KR101260658B1 - A New Economical Synthesis of Mollugin - Google Patents
A New Economical Synthesis of Mollugin Download PDFInfo
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- KR101260658B1 KR101260658B1 KR1020110071410A KR20110071410A KR101260658B1 KR 101260658 B1 KR101260658 B1 KR 101260658B1 KR 1020110071410 A KR1020110071410 A KR 1020110071410A KR 20110071410 A KR20110071410 A KR 20110071410A KR 101260658 B1 KR101260658 B1 KR 101260658B1
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- C—CHEMISTRY; METALLURGY
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
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- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/33—Heterocyclic compounds
- A61K31/335—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin
- A61K31/35—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin having six-membered rings with one oxygen as the only ring hetero atom
- A61K31/352—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin having six-membered rings with one oxygen as the only ring hetero atom condensed with carbocyclic rings, e.g. methantheline
Abstract
본 발명은 꼭두서니과 (Rubiacease)에 속하는 치자나무 (Capejasmine)에서 치자 700g당 0.3g을 추출 분리해 얻을 수 있는 주요 활성성분으로서 매우 강한 항바이러스, 혈압강하 및 해열진정효과를 나타내는 Mollugin의 합성을 값싼 1,4-naphthoquinone 화합물로부터 kinetic resolution 반응을 이용하여 one-pot으로 효율적, 선택적으로 합성하는 방법의 개발에 관한 것으로, 기존 합성법에서 문제가 되는 평형에 의한 출발물질로의 산화와 값비싼 출발물질을 사용 하지 않고 Mollugin을 합성하는 방법의 개발을 포함하는 것을 특징으로 한다.The present invention is a major active ingredient obtained by extracting and separating 0.3 g per 700 g of Gardenia jasminoides from Cape jasmine belonging to Rubiacease , which is an inexpensive synthesis of Mollugin showing very strong antiviral, blood pressure lowering and antipyretic effect. Development of efficient and selective synthesis of one-pot from kinetic resolution reaction using 4,4-naphthoquinone compound. Oxidation of equilibrium starting material and expensive starting material Without the development of a method for synthesizing Mollugin.
Description
항바이러스, 혈압강하 및 해열진정효과를 나타내는 치자의 주요 활성성분 Mollugin의 새로운 경제적 합성법으로 1,4-naphthoquinone 화합물로부터 kinetic resolution을 이용한 one-pot reduction-acylation과 cyclization을 포함한 2단계의 반응으로 효율적, 경제적으로 Mollugin을 전합성 하는 방법의 개발에 관한 것이다.A new economical synthesis method of Mollugin, the main active ingredient of gardenia jasminoides, which has antiviral, hypotension and antipyretic effect. It is about the development of a method for synthesizing Mollugin economically.
Mollugin은 매우 강한 항바이러스작용 [Chem. Pharm. Bull. 1983, 31, 2353] 을 나타내는 물질로서 꼭두서니과 (Rubiacease)에 속하는 치자나무 (Capejasmine)의 주요 활성성분이다 [Phytochemistry, 1989, 28, 3465]. 그러나 치자나무에서 추출시 700g의 건조된 치자에서 유효성분 0.3g정도 밖에 얻어내지 못하는 귀한 물질이다 [Turk J. Chem ., 2006, 30, 15]. 기존의 합성방법들은 8단계의 긴 반응 [Tetrahedron 2006, 62, 8419] 이나 출발물질의 값이 비싼 [Bull . Korean Chem . Soc ., 2007, 28, 1735] 반응으로 경제적, 효율적이 아닌 단점을 갖는다. Mollugin의 새롭고 경제적, 효율적 합성법의 개발로 자연에서 얻기 어려운 Mollugin 및 유도체들을 손쉽게 합성할 수 있어 B형간염등을 위시한 항바이러스연구에 매우 중요한 의미를 갖는다.
