KR100342947B1 - Arylpiperazine derivatives having herbicidal activity - Google Patents
Arylpiperazine derivatives having herbicidal activity Download PDFInfo
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- KR100342947B1 KR100342947B1 KR1019970016758A KR19970016758A KR100342947B1 KR 100342947 B1 KR100342947 B1 KR 100342947B1 KR 1019970016758 A KR1019970016758 A KR 1019970016758A KR 19970016758 A KR19970016758 A KR 19970016758A KR 100342947 B1 KR100342947 B1 KR 100342947B1
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- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
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Abstract
Description
본 발명은 하기 화학식 1 로 표시되는 제초활성 아릴피페라진아미드 유도체, 그의 제조방법 및 이 화합물을 활성성분으로서 함유하는 제초제 조성물에 관한 것이다.The present invention relates to a herbicidal arylpiperazinamide derivative represented by the following formula (1), a method for preparing the same, and a herbicide composition containing the compound as an active ingredient.
[화학식 1][Formula 1]
상기식에서,In the above formula,
X 및 Y 는 각각 독립적으로 수소, 할로겐, 니트로, 시아노, C1-C4알킬, C1-C4알콕시, C1-C4알콕시-카보닐 또는 디-C1-C4알킬-아미노를 나타내며,X and Y are each independently hydrogen, halogen, nitro, cyano, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkoxy-carbonyl or di-C 1 -C 4 alkyl-amino Indicates
m 및 n 은 각각 독립적으로 1 내지 5 의 정수를 나타낸다.m and n each independently represent the integer of 1-5.
피페라진아미드 골격을 갖는 천연물인 니저라진 B 가 제초활성을 가지고 있음은 이미 알려져 있다(참조: Agric. Biol. Chem., 1987, 47(4), 739-743). 이러한 니저라진 B 와 같이 피페라진아미드 골격을 갖는 화합물에 대한 연구가 활발하게 진행되어 왔으나, 이들 선행연구에 의해 밝혀진 화합물들은 대부분 니저라진 B 와는 달리 의약적인 용도로 사용되어져 왔다(참조: Archiv der Pharmazie, 1989, 322(6), p359-361, J. Med. Chem. 1993, 36(19), p2716-2725, 독일특허 제 1810053 호, 4041780 호, 유럽특허 제 1781189, 233461 호, 일본특허공개 제 0113955, 59122453 호 등).It is known that nigerazine B, a natural product having a piperazineamide skeleton, has herbicidal activity (Agric. Biol. Chem., 1987, 47 (4), 739-743). Although studies on compounds having a piperazineamide skeleton such as nirazine B have been actively conducted, most of the compounds identified by the previous studies have been used for medicinal purposes unlike nigerazine B (see: Archiv der Pharmazie). , 1989, 322 (6), p359-361, J. Med. Chem. 1993, 36 (19), p2716-2725, German Patent No. 1810053, 4041780, European Patent No. 1781189, 233461, Japanese Patent Publication 0113955, 59122453 et al.).
이에 본 발명자들은 천연물인 니저라진 B 와 같이 피페라진아미드 골격을 갖는 화합물로서 제초활성을 갖는 화합물을 개발하기 위하여 집중적인 연구를 수행하였으며, 그 결과 이하에서 정의하는 바와 같은 화학식 1 의 아릴페페라진아미드 유도체가 이러한 목적을 달성할 수 있음을 확인하고 본 발명을 완성하게 되었다.Accordingly, the present inventors conducted intensive studies to develop a compound having herbicidal activity as a compound having a piperazineamide skeleton, such as nigerazine B, which is a natural product, and as a result, the arylfeperazineamide of Formula 1 as defined below. It has been found that the derivative can achieve this purpose and has completed the present invention.
본 발명은 하기 화학식 1 로 표시되는 제초활성 아릴피페라진아미드 유도체에 관한 것이다.The present invention relates to a herbicidal aryl piperazineamide derivative represented by the following formula (1).
[화학식 1][Formula 1]
상기식에서,In the above formula,
X 및 Y 는 각각 독립적으로 수소, 할로겐, 니트로, 시아노, C1-C4알킬, C1-C4알콕시, C1-C4알콕시-카보닐 또는 디-C1-C4알킬-아미노를 나타내며,X and Y are each independently hydrogen, halogen, nitro, cyano, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkoxy-carbonyl or di-C 1 -C 4 alkyl-amino Indicates
m 및 n 은 각각 독립적으로 1 내지 5 의 정수를 나타낸다.m and n each independently represent the integer of 1-5.
