KR20030049024A - A method of preparing oxaziclomefone or derivative thereof - Google Patents

A method of preparing oxaziclomefone or derivative thereof Download PDF

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KR20030049024A
KR20030049024A KR1020010079094A KR20010079094A KR20030049024A KR 20030049024 A KR20030049024 A KR 20030049024A KR 1020010079094 A KR1020010079094 A KR 1020010079094A KR 20010079094 A KR20010079094 A KR 20010079094A KR 20030049024 A KR20030049024 A KR 20030049024A
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compound
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김지영
최태근
박영석
김윤철
박호진
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주식회사 코오롱
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
    • C07D265/06—1,3-Oxazines; Hydrogenated 1,3-oxazines not condensed with other rings
    • C07D265/08—1,3-Oxazines; Hydrogenated 1,3-oxazines not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D265/10—1,3-Oxazines; Hydrogenated 1,3-oxazines not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with oxygen atoms directly attached to ring carbon atoms
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/86—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3

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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
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  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Abstract

PURPOSE: A process for preparing oxaziclomefone or derivatives thereof are provided, thereby simply and cheaply preparing oxaziclomefone or derivatives thereof without producing any by-products. CONSTITUTION: A process for preparing oxaziclomefone or derivatives thereof comprises the steps of: (a) reacting a benzene compound with magnesium, then reacting the reaction product with a ketone compound to prepare a compound of formula(1); (b) reacting the compound of formula(1) with a phenylacetonitrile compound of formula(2) under acid catalyst to prepare a compound of formula(3); (c) reacting the compound of formula(3) with sodium alkoxide and alkylacetate to prepare a compound of formula(4); and (d) reacting the compound of formula(4) with acid and at least one aldehyde compound selected from para-formaldehyde and formalin to prepare oxaziclomefone of formula(5) or derivatives thereof, wherein R1 and R2 are independently alkyl having carbon number of 1 to 6; X is halogen; Y is halogen or alkyl having carbon number of 1 to 6; n is an integer of 0 to 3; and m is 0 or 1.

Description

옥사지클로메폰 또는 그 유도체의 제조방법{A METHOD OF PREPARING OXAZICLOMEFONE OR DERIVATIVE THEREOF}A method for producing oxazilomethone or derivatives thereof {A METHOD OF PREPARING OXAZICLOMEFONE OR DERIVATIVE THEREOF}

본 발명은 옥사지클로메폰 또는 그 유도체의 제조방법에 관한 것으로, 보다 상세하게는 경제적이며, 부산물이 적은 옥사지클로메폰 또는 그 유도체의 제조방법에 관한 것이다.The present invention relates to a method for producing oxaziclomethone or a derivative thereof, and more particularly, to a method for producing oxaziclomethone or a derivative thereof which is economical and has less by-products.

옥사지클로메폰은 주로 제초제로 사용되고 있는 화합물로 하기 구조식을 가지는 3-[1-(3,5-디클로로페닐)-1-메틸에틸]-3,4-디하이드로-6-메틸-5-페닐-2H-1,3-옥사진-4-온이다:Oxaziclomethone is a compound mainly used as a herbicide and has 3- [1- (3,5-dichlorophenyl) -1-methylethyl] -3,4-dihydro-6-methyl-5-phenyl having the following structural formula: -2 H -1,3-oxazin-4-one is:

옥사지클로메폰의 제조방법으로는 CN 이중결합을 가지는 화합물에 대하여 디케텐류, 2-디아조-1,3-디케톤류, 아디핀산 디클로라이드류, 2,3-디하이드로퓨란-2,3-디온류, 1,3-디옥시-4-온 유도체 등을 반응시켜 제조하는 방법 등이 알려져 있다. 그러나 이들 반응화합물들은 각각 문제점들이 지적되고 있다. 예를 들어 디케텐류와 2-디아조-1,3-디케톤류는 불안정하여 취급, 운송이 어렵고, 아디핀산 디클로라이드류의 경우에는 생성물의 골격이 한정되어 있고, 2,3-디하이드로퓨란-2,3-디온류는 합성비용이 비싸 경제적이지 못하다.As a method for preparing oxazilomethone, diketenes, 2-diazo-1,3-diketones, adipic acid dichlorides, and 2,3-dihydrofuran-2,3- relative to a compound having a CN double bond The method of making diones, a 1, 3- dioxy-4-one derivative, etc. by making it react is known. However, each of these reactive compounds has problems. For example, diketenes and 2-diazo-1,3-diketones are unstable and difficult to handle and transport. In the case of adipic acid dichlorides, the skeleton of the product is limited and 2,3-dihydrofuran- 2,3-diones are expensive and not economical.

