KR800001475B1 - Method for preparing parazol-weedicide - Google Patents

Abstract

5-pyrazolones(I; R1 = H, lower alkyl; R2 = lower alkyl, lower alkenyl; X= halogen; Y = halogen, NO2, lower alkyl, lower alkoxy; n = 0-3), useful as herbicide, were prepd. by reaction of II with halogenation agent. Thus, 2.16g 1,3-dimethyl-4-benzoyl-5-pyrazolone in 200ml C6H6 was reacted at room temp. for 4hr with 1.62g sulfurylchloride followed by recrystallization with n-hexane gives 0.2g 1,3-dimethyl-4-chloro-4-benzoyl-5-pyrazolone(m.p. 70.5-72≰C).

Description

피라졸계 제초제의 제법Preparation of pyrazole herbicides

본 발명은 신규한 피라졸론유도체의 제법 및 이 피라졸론유도체의 제초용조성물의 제법에 관한 것이다. 더 구체적으로는, 본 발명은 식The present invention relates to the production of novel pyrazolone derivatives and the herbicidal composition of the pyrazolone derivatives. More specifically, the present invention is formula

(식중, R₁은 수소원자 또는 저급알킬기를 나타내고, R₂는 저급알킬기 또는 저급알케닐기를 나타내고, X는 할로겐원자를 나타내고, Y는 할로겐원자, 니트로기, 저급알킬기 또는 저급알콜시기를 나타내고, n는 0, 1, 2 또는 3의 정수로 나타내고, n가 2 또는 3일 때 Y는 서로 동일 또는 상이해도 좋다)(Wherein R ₁ represents a hydrogen atom or a lower alkyl group, R ₂ represents a lower alkyl group or a lower alkenyl group, X represents a halogen atom, Y represents a halogen atom, a nitro group, a lower alkyl group or a lower alcohol group, n is represented by an integer of 0, 1, 2 or 3, and when n is 2 or 3, Y may be the same or different from each other)

을 갖는 피라졸론화합물의 제조방법 및 전기 피라졸론화합물(Ⅰ)을 유효성분으로서 함유하는 제초제의 제조방법에 관한 것이다.A method for producing a pyrazolone compound having a compound and a method for producing a herbicide containing the electrical pyrazolone compound (I) as an active ingredient.

전기식(Ⅰ)에 있어서, R₁으로 적합한 것은 메틸, 에틸, n-프로필, 이소프로필, n-부틸, 이소부틸, 이급-부틸, 삼급-부틸, n-펜틸, 이소펜틸, 이급-아밀, 2-메틸부틸, n-삼급-아밀, n-핵실, 2-핵실, 2-메틸펜틸, 3-메틸펜틸, 4-메틸펜틸, 3-핵실, 2-에틸부틸, 2-메틸-2-펜틸 또는 2,2-디메틸부틸과 같은 탄소수 1∼6개 특히 1∼3개를 갖는 직쇄상 또는 측쇄상의 저급알킬기를 나타낸다. R₂로 적합한 것은 R₁에 예시한 것과 동일한 탄소수 1∼6개, 특히 1∼3개를 갖는 직쇄상 또는 측쇄상의 저급알킬기 또는 2-프로페닐, 2-부테닐, 1-메틸-2-프로페닐, 2-메틸-2-프로페닐, 1-메틸-2-부테닐, 2-메틸-2-부테닐, 3-부테닐, 1-메틸-3-부테닐, 2-메틸-3-부페닐, 3-메틸-2-부테닐, 3-펜테닐, 2-핵세닐, 3-핵세닐 또는 4-핵세닐과 같은 탄소수 3∼6개, 특히 3 또는 4개를 갖는 직쇄상 또는 측쇄상의 저급알케닐기를 나타낸다. X로 적합한 것은, 염소, 취소, 불소 또는 옥소와 같은 할로겐원자를 나타낸다. Y로 적합한 것은, X에 예시한 것과 동일한 할로겐원자; 메틸, 에틸, n-프로필, 이소프로필, n-부틸, 이소부틸 또는 삼급-부틸과 같은 탄소수 1∼4개를 갖는 직쇄상 또는 측쇄상의 저급알킬기 또는 메톡시, 에톡시, n-프로폭시, 이소프로폭시, n-부톡시 또는 이소부톡시와 같은 탄소수 1∼4개를 갖는 직쇄상 또는 측쇄상의 저급알콕시기를 나타낸다.In Formula (I), suitable as R ₁ are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary-butyl, tert-butyl, n-pentyl, isopentyl, secondary-amyl, 2 -Methylbutyl, n-tert-amyl, n-nuclear, 2-nuclear, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 3-nuclear, 2-ethylbutyl, 2-methyl-2-pentyl or A straight or branched lower alkyl group having 1 to 6 carbon atoms, particularly 1 to 3 carbon atoms, such as 2,2-dimethylbutyl. Suitable for R ₂ are linear or branched lower alkyl groups or 2-propenyl, 2-butenyl, 1-methyl-2-prop having 1 to 6 carbon atoms, especially 1 to 3 carbon atoms, as exemplified for R ₁ . Phenyl, 2-methyl-2-propenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-butenyl, 1-methyl-3-butenyl, 2-methyl-3-part Straight or branched chain having 3 to 6 carbon atoms, especially 3 or 4, such as phenyl, 3-methyl-2-butenyl, 3-pentenyl, 2-nuxenyl, 3-nuxenyl or 4-nuxenyl Lower alkenyl group is shown. Suitable for X represent halogen atoms such as chlorine, cancellation, fluorine or oxo. Suitable for Y include halogen atoms same as those exemplified for X; Linear or branched lower alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl or methoxy, ethoxy, n-propoxy, iso Linear or branched lower alkoxy groups having 1 to 4 carbon atoms such as propoxy, n-butoxy or isobutoxy.

본 발명에 의한 전기 식(Ⅰ)을 갖는 피라졸론유도체는 어느 것도 문헌에 기재되어 있지 않은 신규한 화합물이며, 우수한 제초활성을 갖고, 제초제로서 유용한 것이다.The pyrazolone derivatives having the electric formula (I) according to the present invention are novel compounds, none of which are described in the literature, have excellent herbicidal activity and are useful as herbicides.

전기 식(Ⅰ)에 있어서, 우수한 제초효과를 나타내는 화합물은 R₁이 메틸기를 나타내고, R₂가 메틸기 또는 2-프로페닐기를 나타내고, X가 클로로원자 또는 브로모원자를 나타내고, Y가 할로겐원자 특히 클로로원자 또는 브로모원자, 니트로기, 메틸기 또는 메톡시기를 나타내고, n는 1 또는 2를 나타내며, n가 2일 때 Y는 동일하거나 상이해도 좋다. 특히 Yn이 2,4-디클로로 또는 2-클로로-4-니트로인 경우가 적합하다.In Formula (I), the compound which shows the outstanding herbicidal effect R <_1> represents a methyl group, R <_2> represents a methyl group or 2-propenyl group, X represents a chloro atom or a bromo atom, Y represents a halogen atom especially A chloro atom or a bromo atom, a nitro group, a methyl group or a methoxy group, n represents 1 or 2, and when n is 2, Y may be the same or different. Especially when Yn is 2,4-dichloro or 2-chloro-4-nitro, it is suitable.

