KR810000802B1 - Preparing process for 4-benzoyl pyrazol derivatives and its aluminum salts - Google Patents

Preparing process for 4-benzoyl pyrazol derivatives and its aluminum salts Download PDF

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KR810000802B1
KR810000802B1 KR7600010A KR760000010A KR810000802B1 KR 810000802 B1 KR810000802 B1 KR 810000802B1 KR 7600010 A KR7600010 A KR 7600010A KR 760000010 A KR760000010 A KR 760000010A KR 810000802 B1 KR810000802 B1 KR 810000802B1
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dimethyl
hydroxypyrazole
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lower alkyl
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다까시 마쓰이
쥰조오 도비즈까
다꾸오 고노쓰네
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가와무라 요시부미
산교 가부시기 가이샤
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
    • C07D231/18—One oxygen or sulfur atom
    • C07D231/20—One oxygen atom attached in position 3 or 5
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
    • C07D231/18—One oxygen or sulfur atom
    • C07D231/20—One oxygen atom attached in position 3 or 5
    • C07D231/22—One oxygen atom attached in position 3 or 5 with aryl radicals attached to ring nitrogen atoms

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  • Organic Chemistry (AREA)
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  • Agronomy & Crop Science (AREA)
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Abstract

About 20 title compds. (I; R1 = lower alkyl, alkenyl; R2= lower alkyl; X = halogen, lower alkyl, alkoxy, nitro; n = 1-3) useful as herbicide, were prepd. by conversion of II in the presence of basic alkali metal salt or alkali earthmetal salt. Thus, 2.85 g 1,3-dimethyl-5-(2,4-dichlorobenzoyloxy)pyrazole and 2.5 g Na2CO3 were heated and stirred at 120-150oC, 30-60 min. 10 ml Isopropanol was added to the reactant and was heated for 60 min to give sodium1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-hydroxypyrazole.

Description

4-벤조일피라졸 유도체 및 그의 금속염의 제조방법4-benzoylpyrazole derivatives and preparation method thereof

본 발명은 일본국 특개소 50-126830호에 공개된 하기 일반식(Ⅰ)의 4-벤조일피라졸 유도체 및 그의 금속염의 제조방법에 관한 것이다.The present invention relates to a 4-benzoylpyrazole derivative of the following general formula (I) disclosed in Japanese Patent Laid-Open No. 50-126830 and a method for producing a metal salt thereof.

Figure kpo00001
Figure kpo00001

상기 식중에서, R1은 저급알킬기 또는 저급알케닐기를 나타내고, R2는 저급알킬기를 나타내고, X는 할로겐원자, 저급알킬기, 저급알콕시기 또는 니트로기를 나타내고, n는 1-3의 정수를 나타내며, n가 2 또는 3일때 X는 서로 동일 또는 상이해도 좋으며, 단 R1및 R2가 메틸기 일때 Xn이 2-클로로 또는 4-니트로는 안된다.Wherein R 1 represents a lower alkyl group or a lower alkenyl group, R 2 represents a lower alkyl group, X represents a halogen atom, a lower alkyl group, a lower alkoxy group or a nitro group, n represents an integer of 1-3, X may be the same or different from each other when n is 2 or 3, provided that Xn is not 2-chloro or 4-nitro when R 1 and R 2 are methyl groups.

본 발명의 방법에 의해서 얻어지는 전기 일반식(Ⅰ)의 화합물은 이하에 나타낸 바와 같이 호변이성체로서 존재하는 것이며, 이들의 이성체는 어느 것도 본 발명의 범위내에 포괄되는 것이다.The compounds of the general formula (I) obtained by the method of the present invention exist as tautomers as shown below, and all of these isomers are encompassed within the scope of the present invention.

Figure kpo00002
Figure kpo00002

(식중, R1, R2, X 및 n는 전술한 것과 동일함)Wherein R 1 , R 2 , X and n are the same as described above