이러한 문제를 해결하기 위하여 일본특허공개 평7-101946호에는 특정 화학식을 가지는 에스테르 화합물과 이민류의 화합물을 반응시켜 옥사지클로메폰을 경제적으로 제조하는 방법이 기재되어 있다. 상기 일본특허공개 평7-101946호에 기재된 바람직한 실시예에 따른 제조공정은 에틸 아세토페닐아세테이트(EAPA)와 3,5-디클로로페닐디메틸 이민(DCIM)을 각각 제조한 후 이를 반응시켜 옥사지클로메폰을 제조하는 방법이다. 이를 하기 반응식 1에 나타내었다:In order to solve this problem, Japanese Patent Application Laid-open No. Hei 7-101946 describes a method for economically producing oxazilomepon by reacting an ester compound having a specific chemical formula with an imine compound. In the manufacturing process according to the preferred embodiment described in Japanese Patent Application Laid-Open No. 7-101946, ethyl acetophenyl acetate (EAPA) and 3,5-dichlorophenyldimethyl imine (DCIM) are prepared, respectively, and then reacted with the oxazilomethone. It is a method of manufacturing. This is shown in Scheme 1:

[반응식 1]Scheme 1

상기 일본특허공개 평7-101946호의 옥사지클로메폰의 제조공정은 반응물인 EAPA와 같은 에스테르계 화합물을 증류하여 정제하는 공정을 거쳐야 하는데 이 공정이 매우 까다롭다. 최종 생성물인 옥사지클로메폰을 정제하는 과정중 생기는 불순물을 제거하기 어렵다는 문제점도 발생한다. 또한 반응 공정도 총 6단계를 거쳐야 하므로 공정시간이 오래 걸린다는 문제점도 있다.Oxyclomethone production process of Japanese Patent Application Laid-Open No. 7-101946 requires a process of distilling and purifying an ester compound such as EAPA, which is a reactant, which is very difficult. There is also a problem that it is difficult to remove impurities generated during the purification of the final product of oxazilomethone. In addition, the reaction process also has to go through a total of six steps, there is a problem that takes a long time.

본 발명은 상기한 문제점을 해결하기 위한 것으로서, 본 발명의 목적은 반응공정이 짧고 간단하며, 부산물이 생성되지 않는 옥사지클로메폰의 제조방법을 제공하기 위한 것이다.The present invention has been made to solve the above problems, and an object of the present invention is to provide a method for preparing an oxazilomethone in which the reaction process is short and simple and by-products are not produced.

상기 목적을 달성하기 위하여, 본 발명은 하기 반응식 2에 나타낸 바와 같이 하기 화학식 (1)의 벤젠계 화합물과 마그네슘을 반응시킨 후 케톤류 화합물과 반응시켜 하기 화학식 (2)의 화합물을 제조하는 단계; 상기 화학식 (2)의 화합물과 화학식 (3)의 화합물을 산촉매하에서 반응시켜 하기 화학식 (4)의 화합물을 제조하는 단계; 상기 화학식 (4)의 화합물을 소듐 알콕사이드와 알킬 아세테이트를 반응시켜 하기 화학식 (5)의 화합물을 제조하는 단계; 및 상기 화학식 (5)의 화합물을 파라포름알데이드 및 포르말린으로 이루어진 군에서 선택되는 적어도 하나의 알데히드계 화합물 및 산과 반응시켜 하기 화학식 (6)의 옥사지클로메폰 또는 그 유도체를 얻는 단계를 포함한다: In order to achieve the above object, the present invention comprises the steps of preparing a compound of formula (2) by reacting a benzene-based compound of formula (1) and magnesium and then a ketone compound as shown in Scheme 2; Preparing a compound of formula (4) by reacting the compound of formula (2) with a compound of formula (3) under an acid catalyst; Reacting the compound of formula (4) with sodium alkoxide and alkyl acetate to prepare a compound of formula (5); And reacting the compound of formula (5) with at least one aldehyde-based compound and acid selected from the group consisting of paraformaldehyde and formalin to obtain oxazilomepon or a derivative thereof of formula (6) :