상기 정의중에서 용어 "C1-C4알킬"은 단독으로 사용될 때나 "디-C1-C4알킬-아미노" 와 같이 합성어로 사용될 때나 메틸, 에틸, n-프로필, 이소프로필, n-부틸, 이소부틸, s-부틸 및 t-부틸과 같은 탄소수 1 내지 4 의 알킬기를 의미하고, 용어 "C1-C4알콕시"는 단독으로 사용될 때나 "C1-C4알콕시-카보닐"과 같이 합성어로 사용될 때나 메톡시, 에톡시, n-프로폭시, 이소프로폭시, n-부톡시, 이소부톡시, s-부톡시 또는 t-부톡시와 같이 탄소수 1 내지 4 의 알콕시를 의미하고, 용어 "할로겐"은 불소, 염소, 브롬 또는 요오드를 의미한다.The term "C 1 -C 4 alkyl" in the above definitions, when used alone or in synonyms such as "di-C 1 -C 4 alkyl-amino," or methyl, ethyl, n-propyl, isopropyl, n-butyl, Refers to an alkyl group having 1 to 4 carbon atoms such as isobutyl, s-butyl and t-butyl, the term "C 1 -C 4 alkoxy" when used alone or as synthesized as "C 1 -C 4 alkoxy-carbonyl" When used as or means alkoxy having 1 to 4 carbon atoms, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy or t-butoxy, and the term "halogen "Means fluorine, chlorine, bromine or iodine.
본 발명에 따르는 화학식 1 의 화합물중에서 바람직한 화합물은 X 및 Y 가 각각 독립적으로 수소, 염소, 불소, 니트로, 시아노, C1-C2알킬, C1-C2알콕시, C1-C2알콕시-카보닐 또는 디-C1-C2알킬-아미노를 나타내며, m 및 n 은 각각 독립적으로 1 내지 3 의 정수를 나타내는 화합물이다.Preferred compounds among the compounds of formula (I) according to the invention are those in which X and Y are each independently hydrogen, chlorine, fluorine, nitro, cyano, C 1 -C 2 alkyl, C 1 -C 2 alkoxy, C 1 -C 2 alkoxy -carbonyl or di -C 1 -C 2 alkyl-represents an amino, m and n are each independently the compound represented an integer of 1 to 3.
본 발명에 따르는 화학식 1 의 화합물의 구체적인 예로는 하기 표 1 에 기재된 화합물이 언급될 수 있다:As specific examples of the compound of formula 1 according to the present invention, the compounds described in Table 1 may be mentioned:
[표 1a]TABLE 1a
[표 1b]TABLE 1b
본 발명은 또한 상기 화학식 1 의 아릴피페라진아미드 유도체를 제조하는 방법을 제공한다.The present invention also provides a method for preparing the arylpiperazinamide derivative of Chemical Formula 1.
본 발명에 따르는 화학식 1 의 화합물은 (a) 화학식 2 의 카복실산과 화학식 3 의 아릴피페라진을 커플링시키거나, (b) 화학식 4 의 페놀 유도체와 화학식 5 의 α-할로아미드 화합물을 용매와 염기의 존재하에서 환류하에 반응시킴으로써 제조할 수 있다.The compound of formula (1) according to the present invention may be used for (a) coupling a carboxylic acid of formula (2) with an arylpiperazine of formula (3), or (b) a phenol derivative of formula (4) and an α-haloamide compound of formula (5) with a solvent and a base. It can be prepared by reacting under reflux in the presence of.
[화학식 2][Formula 2]
[화학식 3][Formula 3]
[화학식 4][Formula 4]
[화학식 5][Formula 5]
상기식에서, X, Y, m 및 n 은 상기에서 정의한 바와 같고, W 는 염소 또는 브롬 원자를 나타낸다.Wherein X, Y, m and n are as defined above and W represents a chlorine or bromine atom.
본 발명에 따른 상기 방법 (a) 및 (b) 는 각각 하기 반응식 1 및 2 로 나타낼 수 있다.The methods (a) and (b) according to the present invention can be represented by the following schemes 1 and 2, respectively.