본 발명의 제초제에 있어서 사용되는 전기 식(Ⅰ)을 갖는 화합물을 예시하면 다음과 같다.(또 화합물 번호는 이하의 기재에 있어서 참조된다).When the compound which has an electric formula (I) used in the herbicide of this invention is illustrated, it is as follows. (In addition, a compound number is referred to in the following description.).

본 발명의 방법은 다음과 같은 식(Ⅱ)을 갖는 5-피라졸론 유도체에 할로겐화제를 반응시켜서 전기 식(Ⅱ)을 갖는 피라졸론 유도체를 제조하는 것을 특징으로 하는 것이다.The method of the present invention is characterized by producing a pyrazolone derivative having the above formula (II) by reacting a halogenating agent with a 5-pyrazolone derivative having the formula (II) as follows.

(식중, R₁, R₂, X, Y 및 n는 전술한 것과 같은 의미를 갖는다).(Wherein R ₁ , R ₂ , X, Y and n have the same meaning as described above).

본 발명의 방법을 실시함에 있어서, 상기의 반응은 용제의 존재하에서 적합하게 행해진다. 사용되는 용제로서는 본 반응에 관여하지 않는 것이라면 특히 한정은 없으며, 예를 들면 디에틸에에테르, 테트라하이드로푸란, 디에틸에에테르-디옥산, 테트라하이드로푸란-디옥산 등의 에에테르류 또는 이들의 혼합용제; 벤젠, 톨루엔, 키실렌 등의 방향족탄화수소류; 디클로로메탄, 클로로포름, 사염화탄소 등의 할로겐화탄화수소류 등을 들 수가 있으며, 특히 방향족 탄화수소류 및 사염화탄소가 적합하게 사용된다. 또 사용되는 할로겐화제는, 설퍼릴클로라이드, N-클로로숙신이미드, N-브로모숙신아미드, 취소, 1,5-디클로로-3,3-디메틸히단토인, 오염화인, 옥소-옥화칼륨 등을 들 수 있다. 반응온도는 특히 한정은 없으며, 실온 내지 용제의 환류온도에서 행해진다. 반응시간은 주로 반응온도, 사용되는 시약의 종류에 의해서 다르지만 약 1 내지 10시간이다.In carrying out the method of the present invention, the above reaction is suitably carried out in the presence of a solvent. The solvent used is not particularly limited as long as it is not involved in the reaction, and examples thereof include ethers such as diethyl ether, tetrahydrofuran, diethyl ether-dioxane, tetrahydrofuran-dioxane, and the like. Mixed solvents; Aromatic hydrocarbons such as benzene, toluene and xylene; Halogenated hydrocarbons, such as dichloromethane, chloroform, and carbon tetrachloride, etc. are mentioned, Especially aromatic hydrocarbons and carbon tetrachloride are used suitably. In addition, the halogenating agent used may be sulfyl chloride, N-chlorosuccinimide, N-bromosuccinamide, clear, 1,5-dichloro-3,3-dimethylhydantoin, phosphorus pentachloride, oxo-potassium potassium oxide, or the like. Can be mentioned. The reaction temperature is not particularly limited and is performed at room temperature to the reflux temperature of the solvent. The reaction time is mainly about 1 to 10 hours, depending on the reaction temperature and the type of reagent used.

반응종료 후, 목적화합물은 상법에 의해서 반응혼합물로부터 채취, 정제할 수가 있다.After completion of the reaction, the target compound can be collected and purified from the reaction mixture by a conventional method.

또, 본 발명의 방법에서 출발물질로서 사용되는 전기 식(Ⅱ)의 화합물은 일본특허출원 제34939호/1974 명세서 및 동 29939호/1975 명세서에 기재된 방법에 준해서 다음과 같이 제조할 수가 있다.The compound of formula (II) used as a starting material in the method of the present invention can be prepared according to the methods described in Japanese Patent Application Nos. 34939/1974 and 29939/1975.

(식중, R₁, R₂, Y 및 n는 전술한 것과 같은 의미를 갖는다).(Wherein R ₁ , R ₂ , Y and n have the same meaning as described above).

또, 본 발명에 의하면 전기식(Ⅰ)을 갖는 피라졸론유도체의 제초제로서의 용도가 제공된다. 더 구체적으로는, 본 발명은 전기 식(Ⅰ)을 갖는 피라졸론유도체의 유효성분으로서 함유하는 제초제 조성물에 관한 것이다.Moreover, according to this invention, the use as a herbicide of the pyrazolone derivative which has an electric (I) is provided. More specifically, the present invention relates to a herbicide composition containing as an active ingredient of a pyrazolone derivative having the above formula (I).

논에 있어서는, 잡초의 발아전 또는 발아후에 토양처리함으로써, 이식벼 및 직파벼에 대해 해로운 작용을 미침이 없이, 통상의 제초제로서는 방제가 곤란한 올챙이고랭이, 너도방동산이등의 방동산이 과잡초, 벗풀, 올미등의 벗풀과 잡초등 다년생잡초를 특히 강력하게 구제할 수 있고, 또, 대피, 비안야드그라스, 좀물뚝새풀 등의 벼과잡초등 단자엽잡초, 또, 발뚝의 풀, 자초로대, 등에풀등의 호마의 엽초과잡초, 황새냉이, 논냉이, 속속이풀 등의 유채과잡초, 마디꽃, 물쇠털골등의 부처꽃과 잡초, 금불초, 한련초 등의 국화과잡초 등의 광엽잡초까지도 유효하게 구제할 수가 있다.In rice fields, by treating the soil before or after germination of the weeds, there is no detrimental effect on the transplanted rice and the chopped rice, and the weeding acids such as tadpoles, leeks and beetles are difficult to control with conventional herbicides. We can control perennial weeds such as weeds and weeds such as shells, snares particularly strongly, and, in addition, weeds such as weeds such as evacuation, vian yard grass, Japanese green grass, again grass, weeds stand Effectively relieve even broadleaf weeds, such as rapeseed weeds of horses such as grasses, rapeseed weeds like horseradish, paddy field, and genus weeds, buds and flowers such as bud flowers, chrysanthemums, and weeds such as goldweed and nasturtium You can do it.

또, 밭에 있어서는, 잡초의 발아전 또는 발아후에 토양처리함으로써, 밭의 강력한 잡초인 별꽃, 벼룩나물, 이채, 개미자리 등의 무자과잡초에 특히 유효한 것외에 쇠비름 등의 쇠비름과 잡초, 개비름, 털비름등의 비름과 잡초, 명아주, 흰명아주, 좀명아주 등의 명아주과잡초, 닭의장풀등의 닭의장풀과 잡초, 광대나물, 금창소초등의 자소과잡초, 괭이밥, 자주괭이밥 등의 괭이밥과 잡초, 괭이싸리, 새완두, 살갈퀴등의 콩과잡초, 꺼풀, 애기땅빈대등의 등대풀과 잡초등의 광엽잡초를 유효하게 구제할 수가 있다.In the field, the soil treatment before or after germination of the field, which is particularly effective for vulture weeds such as chickweed, flea sprouts, irises and trefoil which are powerful weeds of the field, in addition to purslane and weeds such as purslane, weeds and hairs Amaranth and weeds such as amaranth, weed, mingled, white and medley, chickweeds and weeds such as chicken elders Weeds such as legume weeds such as peas and rakes, lighthouse grasses such as lids, and baby weeds can be effectively removed.