[반응식 2]Scheme 2

상기 식에서 R1및 R2는 각각 독립적으로 탄소수 1 내지 6의 알킬기이고, X는 할로겐이며, Y는 할로겐기 또는 탄소수 1 내지 6의 알킬기이며, n은 0 내지 3의 정수이고, m은 0 또는 1이다.Wherein R 1 and R 2 are each independently an alkyl group having 1 to 6 carbon atoms, X is a halogen, Y is a halogen group or an alkyl group having 1 to 6 carbon atoms, n is an integer of 0 to 3, m is 0 or 1

이하 본 발명을 상세하게 설명한다.Hereinafter, the present invention will be described in detail.

본 발명의 옥사지클로메폰의 제조공정중 전체 4단계의 공정으로 이루어진다.It consists of a total of four steps of the manufacturing process of the oxaji-clomethone of the present invention.

첫 번째 공정으로 벤젠계 화합물과 마그네슘을 반응시킨 후 케톤류 화합물과 반응시켜 하기 화학식 (1)의 화합물을 제조한다:In the first process, a benzene compound and a magnesium are reacted with a ketone compound to prepare a compound of formula (1):

화학식 (1)Formula (1)

상기 화학식 (1)에서 R1및 R2는 각각 독립적으로 탄소수 1 내지 6의 알킬기, 바람직하게는 메틸기이고, X는 할로겐이며, n은 0 내지 3의 정수이다.In Formula (1), R 1 and R 2 are each independently an alkyl group having 1 to 6 carbon atoms, preferably a methyl group, X is a halogen, and n is an integer of 0 to 3.

상기 벤젠계 화합물로는 하기 화학식 (1a)로 나타내어지는 할로벤젠이 바람직하게 사용될 수 있으며, 바람직한 예로는 1-브로모-3,5-디클로로벤젠, 1,3,5-트리클로로벤젠 등이 있다:As the benzene compound, halobenzene represented by the following general formula (1a) may be preferably used, and preferred examples thereof include 1-bromo-3,5-dichlorobenzene, 1,3,5-trichlorobenzene, and the like. :

화학식 (1a)Formula (1a)

상기 화학식 (1a)에서 X와 n은 상기 화학식 (1)에서와 같다.In Formula (1a), X and n are the same as in Formula (1).

상기 마그네슘은 벤젠계 화합물 1 당량에 대하여 0.9 내지 1.1 당량을 사용하는 것이 바람직하며, 반응온도는 0 내지 50℃인 것이 바람직하다.The magnesium is preferably used in the amount of 0.9 to 1.1 equivalents based on 1 equivalent of the benzene compound, and the reaction temperature is preferably 0 to 50 ° C.

상기 케톤류 화합물로는 디메틸 케톤, 메틸에틸 케톤, 디에틸 케톤 등이 바람직하게 사용될 수 있으며, 이에 한정되는 것은 아니다.As the ketone compound, dimethyl ketone, methyl ethyl ketone, diethyl ketone, or the like may be preferably used, but is not limited thereto.

두 번째 공정으로 상기 화학식 (1)의 화합물과 하기 화학식 (2)의 페닐아세토니트릴계 화합물을 산촉매하에서 반응시켜 하기 화학식 (3)의 화합물을 제조한다:In a second process, the compound of formula (1) is reacted with the phenylacetonitrile compound of formula (2) under an acid catalyst to prepare a compound of formula (3):

화학식 (2)Formula (2)

상기 화학식 (2)에서 Y는 할로겐기 또는 탄소수 1 내지 6의 알킬기이며, m은 0 또는 1이다.In Formula (2), Y is a halogen group or an alkyl group having 1 to 6 carbon atoms, and m is 0 or 1.

화학식 (3)Formula (3)

상기 화학식 (3)에서 R1, R2, X 및 n은 상기 화학식 (1)에서와 같고, Y와 m은 상기 화학식 (2)에서와 같다.In Formula (3), R 1 , R 2 , X and n are the same as in Formula (1), and Y and m are the same as in Formula (2).