[반응식 1]Scheme 1
[반응식 2]Scheme 2
상기식에서, X, Y, m 및 n 은 상기 정의한 바와 같으며, W 는 염소 또는 브롬원자를 나타낸다.Wherein X, Y, m and n are as defined above and W represents a chlorine or bromine atom.
상기 반응식 1 에 도시된 방법 (a) 에 따르면 본 발명에 따른 화학식 1 의 화합물은 화학식 2 의 카복실산 화합물과 화학식 3 의 아릴피페라진 유도체를 커플링시킴으로써 제조할 수 있다. 이 커플링 반응은 바람직하게는 용매의 존재하에서 수행할 수 있다. 이러한 목적으로 사용될 수 있는 용매에는 반응에 악영향을 미치지 않는 유기용매이면 어느 것이나 포함될 수 있으며, 바람직하게는 테트라하이드로푸란, 디에틸에테르 등의 에테르류, 디클로로메탄, 클로로포름, 사염화탄소, 1,2-디클로로에탄과 같은 할로겐화탄화수소류 등의 유기용매가 사용될 수 있다. 특히 바람직하게는 디클로로메탄, 테트라하이드로푸란 또는 디에틸에테르를 용매로 사용한다.According to the method (a) shown in Scheme 1, the compound of Formula 1 according to the present invention may be prepared by coupling a carboxylic acid compound of Formula 2 with an arylpiperazine derivative of Formula 3. This coupling reaction can preferably be carried out in the presence of a solvent. The solvent that can be used for this purpose may include any organic solvent that does not adversely affect the reaction, preferably ethers such as tetrahydrofuran, diethyl ether, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloro Organic solvents such as halogenated hydrocarbons such as ethane can be used. Especially preferably, dichloromethane, tetrahydrofuran or diethyl ether is used as a solvent.
또한 방법 (a) 의 반응은 카르복실기를 활성화시키는 커플링시약의 존재하에서 수행하는데, 이러한 목적으로 사용될 수 있는 커플링시약의 예로는 티오닐클로라이드, 옥살릴클로라이드, 포스포러스펜타클로라이드(PCl5) 등의 할로겐 화합물류, 디에틸클로로포스페이트 등의 유기인산류, 디사이클로헥실카르보디이미드 등의 카르보디이미드류, 메틸클로로포르메이트, 에틸클로로포르메이트 등의 클로로포르메이트류, 디이미다졸카보네이트, 톨루엔술포닐클로라이드 등의 시약과 트리에틸아민, 피리딘, 1,8-디아자[5.4.0]비사이클로운데케-7-엔 등의 유기염기의 조합을 광범위하게 이용할 수 있으며, 이중에서 특히 할로겐류-트리에틸아민의 조합이나, 카르보이미드류-트리에틸아민, 할로겐류-피리딘의 조합 등이 바람직하다.The reaction of method (a) is also carried out in the presence of a coupling reagent that activates a carboxyl group. Examples of coupling reagents that can be used for this purpose include thionyl chloride, oxalyl chloride, phosphorus pentachloride (PCl 5 ), and the like. Halogen compounds, organic phosphoric acids such as diethylchlorophosphate, carbodiimides such as dicyclohexylcarbodiimide, chloroformates such as methylchloroformate and ethylchloroformate, diimidazole carbonate and toluene Combinations of reagents such as sulfonyl chloride and organic bases such as triethylamine, pyridine, and 1,8-diaza [5.4.0] bicycloundeke-7-ene can be widely used. The combination of -triethylamine, the combination of carbodiimide-triethylamine, and halogens-pyridine, etc. are preferable.
반응 (a) 에 따르는 반응을 수행하는 온도 및 시간은 특별히 제한되지는 않으나, 일반적으로 30 내지 70℃ 에서 2 내지 10 시간 동안, 바람직하게는 40 내지 50℃ 의 온도에서 2 내지 3 시간 동안 수행한다.The temperature and time for carrying out the reaction according to reaction (a) are not particularly limited, but are generally carried out at 30 to 70 ° C. for 2 to 10 hours, preferably at a temperature of 40 to 50 ° C. for 2 to 3 hours. .