또, 협엽잡초로서는, 방동산이등의 방동산이과잡초에 특히 유효한 것 외에, 벗풀, 바랭이, 좀바랭이, 개피, 여우꼬리풀, 가을여우꼬리풀, 뚝새풀 등의 벼과잡초도 유효하게 구제할 수가 있다. 한편, 실용약량으로서는 벼, 옥수수, 사탕무우, 대두, 목화, 무우, 토마토, 당근, 백채, 상치등의 작물은 약해를 입지는 않는다.In addition, as a narrow weed, it is particularly effective for antidote algae weeds such as Bangdongsan, as well as rice weeds such as bark, bark, scabbard, open, fox tail grass, fall fox tail grass, and nectar grass. On the other hand, as a practical dose, crops such as rice, corn, beets, soybeans, cotton, radishes, tomatoes, carrots, whites, and lettuce are not harmed.

또, 전기식(Ⅰ)을 갖는 화합물은, 과수원, 비농경지, 산림등에 있어서도 제초제로서 유효하게 사용할 수 있다.Moreover, the compound which has electric formula (I) can be used effectively as a herbicide also in an orchard, a non-cultivated land, a forest, etc.

본 발명의 화합물은, 담체 및 필요에 따라서 다른 보조제와 혼합하여, 제초제로서 통상 사용되는 제제형태, 예를 들면 분제, 조분제, 미립제, 입제, 수화제, 유제, 수용액제, 수용제, 유현탁제 등으로 조제되어 사용된다. 여기서 말하는 담체라 함은 처리할 부위에 유효성분화합물의 도달성을 돕고, 또, 유효성분화합물의 저장, 운송 혹은 취급을 용이하게 하기 위해 제초제중에 혼합되는 합성 또는 천연의 무기 또는 유기물질을 의미한다.The compounds of the present invention may be mixed with a carrier and other auxiliaries as necessary to form a formulation commonly used as a herbicide, for example, powders, powders, fines, granules, hydrating agents, emulsions, aqueous solutions, water-soluble agents and suspending agents. It is prepared and used. As used herein, the term "carrier" refers to a synthetic or natural inorganic or organic substance that is mixed in herbicides to help reach the active ingredient compound at the site to be treated and to facilitate storage, transport, or handling of the active ingredient compound. .

적당한 고체담체로서는, 고령토군, 몬트모릴로나이트(montmorillonite)군 혹은 아타풀자이트(attapulgite)군 등으로 대표되는 점토류, 활석, 운모, 엽랍석, 경석, 버어미큘라이트(vermiculite), 석고, 탄산칼슘, 돌로마이트, 규조토, 마그네슘석회, 인회석, 제올라이트, 무수규산, 합성규산칼슘 등의 무기물질, 대두분, 담배가루, 호도분, 소맥분, 목분, 전분, 결정셀룰로오스 등의 식물성유기물질, 쿠마론수지, 석유수지, 알키드수지, 폴리염화비닐, 폴리알킬렌글리크올, 케톤수지, 에스테르캄, 코오발캄, 단말캄 등의 합성 또는 천연의 고분자화합물, 카르나우바왁스, 밀랍등의 왁스류, 혹은 뇨소 등을 들 수가 있다.Suitable solid carriers include clays, talc, mica, chloroplasts, pumice, vermiculite, gypsum, represented by kaolin, montmorillonite, or attapulgite groups, and the like. Inorganic substances such as calcium carbonate, dolomite, diatomaceous earth, magnesium lime, apatite, zeolite, silicic anhydride, synthetic calcium silicate, soybean flour, tobacco powder, archo flour, wheat flour, wood flour, starch, vegetable organic materials such as crystalline cellulose, coumarone Synthetic or natural polymer compounds such as resins, petroleum resins, alkyd resins, polyvinyl chloride, polyalkyleneglycols, ketone resins, estercams, kobalkams, and terminalcams, waxes such as carnauba wax, beeswax, Or urine.

적당한 액체담체로서는, 케로신, 광유, 스핀들유, 화이트오일 등의 파라핀계 혹은 나프텐계탄화수소, 벤젠, 톨루엔, 키실렌, 에틸벤젠, 쿠멘, 메틸나프탈린 등의 방향족탄화수소, 사염화탄소, 클로로포름, 트리클로로에틸렌, 모노클로로벤젠, 0-클로로톨루엔 등의 염소화탄화수소, 디옥산, 테트라하이드로푸란과 같은 에에테르류, 아세톤, 메틸에틸케톤, 디이소부틸케톤, 디클로로헥산, 아세토페론, 이소포론 등의 케톤류, 초산에틸, 초산아밀, 에틸렌글리코올알데히드, 디에틸렌글리코올알데히드, 말레인산디부틸, 호박산디에틸 등의 에스테르류, 메탄올, n-헥산올, 에틸렌글리코올, 디에틸렌글리코올, 사이클로헥산올, 벤질알코올 등의 알코올류, 에틸렌글리코올에틸에에테르, 에틸렌글리코올페닐에에테르, 디에틸렌글리코올에틸에에테르, 디에틸렌글리코올부틸에에테르 등의 에에테르알코올류, 디메틸포름아미드, 디메틸설폭사이드 등의 극성용매 혹은 물 등을 들 수 있다.Suitable liquid carriers include aromatic hydrocarbons such as paraffinic or naphthenic hydrocarbons such as kerosene, mineral oil, spindle oil, white oil, naphthenic hydrocarbons, benzene, toluene, xylene, ethylbenzene, cumene, methylnaphthalin, carbon tetrachloride, chloroform, trichloro Chlorinated hydrocarbons such as ethylene, monochlorobenzene, and 0-chlorotoluene, ethers such as dioxane and tetrahydrofuran, acetone, methyl ethyl ketone, diisobutyl ketone, ketones such as dichlorohexane, acetoferon and isophorone, Esters such as ethyl acetate, amyl acetate, ethylene glycol aldehyde, diethylene glycol aldehyde, dibutyl maleate, diethyl succinate, methanol, n-hexanol, ethylene glycol, diethylene glycol, cyclohexanol, benzyl Alcohols such as alcohols, ethylene glycol ethyl ether, ethylene glycol phenyl ether, diethylene glycol ethyl ether, diethylene glycol Ether alcohols to ethers such as the butyl alcohol, dimethylformamide, and the like polar solvent or water, such as dimethyl sulfoxide.