전기 일반식(Ⅰ)에 있어서, R1으로 적합한 것으로는 메틸, 에틸, n-프로필 또는 이소프로필과 같은 탄소수 1-3개를 갖는 직쇄상 또는 측쇄상의 저급알킬기 특히 메틸기 또는 1-메틸-2-프로페닐, 2-메틸-2-프로페닐, 아릴, 2-부테닐 또는 3-부테닐과 같은 탄소수 3 또는 4개를 갖는 직쇄상 또는 측쇄상의 저급알케닐기 특히 아릴기를 나타낸다. R2로 적합한 것으로는 R1에 예시한 것과 동일한 탄소수 1-3개를 갖는 직쇄상 또는 측쇄상의 저급알킬기 특히 메틸기를 나타낸다. X로 적합한 것으로는 염소, 취소, 불소 또는 옥소와 같은 할로겐원자 특히 염소원자; 니트로기; 메틸, 에틸, n-프로필, 이소프로필, n-부틸, 이소부틸 또는 삼급-부틸과 같은 탄소수 1-4개를 갖는 직쇄상 또는 측쇄상의 저급알킬기 특히 메틸기 또는 메톡시, 에톡시, n-프로폭시, 이소프로폭시, n-부톡시 또는 이소부톡시와 같은 탄소수 1-4개를 갖는 직쇄상 또는 측쇄상의 저급알콕시기 특히 메톡시기를 나타낸다.In the above general formula (I), suitable as R 1 are linear or branched lower alkyl groups having 1 to 3 carbon atoms such as methyl, ethyl, n-propyl or isopropyl, especially methyl or 1-methyl-2- Linear or branched lower alkenyl groups having 3 or 4 carbon atoms such as propenyl, 2-methyl-2-propenyl, aryl, 2-butenyl or 3-butenyl, in particular an aryl group. Suitable as R 2 include a linear or branched lower alkyl group having 1 to 3 carbon atoms as illustrated in R 1, in particular a methyl group. Suitable X are halogen atoms such as chlorine, cancelled, fluorine or oxo, in particular chlorine atoms; Nitro group; 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, in particular methyl or methoxy, ethoxy, n-propoxy And linear or branched lower alkoxy groups having 1 to 4 carbon atoms such as isopropoxy, n-butoxy or isobutoxy, especially methoxy groups.

화합물의 생물학적 활성으로 보아서, 특히 적합한 화합물은 R1이 메틸기 또는 아릴기이고, R2가 메틸기이고, Xn이 2,4-디클로로 또는 2-클로로-4-니트로인 화합물이다.In view of the biological activity of the compounds, particularly suitable compounds are those wherein R 1 is a methyl group or an aryl group, R 2 is a methyl group and Xn is 2,4-dichloro or 2-chloro-4-nitro.

본 발명의 방법에 의해서 얻어지는 전기 일반식(Ⅰ)의 화합물의 금속염으로서는, 예를 들면, 리튬, 나트륨, 칼륨과 같은 알칼리금속의 이온 및 칼슘, 마그네슘과 같은 알칼리토류금속의 이온과의 염을 포함한다.Metal salts of the compounds of the general formula (I) obtained by the method of the present invention include, for example, salts with ions of alkali metals such as lithium, sodium, potassium and ions of alkaline earth metals such as calcium and magnesium. do.

본 발명의 방법에 의해서 얻어지는 전기 일반식(1)을 갖는 화합물 및 그의 금속염은, 제초제 또는 제초제 합성의 중간체로서 유용하다.Compounds having the general formula (1) obtained by the method of the present invention and metal salts thereof are useful as herbicides or intermediates of herbicide synthesis.

본 발명의 방법에 의해서 얻어지는 전기 일반식(Ⅰ)을 갖는 화합물 및 그의 금속염중, 대표적인 화합물을 이하에 기재한다. 단 본 발명은 이들의 예시에 의해서 한정되지 않는다.Representative compounds are described below among the compounds having the general formula (I) obtained by the method of the present invention and metal salts thereof. However, this invention is not limited by these illustrations.

(1) 1-에틸-3-메틸-4-(2,4-디클로로벤조일)-5-하이드록시피라졸 m.p. 176-177℃(1) 1-ethyl-3-methyl-4- (2,4-dichlorobenzoyl) -5-hydroxypyrazole m.p. 176-177 ℃

(2) 1,3-디메틸-4-(2,4-디클로로벤조일)-5-하이드록시피라졸 m.p. 165-166℃(2) 1,3-dimethyl-4- (2,4-dichlorobenzoyl) -5-hydroxypyrazole m.p. 165-166 ℃

(3) 1,3-디메틸-4-(2-브로모벤조일)-5-하이드록시피라졸 m.p. 154-156℃(3) 1,3-dimethyl-4- (2-bromobenzoyl) -5-hydroxypyrazole m.p. 154-156 ℃

(4) 1,3-디메틸-4-(3,4-디메톡시벤조일)-5-하이드록시피라졸 m.p. 154-155℃(4) 1,3-dimethyl-4- (3,4-dimethoxybenzoyl) -5-hydroxypyrazole m.p. 154-155 ℃

