KR19990085333A - Method for preparing 1,3-diphenyl propenone derivative - Google Patents
Method for preparing 1,3-diphenyl propenone derivative Download PDFInfo
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Abstract
본 발명의 하기 화학식 (1)의 1,3-디페닐 프로페논 유도체의 신규한 제조방법에 관한 것이다.The present invention relates to a novel process for the preparation of 1,3-diphenyl propenone derivatives of the general formula (1) below.
상기식에서,In the above formula,
R1및 R3는 각각 독립적으로 수소, C1-C7알킬 또는 벤질을 나타내며,R 1 and R 3 each independently represent hydrogen, C 1 -C 7 alkyl or benzyl,
R2, R4및 R5는 각각 독립적으로 C1-C5알킬 또는 C1-C5알콕시알킬을 나타내고,R 2 , R 4 and R 5 each independently represent C 1 -C 5 alkyl or C 1 -C 5 alkoxyalkyl,
Bn 은 벤질을 나타낸다.Bn represents benzyl.
Description
본 발명은 하기 화학식 (1)의 1,3-디페닐 프로페논 유도체의 신규한 제조방법에 관한 것이다.The present invention relates to a novel process for the preparation of 1,3-diphenyl propenone derivatives of the general formula (1).
화학식 1Formula 1
상기식에서,In the above formula,
R1및 R3는 각각 독립적으로 수소, C1-C7알킬 또는 벤질을 나타내며,R 1 and R 3 each independently represent hydrogen, C 1 -C 7 alkyl or benzyl,
R2, R4및 R5는 각각 독립적으로 C1-C5알킬 또는 C1-C5알콕시알킬을 나타내고,R 2 , R 4 and R 5 each independently represent C 1 -C 5 alkyl or C 1 -C 5 alkoxyalkyl,
Bn 은 벤질을 나타낸다.Bn represents benzyl.
상기 정의에서, 용어 "알킬"은 단독으로 사용될 때나 알킬옥시 또는 알콕시알킬과 같이 합성어로 사용되는 경우, 메틸, 에틸, n-프로필, 이소프로필 또는 여러 가지 부틸 이성질체 등과 같은 직쇄 또는 측쇄 포화 탄화수소 래디칼을 의미한다.In the above definition, the term "alkyl", when used alone or as a compound term such as alkyloxy or alkoxyalkyl, refers to straight or branched chain saturated hydrocarbon radicals such as methyl, ethyl, n-propyl, isopropyl or various butyl isomers and the like. it means.
본 발명자들은 피부 미백효과가 우수하고 구조적으로도 안정한 타이로시네이즈 저해제인 하기 화학식 (2)의 1,3-디페닐프로판 유도체(참조: 대한민국 특허출원 제 97-7452 호)를 연구하던 중 이를 합성하는데 필요한 중간체인 화학식 (1)의 1,3-디페닐프로페논 유도체를 효과적으로 제조하는 방법을 발견하게 되었다(반응식 1 참조).The inventors of the present invention were studying a 1,3-diphenylpropane derivative of the following formula (2), which is a structurally stable tyrosinase inhibitor having excellent skin whitening effect (see Korean Patent Application No. 97-7452). A method for effectively preparing 1,3-diphenylpropenone derivatives of formula (1), which is an intermediate required for synthesis, has been found (see Scheme 1).
상기식에서 R1내지 R5및 Bn 은 상기 언급한 바와 같다.Wherein R 1 to R 5 and Bn are as mentioned above.
상기 화학식 (1) 및 (2)의 화합물 중에서 바람직한 화합물은 R1이 수소, 메틸, 에틸 또는 벤질이고, R3가 수소, 메틸 또는 벤질이며, R4및 R5각 각각 메틸인 화합물이다.Among the compounds of the formulas (1) and (2), preferred compounds are those wherein R 1 is hydrogen, methyl, ethyl or benzyl, R 3 is hydrogen, methyl or benzyl, and R 4 and R 5 are each methyl.
