KR100376173B1 - Process for preparing pyimidine compounds having benzylidine aminoester structure as herbicide - Google Patents
Process for preparing pyimidine compounds having benzylidine aminoester structure as herbicide Download PDFInfo
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- KR100376173B1 KR100376173B1 KR1019950021418A KR19950021418A KR100376173B1 KR 100376173 B1 KR100376173 B1 KR 100376173B1 KR 1019950021418 A KR1019950021418 A KR 1019950021418A KR 19950021418 A KR19950021418 A KR 19950021418A KR 100376173 B1 KR100376173 B1 KR 100376173B1
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Abstract
Description
본 발명은 제초력을 갖는 피리미디닐옥시벤조산 벤질리딘 아미노에스테르 유도체의 신규한 제조방법에 관한 것이다. 보다 구체적으로 본 발명은 하기 일반식 (I) 로 표시되는 2,6-디(4,6-디메톡시피리미딘-2-일)옥시벤조산의 벤질리딘아미노에스테르 유도체를 제조하는 방법에 관한 것이다.The present invention relates to a novel process for preparing pyrimidinyloxybenzoic acid benzylidene aminoester derivatives having herbicidal power. More specifically, the present invention relates to a method for producing a benzylidene amino ester derivative of 2,6-di (4,6-dimethoxypyrimidin-2-yl) oxybenzoic acid represented by the following general formula (I). .
상기식에서,In the above formula,
R1은 수소, 할로겐, 시아노, 니트로, C1-C4알킬, C3-C6시클로알킬, C1-C4알콕시, C2-C4알케닐옥시, C1-C4알킬티오, C1-C4알킬로 치환될 수 있는 아미노, 아릴, 아릴옥시, C1-C4아실 또는 C1-C4아실옥시를 나타내고,R 1 is hydrogen, halogen, cyano, nitro, C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl, C 1 -C 4 alkoxy, C 2 -C 4 alkenyloxy, C 1 -C 4 alkylthio , Amino, aryl, aryloxy, C 1 -C 4 acyl or C 1 -C 4 acyloxy which may be substituted with C 1 -C 4 alkyl,
n 은 1 내지 5 를 나타내며,n represents 1 to 5,
R2는 수소, 할로겐, 시아노, 니트로, C1-C4알킬, C1-C4알콕시, C1-C4알킬티오, C1-C4알콕시카보닐, C2-C4알케닐옥시카보닐, 아릴메톡시카보닐, 헤테로아릴메톡시카보닐, C1-C4알킬아미노카보닐, 디(C1-C4알킬)아미노카보닐, 아릴메틸아미노카보닐, 헤테로아릴메틸아미노카보닐, 또는 R1으로 치환될 수 있는 페닐을 나타낸다.R 2 is hydrogen, halogen, cyano, nitro, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkoxycarbonyl, C 2 -C 4 alkenyl Oxycarbonyl, arylmethoxycarbonyl, heteroarylmethoxycarbonyl, C 1 -C 4 alkylaminocarbonyl, di (C 1 -C 4 alkyl) aminocarbonyl, arylmethylaminocarbonyl, heteroarylmethylamino Carbonyl or phenyl which may be substituted with R 1 .
상기 정의 중에서, 용어 '알킬'은 단독으로 사용될 때나 알킬티오 또는 알킬아미노가보닐 등과 같이 합성어로 사용되는 경우에 모두 메틸, 에틸, n-프로필, 이소프로필 또는 여러가지의 부틸 이성체 등과 같은 직쇄 또는 측쇄 포화 탄화수소 래디칼을 의미하고, '알콕시' 는 메톡시, 에톡시, n-프로폭시, 이소프로폭시 또는 여러가지의 부톡시 이성체를 의미하며, '알케닐' 은 단독으로 사용될 때나 알케닐옥시와 같이 합성어로 사용되는 경우에 모두 비닐, 1-프로페닐, 2-프로페닐 또는 여러가지 부테닐 이성체 등과 같은 직쇄 또는 측쇄 알켄을 의미하고, "할로겐" 은 불소, 염소, 브롬, 요오드를 의미한다.In the above definitions, the term 'alkyl' is used either alone or when used in synthetic terms such as alkylthio or alkylaminocarbonyl, such as straight chain or branched chain saturation such as methyl, ethyl, n-propyl, isopropyl or various butyl isomers. Refers to hydrocarbon radicals, 'alkoxy' means methoxy, ethoxy, n-propoxy, isopropoxy or various butoxy isomers, and 'alkenyl' when used alone or synonymously with alkenyloxy When used, all mean straight or branched chain alkenes such as vinyl, 1-propenyl, 2-propenyl or various butenyl isomers and the like, and "halogen" means fluorine, chlorine, bromine, iodine.