한편, 본 발명에 따르는 화학식 1 의 화합물은 상기 반응식 2 에 도시된 바와 같은 방법 (b) 에 의해 제조될 수도 있다. 방법 (b) 에 따르면 화학식 4 의 페놀 유도체와 화학식 5 의 α-할로아미드 유도체를 반응시킴으로써 목적하는 화학식 1 의 화합물을 수득한다.On the other hand, the compound of formula 1 according to the present invention may be prepared by the method (b) as shown in Scheme 2. According to the method (b), the desired compound of formula 1 is obtained by reacting the phenol derivative of formula 4 with the α-haloamide derivative of formula 5.
이 반응은 용매 및 염기의 존재하에서 수행하는데, 이러한 목적으로 바람직하게 사용되는 용매의 예로는 테트라하이드로푸란, 디에틸에테르, 디메톡시에탄 등의 에테르류, 디메틸포름아미드, 디메틸술폭시드 등의 극성용매류, 디클로로메탄, 사염화탄소 등의 할로겐화탄화수소류, 벤젠, 톨루엔, 크실렌 등의 방향족 탄화수소류 등이 포함될 수 있으며, 염기로는 탄산칼륨, 탄산나트륨, 수소화나트륨, 수소화칼륨, 수산화나트륨, 수산화칼륨 등의 무기염기, 트리에틸아민, 1,8-디아자[5.4.0]비사이클로윤데케-7-엔, 피리딘 등의 유기염기를 사용할 수 있다. 이들중에서 특히 탄산칼륨-디메틸포름아미드, 수소화나트륨-디메틸포름아미드 등과 같은 염기-용매의 조합이 바람직하게 사용된다.This reaction is carried out in the presence of a solvent and a base. Examples of the solvent which are preferably used for this purpose include ethers such as tetrahydrofuran, diethyl ether and dimethoxyethane, polar solvents such as dimethylformamide and dimethyl sulfoxide. And halogenated hydrocarbons such as dichloromethane and carbon tetrachloride, aromatic hydrocarbons such as benzene, toluene and xylene, and the like, and bases include inorganic materials such as potassium carbonate, sodium carbonate, sodium hydride, potassium hydride, sodium hydroxide and potassium hydroxide. Organic bases such as base, triethylamine, 1,8-diaza [5.4.0] bicycloyundeke-7-ene, pyridine and the like can be used. Among them, base-solvent combinations such as potassium carbonate-dimethylformamide, sodium hydride-dimethylformamide and the like are preferably used.
방법 (b) 의 반응은 일반적으로 40 내지 100℃ 의 온도범위에서 수행할 수 있으나, 바람직하게는 40 내지 70℃ 의 온도에서 2 내지 10 시간, 바람직하게는 2 내지 3 시간 동안 수행한다.The reaction of process (b) can generally be carried out at a temperature range of 40 to 100 ° C., but is preferably carried out at a temperature of 40 to 70 ° C. for 2 to 10 hours, preferably 2 to 3 hours.
상기 방법 (a) 및 (b) 의 반응에서 반응물로 사용된 화학식 2 내지 5 의 화합물들은 각각 공지의 화합물이거나, 공지의 방법에 의해 제조할 수 있다. 예를들어 화학식 5 의 화합물은 화학식 3 의 화합물을 커플링 시약의 존재하에 용매중에서 화학식 6 의 화합물과 반응시킴으로써 제조할 수 있다[참조: Larock, Compre- hensive Organic Transformations, p963-995].The compounds of the formulas (2) to (5) used as reactants in the reactions of the methods (a) and (b) are each known compounds or may be prepared by known methods. For example, a compound of formula 5 can be prepared by reacting a compound of formula 3 with a compound of formula 6 in a solvent in the presence of a coupling reagent (Larock, Comprehensive Organic Transformations, p963-995).
[화학식 3][Formula 3]
[화학식 6][Formula 6]
상기식에서, Y, W 및 n 은 상기 정의한 바와 같다.Wherein Y, W and n are as defined above.
상기한 바와 같은 본 발명의 방법에 따라 제조되는 화학식 1 의 아릴피페라진아미드 유도체는 논이나 밭에서 서식하는 광범한 종류의 잡초, 특히 광엽잡초에 대해 선택적으로 강력한 제초활성을 나타낸다.The arylpiperazinamide derivatives of the formula (1) prepared according to the process of the present invention as described above exhibit selective potent herbicidal activity against a wide range of weeds, particularly broadleaf weeds, which inhabit rice fields or fields.