1,3-디페닐프로페논 유도체는 일반적으로 하기 반응도식 (2)와 같이 화학식 (3)의 아세토페논 유도체와 화학식 (4)의 벤즈알데하이드 유도체를 염기의 조건에서 클라이젠-슈미트 축합반응시킴으로써 제조된다:A 1,3-diphenylpropenone derivative is generally prepared by klyzen-schmidt condensation reaction of an acetophenone derivative of formula (3) and a benzaldehyde derivative of formula (4) under base conditions as shown in Scheme (2) below. do:
상기식에서,In the above formula,
R1내지 R5는 상기 언급한 바와 같다.R 1 to R 5 are as mentioned above.
그러나, 상기와 같은 일반적인 제조방법으로 반응시킬 때, 아세토페논의 2번 위치가 하이드록시인 경우, 즉 R3가 수소이면 부반응이 많이 일어나므로 대체로 수율이 20%이하로 낮아 2번 위치의 하이드록시기를 보호해야만 한다. 따라서, 이를 테트라하이드로피라닐(THP) 보호기로 보호하여 수율을 80%이상으로 향상시킨 예가 보고된 바 있다(미국특허 5,068,364). 벤즈알데하이드 치환기도 위 반응도식에서 벤질옥시기가 있는 2, 4번 위치에 하이드록시가 하나이상 존재하면 수율이 저하되는 문제가 있었다(참조: Boorganic & Chemistry Letter, 1995, 5, 449). 이와같은 문제점을 해결하기 위해서는 이를 테트라하이드로피라닐(THP)같은 보호기를 사용하는데 보호기를 사용하게 되면 반응단계 수가 늘어나 공정 효율성과 경제성을 떨어뜨리는 단점이 있다.However, when reacting with the general preparation method as described above, when the second position of acetophenone is hydroxy, that is, when R 3 is hydrogen, a lot of side reactions occur, so that the yield is generally 20% or less and lower than the hydroxy position 2 The flag must be protected. Therefore, an example of protecting the tetrahydropyranyl (THP) with a protecting group has been reported to improve the yield to more than 80% (US Patent 5,068, 364). Benzaldehyde substituents also had a problem in that the yield was reduced when one or more hydroxy groups were present at the 2nd and 4th positions of the benzyloxy group in the above scheme (see Boorganic & Chemistry Letter, 1995, 5, 449). In order to solve such a problem, a protecting group such as tetrahydropyranyl (THP) is used. However, when the protecting group is used, the number of reaction steps is increased, thereby decreasing process efficiency and economic efficiency.
따라서, 본 발명자들은 보호기를 도입하는 과정에서 클라이젠-슈미트 축합반응과 같은 반응조건을 사용하여 두 공정을 단일공정으로 바꾸어 공정단계를 줄임으로써 경제성을 떨어뜨리지 않으면서도 화학식 (1)의 화합물을 효과적으로 제조할 수 있는 방법을 연구하게 되었다. 또한, 보호기 제거 과정도 이중결합의 환원반응과 같은 조건을 사용하여 이중결합 하나를 환원시키는 반응과 2∼3개의 보호기를 단일공정으로 제거하는 과정을 사용함으로써 전체적으로 보호기의 도입에 의한 새로운 공정이 부가되지 않도록 하였다.Accordingly, the present inventors have effectively changed the two processes into a single process by using reaction conditions such as the Kreisen-Schmid condensation reaction in the process of introducing a protecting group to reduce the process step, thereby effectively reducing the compound of formula (1) without sacrificing economic efficiency. We studied how to make it. In addition, the process of removing a protecting group also uses a reaction such as reducing a single double bond using the same conditions as a reducing reaction of a double bond and a process of removing 2 to 3 protecting groups in a single process, thereby adding a new process by introducing a protecting group as a whole. It was not.
본 발명자들은 아세토페논 유도체와 벤즈알데하이드 유도체의 히드록시기의 보호기로서 벤질기를 사용하면 염기성 조건에서 클라이젠-슈미트 축합반응을 시킬 때 보호되지 않는 하이드록시기가 반응에 참여하는 부반응을 억제할 수 있음을 확인하고 본 발명을 완성하게 되었다.The inventors have found that the use of benzyl as a protecting group for the hydroxy groups of acetophenone derivatives and benzaldehyde derivatives can inhibit side reactions in which unprotected hydroxy groups participate in the reaction when subjected to Klaisen-Schmid condensation under basic conditions. The present invention has been completed.