Mollugin has a very strong antiviral action [ Chem. Pharm. Bull . 1983 , 31 , 2353], which is the main active ingredient of Capejasmine belonging to Rubiacease [ Phytochemistry , 1989, 28 , 3465]. However, it is a rare substance that can extract only 0.3g of active ingredient from 700g of dried gardenia when extracted from gardenia [ Turk J. Chem ., 2006 , 30 , 15]. Existing synthesis methods are eight long reactions [ Tetrahedron 2006 , 62 , 8419] or expensive starting materials [ Bull . Korean Chem . Soc ., 2007 , 28 , 1735] reactions are not economical and efficient. Mollugin's new, economical and efficient synthesis method makes it easy to synthesize mollugin and its derivatives, which are difficult to obtain in nature, and is very important for antiviral research including hepatitis B.
다음의 반응식 1은 상기 반응을 도식적으로 표시한 것이다.The following scheme 1 schematically illustrates the reaction.
반응식 1Scheme 1
Mollugin의 합성은 상업적으로 구할 수 있는 1,4-naphthoquinone (화학식 1)을 sodium hydrosulfite와 ascorbic acid (비타민 C)를 이용한 환원반응으로 1,4-dihydroxynaphthalene (화학식 2)을 합성하고 염기 (KH)와 dimethyl carbonate를 이용한 acylation으로 methyl 1,4-dihydroxy-2-naphthoate (화학식 3)를 합성한다. 여기에 3-methyl-2-butenal, phenylboronic acid 및 propionic acid를 이용한 고리화반응으로 Mollugin (화학식 4)을 합성한다. 기존의 1,4-naphthoquinone (화학식 1)의 환원반응으로 얻은 1,4-dihydroxynaphthalene (화학식 2)은 acylation 과정에서 평형으로 인해 대부분 다시 더 안정한 출발물질 1,4-naphthoquinone (화학식 1) 으로 돌아가 다음반응인 acylation반응이 진행되지 않거나 수율이 매우 저조한 문제점을 갖고 있다.
The synthesis of mollugin was carried out by reduction reaction of commercially available 1,4-naphthoquinone (Formula 1) with sodium hydrosulfite and ascorbic acid (vitamin C) to synthesize 1,4-dihydroxynaphthalene (Formula 2), Methyl 1,4-dihydroxy-2-naphthoate (Formula 3) is synthesized by acylation using dimethyl carbonate. Mollugin (Formula 4) is synthesized by cyclization using 3-methyl-2-butenal, phenylboronic acid, and propionic acid. The 1,4-dihydroxynaphthalene (Formula 2) obtained by the reduction reaction of the existing 1,4-naphthoquinone (Formula 1) is mostly returned to the more stable starting material 1,4-naphthoquinone (Formula 1) due to the equilibrium during the acylation process. The acylation reaction does not proceed or the yield is very poor.
따라서, 본 발명은 이러한 문제점을 해결하고자 1,4-naphthoquinone (화학식 1)의 환원반응으로 얻은 1,4-dihydroxynaphthalene (화학식 2)을 분리하지 않고 한 반응 플라스크내에서 (one-pot반응) 직접 다음반응단계인 acylation과정을 진행시키는 kinetic resolution 방법을 개발하여 화학식 1과 2의 평형상태에서 acylation으로 화학식 3화합물이 생성되면 화학식 3화합물은 비가역물질로 다시는 화학식 2로 돌아가지 않는 성질을 이용하여 르샤틀리에 법칙에 의해 acylation 반응으로 소모된 화학식 2만큼 평형에 의해 계속 화학식 1로부터 만들어져 반응이 완결될 때까지 진행됨으로 가역반응으로 인한 수율의 저하나 반응이 일어나지 않는 문제점을 해결하여 Mollugin (화학식 4) 합성의 경제성 및 효율성을 높이는 합성방법을 제공하는 데 있다.