(5) 1,3-디메틸-4-(2-클로로-4-니트로벤조일)-5-하이드록시피라졸 m.p. 197-197.5℃(5) 1,3-dimethyl-4- (2-chloro-4-nitrobenzoyl) -5-hydroxypyrazole m.p. 197-197.5 ℃

(6) 1,3-디메틸-4-(3,4,5-트리메톡시벤조일)-5-하이드록시피라졸 m.p. 189-191℃(6) 1,3-dimethyl-4- (3,4,5-trimethoxybenzoyl) -5-hydroxypyrazole m.p. 189-191 ℃

(7) 1,3-디메틸-4-(2-니트로-4-클로로벤조일)-5-하이드록시피라졸 m.p. 223-224℃(7) 1,3-dimethyl-4- (2-nitro-4-chlorobenzoyl) -5-hydroxypyrazole m.p. 223-224 ℃

(8) 1-아릴-3-메틸-4-(2,4-디클로로벤조일)-5-하이드록시피라졸 m.p. 161-163℃(8) 1-aryl-3-methyl-4- (2,4-dichlorobenzoyl) -5-hydroxypyrazole m.p. 161-163 ℃

(9) 1,3-디메틸-4-(2-요오도벤조일)-5-하이드록시피라졸 m.p. 171-172℃(9) 1,3-dimethyl-4- (2-iodobenzoyl) -5-hydroxypyrazole m.p. 171-172 ℃

(10) 1,3-디메틸-4-(4-메틸벤조일)-5-하이드록시피라졸 m.p. 114-116℃(10) 1,3-dimethyl-4- (4-methylbenzoyl) -5-hydroxypyrazole m.p. 114-116 ℃

(11) 1,3-디메틸-4-(2-메톡시벤조일)-5-하이드록시피라졸 m.p. 162.5-163.5℃(11) 1,3-dimethyl-4- (2-methoxybenzoyl) -5-hydroxypyrazole m.p. 162.5-163.5 ℃

(12) 1,3-디메틸-4-(2,4-디클로로벤조일)-5-하이드록시피라졸 킬슘얌 m.p. 약 260℃(12) 1,3-dimethyl-4- (2,4-dichlorobenzoyl) -5-hydroxypyrazole chelium yam m.p. About 260 ℃

(13) 1,3-디메틸-4-(2-니트로벤조일)-5-하이드록시피라졸 m.p. 233-234℃(13) 1,3-dimethyl-4- (2-nitrobenzoyl) -5-hydroxypyrazole m.p. 233-234 ℃

(14) 1,3-디메틸-4-(4,5-디클로로벤조일)-5-하이드록시피라졸 m.p. 183-184℃(14) 1,3-dimethyl-4- (4,5-dichlorobenzoyl) -5-hydroxypyrazole m.p. 183-184 ℃

(15) 1,3-디메틸-4-(2,4-디클로로벤조일)-5-하이드록시피라졸 마그네슘염 m.p. 약 270℃(15) 1,3-dimethyl-4- (2,4-dichlorobenzoyl) -5-hydroxypyrazole magnesium salt m.p. About 270 ℃

(16) 1-에틸-3-메틸-4-(2-니트로-4-클로로벤조일)-5-하이드록시피라졸 m.p. 196-197℃(16) 1-ethyl-3-methyl-4- (2-nitro-4-chlorobenzoyl) -5-hydroxypyrazole m.p. 196-197 ℃

(17) 1,3-디메틸-4-(2,4-디클로로벤조일)-5-하이드록시피라졸 구리염 m.p. 300℃ 이상(17) 1,3-dimethyl-4- (2,4-dichlorobenzoyl) -5-hydroxypyrazole copper salt m.p. 300 ℃ or more

(18) 1,3-디메틸-4-(2,4-디클로로벤조일)-5-하이드록시피라졸 나트륨염 m.p. 300℃ 이상(18) 1,3-dimethyl-4- (2,4-dichlorobenzoyl) -5-hydroxypyrazole sodium salt m.p. 300 ℃ or more

(19) 1-메틸-3-n-프로필-4-(2-클로로벤조일)-5-하이드록시피라졸 m.p. 125-126℃(19) 1-methyl-3-n-propyl-4- (2-chlorobenzoyl) -5-hydroxypyrazole m.p. 125-126 ℃

(20) 1,3-디메틸-4-(2,4,5-트리클로로벤조일)-5-하이드록시피라졸 m.p. 156-157℃(20) 1,3-dimethyl-4- (2,4,5-trichlorobenzoyl) -5-hydroxypyrazole m.p. 156-157 ℃

본 발명의 방법에 의하면, 전기 일반식(Ⅰ)을 갖는 화합물 및 그의 금속염은 하기 일반식(Ⅱ)의 피라졸 유도체를 염기성 알칼리 금속염 또는 염기성 알칼리토류 금속염 존재하 전위 반응시켜 제조된다.According to the method of the present invention, a compound having the general formula (I) and a metal salt thereof are prepared by rearranged pyrazole derivatives of the following general formula (II) in the presence of a basic alkali metal salt or basic alkaline earth metal salt.