상기 일반식 (I) 의 화합물들은 화본 잡초, 광엽 잡초 또는 일년생 잡초나 다년생 잡초에 걸쳐 광범위하게 탁월한 제초효과를 나타내고, 특히 직파벼에 대해서는 피를 포함한 문제의 일년생 및 다년생 잡초를 방제하는데 뛰어나다.The compounds of the general formula (I) exhibit a wide range of excellent herbicidal effects over flower weeds, broadleaf weeds or annual weeds or perennial weeds, and are particularly good at controlling annual and perennial weeds, including blood, for direct sowing.
2,6-디(4,6-디메톡시피리미딘-2-일)옥시벤조산 알킬리딘 아미노에스테르 유도체의 제조방법은 하기 반응도식 (A) 에 나타낸 바와 같이, 이미 알려져 있으나(예를 들어 유럽 특허원 제 321,846호 등), 상기 유럽 특허에서 제시하는 알킬리딘아미노 에스테르 유도체를 합성하는 방법으로는 본 발명에서 제시하는 입체적으로 덩어리가 커다란 방향족 고리를 갖는 벤질리딘 아미노에스테르 유도체를 합성할 수 없으며, 특별한 경우에 합성된다고 하더라도 극히 낮은 수율(5 % 미만) 로만 합성되는 것으로 나타났다.The preparation of 2,6-di (4,6-dimethoxypyrimidin-2-yl) oxybenzoic acid alkylidine aminoester derivatives is already known, as shown in Scheme (A) below (e.g. Europe Patent Application No. 321,846, etc.), the method of synthesizing the alkylidine amino ester derivatives described in the European patent, it is not possible to synthesize a benzylidene amino ester derivative having a three-dimensionally large aromatic ring in the present invention, Although synthesized in special cases, it was found to be synthesized only in extremely low yields (less than 5%).
반응 도식 (A)Scheme (A)
상기 반응도식에서, R3및 R4는 각각 독립적으로 알킬기를 나타낸다.In the scheme, R 3 and R 4 each independently represent an alkyl group.
한편, 본 발명자들에 의한 국내 특허출원 제 93-31016호에서는, 방향족 고리를 갖는 벤질리딘 아미노에스테르 유도체를 합성하는 신규한 방법으로서, 구조식 (II) 로 표시되는 2,6-디(4,6-디메톡시피리미딘-2-일)벤조산을 하기 구조식 (III)으로 표시되는 피리미딘티오에스테르 화합물로 변환시켜 반응성을 증가시킨 뒤, 일반식 (IV) 로 표시되는 아릴케톤의 옥심 유도체와 에스테르화 반응을 시킴으로써최종 목적 화합물 (I) 을 얻을 수 있음을 제시하였다.On the other hand, in Korean Patent Application No. 93-31016 by the present inventors, a novel method for synthesizing a benzylidene aminoester derivative having an aromatic ring, 2,6-di (4,6) represented by the formula (II) -Dimethoxypyrimidin-2-yl) benzoic acid is converted to a pyrimidine thioester compound represented by the following structural formula (III) to increase the reactivity, and then an oxime derivative and ester of an aryl ketone represented by the general formula (IV) It was shown that the final target compound (I) can be obtained by subjecting to a polymerization reaction.
상기식에서, R1, R2및 n은 전술한 바와 같다.Wherein R 1 , R 2 and n are as described above.