따라서, 본 발명의 또 다른 목적은 농약제조에 통상적으로 사용되는 담체와 함께 활성성분으로서 화학식 1 의 화합물을 함유함을 특징으로 하는, 농작물에 유해한 식물을 퇴치하기 위한 제초제 조성물을 제공하는 것이다.Accordingly, another object of the present invention is to provide a herbicide composition for combating plants harmful to crops, characterized by containing the compound of formula 1 as an active ingredient together with a carrier commonly used in pesticide preparation.
본 명세서에서 "잡초"는 벼나 밀과 같은 농작물을 재배하고 있거나 재배하려고 하는 지역, 예를들면 논 및 밭에서 성장을 원치않는 모든 식물을 포함하는 것으로 이해되어야 하며, 예를들면 이하에서 언급하는 바와 같은 식물이 포함된다.As used herein, "weeds" should be understood to include all plants that do not want to grow in areas where they are or are going to grow crops, such as rice or wheat, for example paddy fields and fields, for example as described below. Plants are included.
본 발명의 제초성 유제 조성물에 의해 방제될 수 있는 잡초의 구체적인 예로는 밭잡초로서 돌피(Echinochloa crus-galli var. caudata), 왕바랭이(Eleusine indica), 개밀(Agropyron tsukuhiense), 바랭이(Digitaria sanguinalis), 어저귀(Abutilon theophrasti), 자귀풀(Aeschynomene indica), 나팔꽃(Ipomoea spp), 도꼬마리(Xanthium strumarium) 등이 포함되고, 논잡초로서 강피(Echinochloa crus- galli var. oryzicola), 올챙이고랭이(Scirpus juncoides), 물달개비(Monochoria vaginalis), 너도방동산이(Cyperus serotinus), 벗풀(Sagittaria trifolia) 등이 포함된다.Specific examples of weeds that can be controlled by the herbicidal emulsion composition of the present invention include field weeds (Echinochloa crus-galli var.caudata), Eleusine indica, Wheatgrass (Agropyron tsukuhiense), Digitaria sanguinalis. , Abutilon theophrasti, Aeschynomene indica, Ipomoea spp, Xanthium strumarium, and Echinochloa crus- galli var. , Water squirrel (Monochoria vaginalis), beetle (Cyperus serotinus), shell grass (Sagittaria trifolia) and the like.
본 발명 화합물은 점토, 활석, 규조토 등의 고형물질 또는 물, 알콜, 벤젠, 톨루엔, 에테르, 케톤류, 에스테르류, 산류, 아미드류의 액체물질과 혼용하여 액제, 유제, 분제, 입제 등의 농업분야에서 통상적인 제형으로 제조하여 사용할 수 있다. 여기에는 또한 필요에 따라 유화제, 분산제, 침투제, 전착제, 안정화제 등을 첨가할 수 있다.The compound of the present invention is mixed with solid materials such as clay, talc and diatomaceous earth or liquid materials such as water, alcohol, benzene, toluene, ether, ketones, esters, acids and amides, and the agricultural field such as liquids, emulsions, powders and granules. It can be prepared and used in a conventional formulation. It can also add an emulsifier, a dispersing agent, a penetrant, an electrodeposition agent, a stabilizer, etc. as needed.
본 발명에 따른 제초활성 화합물의 사용량은 방제하고자 하는 대상 잡초, 방제시기 및 기간, 기후 조건, 사용되는 화합물의 종류 및 제제 형태, 대상지역에서 재배하고 있는 식물의 종류 및 그의 성장단계 등의 다양한 용인에 따라 달라질 수 있으나, 통상 활성화합물을 0.001 내지 5.0㎏/ha 의 비율로 사용된다.The amount of herbicidally active compound according to the present invention can be controlled in various ways such as the weeds to be controlled, the time and duration of the control, the climatic conditions, the types and preparations of the compounds used, the types of plants grown in the target area, and their growth stages. It can vary depending on, but usually the active compound is used in a ratio of 0.001 to 5.0 kg / ha.