Figure kpo00003
Figure kpo00003

상기 식에서,Where

R1, R2, X 및 n는 전술한 바와 같다.R 1 , R 2 , X and n are as described above.

전기 일반식(Ⅰ)의 피라졸 유도체와 유사한 화합물인 1,3-디메틸-4-(2-클로로벤조일)-5-하이드록시 피라졸 및 1,3-디메틸-4-(4-니트로벤조일)-5-하이드록시피라졸은 공지의 화합물이며, 이들 공지 화합물의 제조방법으로서는 생석회 또는 트리에틸아민을 현탁시킨 디옥산, 피리딘, 디메틸포름아미드 또는 벤젠 중에서, 열시 1,3-디메틸피라졸론과 벤조일클로라이드를 반응시킴으로서, 1,3-디메틸피라졸론의 4위치를 벤조일화하는 방법이 제안되어 있다[이종환식 화합물의 화학 제8권, 722, 1972(Russian origin, 779, 1972)].1,3-dimethyl-4- (2-chlorobenzoyl) -5-hydroxy pyrazole and 1,3-dimethyl-4- (4-nitrobenzoyl), compounds similar to the pyrazole derivatives of the general formula (I) -5-Hydroxypyrazole is a known compound, and as a method for preparing these known compounds, 1,3-dimethylpyrazolone and benzoyl in dioxane, pyridine, dimethylformamide or benzene suspended in quicklime or triethylamine By reacting chloride, a method of benzoylation of the 4-position of 1,3-dimethylpyrazolone has been proposed (Chemical Vol. 8, 722, 1972 of heterocyclic compounds (Russian origin, 779, 1972)).

그러나, 이 종래법에 의하면 목적하는 화합물을 가장 좋은 수율로 제조할 수 있는 방법, 즉 생석회를 현탁시킨 디옥산 중에서 반응을 행하는 방법으로도 70-75% 정도이며, 또한 부산물로서 0-벤조일체가 생성하는 것이다. 또한 벤조일클로라이드 대신에 2,4-디클로로안식향산을 사용하여 이 종래법을 실시한 경우, 피라졸론의 4위치에서의 벤조일화가 진행하기 어렵고, 상당하는 전기 일반식(Ⅰ)의 화합물의 수율은 50% 이하이며, 다량의 2,4-디클로로안식향산이 유리하다.However, according to this conventional method, the method for producing the desired compound in the best yield, that is, the reaction in dioxane suspended in quicklime is also about 70-75%, and 0-benzoyl is used as a by-product. To generate. In addition, when this conventional method is carried out using 2,4-dichlorobenzoic acid instead of benzoyl chloride, benzoylation at the 4-position of pyrazolone is difficult to proceed, and the yield of the corresponding compound of the general formula (I) is 50% or less. And large amounts of 2,4-dichlorobenzoic acid are advantageous.

본 발명자 등은 4-벤조일피라졸 유도체의 공업적으로 유리한 제조방법에 대해서 여러가지 검토한 결과, 염기성 알칼리금속염 또는 염기성 알칼리토류금속염을 전기식(Ⅱ)으로 표시되는 화합물의 피라졸환의 4위치에서의 벤조일기의 전위 촉매로서 사용함으로써, 피라졸론환의 4위치를 직접 벤조일화하는 방법에 비해서 부산물의 생성이 적고, 또 양호한 수율로 목적물(Ⅰ) 및 그의 금속염을 얻는 방법을 발견하고 본 발명을 완성했다.The inventors of the present invention have conducted various studies on industrially advantageous methods for producing 4-benzoylpyrazole derivatives. As a result, the basic alkali metal salts or basic alkaline earth metal salts are selected from the benzo at the 4-position of the pyrazole ring of the compound represented by the formula (II). By using it as a potential catalyst of a diary, compared with the method of directly benzoylating the 4-position of a pyrazolone ring, the production | generation of the target object (I) and its metal salt was discovered and the present invention was completed by the favorable yield, and the present invention was completed.