Therefore, in order to solve this problem, the present invention is directed to directly in a reaction flask (one-pot reaction) without separating 1,4-dihydroxynaphthalene (Formula 2) obtained by the reduction reaction of 1,4-naphthoquinone (Formula 1). By developing a kinetic resolution method that proceeds with the reaction acylation process, when compound 3 is produced by acylation in the equilibrium state of formula 1 and 2, compound 3 is irreversible and does not return to formula 2. Mollugin (Formula 4) solves the problem that the yield does not decrease or the reaction does not occur due to the reversal reaction, which is made from Equation 1 by equilibrium as much as Equation 2 consumed by the acylation reaction according to the law of Tlierie. It is to provide a synthesis method to increase the economics and efficiency of synthesis.
상기 목적에 따라, 본 발명에서는 환원반응으로 한 플라스크내에 출발물질인 화학식 1과 생성물인 화학식 2가 평형상태로 공존하도록 하는 조건에서 염기와 dimethyl carbonate를 이용하여 acetylation 반응을 통해 화학식 2가 화학식 3 화합물로 전환되도록 하고 kinetic resolution 반응에 의해 반응으로 소모된 화학식 2가 계속해서 평형에 의해 화학식 1로부터 공급되게 함으로 궁극적으로 모든 화학식 1 화합물이 가역반응에 의해 화학식 2로 전환되고 화학식 2는 비가역반응인 acetylation 반응으로 화학식 3이 생성 되도록 한 후 고리화반응을 통해 Mollugin을 합성하는 방법을 제공한다.
In accordance with the above object, in the present invention, the compound of Formula 2 is represented by Formula 3 through the acetylation reaction using a base and dimethyl carbonate under conditions such that the starting compound of Formula 1 and the product of Formula 2 coexist in an equilibrium state in a flask subjected to a reduction reaction. And by the kinetic resolution reaction the formula 2 consumed in the reaction continues to feed from formula 1 by equilibrium, ultimately all compounds of formula 1 are converted to formula 2 by reversible reaction and formula 2 is an irreversible acetylation It provides a method of synthesizing Mollugin through the reaction to the formula 3 is produced by the reaction.
화학식 1의 화합물로부터 화학식 4의 Mollugin을 제조하는데 있어 화학식 2, 화학식 3을 거치는 3단계의 합성방법중 화학식 2를 분리하지 않고 kinetic resolution 반응을 이용하여 직접 화학식 3 화합물을 합성하는 신규한 Mollugin 합성방법이다. 특히, 값이 싼 출발물질을 이용하고 두 번째 단계를 분리해 내지 않고 한 플라스크내에서 진행하며 출발물질이 평형에 의해 모두 반응에 이용되게 함으로 경제성과 환경친화성을 크게 높이고 반응단계도 2단계로 줄였다.
Novel Mollugin synthesis method for synthesizing the compound of formula (3) directly by kinetic resolution reaction without separating the formula (2) in the three-step synthesis method through the formulas (2) and (3) to prepare the mollugin of the formula (4) from the compound of the formula (1) to be. In particular, using a cheap starting material and proceeding in one flask without separating the second step, and the starting material is all used for the reaction by equilibrium, greatly improving the economics and environmental friendliness, and also the reaction step to the second step Reduced.
이하 본 발명을 상세히 설명한다. Hereinafter, the present invention will be described in detail.
본 발명에서 출발물질로 사용되는 1,4-naphthoquinone은 하기 화학식 1로 표시된다:1,4-naphthoquinone used as a starting material in the present invention is represented by the following formula (1):
상기 식에서, 1,4-naphthoquinone은 알드리치등의 시약회사에서 쉽게 구입할 수 있으며 methanol 용매에 녹여서 사용한다.In the above formula, 1,4-naphthoquinone can be easily purchased from a reagent company such as Aldrich and dissolved in methanol solvent.
상기식에서 1,4-dihydroxynaphthalene은 출발물질 (화학식 1)로부터 sodium hydrosulfite와 비타민 C를 이용한 환원반응으로 얻어지나 분리하지 않고 one-flask반응으로 직접 다음반응에 이용한다.In the above formula, 1,4-dihydroxynaphthalene is obtained by the reduction reaction using sodium hydrosulfite and vitamin C from the starting material (Formula 1), but is used in the next reaction directly as a one-flask reaction without separation.