그러나, 전술한 선행 기술의 방법들은 모두 2,6-디(4,6-디메톡시피리미딘-2-일)벤조산 (II) 을 중간체로 하여 합성되는 공통점을 갖고 있어서, 이를 합성하는데 카복실산 보호기의 도입 및 제거가 필수적이고, 또한 2,6위치가 치환된 벤조산 화합물은 카복실기가 입체적으로 심하게 감추어져 있으므로 입체적으로 커다란 아릴케톤 옥심의 에스테르화 반응시 통상의 반응으로는 반응성에 한계가 있거나 비경제적인 특수한 반응조건을 사용해야 하는 단점이 있다.However, all of the aforementioned prior art methods have in common that they are synthesized using 2,6-di (4,6-dimethoxypyrimidin-2-yl) benzoic acid (II) as an intermediate, and thus the carboxylic acid protecting group Since the benzoic acid compound substituted with 2,6 positions is essential in the benzoic acid compound substituted with the 2,6 position, the carboxyl group is severely concealed in three-dimensionally. The disadvantage is the use of special reaction conditions.
이에 본 발명자들은 전술한 제조방법들이 갖는 단점들을 해결하기 위해 연구를 계속하던 중, 2,6-디히드록시벤조산에 벤질리딘 아미노에스테르기를 먼저 도입한 후, 입체적으로 덩어리가 큰 4,6-디메톡시피리미딘기를 나중에 도입하는 새로운 제조방법을 발명하게 되었다.Therefore, the present inventors continue to study to solve the disadvantages of the above-described manufacturing method, first introduced the benzylidene amino ester group to 2,6-dihydroxybenzoic acid, and then the three-dimensional bulky 4,6-di It was invented a new process for introducing methoxypyrimidine groups later.
즉 본 발명은 하기 반응도식 (B) 에 기술한 바와같이, 일반식 (V) 로 표시되는 2,6-디아세톡시벤조산 벤질리딘 아미노에스테르와 하기 일반식 (VI) 로 표시되는 디메톡시피리미딘 유도체를 한 용기안에서 용매와 염기의 존재하에서 반응시킴을 특징으로 하여, 일반식 (I) 로 표시되는 2,6-디(4,6-디메톡시피리미딘-2-일)옥시벤조산의 벤질리딘 아미노에스테르 유도체를 제조하는 방법을 제공하는데 그 목적이 있다.That is, this invention is a 2, 6- diacetoxy benzoic acid benzylidene amino ester represented by general formula (V), and dimethoxypyrimi represented by the following general formula (VI), as described in following Reaction Scheme (B). Of a 2,6-di (4,6-dimethoxypyrimidin-2-yl) oxybenzoic acid represented by the general formula (I), characterized by reacting the dean derivative in a vessel in the presence of a solvent and a base. It is an object to provide a method for preparing a benzylidene aminoester derivative.
본 발명에 따른 방법에 사용되는 일반식 (V) 로 표시되는 2,6-디아세톡시 벤조산 벤질리딘 아미노에스테르 화합물은 신규한 화합물로서 일반식 (I) 로 표시되는 2,6-디(4,6-디메톡시피리미딘-2-일)옥시벤조산의 벤질리딘 아미노에스테르 유도체를 제조하기 위한 중간체로서 유용하다.The 2,6-diacetoxy benzoic acid benzylidene aminoester compound represented by general formula (V) used in the method according to the present invention is a novel compound represented by general formula (I). It is useful as an intermediate for preparing the benzylidene aminoester derivative of 6-dimethoxypyrimidin-2-yl) oxybenzoic acid.
따라서 하기 일반식 (V) 의 화합물도 또한 본 발명의 목적이 된다.Therefore, the compound of the following general formula (V) is also an object of the present invention.
반응도식 (B)Scheme (B)
상기식에서,In the above formula,
R1, R2및 n 은 전술한 바와 같고,R 1 , R 2 and n are as described above,
X 는 할로겐, C1-C3알킬술포닐 또는 아릴술포닐을 나타낸다.X represents halogen, C 1 -C 3 alkylsulfonyl or arylsulfonyl.
이하 본 발명의 제조방법을 상세히 설명한다.Hereinafter, the manufacturing method of the present invention will be described in detail.