본 발명의 방법을 실시함에 있어서, 반응은 전기 일반식(Ⅱ)을 갖는 화합물을 등몰 이상의 염기성 알칼리금속염 또는 염기성알칼리토류금속염의 존재하에 가열 교반함으로써 용이하게 수행된다.In carrying out the method of the present invention, the reaction is easily carried out by heating and stirring the compound having the general formula (II) in the presence of equimolar or more basic alkali metal salts or basic alkaline earth metal salts.

또, 본 명세서에 있어서, 염기성 알칼리금속염 및 알칼리토류금속염은 수용액으로 했을때 알칼리성을 나타내는 알칼리금속 또는 알칼리토류금속 화합물을 의미하는 것이며, 약산과 강염기와의 염만이 아니고 수산화물, 시안아미드 및 알콕시드 까지도 포함한다. 예를 들면, 탄산나트륨, 탄산칼륨과 같은 탄산염; 수산화칼슘, 수산화마그네슘과 같은 수산화물; 칼슘시안아미드와 같은 시안아미드류; 나트륨메톡사이드, 칼륨에톡사이드, 나트륨이소프로폭사이드, 칼륨-tert-부톡사이드와 같은 알콕사이드류 등이 포함된다. 또 반응용매 중에서 이들의 「염기성염」이 형성되는 것과 같은 반응계를 사용해도 좋다. 예를 들면, 이소프로파놀 중에 금속나트륨을 용해시키면, 나트륨이소프로폭사이드를 함유하는 용액이 얻어지지만, 이와 같은 알코올용액을 그대로 반응용매로서 사용할 수도 있다.In the present specification, basic alkali metal salts and alkaline earth metal salts refer to alkali metals or alkaline earth metal compounds exhibiting alkalinity when used as aqueous solutions, and not only salts of weak acids and strong bases but also hydroxides, cyanamides and alkoxides. Include. For example, carbonates, such as sodium carbonate and potassium carbonate; Hydroxides such as calcium hydroxide and magnesium hydroxide; Cyanamides such as calcium cyanamide; Alkoxides such as sodium methoxide, potassium ethoxide, sodium isopropoxide, potassium-tert-butoxide and the like. Moreover, you may use the reaction system like these "basic salts" formed in a reaction solvent. For example, when metal sodium is dissolved in isopropanol, a solution containing sodium isopropoxide is obtained, but such an alcohol solution can also be used as a reaction solvent as it is.

반응은 불활성 존재하 또는 부존재하에서 행하지만 반응을 원활히 행하기 위하여는 용매를 사용하는 방법이 바람직하다. 사용되는 용매로서는 본 반응에 관여하지 않으면 특히 한정할 필요는 없으며, 예를 들면 이소프로파놀, 삼급-부타놀 등의 저급알코올류; 디옥산, 디이소프로필에테르, 테트라하이드로푸란-디옥산, 테트라하이드로푸란 등의 에테르류 또는 이들의 혼합용제; 메틸에틸케톤, 디에틸케톤 등의 케톤류 등을 들 수 있고, 특히 저급알코올류 및 에테르류가 적합하게 사용된다.The reaction is carried out in the presence of an inert or in the absence, but in order to perform the reaction smoothly, a method using a solvent is preferable. As a solvent used, if it does not participate in this reaction, it does not need to specifically limit, For example, Lower alcohols, such as isopropanol and tert-butanol; Ethers such as dioxane, diisopropyl ether, tetrahydrofuran-dioxane and tetrahydrofuran or a mixed solvent thereof; Ketones, such as methyl ethyl ketone and a diethyl ketone, etc. are mentioned, In particular, lower alcohols and ethers are used suitably.

단위촉매로서 사용되는 「염기성염」은, 전기 식의 화합물 1몰에 대해서 등몰이상, 바람직하기로는 약 1.0-0.6배몰, 특히 2.0-3.0배 몰로서 사용되고, 또 이들의 염류는 가능한한 미세한 입자로 분쇄하여 전기 식(Ⅱ)의 화합물과 혼화가열하여 용융 교반하던가 혹은 전술한 불활성 용매와의 공존하에서 80-200℃, 바람직하기로는 100-160℃에서 가열 교반한다. 반응 시간은 통상 약 30분으로 부터 약 5시간을 요한다.The “basic salt” used as the unit catalyst is used as equimolar or more, preferably about 1.0-0.6 times molar, especially 2.0-3.0 times mole, per mole of the above-described compound, and their salts are as fine particles as possible. The mixture is pulverized, mixed with the compound of formula (II), heated and melted or stirred at 80-200 ° C, preferably 100-160 ° C, in the presence of the aforementioned inert solvent. The reaction time usually requires about 5 hours from about 30 minutes.