본 발명은 하기 화학식 (3)의 아세토페논 유도체와 벤질클로라이드를 고체 무기염 및 상전이촉매의 존재하에 비양성자성 극성 용매중에서 화학식 (4)의 벤즈알데하이드 유도체와 순차적으로 또는 동시에 반응시킴을 특징으로 하여 하기 화학식 (1)의 1,3-디페닐 프로페논 유도체를 제조하는 방법에 관한 것이다:The present invention is characterized in that the acetophenone derivative of the formula (3) and benzyl chloride are reacted sequentially or simultaneously with the benzaldehyde derivative of the formula (4) in an aprotic polar solvent in the presence of a solid inorganic salt and a phase transfer catalyst. To a 1,3-diphenyl propenone derivative of formula (1):
화학식 1Formula 1
상기식에서,In the above formula,
R1및 R3는 각각 독립적으로 수소, C1-C7-알킬 또는 벤질을 나타내며,R 1 and R 3 each independently represent hydrogen, C 1 -C 7 -alkyl or benzyl,
R2, R4및 R5는 각각 독립적으로 C1-C5-알킬 또는 C1-C5-알콕시알킬을 나타내고,R 2 , R 4 and R 5 each independently represent C 1 -C 5 -alkyl or C 1 -C 5 -alkoxyalkyl,
Bn 은 벤질을 나타낸다.Bn represents benzyl.
본 발명에서 고체 무기염으로는 예를 들어 수산화알칼리 금속염, 탄산알칼리 금속염 또는 알칼리금속의 수소화물이 사용되고, 비양성자성 극성용매로는 디메틸포름아미드 및 디메틸설폭사이드가 사용되며, 상전이촉매로는 탄소수 15 내지 25인 테트라알킬암모늄 양이온과 불소, 염소, 브롬 또는 요오드와 같은 할로겐의 음이온 또는 황산수소염과 같은 음이온이 결합된 암모늄염이 사용된다.In the present invention, for example, an alkali metal hydroxide, an alkali metal carbonate, or a hydride of an alkali metal is used as the solid inorganic salt, and dimethylformamide and dimethyl sulfoxide are used as the aprotic polar solvent, and the carbon number is used as the phase transfer catalyst. Ammonium salts in which a tetraalkylammonium cation of 15 to 25 and an anion such as an anion such as hydrogen sulfate or an anion of halogen such as fluorine, chlorine, bromine or iodine are used.
비양성자성 극성용매내에서 고체-액체간 상전이 반응을 사용하여 아세토페논 유도체에 벤질기를 도입할 수 있다. 벤질기의 도입과 클라이젠 축합반응은 같은 반응기 내에서 순차적으로 혹은 동시에 수행할 수 있다. 순차적으로 하는 공정은 다음과 같다.A benzyl group can be introduced into the acetophenone derivative using a solid-liquid phase transfer reaction in an aprotic polar solvent. Introduction of the benzyl group and the Klyzen condensation reaction can be carried out sequentially or simultaneously in the same reactor. The process performed sequentially is as follows.
아세토페논 유도체를 상온에서 테트라알킬 암모늄과 1 당량의 벤질클로라이드와 함께 비양성자성 극성용매에 용해시키고 1.5 ∼ 2.5 당량의 알칼리 금속의 염을 가해준 후 상온에서 0.5 ∼ 3 시간동안 강하게 교반시키면 벤질기의 도입이 완료되고 이 상태에서 각각 1 당량의 벤즈알데하이드 유도체와 알칼리 금속의 수산화염이나 탄산염을 가해주고 상온에서 2 ∼ 4 시간동안 강하게 교반시키면 클라이젠-슈미트 축합반응이 완료된다. 이를 저급 알콜 또는 물로 재결정 분리해내면 칼콘 유도체를 높은 수율과 순도로 얻을 수 있다.When the acetophenone derivative is dissolved in aprotic polar solvent with tetraalkyl ammonium and 1 equivalent of benzyl chloride at room temperature, 1.5-2.5 equivalents of alkali metal salt is added, and the mixture is stirred vigorously at room temperature for 0.5 to 3 hours. After the introduction of, the equivalent of benzaldehyde derivatives and alkali metal hydroxides or carbonates in each state is added and vigorously stirred at room temperature for 2 to 4 hours to complete the Klyzen-Schmid condensation reaction. This can be recrystallized with lower alcohol or water to obtain chalcone derivatives in high yield and purity.