본 발명에서 목적 화합물인 일반식 (I) 의 화합물은 상기 반응도식 (B)에 따라 제조된다. 즉, 일반식 (V) 의 화합물을 용매하에서 2 내지 3 당량의 일반식(VI) 의 화합물과 동량의 염기의 존재하에 한 반응 용기내에서 반응시켜 디아세틸 반응과 피리미딘기의 도입을 동시에 진행시킴으로써 일반식 (I) 의 목적 화합물을 제조하였다.Compounds of the general formula (I) which are the target compounds in the present invention are prepared according to the above scheme (B). That is, the compound of general formula (V) is reacted in a reaction vessel in the presence of 2 to 3 equivalents of the compound of general formula (VI) with the same amount of base in a solvent to simultaneously proceed with the introduction of the diacetyl reaction and the pyrimidine group. The target compound of general formula (I) was manufactured by this.
이때 염기로는 탄산칼륨, 탄산나트륨, 수소화나트륨, 탄산수소나트륨 등의 무기 염기를 사용할 수 있는데, 탄산칼륨 또는 수소화나트륨이 바람직하며, 용매로는 테트라하이드로푸란, 디에틸에테르 등의 에테르류, 디메틸포름아미드, 디메틸술폭사이드 등의 극성 용매를 사용할 수 있으며, 이중에서 테트라하이드로푸란 또는 디메틸포름아미드가 바람직하다. 반응온도는 상온 내지 100 ℃ 의 범위가 가능하나, 50 내지 80 ℃ 가 적절하다.In this case, inorganic bases such as potassium carbonate, sodium carbonate, sodium hydride and sodium hydrogen carbonate may be used. Potassium carbonate or sodium hydride is preferable, and ethers such as tetrahydrofuran and diethyl ether, dimethylform Polar solvents such as amide and dimethyl sulfoxide can be used, of which tetrahydrofuran or dimethylformamide is preferable. The reaction temperature may be in the range of room temperature to 100 ° C., but 50 to 80 ° C. is appropriate.
본 발명의 특징은 전술한 유럽 특허원 제 321,846 호 및 본 발명자들에 의한 특허출원 제 93-31016 호에서와는 달리 아미노에스테르기와 4,6-디메톡시피리미딘기의 도입 순서를 바꾸어 2,6-다아세톡시벤조산 (VII) 에 옥심 유도체와의 커플링을 먼저 수행하여 입체적 장애를 받지 않는 경로로 벤질리딘 아미노 에스테르기를 도입함으로써 신규한 중간체 (V) 를 통하여 목적 화합물 (I) 을 제조한 것과, 또한 중간체 (V) 에서 옥심 유도체 (IV) 가 결합된 아미노에스테르기가 카복실산의 보호기로서의 역할을 동시에 수행하여 보호기의 도입 및 제거 과정을 줄일수 있다는 것에 있다.The characteristics of the present invention differ from the aforementioned European Patent Application No. 321,846 and the Patent Application Nos. 93-31016 by the present inventors to reverse the order of introduction of aminoester groups and 4,6-dimethoxypyrimidine groups. Preparation of the target compound (I) through the novel intermediate (V) by first performing coupling with the oxime derivative to acetoxybenzoic acid (VII) to introduce a benzylidene amino ester group in a path that is free of steric hindrance; The amino ester group to which the oxime derivative (IV) is bonded in the intermediate (V) simultaneously serves as a protecting group of the carboxylic acid, thereby reducing the introduction and removal of the protecting group.
상기 일반식 (V) 로 표시되는 화합물들은 하기 반응도식 (C) 의 2,6-디아세톡시벤조산 (VII) 을 통상의 커플링 시약을 사용하여 활성화시킨 후, 하기 일반식(IV) 로 표시되는 옥심 화합물과 반응시킴으로써 얻을 수 있다.The compounds represented by the general formula (V) are represented by the following general formula (IV) after activating 2,6-diacetoxybenzoic acid (VII) of the following scheme (C) using a conventional coupling reagent. It is obtained by reacting with an oxime compound.