용제의 부 존재하에서는 일반적으로 전위 반응의 진행과 더불어 반응 혼합물이 고화하여, 교반이 곤란하게 되는 것이 많다. 이와 같은 경우에는 전술한 불활성용매의 적당량을 첨가하는 것이 적합하다. 중요한 것은 전기 식(Ⅱ)의 화합물과 전위 촉매와의 촉매를 충분히 보유함에 있고, 용매의 사용은 가능한한 소량으로 멈추는 것이 바람직하다. 또 미량의 수분의 존재는 반응을 촉진시키기 때문에 바람직하지만, 동시에 유리의 안식향산의 부생은 피할 수 없으므로 용매중의 수분 함량은 1% 이내로 하는 것이 바람직하다.In the presence of a solvent, in general, the reaction mixture is solidified along with the advancement of the dislocation reaction, which makes it difficult to stir. In such a case, it is suitable to add an appropriate amount of the above-mentioned inert solvent. It is important to sufficiently retain the catalyst of the compound of formula (II) and the potential catalyst, and the use of the solvent is preferably stopped in a small amount as much as possible. The presence of a small amount of water is preferable because it promotes the reaction, but at the same time, the by-product of the benzoic acid of the glass cannot be avoided, so the water content in the solvent is preferably within 1%.

반응 종료 후 본 발명의 방법의 목적 화합물은 상법에 의해서 반응혼합물로 부터 채취된다.After completion of the reaction, the target compound of the method of the present invention is taken from the reaction mixture by a conventional method.

예를 들면, 반응 종료 후 반응 혼합물로 부터 용매를 유거함으로써 목적 화합물의 전위촉매로서 사용한 알칼리금속 혹은 알칼리토류금속의 염으로서 얻어진다. 수득된 이들의 염류는, 통상 산을 가해서 pH 3이하로 조정함으로써 목적 화합물을 유리의 상태로 단리할 수 있다. 이것은 또 재결정법 등의 상법에 의해서 정제하여 그의 순수한 제품을 얻을 수 있다.For example, after completion | finish of reaction, a solvent is distilled off from the reaction mixture, and it is obtained as a salt of the alkali metal or alkaline earth metal used as a potential catalyst of a target compound. These obtained salts can normally isolate a target compound in a free state by adding an acid and adjusting to pH3 or less. This can also be purified by ordinary methods such as recrystallization to obtain its pure product.

또, 전기식(Ⅱ)의 원료 화합물은 공지의 방법 예를 들면, 일본 특허청 공개특허공보 특허공개37776호 1975 명세서에 기재한 방법에 준해서 1,3-디치환피라졸론과 치환벤조일클로라이드를 반응시킴으로서 용이하게 제조된다.The raw material compound of formula (II) is reacted with 1,3-disubstituted pyrazolone and substituted benzoyl chloride according to a known method, for example, the method described in JP Patent Application Publication No. 37776 1975. It is easily manufactured.

다음에 실시예를 들어서 본 발명의 방법을 더 구체적으로 설명한다.Next, the method of the present invention will be described in more detail with reference to Examples.

[실시예 1]Example 1

1,3-디메틸-4-(2,4-디클로로벤조일)-5-하이드록시피라졸1,3-dimethyl-4- (2,4-dichlorobenzoyl) -5-hydroxypyrazole

(1) 1,3-디메틸-5-(2,4-디클로로벤조일옥시) 피라졸 2.85g 및 탄산나트륨(무수) 2.5g을 혼화하고, 가열한다. 결정을 용융(약 100℃에서 용해함)한 후, 120-150℃에서 반응물이 고화할 때까지 교반한다(약 30-60분으로 고화). 이어서 이소프로파놀 10ml를 가해서 또 60분간 가열교반한다. 냉각후 1,3-디메틸-4-(2,4-디클로로벤조일)-5-하이드록시피라졸의 나트륨염이 석출한다. 반응 혼합물에 6N 염산용액 10ml 및 벤젠 30ml를 가해서 교반하고, 고형물을 용해한 후 벤젠층을 분취, 농축하여 석출하는 결정을 메타놀로 세정하면 융점 165-166℃를 갖는 담황색 결정의 목적 화합물 2.28g이 얻어진다. 수율 80%(1) 2.85 g of 1,3-dimethyl-5- (2,4-dichlorobenzoyloxy) pyrazole and 2.5 g of sodium carbonate (anhydrous) are mixed and heated. The crystals are melted (dissolved at about 100 ° C.) and then stirred at 120-150 ° C. until the reaction solidifies (solidified at about 30-60 minutes). Subsequently, 10 ml of isopropanol are added, and the mixture is heated and stirred for 60 minutes. After cooling, the sodium salt of 1,3-dimethyl-4- (2,4-dichlorobenzoyl) -5-hydroxypyrazole precipitates. 10 ml of 6N hydrochloric acid solution and 30 ml of benzene were added to the reaction mixture, the solid was dissolved, the benzene layer was separated, concentrated and precipitated, and the precipitated crystals were washed with methanol to obtain 2.28 g of the target compound as a pale yellow crystal having a melting point of 165-166 ° C. Lose. Yield 80%