상기식에서 methyl 1,4-dihydroxy-2-naphthoate는 화학식 2에 potassium hydride, 18-crown-6와의 acylation 반응으로 얻어진다.In the above formula, methyl 1,4-dihydroxy-2-naphthoate is obtained by acylation reaction with potassium hydride and 18-crown-6 in Chemical Formula 2.
상기식에서 Mollugin은 화학식 3에 알드리치등의 시약회사에서 쉽게 구입할 수 있는 3-methyl-2-butenal, phenylboronic acid, propionic acid와의 고리화반응으로 얻어진다.
In the formula, Mollugin is obtained by cyclization reaction with 3-methyl-2-butenal, phenylboronic acid, and propionic acid, which can be easily purchased from a reagent company such as Aldrich in Formula 3.
이하 본 발명을 하기 실시예에 의하여 더욱 상세하게 설명하고자 한다. 단, 하기 실시예는 본 발명을 예시하기 위한 것일 뿐, 본 발명의 범위가 이들만으로 한정되는 것은 아니다.
Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
실시예Example
실시예 1Example 1
1,4-naphthoquinone (화학식 1)으로부터 화학식 3의 합성방법Synthesis of Chemical Formula 3 from 1,4-naphthoquinone
화학식 1의 화합물 (0.20g, 1.26mmol)을 sodium hydrosulfite (0.33g, 1.90mmol), ascorbic acid (0.18g, 1.01mmol)와 질소 분위기 하에서 증류한 methanol (10mL)을 이용하여 녹이고, 빛을 차단시킨 후 실온에서 5시간 교반한다. 반응이 종결되면 potassium hydride (0.16g, 1.39mmol)와 18-crown-6 (0.51g, 1.39mmol)을 질소 분위기 하에 증류한 THF (10mL)에 넣고, 앞에서 반응한 반응물을 methanol을 제거하고 증류한 THF (10mL)에 녹여 0에서 천천히 첨가하고 실온에서 10분 동안 교반한다. 이 반응물에 dimethyl carbonate (0.12mL, 1.39mmol)을 천천히 0에서 첨가하고 실온에서 10시간동안 교반한 뒤 반응을 종결시키고 Celite 545 로 여과 후 ethyl acetate (20mL3) 추출 후 유기층을 brine으로 씻어주고, MgSO4로 건조 후 감압 증류하여 남은 물질을 컬럼크로마토그래피 (Pet Ether:EtOAc=25:1)로 분리하여 연노란색 고체인 목적화합물 3을 얻었다.
The compound of formula 1 (0.20g, 1.26mmol) was dissolved in sodium hydrosulfite (0.33g, 1.90mmol), ascorbic acid (0.18g, 1.01mmol) and methanol (10mL) distilled under nitrogen atmosphere. After stirring at room temperature for 5 hours. At the end of the reaction, potassium hydride (0.16g, 1.39mmol) and 18-crown-6 (0.51g, 1.39mmol) were added to THF (10mL) distilled under nitrogen atmosphere. Dissolve in THF (10 mL), add slowly at 0, and stir at room temperature for 10 minutes. Dimethyl carbonate (0.12 mL, 1.39 mmol) was slowly added to the reaction at 0, stirred at room temperature for 10 hours, and the reaction was terminated. After filtration with 545 and ethyl acetate (20mL3) extraction, the organic layer was washed with brine, dried over MgSO 4, and distilled under reduced pressure to separate the remaining material by column chromatography (Pet Ether: EtOAc = 25: 1) to give a pale yellow solid. Compound 3 was obtained.