상기 산촉매로는 염산, 황산, 아세트산 등이 바람직하게 사용된다. 상기 산촉매는 상기 화학식 (1)의 화합물 1 당량에 대하여 0.01 내지 0.5 당량을 사용하는 것이 바람직하며, 반응온도는 -20 내지 40℃인 것이 바람직하다.As the acid catalyst, hydrochloric acid, sulfuric acid, acetic acid and the like are preferably used. The acid catalyst is preferably used in an amount of 0.01 to 0.5 equivalents based on 1 equivalent of the compound of formula (1), and the reaction temperature is preferably -20 to 40 ° C.

세 번째 공정으로 상기 화학식 (3)의 화합물을 소듐 알콕사이드와 알킬아세테이트를 반응시켜 하기 화학식 (4)의 화합물을 제조한다:In a third process, the compound of formula (3) is reacted with sodium alkoxide and alkyl acetate to prepare a compound of formula (4):

화학식 (4)Formula (4)

상기 화학식 (4)에서 R1, R2, X 및 n은 상기 화학식 (1)에서와 같고, Y와 m은 상기 화학식 (2)에서와 같다.In Formula (4), R 1 , R 2 , X and n are the same as in Formula (1), and Y and m are the same as in Formula (2).

상기 소듐 알콕사이드는 상기 화학식 (3)의 화합물 1 당량에 대하여 1.1 내지 3 당량을 사용하는 것이 바람직하며, 반응온도는 0 내지 50℃인 것이 바람직하다.The sodium alkoxide is preferably used in the amount of 1.1 to 3 equivalents based on 1 equivalent of the compound of formula (3), and the reaction temperature is preferably 0 to 50 ° C.

네 번째 공정으로 상기 화학식 (4)의 화합물을 파라포름알데이드(HO(CH2O)xH) 및 포르말린으로 이루어진 군에서 선택되는 적어도 하나의 알데히드계 화합물 및 산과 반응시켜 하기 화학식 (5)의 옥사지클로메폰 또는 그 유도체를 얻는다:In a fourth process, the compound of formula (4) is reacted with at least one aldehyde compound and an acid selected from the group consisting of paraformaldehyde (HO (CH 2 O) x H) and formalin to Obtain oxazilomethone or its derivatives:

화학식 (5)Formula (5)

상기 화학식 (5)에서 R1, R2, X 및 n은 상기 화학식 (1)에서와 같고, Y와 m은 상기 화학식 (2)에서와 같다.In Formula (5), R 1 , R 2 , X and n are the same as in Formula (1), and Y and m are the same as in Formula (2).

상기 알데히드계 화합물은 상기 화학식 (4)의 화합물 1 당량에 대하여 1 내지 10 당량의 양으로 사용되는 것이 바람직하며, 2 내지 3.5 당량으로 사용되는 것이 더 바람직하다. 상기 산으로는 염산, 황산, 아세트산 등이 사용가능하며, 이들중 염산을 사용하는 것이 바람직하다. 반응온도는 50 내지 100℃인 것이 바람직하며, 70 내지 80℃인 것이 더 바람직하다.The aldehyde-based compound is preferably used in an amount of 1 to 10 equivalents, more preferably 2 to 3.5 equivalents, based on 1 equivalent of the compound of formula (4). As the acid, hydrochloric acid, sulfuric acid, acetic acid, etc. may be used, and among them, hydrochloric acid is preferably used. It is preferable that reaction temperature is 50-100 degreeC, and it is more preferable that it is 70-80 degreeC.

이하 본 발명의 바람직한 실시예 및 비교예를 기재한다. 그러나, 하기한 실시예는 본 발명의 바람직한 일 실시예일 뿐 본 발명이 하기한 실시예에 한정되는 것은 아니다.Hereinafter, preferred examples and comparative examples of the present invention are described. However, the following examples are only preferred embodiments of the present invention and the present invention is not limited to the following examples.