유화, 분산, 습윤, 확전, 결합, 붕괴성조절, 유효성분안정화, 유동성개량, 방청 등의 목적으로 온성 및 양성이온성중 어느 것이든지 사용할 수 있지만, 통상은 비이온성 및(또는)음이온성의 것이 사용된다. 적당한 비이온성계면활성제로서는, 예를들면 라우릴알코올, 스테아릴알코올, 올레일알코올 등의 고급알코올에 에틸렌옥사이드를 중합부가시킨 것, 이소옥틸페놀, 노닐페놀 등의 알킬페놀에 에틸렌옥사이드를 중합부가시킨 것, 부틸나프톨, 옥틸나프톨 등의 알킬나프톨에 에틸렌옥사이드를 중합부가시킨 것, 팔미틴산, 스테아린산, 올레인산 등의 고급지방산에 에틸렌옥사이드를 중합부가시킨 것, 스테아릴인산, 디라우릴인산 등의 모노 혹은 디알킬인산에 에틸렌옥사이드를 중합부가시킨 것, 도데실아민, 스테아린산아미드 등의 아민에 에틸렌옥사이드를 중합부가 시킨것, 솔비탄 등의 다가알코올의 고급지방산에스테르 및 여기에 에틸렌옥사이드를 중합부가시킨 것, 에틸렌옥사이드와 프로필렌옥사이드를 중합부가시킨 것을 들 수가 있다. 적당한 음이온성 계면활성제로서는, 예를 들면 라우릴황산나트륨, 올레일알코올황산에스테르아연염 등의 알킬황산에스테르염, 슬포호박산디옥틸에스테르나트륨, 2-에틸헥센슬폰산나트륨 등의 알킬슬폰산염, 이소프로필나트탈렌슬폰산나트륨, 메틸렌비스나프탈렌슬폰산나트륨, 리그닌슬폰산나트륨, 도데실벤젠슬폰산나트륨 등의 아릴슬폰산염 등을 들 수가 있다.Either ionic or zwitterionic can be used for the purpose of emulsification, dispersion, wetting, expansion, binding, disintegration control, stabilization of effective fraction, improved fluidity, rust prevention, etc., but generally nonionic and / or anionic Used. Suitable nonionic surfactants include those in which ethylene oxide is polymerized with higher alcohols such as lauryl alcohol, stearyl alcohol and oleyl alcohol, and ethylene oxide is polymerized with alkylphenols such as isooctylphenol and nonylphenol. Polymerized parts of ethylene oxide to alkylnaphthol, such as butylnaphthol and octylnaphthol; polymerized parts of ethylene oxide to higher fatty acids such as palmitic acid, stearic acid, and oleic acid; mono or such as stearylphosphoric acid and dilauryl phosphate. Polymerized addition of ethylene oxide to dialkylphosphoric acid, polymerization addition of ethylene oxide to amines such as dodecylamine and stearic acid amide, higher fatty acid esters of polyhydric alcohols such as sorbitan, and polymerization addition of ethylene oxide thereto. And polymerized parts of ethylene oxide and propylene oxide can be mentioned. Examples of suitable anionic surfactants include alkyl sulfonates such as sodium lauryl sulfate and oleyl alcohol sulfate zinc salts, alkyl sulfonates such as sodium sulfobacterium dioctyl ester sodium and sodium 2-ethylhexene sulfonate, and isopropyl. Aryl sulfonates, such as sodium naphthalene sulfonate, sodium methylene bis naphthalene sulfonate, sodium lignin sulfonate, and sodium dodecyl benzene sulfonate, etc. are mentioned.

또, 본 발명의 제초제에는 제제의 성상을 개선하고, 생물효과를 높이기 위한 목적으로 카제인, 젤라틴, 알부민, 니카와, 알긴산소오다, 카아복시메틸셀룰로오스, 메틸셀룰로오스, 하이드록시에틸셀룰로오스, 폴리비닐알코올등의 고분자화합물이나 기타의 보조제를 병용할 수도 있다.In addition, the herbicide of the present invention contains casein, gelatin, albumin, nikawa, sodium alginate, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol for the purpose of improving the properties of the formulation and enhancing the biological effect. Polymer compounds, such as these, and other adjuvant can also be used together.

상기의 담체 및 여러가지의 보조제는 제제의 제형, 적용장소등을 고려하여, 목적에 따라서 각각 단독 혹은 조합시켜서 적당히 사용한다.The above carriers and various auxiliaries are appropriately used alone or in combination according to the purpose in consideration of the formulation of the preparation, the place of application, and the like.

분제는, 예를 들면 유효성분화합물을 통상 1 내지 25중량부 함유하고, 잔부는 고체담체이다.The powder is, for example, usually contains 1 to 25 parts by weight of the active ingredient compound, and the balance is a solid carrier.

수화제는, 예를 들면 유효성분화합물을 통상 25 내지 90중량부 함유하고, 잔부는 고체담체, 분산흡윤제이며, 필요에 따라서 보호콜로이드제, 요변제, 소포제 등을 부가한다.A hydrating agent contains 25-90 weight part of active ingredient compounds normally, for example, remainder is a solid support | carrier and a dispersing absorbing agent, A protective colloid, a thixotropic agent, an antifoamer, etc. are added as needed.

입제는 예를 들면 유효성분 화합물을 통상 1 내지 35중량부 함유하고, 잔부는 대부분이 고체담체이다. 유효성분화합물은 고체담체와 균일하게 혼합되어 있든가, 혹은 고체담체의 표면에 균일하게 고착 혹은 흡착되어 있고, 입자의 입경은 약 0.2 내지 1.5mm이다.For example, the granules usually contain 1 to 35 parts by weight of the active ingredient compound, and most of the residue is a solid carrier. The active ingredient compound is uniformly mixed with the solid carrier or is uniformly fixed or adsorbed on the surface of the solid carrier, and the particle size of the particles is about 0.2 to 1.5 mm.

유제는, 예를 들면 유효성분화합물을 통상 5 내지 50중량부 함유하고 있고, 여기에 약 5 내지 20중량부의 유효제가 함유되고, 잔부는 액체담체이고, 필요에 따라서 방청제를 가한다.The emulsion contains, for example, 5 to 50 parts by weight of an active ingredient compound, about 5 to 20 parts by weight of an active agent, the remainder is a liquid carrier, and a rust inhibitor is added as necessary.

이와 같이하여, 여러가지의 제형에 조제된 본 발명의 제초제를, 예를들면, 논 또는 밭에 있어서 잡초의 발아전 또는 발아후에 토양처리할 때에는, 10a당 유효성분으로서 10 내지 2000g, 바람직하기로는 100∼500g을 투약함으로서, 유효하게 잡초를 구제할 수 있다. 또, 비농경지, 예를들면 도로, 정원, 가옥부지, 선로 등에 있어서 비선택적으로 잡초를 구제하려고 할 경우에는 10a당 유효성분으로서 200 내지 4000g을 투약함으로서 유효하게 잡초를 구제할 수 있다.Thus, when the herbicide of the present invention prepared in various formulations is subjected to soil treatment before or after germination of weeds in rice fields or fields, for example, 10 to 2000 g, preferably 100, per 10a. By administering ˜500 g, weeds can be effectively controlled. When weeds are to be selectively removed in non-crop lands such as roads, gardens, houses, tracks, etc., weeds can be effectively controlled by administering 200 to 4000 g as an active ingredient per 10 a.