원소분석치(%) : C12H10Cl2N2O2 Elemental Analysis Value (%): C 12 H 10 Cl 2 N 2 O 2

계산치 : C, 50.55; H, 3.54; N, 9.82; Cl, 24.87Calculated: C, 50.55; H, 3.54; N, 9.82; Cl, 24.87

실험치 : C, 50.70; H, 3.52; N, 9.86; Cl, 24.77Experimental Value: C, 50.70; H, 3.52; N, 9.86; Cl, 24.77

(2) 실시예 1의 (1)에 있어서, 탄산나트륨 2.5g을 사용하는 대신에 나트륨메톡사이드 1.0g 및 이소프로파놀 5ml를 사용하는 것 이외는 실시예 1의 (1)과 동일하게 반응을 행하여 반응 후의 처리를 하면 목적화합물이 71%의 수율로 얻어진다.(2) In Example 1 (1), it reacts like Example 1 (1) except using 1.0 g of sodium methoxides and 5 ml of isopropanol instead of using 2.5 g of sodium carbonates, The treatment after the reaction yields the target compound in a yield of 71%.

(3) 실시예 1의 (1)에 있어서, 탄산나트륨 2.5g을 사용하는 대신에 탄산칼륨 3.0g을 사용하는 것 이외는 실시예 1의 (1)과 동일하게 반응을 행하여 반응 후의 처리를 하면 목적 화합물이 80%의 수율로 얻어진다.(3) In Example (1) of Example 1, except that instead of using 2.5 g of sodium carbonate, 3.0 g of potassium carbonate is used, the reaction is carried out in the same manner as in Example 1 (1), and the treatment after the reaction is carried out. The compound is obtained in a yield of 80%.

(1)(2)(3)에서 얻어진 화합물의 적외 흡수 스펙트럼은 모두 일치했다.The infrared absorption spectra of the compound obtained in (1) (2) (3) were all consistent.

또, 공지의 방법 즉, 1,3-대메틸피라졸론과 2,4-디클로로안식향산클로라이드를 출발원료로 하고, 수산화칼슘 1.0g을 사용해서 벤조일화를 실시한 결과(악타, 케미카, 스칸디나비카 제13권 1668페이지 기재의 방법에 준함), 피라졸론환의 4위치의 벤조일화의 수율은 50%이하 이고, 다량의 2,4-디클로로안식향산의 부생이 인정되었다.In addition, a known method, i.e., 1,3-methylpyrazolone and 2,4-dichlorobenzoic acid chloride, was used as a starting material, and benzoylation was performed using 1.0 g of calcium hydroxide (Acta, Chemica, Scandinavian Chemicals). 13, page 1668), the yield of benzoylation in the 4-position of the pyrazolone ring was 50% or less, and a large amount of by-product of 2,4-dichlorobenzoic acid was recognized.

[실시예 2]Example 2

1,3-디메틸-4-(4-메틸벤조일)-5-하이드록시피라졸.1,3-dimethyl-4- (4-methylbenzoyl) -5-hydroxypyrazole.

1,3-디메틸-5-(4-메틸벤조일옥시) 피라졸 2.3g 탄산나트륨(무수) 2.5g 및 이소프로파놀 5ml를 사용해서 실시예1의 (1)과 동일하게 반응을 행하여 반응후의 처리를 하면 114-116℃를 갖는 담황색 프리즘상 결정의 목적화합물 1.2g이 얻어진다. 수율 52%1,3-dimethyl-5- (4-methylbenzoyloxy) pyrazole 2.3 g Sodium carbonate (anhydrous) 2.5 g and 5 ml of isopropanol were reacted in the same manner as in Example 1 (1), and the treatment after the reaction was carried out. 1.2 g of the target compound of the pale yellow prism phase crystal having a lower surface of 114-116 ° C. was obtained. Yield 52%

원소분석치(%) : C13H14N2O2 Elemental Analysis Value (%): C 13 H 14 N 2 O 2

계산치 : C, 67.81; H, 6.28; N, 12.17Calculated: C, 67.81; H, 6. 28; N, 12.17

실험치 : C, 67.50; H, 6.13; N, 12.21Experimental Value: C, 67.50; H, 6. 13; N, 12.21