(실시예 1)(Example 1)

(1) α,α-디메틸-3,5-디클로로벤질알콜의 제조(1) Preparation of α, α-dimethyl-3,5-dichlorobenzyl alcohol

테트라하이드로퓨란 25g과 마그네슘 2.4g의 혼합물에 1-브로모-3,5-디클로로벤젠 22.6g을 테트라하이드로퓨란 25g에 녹인 용액을 30℃이하의 온도에서 서서히 적가하였다. 적가가 완료된 후 같은 온도에서 3시간 더 교반하여 3,5-디클로로마그네슘브로마이드를 제조하였다. 이 반응액에 아세톤 8.7g과 테트라하이드로퓨란 8.7g을 혼합하여 30℃ 이하의 온도에서 서서히 적가하였다. 적가완료후 30분간 더 교반하고 17% 염산 용액을 투입하여 1시간 교반한 후 방치하여 유기층과 물층으로 층분리하였다. 물층을 디클로로메탄 50g으로 추출한 뒤 이 추출용액을 상기 층분리하여 얻은 유기층과 혼합한 후 용매를 감압증류하여 α,α-디메틸-3,5-디클로로벤질알콜 18.6g(수율 91%)을 얻었다.A solution of 22.6 g of 1-bromo-3,5-dichlorobenzene in 25 g of tetrahydrofuran was slowly added dropwise to a mixture of 25 g of tetrahydrofuran and 2.4 g of magnesium at a temperature of 30 ° C. or lower. After the addition was completed, the mixture was stirred for 3 hours at the same temperature to prepare 3,5-dichloromagnesium bromide. 8.7 g of acetone and 8.7 g of tetrahydrofuran were mixed and slowly added dropwise to the reaction solution at a temperature of 30 ° C or lower. After completion of the dropwise addition, the mixture was further stirred for 30 minutes, 17% hydrochloric acid solution was added thereto, stirred for 1 hour, and left to separate. The layer was separated into an organic layer and a water layer. The water layer was extracted with 50 g of dichloromethane, and the extract solution was mixed with the organic layer obtained by layer separation. The solvent was distilled under reduced pressure to obtain 18.6 g (yield 91%) of α, α-dimethyl-3,5-dichlorobenzyl alcohol.

(2) N-[1-(3,5-디클로로페닐-에틸]-2-페닐-아세트아미드(화학식 (3))의 제조(2) Preparation of N- [1- (3,5-dichlorophenyl-ethyl] -2-phenyl-acetamide (Formula (3))

상기 α,α-디메틸-3,5-디클로로벤질알콜 18g과 페닐아세토니트릴(C6H5CH2CN)을 100ml에 용해시킨 후에 반응액을 15℃ 이하로 냉각하였다. 이 반응액에 진한 황산 20ml를 서서히 적가하였다. 이 반응액을 10분동안 교반한 후 얼음물을 붓고 테트라하이드로퓨란 300ml로 추출한 후 감압증류하여 N-[1-(3,5-디클로로-페닐-에틸]-2-페닐-아세트아미드 21.7g(수율 77%)를 얻었다.After dissolving 18 g of α, α-dimethyl-3,5-dichlorobenzyl alcohol and phenylacetonitrile (C 6 H 5 CH 2 CN) in 100 ml, the reaction solution was cooled to 15 ° C. or lower. 20 ml of concentrated sulfuric acid was slowly added dropwise to the reaction solution. After stirring the reaction solution for 10 minutes, poured ice water, extracted with 300 ml of tetrahydrofuran and distilled under reduced pressure to give 21.7 g of N- [1- (3,5-dichloro-phenyl-ethyl] -2-phenyl-acetamide (yield). 77%).

(3) N-[1-(3,5-디클로로페닐)-1-메틸에틸]-3-옥소-2-페닐-부티르아미드(화학식 (4))의 제조(3) Preparation of N- [1- (3,5-dichlorophenyl) -1-methylethyl] -3-oxo-2-phenyl-butyramide (Formula (4))