반응 도식 (C)Scheme (C)
상기식에서, R1, R2및 n 은 전술한 바와 같다.Wherein R 1 , R 2 and n are as described above.
상기 반응도식 (C) 에서 카복실기를 활성화시키는 커플링 시약으로는 디에틸클로로포스페이트를 포함한 유기인산류, 디시클로헥실카보이미드를 포함한 카보이미드류, 알킬 클로로포르메이트류, 디이미다졸카보네이트, 톨루엔술포닐클로라이드 등의 시약을 광범위하게 사용할 수 있으며, 카보이미드류나, 톨루엔술포닐클로라이드 등이 바람직하다.Coupling reagents for activating the carboxyl group in the above scheme (C) include organophosphates including diethylchlorophosphate, carbodiimide including dicyclohexylcarbodiimide, alkyl chloroformates, diimidazole carbonate and toluene sulphate. Reagents, such as a polyvinyl chloride, can be used extensively, Carbodiimide, toluenesulfonyl chloride, etc. are preferable.
전술한 제조방법에 따르면 벤질리딘 아미노에스테르기의 도입반응을 통상의 방법을 사용해서도 보편적으로 진행시킬 수 있고, 상대적으로 값이 비싼 4,6-디메톡시피리미딘기의 도입을 최종 단계에서 수행할 뿐 아니라, 디아세틸 반응과 피리미딘기의 도입을 한 반응 용기에서 동시에 진행시킴으로써 경제적으로 장점이 있다.According to the above-mentioned preparation method, the introduction reaction of benzylidene aminoester group can be generally proceeded by using a conventional method, and the introduction of relatively expensive 4,6-dimethoxypyrimidine group is carried out in the final step. In addition, the diacetyl reaction and the introduction of pyrimidine groups are simultaneously carried out in one reaction vessel, which is economically advantageous.
본 발명에 따른 일반식 (I) 과 일반식 (V) 로 표시되는 화합물의 대표적 안 예를 하기 표 1 에 제시한다.Representative examples of the compounds represented by the general formula (I) and the general formula (V) according to the present invention are shown in Table 1 below.
표 1Table 1
이하, 본 발명을 제조예와 실시예에 의거하여 보다 구체적으로 설명한다. 그러나, 이들 제조예와 실시예는 본 발명에 대한 이해를 돕기위한 것일 뿐, 본 발명이 여기에 한정되는 것은 아니다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated further more concretely based on a manufacture example and an Example. However, these preparation examples and examples are merely to aid the understanding of the present invention, the present invention is not limited thereto.
제조예 1 : 2,6-디아세톡시벤조산 (VII)의 합성Preparation Example 1 Synthesis of 2,6-Diacetoxybenzoic Acid (VII)
디히드록시벤조산 15 g 을 100 ml 의 무수 초산 용매에 가한 후, 80 ℃로 가열한다. 반응이 완결된 후, 냉각수에 넣고, 고체화시킨 후, 여과하여 백색의 표제 화합물 21 g을 얻었다(수율 90 %).15 g of dihydroxybenzoic acid is added to 100 ml of anhydrous acetic acid solvent and then heated to 80 ° C. After completion of the reaction, the mixture was poured into cooling water, solidified and filtered to give 21 g of a white title compound (yield 90%).
실시예 1 : 2,6-디아세톡시벤조산 벤즈히드릴리딘 아미노에스테르 (V-1의 합성)Example 1 2,6-Diacetoxybenzoic Acid Benzhydryridine Aminoester (Synthesis of V-1)
벤조페논 옥심 1.9 g 과 2,6-디아세톡시벤조산 2.4 g을 디클로로메탄 50 ml 에 가하고, 디시클로헥실카보디이미드 2.1 g 과 트리에틸아민 1.5 ml 를 가한다. 상온에서 12 시간동안 교반한 후, 물을 가하고, 유기층을 추출해 낸다. 유기층을 분리하여 무수 망초로 건조, 증발시키고, 실리카겔 칼럼 크로마토그래피로 분리하여 표제 화합물 2.6 g을 얻었다(수율 65 %).1.9 g of benzophenone oxime and 2.4 g of 2,6-diacetoxybenzoic acid are added to 50 ml of dichloromethane, 2.1 g of dicyclohexylcarbodiimide and 1.5 ml of triethylamine are added. After stirring for 12 hours at room temperature, water is added and the organic layer is extracted. The organic layer was separated, dried over anhydrous manganese, evaporated and separated by silica gel column chromatography to give 2.6 g of the title compound (yield 65%).