본 발명은 이하의 제조예 및 실시예에 의해 보다 구체적으로 설명된다. 그러나, 이들 예는 본 발명에 대한 이해를 돕기 위해 제공된 것일 뿐이며, 본 발명의 범위가 이들에 의해 어떤 의미로든 제한되는 것은 아니다.The invention is explained in more detail by the following preparation examples and examples. However, these examples are provided only to assist in understanding the present invention, and the scope of the present invention is not limited in any way by them.
제조예 1 : 1-(2-브로모-1-옥소에틸)-4-(2-에톡시페닐)피페라진의 합성Preparation Example 1 Synthesis of 1- (2-bromo-1-oxoethyl) -4- (2-ethoxyphenyl) piperazine
α-브로모아세트산 2.8g 을 티오닐클로라이드 5㎖ 에 가하고 50℃ 로 가열하였다. 1 시간 후에, 과량의 티오닐클로라이드를 증류시켜 제거하였다. 생성된 아실할라이드를 디클로로메탄 20㎖ 에 용해시킨 후, 반응혼합물에 4-(2-에톡시페닐)피페라진 4.0g 을 적가하였다. 반응이 완료된 후 반응혼합물을 물과 디클로로메탄으로 추출하였다. 유기층을 분리하여 무수망초로 건조시키고 감압증류한 후 컬럼크로마토그라피에 의해 분리하여 표제화합물 1.8g 을 수득하였다(수율 55%).2.8 g of α-bromoacetic acid was added to 5 ml of thionyl chloride and heated to 50 ° C. After 1 hour, excess thionylchloride was removed by distillation. After dissolving the resulting acyl halide in 20 ml of dichloromethane, 4.0 g of 4- (2-ethoxyphenyl) piperazine was added dropwise to the reaction mixture. After the reaction was completed, the reaction mixture was extracted with water and dichloromethane. The organic layer was separated, dried over anhydrous forget-me-not, distilled under reduced pressure, and separated by column chromatography to obtain 1.8 g of the title compound (yield 55%).
실시예 1 : 1-[2-(2-클로로-4-플루오로페녹시)-1-옥소에틸]-4-(2-에톡시페닐)피페라진의 합성Example 1 Synthesis of 1- [2- (2-chloro-4-fluorophenoxy) -1-oxoethyl] -4- (2-ethoxyphenyl) piperazine
제조예 1 에서 수득한 1-(2-브로모-1-옥소에틸)-4-(2-에톡시페닐)피페라진 1.6g 과 2-클로로-4-플루오로페놀 0.7g 및 탄산칼륨 0.7g 의 혼합물을 디메틸포름아미드 10㎖ 에 용해시키고 70℃ 에서 가열하였다. 반응이 완결된 후에 반응용액을 물과 에틸에테르로 추출하였다. 유기층을 분리하여 무수망초로 건조시키고 감압증류한 후 컬럼크로마토그라피에 의해 분리하여 표제화합물 1.7g 을 수득하였다(수율 90%).1.6 g of 1- (2-bromo-1-oxoethyl) -4- (2-ethoxyphenyl) piperazine, 0.7 g of 2-chloro-4-fluorophenol and 0.7 g of potassium carbonate obtained in Preparation Example 1 Was dissolved in 10 ml of dimethylformamide and heated at 70 < 0 > C. After the reaction was completed, the reaction solution was extracted with water and ethyl ether. The organic layer was separated, dried over anhydrous forget-me-not, distilled under reduced pressure, and separated by column chromatography to obtain 1.7 g of the title compound (yield 90%).
실시예 2 : 1-[2-(4-클로로페녹시)-1-옥소에틸]-4-(4-플루오로페닐)피페라진의 합성Example 2: Synthesis of 1- [2- (4-chlorophenoxy) -1-oxoethyl] -4- (4-fluorophenyl) piperazine
α-(4-클로로페녹시)아세트산 1.9g 을 티오닐클로라이드 5㎖ 에 가하고 50℃ 로 가열하였다. 1 시간 후에 과량의 티오닐클로라이드를 증류시켜 제거하였다. 생성된 아실할라이드를 피리딘 20㎖ 에 용해시킨 후 반응혼합물에 4-(4-플루오로페닐)피페라진 1.8g 을 적가하였다. 반응이 완결된 후 반응혼합물을 물과 디클로로메탄으로 추출하였다. 유기층을 분리하여 무수망초로 건조시키고 감압증류한 후 컬럼크로마토그라피에 의해 분리하여 표제화합물 2.8g 을 수득하였다(수율 80%).1.9 g of α- (4-chlorophenoxy) acetic acid was added to 5 ml of thionyl chloride and heated to 50 ° C. After 1 hour excess thionylchloride was distilled off. After dissolving the resulting acyl halide in 20 ml of pyridine, 1.8 g of 4- (4-fluorophenyl) piperazine was added dropwise to the reaction mixture. After the reaction was completed, the reaction mixture was extracted with water and dichloromethane. The organic layer was separated, dried over anhydrous forget-me-not, distilled under reduced pressure, and separated by column chromatography to obtain 2.8 g of the title compound (yield 80%).