반응용기에 에틸아세테이트 8.8g을 투입한 후 소듐 메톡사이드 1.2g을 투입하였다. 이 반응액에 상기 (2)에서 얻은 N-[1-(3,5-디클로로-페닐에틸]-2-페닐-아세트아미드 3.22g을 서서히 적가한 뒤 상온에서 교반하였다. 염산 2.4g을 녹인 물 5g에 위의 반응액을 서서히 적가하였다. 그런 다음 1시간동안 추가로 교반하여 층분리한 뒤 유기층을 감압증류하여 N-[1-(3,5-디클로로-페닐)-1-메틸에틸]-3-옥소-2-페닐-부티르아미드를 얻었다.8.8 g of ethyl acetate was added to the reaction vessel, followed by 1.2 g of sodium methoxide. 3.22 g of N- [1- (3,5-dichloro-phenylethyl] -2-phenyl-acetamide obtained in the above (2) was slowly added dropwise to the reaction solution, followed by stirring at room temperature. The reaction solution was slowly added dropwise to 5 g, and then the mixture was separated by further stirring for 1 hour, and the organic layer was distilled under reduced pressure to give N- [1- (3,5-dichloro-phenyl) -1-methylethyl]-. 3-oxo-2-phenyl-butyramide was obtained.

(4) N-[1-(3,5-디클로로페닐)-1-메틸에틸]-3,4-디하이드로-6-메틸-5-페닐-2(4) N- [1- (3,5-dichlorophenyl) -1-methylethyl] -3,4-dihydro-6-methyl-5-phenyl-2 HH -1,3-옥사진-4-온(화학식 (5))의 제조Preparation of -1,3-oxazin-4-one (Formula (5))

N-[1-(3,5-디클로로-페닐)-1-메틸에틸]-3-옥소-2-페닐-부티르아미드 3.6g(10 mmol)과 파라포름알데히드 2.4g(30mmol)을 디클로로메탄 50ml에 투입하여 혼합한 후 2N 염산 용액 4g을 적가하여 반응시켰다. 이 반응액을 상온에서 24시간 교반하여 생기는 고체를 필터하여 용액을 얻었다. 이 용액을 감압증류하여 화학식 (6)을 가지는 N-[1-(3,5-디클로로페닐)-1-메틸에틸]-3,4-디하이드로-6-메틸-5-페닐-2H-1,3-옥사진-4-온 2.5g(수율 70%)로 얻었다.3.6 g (10 mmol) of N- [1- (3,5-dichloro-phenyl) -1-methylethyl] -3-oxo-2-phenyl-butyramide and 2.4 g (30 mmol) of paraformaldehyde were dichloromethane. 50 ml of 2N hydrochloric acid solution was added dropwise and reacted. The reaction liquid was stirred at room temperature for 24 hours to filter the solid produced, thereby obtaining a solution. N- having the general formula (6) by distillation under reduced pressure to a solution [1- (3,5-dichlorophenyl) -1-methylethyl] -3,4-dihydro-6-methyl-5-phenyl -2 H - 2.5 g (yield 70%) of 1, 3-oxazine-4-ones were obtained.

실시예 2Example 2

상기 실시예 1에서 α,α-디메틸-3,5-디클로로벤질알콜 제조단계((1) 단계)에서 1-브로모-3,5-디클로로벤젠 대신에 1,3,5-트리클로로벤젠을 사용하여 α,α-디메틸-3,5-디클로로벤질알콜 18.1g(수율 88%)를 얻은 것을 제외하고 상기 실시예 1과 동일한 방법으로 실시하였다.In Example 1 1,3,5-trichlorobenzene instead of 1-bromo-3,5-dichlorobenzene in the α, α-dimethyl-3,5-dichlorobenzyl alcohol production step (step (1)) It was carried out in the same manner as in Example 1 except that 18.1 g (yield 88%) of α, α-dimethyl-3,5-dichlorobenzyl alcohol was obtained.

실시예 3Example 3

상기 실시예 1에서 N-[1-(3,5-디클로로페닐)-1-메틸에틸]-3,4-디하이드로-6-메틸-5-페닐-2H-1,3-옥사진-4-온 제조단계((4) 단계)에서 반응온도를 80℃로 상승시켜 N-[1-(3,5-디클로로페닐)-1-메틸에틸]-3,4-디하이드로-6-메틸-5-페닐-2H-1,3-옥사진-4-온 2.7g(수율 75%)을 얻은 것을 제외하고 상기 실시예 1과 동일한 방법으로 실시하였다.In Example 1 N- [1- (3,5- dichloro-phenyl) -1-methylethyl] -3,4-dihydro-6-methyl-5-phenyl -2 H -1,3- oxazin- In the 4-one preparation step (step (4)), the reaction temperature was raised to 80 ° C. to yield N- [1- (3,5-dichlorophenyl) -1-methylethyl] -3,4-dihydro-6-methyl The same procedure as in Example 1 was conducted except that 2.7 g (yield 75%) of -5-phenyl- 2H -1,3-oxazin-4-one was obtained.