1H NMR : δ2.12(s, 6H), 7.00-7.58(m, 13H) 1 H NMR: δ 2.12 (s, 6H), 7.00-7.58 (m, 13H)
FAB MS : 418(M+H)FAB MS: 418 (M + H)
실시예 2 : 2,6-디아세톡시벤조산 벤질리딘 아미노에스테르 (V-2)의 합성Example 2 Synthesis of 2,6-Diacetoxybenzoic Acid Benzylidene Aminoester (V-2)
벤즈알데하이드 옥심 1.2 g 과 2,6-디아세톡시벤조산 2.3 g을 디클로로메탄 50 ml 에 가하고, 0℃ 에서 톨루엔술포닐클로라이드 1.9 g 과 탄산칼륨 1.3 g을 넣고, 30 분간 교반한 후, 상온에서 교반한다. TLC로 반응 완결을 확인한후, 물을 가하고, 유기층을 분리하여 무수 망초로 건조, 증발시키고, 실리카겔 칼럼 크로마토그래피로 분리하여 표제 화합물 1.7 g 을 얻었다(수율 50 %).1.2 g of benzaldehyde oxime and 2.3 g of 2,6-diacetoxybenzoic acid were added to 50 ml of dichloromethane, 1.9 g of toluenesulfonyl chloride and 1.3 g of potassium carbonate were added at 0 ° C, followed by stirring for 30 minutes, followed by stirring at room temperature. do. After completion of the reaction by TLC, water was added, the organic layer was separated, dried over anhydrous manganese, evaporated, and separated by silica gel column chromatography to obtain 1.7 g of the title compound (yield 50%).
1H NMR : δ2.11(s, 6H), 7.20-7.61(m, 8H), 8.09(s, 1H) 1 H NMR: δ 2.11 (s, 6H), 7.20-7.61 (m, 8H), 8.09 (s, 1H)
FAB MS : 442(M+H)FAB MS: 442 (M + H)
실시예 3 내지 5Examples 3 to 5
실시예 1 또는 2 와 동일한 방법으로 하기 표 2 에 기재된 화합물 (V-3 내지 V-5) 을 합성할 수 있었다.In the same manner as in Example 1 or 2, the compounds (V-3 to V-5) shown in Table 2 below were synthesized.
표 2.Table 2.
실시예 6 : 2,6-디(4,6-디메톡시피리미딘-2-일)옥시벤조산 벤즈히드릴리딘 아미노에스테르 (I-1)의 합성Example 6: Synthesis of 2,6-di (4,6-dimethoxypyrimidin-2-yl) oxybenzoic acid benzhydryridine aminoester (I-1)
2,6-디아세톡시벤조산 벤즈히드릴리딘 아미노에스테르 1.0 g 과 탄산칼륨 0.83g, 4,6-디메톡시-2-(메틸술포닐)-피리미딘 1.0 g 을 디메틸포름아미드 용매 30 ml 에 가하고, 70 내지 75 ℃ 로 가열하면서 3 시간동안 교반한 후, 용매를 증발시키고, 물과 디클로로메탄을 가해 유기층을 추출한다. 분리한 유기층을 무수 망초로 건조, 증발시키고, 실리카겔 칼럼 크로마토그래피로 정제하여 표제 화합물 0.73 g 을 얻었다(수율 50 %).1.0 g of 2,6-diacetoxybenzoic acid benzhydryridine aminoester, 0.83 g of potassium carbonate, and 1.0 g of 4,6-dimethoxy-2- (methylsulfonyl) -pyrimidine were added to 30 ml of a dimethylformamide solvent. After stirring for 3 hours while heating to 70 to 75 ℃, the solvent is evaporated, water and dichloromethane are added to extract the organic layer. The separated organic layer was dried over anhydrous manganese, evaporated and purified by silica gel column chromatography to obtain 0.73 g of the title compound (yield 50%).