본 발명의 제초제는, 살초스펙트럼을 넓히기 위해 다른 제초제를 배합시키는 것은 바람직하며, 경우에 따라서는 상승효과를 기대할 수도 있다. 이와 같은 다른 제초제의 예로서는, 예를들면, 2-메틸티오-4,6-비스에틸아미노-1,3,5-트리아진; 2-클로로-4,6-비스에틸아미노-1,3,5-트리아진; 2-메톡시-4-에틸아미노-6-이소프로필아미노-1,3,5-트리아진; 2-클로로-4-에틸아미노-6-이소프로필아미노-S-트리아진; 2-메틸티오-4,6-비스(이소프로필아미노)-S-트리아진; 2-에틸티오-4-에틸아미노-6-이소프로필아미노-S-트리아진 등의 트리아진계제초제, 2,4-디클로로펜옥시초산 및 그의 메틸, 에틸 또는 부틸에스테르; 2-클로로-4-메틸펜옥시초산; 4-클로로-2-메틸펜옥시초산, 에틸-2-메틸-4-클로로펜옥시부틸레이트 등의 펜옥시계제초제, 2,4,6-트리클로로페닐-4'-니트로페닐에에테르; 2,4-디클로로페닐-4'-니트로페닐에에테르; 3,5-디메틸페닐-4'-니트로페닐에에테르 등의 디페닐에에테르계제초제, 3-(3,4-디클로로페닐)-1-메톡시-1-메틸우레아; 3-(3,4-디클로로페닐)-1,1-디메틸우레아; 3-(4-클로로페닐)-1,1-디메틸우레아 등의 요소계제초제, 3-메톡시카아보닐아미노페닐-N-(3-메틸페닐카아바메이트; 이소프로필-N-(3-클로로페닐)카아바메이트; 메틸 N-(3,4-디클로로페닐)카아바메이트 등의 카아바메이트계제초제, 5-브로모-3-이급-부틸-6-메틸우라실; 1-사이클로헥실-3,5-프로필렌우라실 등의 우라실계제초제, S-(4-클로로벤질)-N,N-디메틸티올카아바메이트; S-에틸N-사이클로헥실-N-에틸티올카아바메이트; S-에틸-헥사이드로-1H-아제핀-1-카아보티오에이트; S-에틸-N,N-디노르말프로필티오카아바메이트 등의 티올카아바메이트계 제초제, 1,1'-디메틸-4,4'-비스피리디늄디클로라이드 등의 피리디늄염계 제조제, N-(포스포노메틸)글리신 등의 인계제초제, a,a,a-트리플루오로-2,6-디니트로-N,N-디프로필-P-톨루이딘; 4-(메틸슬포닐) 2,6-디니트로-N,N-디프로필아닐린; N³,N³-디에틸-2,4-디니트로-6-트리플루오로메틸-1,3-페닐디아민 등의 아닐린계제초제, 2-클로로-2',6'-디에틸-N-(부톡시메틸)아세토아닐리드; 2-클로로-2',6'-디에틸-N-(메톡시메틸)아세토아닐리드; 3,4-디클로로프로피온아닐리드 등의 산아닐리드계제초제, 5-삼급-부틸-3-(2,4-디클로로-5-이소프로폭시페닐)-1,3,4-옥사디아졸린-2-온; 2-[N-이소프로필-N-(4-클로로페닐)카아바모일]-4-클로로-5-메틸-4-이속사졸린-3-온; 3-이소프로필-벤조-2-티아-1,3-디아지논-(4)-2,2-디옥사이드; 3-(2-메틸펜옥시)피리다진 등을 들 수가 있지만, 이들에 한정되는 것은 아니다.The herbicide of the present invention is preferably blended with other herbicides in order to broaden the herbicidal spectrum, and in some cases, a synergistic effect may be expected. Examples of such other herbicides include, for example, 2-methylthio-4,6-bisethylamino-1,3,5-triazine; 2-chloro-4,6-bisethylamino-1,3,5-triazine; 2-methoxy-4-ethylamino-6-isopropylamino-1,3,5-triazine; 2-chloro-4-ethylamino-6-isopropylamino-S-triazine; 2-methylthio-4,6-bis (isopropylamino) -S-triazine; Triazine herbicides such as 2-ethylthio-4-ethylamino-6-isopropylamino-S-triazine, 2,4-dichlorophenoxyacetic acid and methyl, ethyl or butyl esters thereof; 2-chloro-4-methylphenoxyacetic acid; Phenoxy herbicides such as 4-chloro-2-methylphenoxyacetic acid and ethyl-2-methyl-4-chlorophenoxybutylate, 2,4,6-trichlorophenyl-4'-nitrophenyl ether; 2,4-dichlorophenyl-4'-nitrophenyl ether; Diphenyl ether herbicides such as 3,5-dimethylphenyl-4'-nitrophenyl ether, 3- (3,4-dichlorophenyl) -1-methoxy-1-methylurea; 3- (3,4-dichlorophenyl) -1,1-dimethylurea; Urea herbicides such as 3- (4-chlorophenyl) -1,1-dimethylurea, 3-methoxycarboylaminophenyl-N- (3-methylphenylcarbamate; isopropyl-N- (3-chlorophenyl Carbamate, carbamate herbicides such as methyl N- (3,4-dichlorophenyl) carbamate, 5-bromo-3-secondary-butyl-6-methyluracil, 1-cyclohexyl-3, Uracil herbicides such as 5-propylene uracil, S- (4-chlorobenzyl) -N, N-dimethylthiol carbamate; S-ethyl N-cyclohexyl-N-ethylthiol carbamate; S-ethyl-hexa Thiol carbamate herbicides such as idro-1H-azepine-1-carabothioate, S-ethyl-N, N-dinomalpropylthiocarabamate, 1,1'-dimethyl-4,4'- Pyridinium salt-based preparations such as bispyridinium dichloride, phosphorus herbicides such as N- (phosphonomethyl) glycine, a, a, a-trifluoro-2,6-dinitro-N, N-dipropyl- P-toluidine; 4- (methylsulfonyl) 2,6-dinitro-N, N-dipropylanyl ; N ^3, N ³ - diethyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylene diamine such as an aniline-based herbicide, 2-chloro-2 ', the 6'-ethyl -N Acid anhydride herbicides such as (butoxymethyl) acetoanilide; 2-chloro-2 ', 6'-diethyl-N- (methoxymethyl) acetoanilide; 3,4-dichloropropionanilide, 5-tertiary- Butyl-3- (2,4-dichloro-5-isopropoxyphenyl) -1,3,4-oxadiazolin-2-one; 2- [N-isopropyl-N- (4-chlorophenyl) car Abamoyl] -4-chloro-5-methyl-4-isoxazolin-3-one: 3-isopropyl-benzo-2-thia-1,3-diazinone- (4) -2,2-dioxide; Although 3- (2-methylphenoxy) pyridazine etc. are mentioned, It is not limited to these.