본 발명의 옥사지클로메폰 및 그 유도체의 제조방법에 따르면 보다 간단한 공정으로 옥사지클로메폰 또는 그 유도체을 제조할 수 있어 경제적이며, 부산물이 생기지 않는 발명의 효과가 있다.According to the method for preparing the oxazilomethone and its derivatives according to the present invention, it is economical to produce the oxazilomethone or its derivatives in a simpler process, and there is an effect of the invention that no by-products are produced.

Claims (5)

a) 벤젠계 화합물과 마그네슘을 반응시킨 후 케톤류 화합물과 반응시켜 하기 화학식 (1)의 화합물을 제조하는 단계;a) reacting a benzene compound with magnesium and reacting with a ketone compound to prepare a compound of formula (1); b) 상기 화학식 (1)의 화합물과 하기 화학식 (2)의 페닐아세토니트릴계 화합물을 산촉매하에서 반응시켜 하기 화학식 (3)의 화합물을 제조하는 단계;b) preparing a compound of formula (3) by reacting the compound of formula (1) with a phenylacetonitrile compound of formula (2) under an acid catalyst; c) 상기 화학식 (3)의 화합물을 소듐 알콕사이드와 알킬아세테이트를 반응시켜 하기 화학식 (4)의 화합물을 제조하는 단계; 및c) reacting the compound of formula (3) with sodium alkoxide and alkyl acetate to prepare a compound of formula (4); And d) 상기 화학식 (4)의 화합물을 파라포름알데이드 및 포르말린으로 이루어진 군에서 선택되는 적어도 하나의 알데히드계 화합물 및 산과 반응시켜 하기 화학식 (5)의 옥사지클로메폰 또는 그 유도체를 얻는 단계를 포함하는 옥사지클로메폰의 제조방법:d) reacting the compound of formula (4) with at least one aldehyde-based compound and acid selected from the group consisting of paraformaldehyde and formalin to obtain oxazilomethone of formula (5) or a derivative thereof Method for the preparation of oxaziclomethone [반응식 2]Scheme 2 상기 식에서 R1및 R2는 각각 독립적으로 탄소수 1 내지 6의 알킬기이고, X는할로겐이며, Y는 할로겐기 또는 탄소수 1 내지 6의 알킬기이며, n은 0 내지 3의 정수이고, m은 0 또는 1임.Wherein R 1 and R 2 are each independently an alkyl group having 1 to 6 carbon atoms, X is a halogen, Y is a halogen group or an alkyl group having 1 to 6 carbon atoms, n is an integer of 0 to 3, m is 0 or 1 제1항에 있어서, 상기 a) 단계에서 마그네슘은 벤젠계 화합물 1 당량에 대하여 0.9 내지 1.1 당량인 옥사지클로메폰의 제조방법.The method of claim 1, wherein in step a), magnesium is 0.9 to 1.1 equivalents based on 1 equivalent of benzene compound. 제1항에 있어서, 상기 a) 단계에서 반응온도는 0 내지 50℃인 옥사지클로메폰의 제조방법.The method of claim 1, wherein the reaction temperature in step a) is 0 to 50 ° C. 제1항에 있어서, 상기 d) 단계에서 파라포름알데히드의 사용량은 상기 화학식 (4)의 화합물 1 당량에 대하여 1 내지 10 당량인 옥사지클로메폰의 제조방법.The method of claim 1, wherein the amount of paraformaldehyde used in step d) is 1 to 10 equivalents based on 1 equivalent of the compound of formula (4). 제1항에 있어서, 상기 d) 단계에서 반응온도는 50 내지 100℃인 옥사지클로메폰의 제조방법.The method of claim 1, wherein the reaction temperature in step d) is 50 to 100 ° C.
KR1020010079094A 2001-12-13 2001-12-13 A method of preparing oxaziclomefone or derivative thereof KR20030049024A (en)

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