1H NMR(CDCl)S ppm : 3.72(s, 12H), 5.72(s, 2H), 7.10 - 7.48(m, 13H) MS(FAB) : 610 1 H NMR (CDCl) S ppm: 3.72 (s, 12H), 5.72 (s, 2H), 7.10-7.48 (m, 13H) MS (FAB): 610
융점 : 128 - 130℃Melting Point: 128-130 ℃
실시예 7 : 2,6-디(4,6-디메톡시피리미딘-2-일)옥시벤조산 벤질리딘 아미노에스테르 (I-2)의 합성Example 7: Synthesis of 2,6-di (4,6-dimethoxypyrimidin-2-yl) oxybenzoic acid benzylidene aminoester (I-2)
2,6-디아세톡시벤조산 벤질리딘 아미노에스테르 3.4 g 과 탄산칼륨 3.5 g, 4,6-디메톡시-2-(메틸술포닐)-피리미딘 4.8 g 을 디메틸포름아미드 용매 30 ml 에 가하고, 70 내지 75 ℃ 로 가열하면서 3 시간동안 교반한 후, 실시예 1 과 동일한 과정을 거쳐 표제 화합물 3.2 g을 얻었다(수율 60 %).3.4 g of 2,6-diacetoxybenzoic acid benzylidene aminoester, 3.5 g of potassium carbonate, and 4.8 g of 4,6-dimethoxy-2- (methylsulfonyl) -pyrimidine were added to 30 ml of a dimethylformamide solvent, and 70 After stirring for 3 hours while heating to ~ 75 ℃, 3.2 g of the title compound was obtained in the same manner as in Example 1 (yield 60%).
1H NMR(CDCl)S ppm : 3.78(s, 12H), 5.73(s, 2H), 7.20 - 7.61(m, 8H), 8.09(s, 1H) 1 H NMR (CDCl) S ppm: 3.78 (s, 12H), 5.73 (s, 2H), 7.20-7.61 (m, 8H), 8.09 (s, 1H)
MS(FAB) : 534MS (FAB): 534
융점 : 60 - 65 ℃Melting Point: 60-65 ℃
실시예 8 : N-벤질-2-[(2,6-디(4,6-디메톡시피리미딘-2-일)옥시벤조일)옥시]아미노-2-페닐아세트아미드 (I-3)의 합성Example 8 of N-benzyl-2-[(2,6-di (4,6-dimethoxypyrimidin-2-yl) oxybenzoyl) oxy] amino-2-phenylacetamide (I-3) synthesis
N-벤질-2-[(2,6-디아세톡시벤조일)옥시]아미노-2-페닐아세트아미드 4.7 g과 탄산칼륨 3.5 g, 4,6-디메톡시-2-(메틸술포닐)-피리미딘 4.8 g을 디메틸포름아미드 용매 30 ml 에 가하고, 70 내지 75 ℃ 로 가열하면서 3 시간동안 교반한 후, 실시예 1 과 동일한 과정을 거쳐 표제 화합물 2.8 g 을 얻었다(수율 42 %).4.7 g of N-benzyl-2-[(2,6-diacetoxybenzoyl) oxy] amino-2-phenylacetamide and 3.5 g of potassium carbonate, 4,6-dimethoxy-2- (methylsulfonyl) -pyridine 4.8 g of midine was added to 30 ml of a dimethylformamide solvent, and the mixture was stirred for 3 hours while heating to 70 to 75 ° C., and then 2.8 g of the title compound was obtained in the same manner as in Example 1 (yield 42%).