본 발명의 제초제는 또 나프탈린초산나트륨; N'-메톡시카아보닐-N'-4-메틸페닐카아바모일 에틸이소우레아; 1-(4-클로로페닐카아바모일)-3-에톡시카아보닐-2-메틸이소우레아; 1,2-디하이드로피리다진-3,6-디온; 디벨레린 등의 식물생장조절제, N-(2,6-디에틸페닐)프탈이미드; N-(2,6-디에틸페닐)-4-메틸프탈이미드 등의 프탈이미드계살균제, 6-(3,5-디클로로-4-메틸페닐)-3(2H)피리다지논; 6-(3,4-디클로로페닐)-3(2H)피리다지논; 6-(3,5-디브로모-4-메틸페닐)-3(2H)피리다지논; 6-(3-클로로 -4-메틸-5-브로모페닐)-3(2H)피리다지논; 6-(3,5-디클로로-4-메톡시페닐)-3(2H)피리다지논; 6-(3,5-디클로로-4-메틸페닐)-4,5-디하이드로-3(2H)피리다지논; 6-(3,4-디클로로페닐)-4,5-디하이드로-3(2H)피리다지논; 6-(3,5-디브로모-4-메틸페닐)-4, [5-디하이드로-3(2H)피리다지논; 6-(3-클로로-4-메틸-5-브로모페닐)-4,5-디하이드로-3(2H)피리다지논; 6-(3,5-디클로로페닐)-4,5-디하이드로-3(2H)피리다지논 등의 피리다지논계살균제, 메틸 1 -(부틸카아바모일)-2-벤즈이미다졸카아바메이트; 1,2-비스(3-메톡시카아보닐-2-티오우레이도)벤젠; 3-하이드록시-5-메틸이속사졸; N-2, 3-디클로로페닐테트라클로로프탈아미도산; 5-메틸 S-트리아졸(3,4-b)벤즈티아졸; 0,0-디이소프로필-S-벤질포스포로티오에이트; 펜타클로로니트로벤젠; 가스가마이신; 브라스토사이징 S; 4,5,6,7-테트라클로로프탈리드 등의 살균제; 0,0-디에틸 0-(2-이소프로필-4-메틸-6-피리미디닐)포스포로티오에이트; 0,0-디에틸 S-2-[(에틸티오)에틸]포스포로디티오에이트; 1-나프틸 N-메틸카아바메이트; 0,0-디메틸 0-(3-메틸-4-니트로페닐)티오포스페이트; 0,0-디메틸 S-(N-메틸카아바모일) 포스포로디티오에이트; S-메틸-N-[(메틸카아바모일)옥시] 티오아세토이미데이트: 0,0-디메틸 S-(N-메틸-N-포르밀카아바모일메틸) 포스포로디티오에이트; 0,0-디메틸 S-2-(에틸티오)에틸포스포로디티오에이트; 0,0-디메틸 S-2[(에틸티오)에틸]포스포로디티오에이트; 0,0-디메틸-1-하이드록시-2,2-2-트리클로로에틸포스포네이트, 밀베마이신 등의 살충제 혹은 비료 등을 혼합하여 사용할 수 있다.The herbicide of the present invention is also sodium naphthalin acetate; N'-methoxycaraboyl-N'-4-methylphenylcarabamoyl ethylisourea; 1- (4-chlorophenylcarbamoyl) -3-ethoxycaraboyl-2-methylisourea; 1,2-dihydropyridazine-3,6-dione; Plant growth regulators such as dibelin, N- (2,6-diethylphenyl) phthalimide; Phthalimide disinfectants such as N- (2,6-diethylphenyl) -4-methylphthalimide and 6- (3,5-dichloro-4-methylphenyl) -3 (2H) pyridazinone; 6- (3,4-dichlorophenyl) -3 (2H) pyridazinone; 6- (3,5-dibromo-4-methylphenyl) -3 (2H) pyridazinone; 6- (3-chloro-4-methyl-5-bromophenyl) -3 (2H) pyridazinone; 6- (3,5-dichloro-4-methoxyphenyl) -3 (2H) pyridazinone; 6- (3,5-dichloro-4-methylphenyl) -4,5-dihydro-3 (2H) pyridazinone; 6- (3,4-dichlorophenyl) -4,5-dihydro-3 (2H) pyridazinone; 6- (3,5-dibromo-4-methylphenyl) -4, [5-dihydro-3 (2H) pyridazinone; 6- (3-chloro-4-methyl-5-bromophenyl) -4,5-dihydro-3 (2H) pyridazinone; Pyridazinone disinfectants such as 6- (3,5-dichlorophenyl) -4,5-dihydro-3 (2H) pyridazinone and methyl 1- (butylcarbamoyl) -2-benzimidazolecarbamate ; 1,2-bis (3-methoxycarboyl-2-thioureido) benzene; 3-hydroxy-5-methylisoxazole; N-2, 3-dichlorophenyltetrachlorophthalamidoic acid; 5-methyl S-triazole (3,4-b) benzthiazole; 0,0-diisopropyl-S-benzylphosphothioate; Pentachloronitrobenzene; Gasgamycin; Brasizing S; Fungicides such as 4,5,6,7-tetrachlorophthalide; 0,0-diethyl 0- (2-isopropyl-4-methyl-6-pyrimidinyl) phosphothioate; 0,0-diethyl S-2-[(ethylthio) ethyl] phosphodithioate; 1-naphthyl N-methylcarbamate; 0,0-dimethyl 0- (3-methyl-4-nitrophenyl) thiophosphate; 0,0-dimethyl S- (N-methylcarabamoyl) phosphorodithioate; S-methyl-N-[(methylcarabamoyl) oxy] thioacetoimidate: 0,0-dimethyl S- (N-methyl-N-formylcarabamoylmethyl) phosphorodithioate; 0,0-dimethyl S-2- (ethylthio) ethylphosphorodithioate; 0,0-dimethyl S-2 [(ethylthio) ethyl] phosphorodithioate; Pesticides, fertilizers, etc., such as 0,0- dimethyl- 1-hydroxy- 2,2-2- trichloroethyl phosphonate and a milbemycin, can be used in mixture.

다음에, 전기 일반식(Ⅰ)을 갖는 화합물의 제조법을 실시예를 들어 더 구체적으로 설명한다.Next, the production method of the compound having the general formula (I) will be described in more detail with reference to Examples.

[실시예 1]Example 1

[1,3-디메틸-4-클로로-4-벤조일-5-피라졸론][1,3-dimethyl-4-chloro-4-benzoyl-5-pyrazolone]

1,3-디메틸-4-벤조일-5-피라졸론 2.16g을 건조 벤젠 20ml에 용해한 후, 설퍼릴클로라이드 1.62g을 가해 실온에서 4시간 교반했다. 반응종료 후, 반응혼합물에 물을 가해서 진탕한 후 유기층을 분취했다. 유기층은 포화탄화수소나트륨 수용액, 물의 순서로 순차적으로 세정한 후에, 무수황산나트륨으로 건조하고, 이어서 용액으로부터 용제를 유거하여 수득된 잔류물을 n-헥산으로 재결정하면 융점 70.5∼72℃를 갖는 목적화합물 0.2g이 얻어졌다.(수율 7.6%)After dissolving 2.16 g of 1,3-dimethyl-4-benzoyl-5-pyrazolone in 20 ml of dry benzene, 1.62 g of sulfuryl chloride was added, followed by stirring at room temperature for 4 hours. After completion of the reaction, water was added to the reaction mixture to shake the mixture, and the organic layer was separated. The organic layer was washed sequentially with a saturated aqueous solution of sodium hydrocarbon, followed by water, dried over anhydrous sodium sulfate, and then the residue obtained by distilling off the solvent from the solution was recrystallized with n-hexane to give a target compound having a melting point of 70.5 to 72 ° C. g was obtained (yield 7.6%).