이하에서는 본 발명에 따른 화합물을 유효성분으로 함유하는 제초제의 배합예를 예를들어 나타내었다. 그러나, 이들 배합예도 하나의 예시일 뿐 본 발명의 기술적 범위가 이들로 한정되는 것은 아니다. 이하의 배합에에서 "활성화합물"은 본 발명에 따르는 화학식 1 의 화합물을 의미하는 것이다.Hereinafter, an example of the formulation of the herbicide containing the compound according to the present invention as an active ingredient is shown. However, these compounding examples are only one illustration, and the technical scope of this invention is not limited to these. In the following combinations, "active compound" means a compound of formula 1 according to the present invention.
배합예 1 : 유제Formulation Example 1: Emulsion
활성화합물(10%)을 유기용매(60%, 아세톤 또는 크실렌 등의 반향족 탄화수소)에 용해시킨 후, 계면활성제(30%, 트윈 20 또는 트라이톤)를 첨가하여 유제를 수득하였다.The active compound (10%) was dissolved in an organic solvent (60%, an aromatic hydrocarbon such as acetone or xylene), and then a surfactant (30%, Tween 20 or Triton) was added to obtain an emulsion.
배합예 2 : 수화제Formulation Example 2: Hydration
활성화합물(10%)을 증량제(80%, 제올라이트, 화이트 카본, 벤토나이트) 및 계면활성제(10%, 폴리옥시에틸렌알킬아릴설페이트)와 균일하게 혼합한 후, 에어밀로 곱게 분쇄하여 수화제를 수득하였다.The active compound (10%) was uniformly mixed with an extender (80%, zeolite, white carbon, bentonite) and a surfactant (10%, polyoxyethylene alkylarylsulfate), and then finely ground with an air mill to obtain a hydrating agent.
배합예 3 : 입제Formulation Example 3: Granulation
활성화합물(3%)을 증량제(92%, 탈크와 벤토나이트, 화이트카본) 및 계면활성제(5%, 폴리비닐아세테이트 또는 리그노설페이트)와 균일하게 혼합하여 펠릿 형태로 살포용 혼합물을 수득하였다.The active compound (3%) was uniformly mixed with an extender (92%, talc and bentonite, white carbon) and a surfactant (5%, polyvinylacetate or lignosulfate) to obtain a spraying mixture in the form of pellets.
배합예 4 : 액제Formulation Example 4 Liquid
활성화합물(20%)을 용매(70%, 이소프로필알콜 또는 물)에 용해시킨 후 계면활성제(10%, 폴리옥시에틸알킬페닐에테르)를 첨가하여 액제를 수득하였다.The active compound (20%) was dissolved in a solvent (70%, isopropyl alcohol or water), and then a surfactant (10%, polyoxyethylalkylphenyl ether) was added to obtain a liquid.
본 발명에 따르는 화학식 1 의 화합물이 목적하는 소기의 제초효력을 나타내는지를 검정하기 위하여 온실에서 검정식물을 밭조건하에 포트재배하고 약제처리하였으며, 효력판정은 하기 표 2 의 제초력 평가기준표에 따라 달관평가를 실시함으로써 수행하였다.In order to test whether the compound of Formula 1 according to the present invention exhibits the desired herbicidal efficacy, pot plants were cultivated and treated under field conditions in a greenhouse, and the efficacy was determined by the herbicidal evaluation criteria table in Table 2 below. It was carried out by carrying out.