1H NMR(CDCl)S ppm : 3.63(s 12H), 4.71 - 4.73(d, 2H), 5.69(s, 2H), 7.14 - 7.69(m, 13H), 8.68- 8.72(t, 1H) 1 H NMR (CDCl) S ppm: 3.63 (s 12H), 4.71-4.73 (d, 2H), 5.69 (s, 2H), 7.14-7.69 (m, 13H), 8.68-8.72 (t, 1H)
MS(FAB) : 668MS (FAB): 668
실시예 9 : 2,6-디(4,6-디메톡시피리미딘-2-일)옥시벤조산 4-메톡시벤질리딘 아미노에스테르 (I-4)의 합성Example 9: Synthesis of 2,6-di (4,6-dimethoxypyrimidin-2-yl) oxybenzoic acid 4-methoxybenzylidine aminoester (I-4)
2,6-디아세톡시벤조산 4-메톡시벤질리딘 아미노에스테르 3.7 g 과 탄산칼륨 3.5 g, 4,6-디메톡시-2-(메틸술포닐)-피리미딘 4.8 g 을 디메틸포름아미드 용매 30 ml 에 가하고, 70 내지 75 ℃ 로 가열하면서 3 시간동안 교반한 후, 실시예 1 과 동일한 과정을 거쳐 표제 화합물 3.2 g을 얻었다(수율 57 %).3.7 g of 2,6-diacetoxybenzoic acid 4-methoxybenzylidine aminoester, 3.5 g of potassium carbonate, and 4.8 g of 4,6-dimethoxy-2- (methylsulfonyl) -pyrimidine in 30 ml of dimethylformamide solvent After stirring for 3 hours while heating to 70 to 75 ℃, 3.2 g of the title compound was obtained in the same manner as in Example 1 (yield 57%).
1H NMR(CDCl)S ppm : 3.78(s, 12H), 3.82(s, 3H), 5.73(s, 2H), 6.84 - 7.62(m, 7H), 8.04(s, 1H), 1 H NMR (CDCl) S ppm: 3.78 (s, 12H), 3.82 (s, 3H), 5.73 (s, 2H), 6.84-7.62 (m, 7H), 8.04 (s, 1H),
MS(FAB) : 564MS (FAB): 564
융점 : 126 - 129 ℃Melting Point: 126-129 ℃
실시예 10 : N,N-디메틸-2-[(2,6-디(4,6-디메톡시피리미딘-2-일)옥시벤조일)옥시]아미노-2-페닐아세트아미드 (I-5)의 합성Example 10 N, N-dimethyl-2-[(2,6-di (4,6-dimethoxypyrimidin-2-yl) oxybenzoyl) oxy] amino-2-phenylacetamide (I-5 ) Synthesis
N,N-디메틸-2-[(2,6-디아세톡시벤조일)옥시]아미노-2-페닐아세트아미드 4.1 g 과 탄산칼륨 3.5 g, 4,6-디메톡시-2-(메틸술포닐)-피리미딘 4.8 g 을 디메틸포름아미드 용매 30 ml 에 가하고, 70 내지 75 ℃ 로 가열하면서 3 시간동안 교반한 후, 실시예 1 과 동일한 과정을 거쳐 표제 화합물 2.9 g 을 얻었다(수율 48 %).4.1 g of N, N-dimethyl-2-[(2,6-diacetoxybenzoyl) oxy] amino-2-phenylacetamide and 3.5 g of potassium carbonate, 4,6-dimethoxy-2- (methylsulfonyl) 4.8 g of -pyrimidine was added to 30 ml of a dimethylformamide solvent, and stirred for 3 hours while heating to 70 to 75 ° C., followed by the same procedure as in Example 1 to obtain 2.9 g of the title compound (yield 48%).
1H NMR(CDCl)S ppm : 2.89(s, 3H), 2.98(s, 3H), 3.70(s, 12H), 5.68(s, 2H), 7.17 - 7.84(m, 8H), 1 H NMR (CDCl) S ppm: 2.89 (s, 3H), 2.98 (s, 3H), 3.70 (s, 12H), 5.68 (s, 2H), 7.17-7.84 (m, 8H),
MS(FAB) : 605MS (FAB): 605
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| JPH01250365A (en) * | 1987-12-22 | 1989-10-05 | Kumiai Chem Ind Co Ltd | Pyrimidine derivative and herbicide |
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| JPH01250378A (en) * | 1988-03-31 | 1989-10-05 | Kumiai Chem Ind Co Ltd | Pyrimidine derivative and herbicide |
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