 효과를 각각 하기 표 4 및 5에 나타내었다.The appropriate amount of fertilizer sterilized a sandy soil mix, and then, the test port was em in (to condition:: 348cm 2 paddy conditions 115cm 2), wherein the number of ports used by the field conditions sugar compound 2-port, in the non-condition 1 It was a port. Next, seeds or underground diameters such as sorghum, blood, wheat, barley, American total ground, crows, larvae, motherbirds, skewers, buckthorns, etc., as field crops and weeds, are placed in pots of field conditions; As crops and weeds, seed, such as rice, paddy, beetle, snare, tadpole rings, and water canes, were sown in pots of rice fields, and then poured into fine soil and placed in a greenhouse. 1 day after sowing in soil before germination, 9-14 days after sowing in foliage after germination, test compound was prepared so that the dose would be 4kg / ha (field condition: 14mg / port, paddy condition: 4mg / port). After dissolving in the same amount of acetone, the test soil was sprayed with 14 ml of paddy and field conditions, respectively. After the treatment, grow at room temperature for 2-3 weeks, and then remove the herbicidal effect from the morphological and physiological criteria (0% no herbicidal effect; 10-30% slight herbicidal effect; 40-60% moderate effect; 70-90% severe effect). And 100% complete herbicidal effect). The herbicidal effects in the evaluated field conditions and paddy conditions are shown in Tables 4 and 5, respectively.

Figure 112004038983111-pat00018
Figure 112004038983111-pat00018

Figure 112004038983111-pat00019
Figure 112004038983111-pat00019

상기 표 2 내지 5의 결과로부터 알 수 있듯이, 본 발명에 따른 2-아미노-4-퀴놀린온 유도체를 포함하는 조성물은 넓은 살균 스펙트럼을 가지면서 특히 밀녹병과 벼도열병에 탁월한 효과가 있고, 배추좀나방과 점박이응애 등의 해충에 선택적 인 살충효과를 나타내며, 밭잡초 및 논잡초에도 좋은 제초효과를 가진다.As can be seen from the results of Tables 2 to 5, the composition comprising the 2-amino-4-quinolinone derivatives according to the present invention has a wide bactericidal spectrum, and in particular, has an excellent effect on wheat rust and rice fever, It has a selective insecticidal effect on pests such as moths and spotted mites, and has a good herbicidal effect on field weeds and paddy fields.

Claims (4)

하기 화학식 1의 2-아미노-4-퀴놀린온 유도체:2-Amino-4-quinolinone derivatives of Formula 화학식 1Formula 1
Figure 112006019885416-pat00020
Figure 112006019885416-pat00020
 상기 식에서,Where R1 내지 R4는 각각 수소, 할로겐, C1-10의 선형 또는 분지형 알킬기, C1-6의 선형 또는 분지형 할로알킬기, C1-10의 선형 또는 분지형 알콕시기, 페닐기, 페녹시기, 벤질기, 니트로기 또는 사이아노기이고;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 group, nitro group or cyano group; R5는 C1-6의 선형 또는 분지형 알킬기, C3-6의 사이클로알킬기, 페닐기, 페녹시기 또는 벤질기이고;R 5 is a C 1-6 linear or branched alkyl group, a C 3-6 cycloalkyl group, a phenyl group, a phenoxy group or a benzyl group; R6는 수소 또는 포화되거나 불포화된 C1-5의 선형 또는 분지형 알킬기이고;R 6 is hydrogen or a saturated or unsaturated C 1-5 linear or branched alkyl group; R7은 수소,
Figure 112006019885416-pat00021
R 7 is hydrogen,
Figure 112006019885416-pat00021
Figure 112006019885416-pat00022
또는 -CH2CN 이며, 여기에서
Figure 112006019885416-pat00022
Or -CH 2 CN, where R8 내지 R16은 각각 수소, 할로겐, 포화되거나 불포화된 C1-6의 선형 또는 분지형 알킬기, 페닐기, 할로겐 치환된 페닐기, C1-3의 알콕시알킬기 또는 (R19)3Si(이때, R19는 C1-5의 선형 또는 분지형 알킬기임)이고,R 8 to R 16 are each hydrogen, halogen, saturated or unsaturated C 1-6 linear or branched alkyl group, phenyl group, halogen substituted phenyl group, C 1-3 alkoxyalkyl group or (R 19 ) 3 Si, wherein R 19 is a C 1-5 linear or branched alkyl group), R17 및 R18은 각각 수소, 또는 C1-5의 선형 또는 분지형 알킬기이고,R 17 and R 18 are each hydrogen or a C 1-5 linear or branched alkyl group, X 및 X'는 각각 C1-3의 알콕시, C1-3의 티오알콕시이거나, 함께 -O-(CH2)r-O-, -S-(CH2)r-S- 를 형성하고,X and X 'are each C 1-3 alkoxy, C 1-3 thioalkoxy, or together form -O- (CH 2 ) rO-, -S- (CH 2 ) rS-, Y는 O, S 또는 S=O 이고,Y is O, S or S = O, Z는 5원의 질소 함유 헤테로사이클릭기이고,Z is a 5-membered nitrogen-containing heterocyclic group, m는 0 내지 4의 정수이며, m is an integer from 0 to 4, n, p, q, r은 각각 1 내지 4의 정수이다.n, p, q, and r are integers of 1-4, respectively. 유효 성분으로서 제1항에 따른 2-아미노-4-퀴놀린온 유도체 및 약제학적으로 허용되는 담체를 포함하는, 농원예용 살균제 조성물.Agrohorticultural fungicide composition comprising the 2-amino-4-quinolinone derivative according to claim 1 as an active ingredient and a pharmaceutically acceptable carrier. 유효 성분으로서 제1항에 따른 2-아미노-4-퀴놀린온 유도체 및 약제학적으로 허용 되는 담체를 포함하는, 농원예용 살충제 조성물.Agrohorticultural insecticide composition comprising the 2-amino-4-quinolinone derivative according to claim 1 as a active ingredient and a pharmaceutically acceptable carrier. 유효 성분으로서 제1항에 따른 2-아미노-4-퀴놀린온 유도체 및 약제학적으로 허용되는 담체를 포함하는, 농원예용 제초제 조성물.A herbicide composition for agrohorticulture, comprising the 2-amino-4-quinolinone derivative according to claim 1 as a active ingredient and a pharmaceutically acceptable carrier.
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WO2008102932A1 (en) 2007-02-21 2008-08-28 Biobud Co., Ltd. Compositions for treating hyperproliferative vascular disorders and cancers
EP2124948A4 (en) * 2007-02-21 2010-08-18 Biobud Co Ltd Compositions for treating hyperproliferative vascular disorders and cancers

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