또한, 위의 순차적인 반응은 다음과 같이 동시에 진행시켜도 비슷한 결과를 얻을 수 있다.In addition, the above sequential reactions can be similarly obtained by simultaneously proceeding as follows.
즉, 벤즈알데하이드 유도체를 아세토페논 유도체와 테트라알킬 암모늄염, 벤질클로라이드와 함께 비양성자성 극성용매에 용해시키고 2∼2.5 당량의 알칼리 금속의 염을 가한 후 상온에서 강하게 교반시키면 벤질기의 도입과 클라이젠 축합반응이 동시에 일어나 위의 순차적으로 진행시킨 결과와 같이 원하는 칼콘 유도체를 비슷한 수율과 순도로 얻을 수 있다.That is, benzaldehyde derivatives are dissolved in an aprotic polar solvent together with acetophenone derivatives, tetraalkyl ammonium salts, and benzyl chloride, and 2 to 2.5 equivalents of alkali metal salts are added, followed by vigorous stirring at room temperature. Condensation reactions occur simultaneously and the desired chalcone derivatives can be obtained in similar yields and purity as shown in the above sequential process.
본 발명에 따른 화학식 (1)의 대표적인 예를 하기 표 1에 나타내었다.Representative examples of formula (1) according to the present invention are shown in Table 1 below.
전술한 방법으로 제조하면 아세토페논 유도체로부터 칼콘의 유도체를 수율 75%이상, 순도 95% 이상으로 수득할 수 있으며 이는 피부 미백작용을 갖는 타이로시네이즈 저해제인 1,3-디페닐프로판 유도체의 제조과정중에 유용한 중간체로 사용될 수 있다.When prepared by the above-described method, a derivative of chalcone can be obtained from acetophenone derivative in yield of 75% or higher and purity of 95% or higher, which is used to prepare 1,3-diphenylpropane derivative which is a tyrosinase inhibitor having skin whitening effect. It can be used as a useful intermediate in the process.
이하, 본 발명을 실시예에 의거하여 구체적으로 설명한다. 이들 실시예는 본 발명에 대한 이해를 돕기 위한 것일 뿐, 본 발명이 여기에 한정되는 것은 아니다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated concretely based on an Example. These examples are only for the understanding of the present invention, but the present invention is not limited thereto.
실시예 1: 1-(2-벤질옥시-5-메톡시-3,4,6-트리메틸-페닐)-3-(2,4-디벤질옥시-페닐)-프로페논의 제조Example 1 Preparation of 1- (2-benzyloxy-5-methoxy-3,4,6-trimethyl-phenyl) -3- (2,4-dibenzyloxy-phenyl) -propenone
1-(2-하이드록시-5-메톡시-3,4,6-트리메틸-페닐)-에타논 155g(0.74mole)과 테트라부틸 암모늄 브롬염 13g, 벤질클로라이드 110g(0.87mole)을 330g의 디메틸포름아미드에 용해시키고, 고체상태의 수산화 나트륨 63g(1.58mole)을 가한 후, 상온에서 강하게 교반시켜 주었다. 2시간후 반응의 완결을 확인하고(기체 크로마토그래피), 2,4-디벤질옥시-벤즈알데하이드 239g(0.75mole)과 수산화나트륨 30g(0.75mole)을 반응혼합물에 가하고 상온에서 강하게 교반시켰다. 2시간후 반응의 완결을 확인하고(액체 크로마토그래피; 수율 99%), 메탄올 1320g을 넣고 5℃로 냉각하여 교반시키면 노란색의 결정이 형성되고, 이를 여과하고 얻어진 고체를 메탄올 500g과 물 1,500g으로 순차적으로 세척하고 진공오븐에서 건조하여 373g(0.62mole, 수율 80%)의 표제화합물을 수득하였다.155 g (0.74 mole) of 1- (2-hydroxy-5-methoxy-3,4,6-trimethyl-phenyl) -ethanone, 13 g of tetrabutyl ammonium bromine salt, 110 g (0.87 mole) of benzyl chloride, and 330 g of dimethyl After dissolving in formamide, 63 g (1.58 mole) of sodium hydroxide in solid state was added, followed by vigorous stirring at room temperature. After 2 hours, the reaction was confirmed to be complete (gas chromatography), and 239 g (0.75 mole) of 2,4-dibenzyloxy-benzaldehyde and 30 g (0.75 mole) of sodium hydroxide were added to the reaction mixture, followed by strong stirring at room temperature. After 2 hours, the reaction was confirmed to be complete (liquid chromatography; yield 99%), 1320 g of methanol was added thereto, and the mixture was cooled to 5 ° C. and stirred to form yellow crystals. The solid was filtered and the obtained solid was purified using 500 g of methanol and 1,500 g of water. It was washed sequentially and dried in a vacuum oven to give 373g (0.62mole, 80% yield) of the title compound.