원소분석(%) : C₁₂H₁₁CIN₂O₂ Elemental analysis (%): C ₁₂ H ₁₁ CIN ₂ O ₂

계산치 : C,57.49; H,4.43; N,11.18; CI,14.14Calc .: C, 57.49; H, 4.43; N, 11.18; CI, 14.14

실험치 : C,56.97; H,4.49; N,10.46; CI,13.63Found: C, 56.97; H, 4.49; N, 10.46; CI, 13.63

[실시예 2]Example 2

[1,3-디메틸-4-클로로-4-(2-니트로-5-메틸벤조일)-5-피라졸론][1,3-dimethyl-4-chloro-4- (2-nitro-5-methylbenzoyl) -5-pyrazolone]

1,3-디메틸-4-(2-니트로-5-메틸벤조일)-5-피라졸론 2.65g 건조 벤젠 20ml에 현탁한 후, 설퍼릴클로라이드 1.62g을 가해 실온에서 4시간 교반했다. 반응종료 후, 반응혼합물을 이하, 실시예 1과 동일하게 처리정제하면 융점 110∼111℃를 갖는 목적화합물 2.0g이 얻어졌다.(수율 64.72%)2.65 g of 1,3-dimethyl-4- (2-nitro-5-methylbenzoyl) -5-pyrazolone After suspending in 20 ml of dry benzene, 1.62 g of sulfuryl chloride was added and stirred at room temperature for 4 hours. After the completion of the reaction, the reaction mixture was treated and purified in the same manner as in Example 1 below to obtain 2.0 g of the target compound having a melting point of 110 to 111 ° C. (Yield 64.72%)

원소분석(%) : C₁₃H₁₂CIN₃O₄ Elemental analysis (%): C ₁₃ H ₁₂ CIN ₃ O ₄

계산치 : C,50.41; H,3.90; N,13.57; CI,11.45Calculated: C, 50.41; H, 3.90; N, 13.57; CI, 11.45

실험치 : C,50.58; H,3.89; N,13.80; CI,11.38Experimental Value: C, 50.58; H, 3.89; N, 13.80; CI, 11.38

[실시예 3]Example 3

[1,3-디메틸-4-브로모-4-(2,4-디클로로벤조일)-5-피라졸론][1,3-dimethyl-4-bromo-4- (2,4-dichlorobenzoyl) -5-pyrazolone]

1,3-디메틸-4-(2,4-디클로로벤조일)-5-피라졸론 0.285g을 사염화탄소 5ml에 용해한 후 N-브로모숙신이미드 0.356g을 가해 1.5시간 가열 환류했다. 방냉 후, 반응혼합물을 여과하고 이어서 여액으로부터 감압하에 용제를 유거하여 수득된 잔류물을 n-헥산으로 재결정하면 융점 89∼90℃를 갖는 목적화합물 0.32g이 얻어졌다(수율 85.9%)0.285 g of 1,3-dimethyl-4- (2,4-dichlorobenzoyl) -5-pyrazolone was dissolved in 5 ml of carbon tetrachloride, and 0.356 g of N-bromosuccinimide was added thereto, followed by heating to reflux for 1.5 hours. After allowing to cool, the reaction mixture was filtered and the residue obtained by distilling off the solvent from the filtrate under reduced pressure was recrystallized with n-hexane to give 0.32 g of the target compound having a melting point of 89 to 90 ° C (yield 85.9%).

원소분석(%) : C₁₂H₉BrCl₂H₂O₂ Elemental Analysis (%): C ₁₂ H ₉ BrCl ₂ H ₂ O ₂

계산치 : C,39.59; H,2.49; N,7.70; Br,21.95; Cl,19.48Calculated: C, 39.59; H, 2.49; N, 7.70; Br, 21.95; Cl, 19.48

실험치 : C,40.08; H,2.59; N,7.83; Br,21.72; Cl,19.29Experimental Value: C, 40.08; H, 2.59; N, 7.83; Br, 21.72; Cl, 19.29

상기 실시예 1∼3의 방법에 준해서 다음과 같은 화합물이 제조되었다.According to the method of Examples 1 to 3, the following compounds were prepared.

1,3-디메틸-4-클로로-4-(2,4-디클로로벤조일)-5-피라졸론, 융점 83∼84℃1,3-dimethyl-4-chloro-4- (2,4-dichlorobenzoyl) -5-pyrazolone, melting point 83 ° C to 84 ° C

1,3-디메틸-4-클로로-4-(2-클로로-4-니트로벤조일)-5-피라졸론, 융점 74∼75℃1,3-dimethyl-4-chloro-4- (2-chloro-4-nitrobenzoyl) -5-pyrazolone, melting point 74 ° C to 75 ° C

1,3-디메틸-4-클로로-4-(3,4-디메톡시벤조일)-5-피라졸론, 융점 107∼108℃1,3-dimethyl-4-chloro-4- (3,4-dimethoxybenzoyl) -5-pyrazolone, melting point 107-108 ° C

1-에틸-3-메틸-4-클로로-4-(2,4-디클로로벤조일)-5-피라졸론, 융점 54∼55℃1-ethyl-3-methyl-4-chloro-4- (2,4-dichlorobenzoyl) -5-pyrazolone, melting point 54-55 ° C

1-(2-프로페닐)-3-메틸-4-클로로-4-(2,4-디클로로벤조일)-5-피라졸론, 융점 54∼55℃1- (2-propenyl) -3-methyl-4-chloro-4- (2,4-dichlorobenzoyl) -5-pyrazolone, melting point 54-55 ° C

1,3-디메틸-4-브로모-4-(4-니트로벤조일)-5-피라졸론, 융점 125∼126℃1,3-dimethyl-4-bromo-4- (4-nitrobenzoyl) -5-pyrazolone, melting point 125-126 degreeC

다음에, 본 발명의 제초제에 대해서 실시예를 들어 더 구체적으로 설명한다. 명세서 중 간단히 「부」라 함은 모두 「중량부」를 의미하는 것이다.Next, the herbicide of the present invention will be described in more detail with reference to Examples. In the specification, "parts" simply means "parts by weight".

[실시예 4]Example 4

[입제][Participation]

화합물 번호 3의 화합물 70부를 미세하게 분쇄하고, 여기에 점토 30부를 가해서 혼합기 중에 혼화하여 프레믹스로 한다. 이 프레믹스 10부를 점토 60부 및 벤토나이트 30부와 함께 혼합기 중에서 균일하게 혼화한다. 이것에 적당량의 물을 가해, 니이더 중에서 날화하고, 직경 0.8mm의 스크리인에 의해 압출하고, 50℃의 통풍건조기 중에서 건조한다. 이것을 시후타에 의해서 정립하여 입제를 얻었다.70 parts of the compound of compound No. 3 are finely ground, 30 parts of clay is added thereto, mixed in a mixer to prepare a premix. 10 parts of this premix are mixed uniformly in a mixer together with 60 parts of clay and 30 parts of bentonite. Appropriate amount of water is added to this, and it is quenched in kneader, extruded with the screen of diameter 0.8mm, and dried in 50 degreeC ventilation dryer. This was established by Sifuta and granules were obtained.

[실시예 5]Example 5

[입제][Participation]

화합물 번호 4의 화합물 35부 및 S-(4-클로로벤질) N,N-디에틸티올카아바메이트 35부를 미세하게 분쇄하고, 여기에 화이트카아본 30부를 가해서 혼합기 중에서 혼화하여 프레믹스를 얻었다. 이 프레믹스 20부를 점토 50부 및 벤토나이트 30부와 함께 혼합기 중에서 균일하게 혼화한다. 여기에 적당량의 물을 가하고, 니이더 중에서 날화하고, 직경 0.8mm의 스크리인으로 압출하고, 50℃의 통풍건조기 중에서 건조한다. 이것을 시후타에 의해서 정립하여 혼합입제를 얻었다.35 parts of the compound of compound No. 4 and 35 parts of S- (4-chlorobenzyl) N, N-diethylthiol carbamate were finely ground, and 30 parts of white carbon was added thereto and mixed in a mixer to obtain a premix. 20 parts of this premix are mixed uniformly in a mixer together with 50 parts of clay and 30 parts of bentonite. Appropriate amount of water is added to this, it is quenched in kneader, extruded by the screen of diameter 0.8mm, and dried in 50 degreeC ventilation dryer. This was established by sifuta to obtain a mixed granule.