수율 : 0.11g, 41%Yield: 0.11 g, 41%
Rf=0.43 (EtOAc:Hex=1:3); m.p. 192-193R f = 0.43 (EtOAc: Hex = 1: 3); mp 192-193
1H NMR (300 MHz, CDCl3) 3.90 (3H, s), 7.09 (1H, s), 7.56 (1H, d, J=7.0 Hz), 7.64 (1H, d, J=7.0 Hz), 7.80 (1H, s), 8.12 (1H, d, J=8.0 Hz), 8.38 (1H, d, J=8.0 Hz), 11.52 (1H, s). 1 H NMR (300 MHz, CDCl 3 ) 3.90 (3H, s), 7.09 (1H, s), 7.56 (1H, d, J = 7.0 Hz), 7.64 (1H, d, J = 7.0 Hz), 7.80 ( 1H, s), 8.12 (1H, d, J = 8.0 Hz), 8.38 (1H, d, J = 8.0 Hz), 11.52 (1H, s).
13C NMR (75 MHz, CDCl3) 51.5, 105.2, 110.4, 147.1, 112.5, 124.6, 127.7, 128.0, 129.5, 147.1, 153.7, 169.7.
13 C NMR (75 MHz, CDCl 3 ) 51.5, 105.2, 110.4, 147.1, 112.5, 124.6, 127.7, 128.0, 129.5, 147.1, 153.7, 169.7.
실시예 2Example 2
화학식 3으로부터 화학식 4의 합성방법
Synthesis of Chemical Formula 4 from Chemical Formula 3
화학식 3의 화합물 (0.10g, 0.46mmol)과 3-methyl-2-butenal (0.05mL, 0.50mmol), phenylboronic acid(0.18g, 1.38mmol), propionic acid(0.10mL, 1.38mmol)를 질소 분위기 하에 증류한 toluene (5mL)에 넣고 Dean-stark trap을 이용하여 15시간동안 환류 시킨다. 반응 종결 후 실온으로 냉각시킨 후 감압 증류하여 toluene을 제거하고, ether를 넣어 희석시킨 후 H2O, 포화 NaHCO3수용액, Brine으로 유기층을 씻어준다. 유기층을 Na2SO4를 넣어 건조시킨 후 용매를 감압 증류하여 남은 물질을 컬럼크로마토그래피 (Pet Ether: EtOAc=30:1)로 분리하여 연녹색 고체인 Mollugin (화합물 4)을 얻었다.
Compound of formula 3 (0.10 g, 0.46 mmol), 3-methyl-2-butenal (0.05 mL, 0.50 mmol), phenylboronic acid (0.18 g, 1.38 mmol), propionic acid (0.10 mL, 1.38 mmol) under nitrogen atmosphere Place in distilled toluene (5mL) and reflux for 15 hours using Dean-stark trap. After completion of the reaction, the mixture was cooled to room temperature, distilled under reduced pressure to remove toluene, diluted with ether, and the organic layer was washed with H 2 O, saturated aqueous NaHCO 3 , and Brine. The organic layer was dried with Na 2 SO 4, and the solvent was distilled off under reduced pressure. The remaining material was separated by column chromatography (Pet Ether: EtOAc = 30: 1) to obtain a light green solid, Mollugin (Compound 4).
수율 : 0.11g, 81%Yield: 0.11 g, 81%
Rf=0.68 (EtOAc:Hex=1:3); m.p. 129-133R f = 0.68 (EtOAc: Hex = 1: 3); mp 129-133
1H NMR (300 MHz, CDCl3) 1.48 (6H, s), 3.91 (3H, s), 5.61 (1H, d, J=9.9 Hz), 7.09 (1H, d, J=9.9 Hz), 7.486 (1H, t, J=7.2 Hz), 7.59 (1H, t, J=6.9 Hz), 8.15 (1H, d, J=8.4 Hz), 8.34 (1H, d, J=8.4 Hz), 12.15 (1H, s). 1 H NMR (300 MHz, CDCl 3 ) 1.48 (6H, s), 3.91 (3H, s), 5.61 (1H, d, J = 9.9 Hz), 7.09 (1H, d, J = 9.9 Hz), 7.486 ( 1H, t, J = 7.2 Hz), 7.59 (1H, t, J = 6.9 Hz), 8.15 (1H, d, J = 8.4 Hz), 8.34 (1H, d, J = 8.4 Hz), 12.15 (1H, s).