실시예 2: 1-(2-벤질옥시-5-메톡시-3,4,6-트리메틸-페닐)-3-(2,4-디벤질옥시-페닐)-프로페논의 제조Example 2: Preparation of 1- (2-benzyloxy-5-methoxy-3,4,6-trimethyl-phenyl) -3- (2,4-dibenzyloxy-phenyl) -propenone
1-(2-하이드록시-5-메톡시-3,4,6-트리메틸-페닐)-에타논 25g(0.12mole)과 2,4-디벤질옥시-벤즈알데하이드 42g(0.13mole), 테트라부틸암모늄 브롬염 2g, 벤질클로라이드 17g(0.13mole)을 75g의 디메틸포름아미드에 용해시키고, 고체상태의 수산화나트륨 14g(0.36mole)을 가한 후, 상온에서 강하게 교반시켜 주었다. 5시간후 반응의 완결을 확인하고(액체 크로마토그래피; 수율 95%), 에탄올 94g을 넣고 5℃로 냉각하여 교반시키면 노란색의 결정이 형성되고 이를 실시예 1과 같이 후처리하여 55g(0.09mole, 수율 76%)의 표제화합물을 수득하였다.25 g (0.12 mole) of 1- (2-hydroxy-5-methoxy-3,4,6-trimethyl-phenyl) -ethanone and 42 g (0.13 mole) of 2,4-dibenzyloxy-benzaldehyde, tetrabutyl 2 g of ammonium bromine salt and 17 g (0.13 mole) of benzyl chloride were dissolved in 75 g of dimethylformamide, and 14 g (0.36 mole) of sodium hydroxide in solid state was added thereto, followed by vigorous stirring at room temperature. After 5 hours, the reaction was confirmed to be complete (liquid chromatography; yield 95%), 94 g of ethanol was added thereto, and the mixture was cooled to 5 ° C. and stirred to form yellow crystals. The resultant was treated as in Example 1 to 55 g (0.09 mole, Yield 76%) of the title compound.
실시예 3: 1-(2-벤질옥시-5-에톡시-3,4,6-트리메틸-페닐)-3-(2,4-디벤질옥시-페닐)-프로페논의 제조Example 3: Preparation of 1- (2-benzyloxy-5-ethoxy-3,4,6-trimethyl-phenyl) -3- (2,4-dibenzyloxy-phenyl) -propenone
실시예 1에서 1-(2-하이드록시-5-메톡시-3,4,6-트리메틸페논)에타논 대신에 1-(2-하이드록시-5-에톡시-3,4,6-트리메틸-페닐)-에타논 25g(0.11mole)을 사용하여 표제화합물 53g(0.087mole, 수율 79%)을 수득하였다.Example 1 1- (2-hydroxy-5-ethoxy-3,4,6-trimethyl instead of 1- (2-hydroxy-5-methoxy-3,4,6-trimethylphenone) ethanone 25 g (0.11 mole) of -phenyl) -ethanone were used to obtain 53 g (0.087 mole, yield 79%) of the title compound.