[실시예 3]Example 3

1,3-디메틸-4-(3,4,5-트리메톡시벤조일)-5-하이드록시피라졸1,3-dimethyl-4- (3,4,5-trimethoxybenzoyl) -5-hydroxypyrazole

1,3-디메틸-5-(3,4,5-트리메톡시벤조일) 옥시피라졸 3.06g 및 수산화칼슘 0.75g을 사용해서 실시예1의 (1)과 동일하게 반응을 행하여 반응 후의 처리를 하면 융점 189-191℃를 갖는 무색프리즘결정의 목적화합물 1.7g이 얻어진다. 수율55%When the reaction is carried out in the same manner as in Example 1 (1) using 3.06 g of 1,3-dimethyl-5- (3,4,5-trimethoxybenzoyl) oxypyrazole and 0.75 g of calcium hydroxide, 1.7 g of the target compound of the colorless prism crystal having a melting point of 189-191 ° C are obtained. Yield 55%

원소분석치(%) : C15H18N2O5 Elemental Analysis Value (%): C 15 H 18 N 2 O 5

계산치 : C, 58.82; H, 5.92; N, 9.15Calculated: C, 58.82; H, 5.92; N, 9.15

실험치 : C, 58.69; H, 5.88; N, 9.26Experimental Value: C, 58.69; H, 5.88; N, 9.26

[실시예 4]Example 4

1,3-디메틸-4-(2-니트로-4-클로로벤조일)-5-하이드록시피라졸1,3-dimethyl-4- (2-nitro-4-chlorobenzoyl) -5-hydroxypyrazole

1,3-디메틸-5-(2-니트로-4-클로로벤조일옥시) 피라졸 2.96g 및 수산화칼슘 0.75g을 사용해서 실시예 1의 (1)과 동일하게 반응을 행하여 반응 후의 처리를 하면 융점 223-224℃를 갖는 담황색 결정의 목적 화합물 1.57g이 얻어진다. 수율53%The reaction was carried out in the same manner as in Example 1 (1) using 2.96 g of 1,3-dimethyl-5- (2-nitro-4-chlorobenzoyloxy) pyrazole and 0.75 g of calcium hydroxide, and the treatment after the reaction was carried out. 1.57 g of the target compound of the pale yellow crystal having -224 ° C are obtained. Yield 53%

원소분석치(%) : C12H10N3O4ClElemental Analysis Value (%): C 12 H 10 N 3 O 4 Cl

계산치 : C, 48.75; H, 3.41; N, 14.21; Cl, 11.99Calculated: C, 48.75; H, 3.41; N, 14. 21; Cl, 11.99

실험치 : C, 48.89; H, 3.52; N, 14.27; Cl, 11.92Experimental Value: C, 48.89; H, 3.52; N, 14.27; Cl, 11.92

Claims (1)

하기 일반식(Ⅰ)의 화합물을 제조하는 방법에 있어서, 하기 일반식(Ⅱ)의 피라졸유도체를 염기성 알칼리금속염 또는 염기성 토류금속염의 존재하에 전위반응 시킴을 특징으로 하는 하기 일반식 4-벤조일 피라졸 유도체 및 그의 금속염의 제조방법.In the process for preparing the compound of the general formula (I), the pyrazole derivative of the general formula (II) is subjected to a potential reaction in the presence of a basic alkali metal salt or a basic earth metal salt. Method for preparing sol derivatives and metal salts thereof.
Figure kpo00004
Figure kpo00004
 상기 식에서, R1은 저급알킬기 또는 저급 알케닐기를 나타내고, R2는 저극 알킬기를 나타내며, X는 할로겐원자, 저급알킬기, 저급알콕시기 또는 니트로기를 나타내고, n이 2 또는 3일때, X는 서로 같거나 다르고, 다만 R1및 R2가 모두 메틸기인 경우 Xn이 2-클로로 또는 4-니트로는 아니다.In the formula, R 1 represents a lower alkyl group or a lower alkenyl group, R 2 represents a lower polar alkyl group, X represents a halogen atom, a lower alkyl group, a lower alkoxy group or a nitro group, and when n is 2 or 3, X is the same as each other. Or different, provided that when R 1 and R 2 are both methyl groups Xn is not 2-chloro or 4-nitro.
KR7600010A 1976-01-06 1976-01-06 Preparing process for 4-benzoyl pyrazol derivatives and its aluminum salts KR810000802B1 (en)

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