[표 2]TABLE 2
사용예 : 밭조건Example of use: field conditions
사각플라스틱용기(20×15×10㎝)에 살균처리된 토양(사질양토, pH 5.5-6.0)을 충진한 후 표면적이 300㎠ 인 상태에서 시험식물의 종자를 종별로 따로 파종한 후 0.5㎝ 로 복토하였다. 발아후 처치를 위해, 시험식물을 먼저 성장형태에 따라 3 내지 15㎝ 의 성장크기로 자라게 한 후, 정해진 처리약량에 해당하는 유효성분의 배합액을 식물체 경엽부위에 균일하게 살포처리하였다. 식물들은 종에 따라 10-25℃ 내지 20-30℃ 의 온도로 유지시키고, 실험은 2 내지 4 주에 걸쳐 수행하였다. 이 기간 동안 식물을 관찰하여 각 처리에 따른 식물의 반응을 평가하였다. 경엽처리에 의한 본 발명의 화합물의 발아후 제초활성을 하기 표 3 에 나타내었다.Fill the rectangular plastic container (20 × 15 × 10㎝) with sterilized soil (sand loam, pH 5.5-6.0) and sow the seeds of the test plants separately with the surface area of 300㎡ It was covered. For the post-germination treatment, the test plants were first grown to a growth size of 3 to 15 cm depending on the growth type, and then a mixture of the active ingredients corresponding to the prescribed treatment dose was uniformly sprayed on the plant foliage. The plants were kept at a temperature of 10-25 ° C. to 20-30 ° C. depending on the species, and experiments were carried out over 2 to 4 weeks. During this period, plants were observed to assess the plant's response to each treatment. The herbicidal activity after germination of the compound of the present invention by foliage treatment is shown in Table 3 below.
[표 3]TABLE 3
경엽처리에 의한 발아후 제초력(밭조건, 1㎏/ha)Herbicidal power after germination by foliage treatment (field conditions, 1㎏ / ha)
상기 표 3 에 기재된 결과로 부터, 본 발명에 따르는 화학식 1 의 화합물은 광엽의 밭잡초에 대해 선택적으로 우수한 제초활성을 나타냄을 알 수 있다.From the results described in Table 3, it can be seen that the compound of formula 1 according to the present invention selectively shows excellent herbicidal activity against the field weeds of broadleaf.
Claims (8)
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52156879A (en) * | 1976-06-22 | 1977-12-27 | Yoshitomi Pharmaceut Ind Ltd | Preparation of piperazine derivatives |
| US4413006A (en) * | 1980-02-18 | 1983-11-01 | Tanabe Seiyaku Co., Ltd. | N-Aryl-N-phenoxy-alkyl-piperazine compounds useful in decreasing intracranial pressure |
| US5011928A (en) * | 1989-02-28 | 1991-04-30 | Fabrica Espanola De Productos Quimicos Y Farmeceuti Cos S.A. (Faes) | Analgesic and antiinflammatory derivatives of 1-acyl-4-arylalkylpiperazines |
| JPH06263749A (en) * | 1993-01-06 | 1994-09-20 | Ciba Geigy Ag | Aminoalkylphenyl compound |
| KR19980024043A (en) * | 1996-09-18 | 1998-07-06 | 최승주 | Novel pyrazine derivatives and preparation method thereof |
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1997
- 1997-04-30 KR KR1019970016758A patent/KR100342947B1/en not_active IP Right Cessation
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52156879A (en) * | 1976-06-22 | 1977-12-27 | Yoshitomi Pharmaceut Ind Ltd | Preparation of piperazine derivatives |
| US4413006A (en) * | 1980-02-18 | 1983-11-01 | Tanabe Seiyaku Co., Ltd. | N-Aryl-N-phenoxy-alkyl-piperazine compounds useful in decreasing intracranial pressure |
| US5011928A (en) * | 1989-02-28 | 1991-04-30 | Fabrica Espanola De Productos Quimicos Y Farmeceuti Cos S.A. (Faes) | Analgesic and antiinflammatory derivatives of 1-acyl-4-arylalkylpiperazines |
| JPH06263749A (en) * | 1993-01-06 | 1994-09-20 | Ciba Geigy Ag | Aminoalkylphenyl compound |
| KR19980024043A (en) * | 1996-09-18 | 1998-07-06 | 최승주 | Novel pyrazine derivatives and preparation method thereof |
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