실시예 4: 3-(2,4-벤질옥시-페닐)-1-(2,5-디벤질옥시-3,4,6-트리메틸-페닐)-프로페논의 제조Example 4: Preparation of 3- (2,4-benzyloxy-phenyl) -1- (2,5-dibenzyloxy-3,4,6-trimethyl-phenyl) -propenone
1-(2,5-디하이드록시-3,4,6-트리메틸-페닐)-에타논 30g(0.15mole)과 테트라부틸암모늄브롬염 2.5g, 벤질클로라이드 42g(0.33mole)을 75g 의 디메틸포름아미드에 용해시키고, 고체상태의 수산화 나트륨 24g(0.6mole)을 가한 후, 상온에서 강하게 교반시켜 두었다. 2.5시간후 반응의 완결을 확인하고 (기체 크로마토그래피) 2,4-디벤질옥시-벤즈알데하이드 53g(0.17mole)과 수산화나트륨 7g (0.17mole)을 반응혼합물에 가하고 상온에서 강하게 교반시켰다. 2시간후 반응의 완결을 확인하고(액체 크로마토그래피; 수율 95%), 실시예 1과 같이 후처리하여 77g(0.11mole, 수율 76%)의 표제화합물을 수득하였다.30 g (0.15 mole) of 1- (2,5-dihydroxy-3,4,6-trimethyl-phenyl) -ethanone, 2.5 g of tetrabutylammonium bromide, 42 g (0.33 mole) of benzyl chloride, 75 g of dimethylform After dissolving in amide, 24 g (0.6 mole) of sodium hydroxide in solid state was added thereto, followed by vigorous stirring at room temperature. After 2.5 hours, the reaction was confirmed to be complete (gas chromatography). 2,4-dibenzyloxy-benzaldehyde 53g (0.17mole) and sodium hydroxide 7g (0.17mole) were added to the reaction mixture, followed by strong stirring at room temperature. After 2 hours the reaction was complete (liquid chromatography; yield 95%), and worked up as in Example 1 to give 77 g (0.11 mole, yield 76%) of the title compound.
본 발명에 따르면, 피부 미백효과가 우수하고 구조적으로도 안정한 타이로시네이즈 저해제인 1,3-디페닐프로판 유도체의 합성에 사용되는 중간체인 1,3-디페닐프로페논 유도체를 효과적으로 제조할 수 있다.According to the present invention, it is possible to effectively prepare a 1,3-diphenylpropenone derivative which is an intermediate used in the synthesis of a 1,3-diphenylpropane derivative which is a structurally stable tyrosinase inhibitor having excellent skin whitening effect. have.
Claims (8)
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57142944A (en) * | 1981-02-27 | 1982-09-03 | Agency Of Ind Science & Technol | Chalcone derivative and its preparation |
| JPS62185037A (en) * | 1986-02-12 | 1987-08-13 | Tsumura Juntendo Inc | Chalcone derivative |
| JPH01242540A (en) * | 1988-03-22 | 1989-09-27 | Tsumura & Co | Novel chalcone derivative and antiulcer agent containing said derivative as active ingredient |
| US5068364A (en) * | 1988-11-21 | 1991-11-26 | Dainippon Ink And Chemicals, Inc. | Chalcone derivatives and process for producing the same |
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1998
- 1998-05-15 KR KR1019980017686A patent/KR19990085333A/en not_active Application Discontinuation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57142944A (en) * | 1981-02-27 | 1982-09-03 | Agency Of Ind Science & Technol | Chalcone derivative and its preparation |
| JPS62185037A (en) * | 1986-02-12 | 1987-08-13 | Tsumura Juntendo Inc | Chalcone derivative |
| JPH01242540A (en) * | 1988-03-22 | 1989-09-27 | Tsumura & Co | Novel chalcone derivative and antiulcer agent containing said derivative as active ingredient |
| US5068364A (en) * | 1988-11-21 | 1991-11-26 | Dainippon Ink And Chemicals, Inc. | Chalcone derivatives and process for producing the same |
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