[실시예 6]Example 6

[수화제][Hydrating]

화합물 번호 18의 화합물 50부, 점토 29부, 규조토 10부, 화이트카아본 5부, 리그닌슬폰산나트륨 3부, 뉴우코올 1106(닛뽕유까자이사 상품명) 2부 및 폴리비닐알코올 1부를 혼합기 중에서 균일하게 혼합하고, 함마 밑에서 3회 분쇄하여 수화제를 얻었다.50 parts of the compound of compound No. 18, 29 parts of clay, 10 parts of diatomaceous earth, 5 parts of white carbonone, 3 parts of sodium lignin sulfonate, 2 parts of New Ucool 1106 (trade name of Nippon Yuka Corporation) and 1 part of polyvinyl alcohol in a mixer Mixed, and triturated three times under a hammer to obtain a hydrating agent.

[실시예 7]Example 7

[유제][emulsion]

화합물 번호 21의 화합물 20부, 키실렌 65부 및 파라콜 PS(닛뽕유까자이사 상품명) 15부를 혼합하고, 균일하게 용해시켜서 유제를 얻었다.20 parts of the compound of the compound number 21, 65 parts of xylene, and 15 parts of para-coll PS (Nippon Yuka Corporation) were mixed, and it melt | dissolved uniformly and obtained the oil agent.

이와 같이하여 조제된 본 발명의 제초제의 시험예를 다음에 열거한다. 또, 공시약제는 전기 실시예 6에 준해서 제조하고, 본 발명의 유효성분 화합물을 50% 함유하는 수화제를 사용했다.The test example of the herbicide of this invention prepared in this way is listed next. In addition, the starting reagent was prepared according to Example 6, and a hydrated agent containing 50% of the active ingredient compound of the present invention was used.

[시험예 1][Test Example 1]

[논 잡초침수토양처리시험][Paddy weed submerged soil treatment test]

표면적 45cm²의 폴리에틸렌계 폿트 3개(A,B,C라고 약칭함)에 논흙을 넣고, 폿트 A에 벼(품종:금낭풍) 2.5엽기의 묘를 1주(2본) 이식하고, 다년생 잡초의 대표예로서 올미의 괴경을 2개 심는다. 폿트 B에 광엽잡초의 대표예로서 물달개비, 밭뚝의풀, 등에풀의 각 종자를 흙과 잘 혼화한다. 또 쇠털골의 생육주를 1주 이식하고, 다년생잡초의 너도방동산이의 괴경을 폿트당 2개를 심었다. 폿트 C에는 협엽잡초의 대표예로서 대피 및 올챙이 고랭이의 각 종자를 흙과 잘 혼화한다. 또, 다년생 잡초의 벗풀의 괴경을 폿트당 2개 심는다. 폿트 A,B 및 C를 논 상태로서 3일간 온실 내에서 재배하고, 식물의 활착 후 공시약제의 현탁액을 폿트당 10cc씩 침수상태에서 토양처리했다. 처리 20일 후에 각 잡초에 대한 제초효과 및 벼에 대한 약해를 관찰판정했다. 그 결과를 제1표에 나타낸다. 단, 표 중에 있어서의 유효약량(g/a)은 각 식물의 생육저해 정도(식물체표면의 백화면적)가 70% 이상이 되는 최저약량을 나타낸다.Put the paddy soil into three polyethylene pots (abbreviated as A, B, and C) having a surface area of 45 cm ² , and transplant seedlings of 2.5 leaves of rice (variety: golden breeze) into pot A for 1 week (two), and perennial weeds As a representative example, two tubers of Olme are planted. As a representative example of broad weeds in pot B, each of the seeds of the cochlea, the grass of the grass and the back grass is mixed well with the soil. In addition, the growth liquor of the femur was transplanted for one week, and two tubers of perennial weeds were planted per pot. Pot C is a representative example of cotyledon weeds, and the seeds of the evacuation and tadpoles are well mixed with the soil. In addition, plant 2 tubers of perennial weeds per pot. Pots A, B and C were cultivated in a greenhouse for 3 days in a paddy state, and the plants were subjected to soil treatment in the submerged state by 10 cc per pot after suspension of plants. After 20 days of treatment, the herbicidal effect on each weed and the damage to rice were observed. The results are shown in the first table. However, the effective dose (g / a) in the table indicates the minimum dose such that the degree of growth inhibition (white surface area of the plant surface) of each plant is 70% or more.

[제1표][Table 1]

[시험예 2][Test Example 2]

[밭잡초발아전토양처리시험][Field weed germination soil treatment test]

표면적 150cm²의 폴리에틸제폿트에 밭흙을 넣고, 협엽잡초의 대표예로서 강피, 바랭이, 여우꼬리풀, 왕바랭이, 방동산이 및 광엽잡초의 대표예로서 냉이의 각 종자를 파종하여 흙을 덮었다.Field soil was put in a 150 cm ² surface polyethyl zepot, and each seed of a washer was sown as a representative example of bark, barley, fox tail grass, king breeze, Bangdongsan and broadleaf weeds as a representative example of a narrow weed.

별도로, 표면적 150cm²의 폴리에틸렌제 폿트에 밭흙을 넣고, 협엽잡초의 닭의장풀, 광엽 잡초의 별꽃, 왕개미자리, 개비름, 쇠비름, 명아주의 각 종자를 파종하여 흙을 덮었다.Separately, the soil was put in a polyethylene pot having a surface area of 150 cm ² , and each seed was sown by the seedlings of cotyledon weeds, broadleaf weeds, king trefoils, purslane, purslane and mallow.

양 폿트를 복토직후에 공시약제의 현탁액을 폿트당 10cc씩 토양표면에 처리했다. 처리 20일 후에 각 잡초에 대한 제초효과를 관찰했다. 그 결과를 제2표에 나타냈다. 단 판정기준은 시험예 1과 동일하며, 유효약량(g/a)으로 나타냈다.Immediately after both pots were covered, a suspension of coagent was treated on the soil surface at 10 cc per pot. Twenty days after the treatment, the herbicidal effect on each weed was observed. The results are shown in the second table. However, the criterion for determination was the same as in Test Example 1, and was represented by the effective dose (g / a).

[제2표][Table 2]

Claims (1)

하기 일반식(Ⅱ)의 화합물을 할로겐화제와 반응시킴을 특징으로 하는 하기 일반식(Ⅰ)의 피라졸론 유도체의 제조방법.A process for preparing a pyrazolone derivative of the general formula (I), characterized by reacting a compound of the general formula (II) with a halogenating agent.

상기 식에서, R₁은 수소원자 또는 저급알킬기를 나타내고, R₂는 저급알킬기 또는 저급 알케닐기를 나타내고, Y는 할로겐원자, 니트로기, 저급알킬기 또는 저급알콕시기를 나타내고, n는 0, 1, 2 또는 3의 정수로 나타내고, n이 2 또는 3일 때 Y는 서로 동일 또는 상이해도 좋으며 X는 할로겐 원자를 나타낸다.Wherein R ₁ represents a hydrogen atom or a lower alkyl group, R ₂ represents a lower alkyl group or a lower alkenyl group, Y represents a halogen atom, a nitro group, a lower alkyl group or a lower alkoxy group, n is 0, 1, 2 or It is represented by the integer of 3, and when n is 2 or 3, Y may mutually be same or different, and X represents a halogen atom.