13C NMR (75 MHz, CDCl3) 27.21 (x2), 52.64, 75.03, 102.42, 112.76, 122,10, 122.50, 124.20, 125.24, 126.48, 129.02, 129.17, 129.51, 141.71, 156.60, 172.56.
13 C NMR (75 MHz, CDCl 3 ) 27.21 (x2), 52.64, 75.03, 102.42, 112.76, 122,10, 122.50, 124.20, 125.24, 126.48, 129.02, 129.17, 129.51, 141.71, 156.60, 172.56.
Claims (3)
(가) 하나의 용기 내에서 1,4-나프토퀴논 (화학식 1)을 환원 반응 시켜 1,4-다이하이드록시나프탈렌 (1,4-dihydroxynaphthalene) (화학식 2)을 합성하고, 합성된 1,4-다이하이드록시나프탈렌을 아실화 반응 시켜 메틸 1,4-다이하이드록시-2-나프토에이트 (methyl 1,4-dihydroxy-2-naphthoate) (화학식 3)를 합성하는 단계; 및
(나) 상기 (가) 단계에서 얻어진 메틸 1,4-다이하이드록시-2-나프토에이트 (methyl 1,4-dihydroxy-2-naphthoate) (화학식 3)를 고리화 반응 시켜 몰루진 (화학식 4)을 합성하는 단계; 의 두 단계로 몰루진을 합성하는 것을 특징으로 하는 몰루진 합성방법.
화학식 1
화학식 2
화학식 3
화학식 4
In the method for synthesizing mollugin (Mollugin) represented by the formula (4) from 1,4-naphthoquinone represented by the formula (1),
(A) Synthesis of 1,4-dihydroxynaphthalene (Formula 2) by reduction reaction of 1,4-naphthoquinone (Formula 1) in one vessel, and synthesized 1,4-dihydroxynaphthalene (Formula 2). Acylating 4-dihydroxynaphthalene to synthesize methyl 1,4-dihydroxy-2-naphthoate (Formula 3); And
(B) Cyclization reaction of methyl 1,4-dihydroxy-2-naphthoate (Formula 3) obtained in the step (A) above Synthesizing); A method for synthesizing molluzine, characterized in that to synthesize molluzine in two steps.
Formula 1
(2)
(3)
Formula 4
상기 (가) 단계는 하나의 용기 내에서 1,4-나프토퀴논 (화학식 1)에 차아황산나트륨 (sodium hydrosulfite)과 아스코르빈산 (ascorbic acid)을 가하여 환원반응으로 1,4-다이하이드록시나프탈렌 (1,4-dihydroxynaphthalene) (화학식 2)을 합성하고, 합성된 1,4-다이하이드록시나프탈렌에 염기와 다이메틸카보네이트 (dimethyl carbonate)를 가하여 아실화반응으로 메틸 1,4-다이하이드록시-2-나프토에이트 (methyl 1,4-dihydroxy-2-naphthoate) (화학식 3)를 합성함을 특징으로 하는, 몰루진 합성방법.
The method of claim 1,
In step (a), 1,4-dihydroxynaphthalene is reduced by adding sodium hydrosulfite and ascorbic acid to 1,4-naphthoquinone (Formula 1) in one vessel. (1,4-dihydroxynaphthalene) (Formula 2) was synthesized, and base and dimethyl carbonate were added to the synthesized 1,4-dihydroxynaphthalene and methyl 1,4-dihydroxy- was obtained by acylation. Molazine synthesis method characterized in that to synthesize 2-naphthoate (methyl 1,4-dihydroxy-2-naphthoate) (Formula 3).
상기 (가) 단계의 염기는 수산화칼륨임을 특징으로 하는 몰루진 합성방법.
The method of claim 1,
The method of claim 1, wherein the base of step (a) is potassium hydroxide.
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| Bull. Korean Chem. Soc. 2007. Vol. 28, No. 10, pp. 1863-1866* |
| Tetrahedron. 2006. Vol. 62, pp. 8419-8424 |
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