KR101215394B1 - Novel fluoranthene derivatives and its preparation method - Google Patents

Novel fluoranthene derivatives and its preparation method Download PDF

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KR101215394B1
KR101215394B1 KR1020120059918A KR20120059918A KR101215394B1 KR 101215394 B1 KR101215394 B1 KR 101215394B1 KR 1020120059918 A KR1020120059918 A KR 1020120059918A KR 20120059918 A KR20120059918 A KR 20120059918A KR 101215394 B1 KR101215394 B1 KR 101215394B1
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fluoranthene
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alkoxy
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이필호
모준태
류태규
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강원대학교산학협력단
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
    • C07C7/17—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with acids or sulfur oxides
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
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    • C07C13/62—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with more than three condensed rings
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    • C07—ORGANIC CHEMISTRY
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    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
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    • C07C41/38—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
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Abstract

PURPOSE: A method of manufacturing fluoranthene derivative is provided to manufacture various fluoranthene derivatives in a simple process, short reaction time, and high yield under the presence of acid. CONSTITUTION: A method of manufacturing fluoranthene derivative comprises the following steps. Manufacturing Fluoranthene derivative represented by chemical formula1 below from the compound represented by chemical formula2 below under the presence of trifluoromethanesulfonic acid. In the chemical formula 1 or 2, X represents CH2 or O. R1 and R4 are identical, and selected from hydrogen and halogen, alkyl(C1-C8), alkoxy(C1-C8), or aryl(C6-C20). R2 and R5 are identical, and selected from hydrogen or alkoxy(C1-C8). R3 and R6 are identical, and selected from hydrogen, halogen, alkyl(C1-C8), or alkoxy(C1-C8).

Description

플루오란센 유도체와 이의 제조 방법 {Novel fluoranthene derivatives and its preparation method}Fluoranthene derivatives and its preparation method {Novel fluoranthene derivatives and its preparation method}

본 발명은 플루오란센 유도체와 이의 제조방법에 관한 것으로 보다 상세하게 바이나프틸 유도체 또는 바이크로멘 유도체로부터 플루오란센 유도체를 효율적으로 제조하는 방법과 이에 따라 제조된 플루오란센 유도체에 관한 것이다.The present invention relates to a fluoranthene derivative and a method for preparing the same, and more particularly, to a method for efficiently preparing a fluoranthene derivative from a binaphthyl derivative or a bichromene derivative and a fluoranthene derivative prepared accordingly.

플루오로란센 유도체들은 치환된 작용기에 따라 다른 영역에서 형광을 나타내는 특성을 가지고 있어 화학센서(chemosensor) 전구체로 많은 연구가 진행되고 있다. Fluororansen derivatives have fluorescence properties in different regions depending on the substituted functional groups, and thus, many studies are being conducted as precursors of chemical sensors.

이러한 일례로 한국등록특허공보 제 10-1011847에 벤조플루오란센 유도체를 이용한 유기 전계 발광소자를 개시하고 있다.For example, Korean Patent Publication No. 10-1011847 discloses an organic electroluminescent device using a benzofluoranthene derivative.

또한 한국등록특허공보 제 10-1101963호에 시멘트용 안료분산제로 사용될 수 있는 고분자에 플루오란센이 치환기로 채용되었다.Also in Korean Patent Publication No. 10-1101963, fluoranthene is employed as a substituent in a polymer that can be used as a pigment dispersant for cement.

상술한 바와 같이 다양한 용도의 원료물질 또는 중간체로 플루오란센 유도체가 사용되지만 다양한 구조를 갖는 플루오란센 유도체의 합성법은 거의 보고가 되고 있지 않은 실정이다. As described above, although fluoranthene derivatives are used as raw materials or intermediates for various purposes, the synthesis of fluoranthene derivatives having various structures has been rarely reported.

한편 Amberlyst-15 촉매를 이용한 간단한 구조의 플루오란센 유도체의 제조방법이 알려져 있긴 하지만 반응시간이 길고, 다양한 유도체에 대한 촉매의 적용범위에 있어서 제한이 있다(J. Org . Chem. 1984, 49, 1030). On the other hand, a method of preparing a fluoranthene derivative having a simple structure using an Amberlyst-15 catalyst is known, but the reaction time is long, and there is a limitation in the scope of application of the catalyst to various derivatives ( J. Org . Chem . 1984 , 49 , 1030).

따라서 다양한 치환기를 가진 플루오란센 유도체와 이의 효율적인 제조방법에 관한 연구가 요구되고 있는 실정이다.Therefore, there is a need for a study on a fluoranthene derivative having various substituents and an efficient preparation method thereof.

한국등록특허공보 제 10-1011847Korean Registered Patent Publication No. 10-1011847 한국등록특허공보 제 10-1101963호Korean Patent Publication No. 10-1101963

J. Org. Chem. 1984, 49, 1030J. Org. Chem. 1984, 49, 1030

본 발명은 다양한 용도에 사용 가능한 플루오란센 유도체와 이의 제조방법을 제공한다.The present invention provides fluoranthene derivatives that can be used in various applications and methods for their preparation.

본 발명은 의약품 또는 OLED의 원료물질 또는 중간물질로 사용 가능한 플루오란센 유도체, 보다 상세하게는 5,6,12,12a-테트라하이드로벤조[j]플루오란센 유도체를 제공한다.The present invention provides fluoranthene derivatives, more particularly 5,6,12,12a-tetrahydrobenzo [ j ] fluoranthene derivatives, which can be used as raw materials or intermediates of pharmaceuticals or OLEDs.

본 발명에 따른 플루오란센 유도체는 하기 화학식 1로 표시된다.Fluoranthene derivatives according to the present invention are represented by the following formula (1).

[화학식 1][Formula 1]

Figure 112012044607020-pat00001
Figure 112012044607020-pat00001

[상기 화학식 1 에서,[In Formula 1,

X는 CH2 또는 O를 나타내며;X represents CH 2 or O;

R1 내지 R6는 서로 독립적으로, 수소, 할로겐, (C1~C8)알킬, (C1~C8)알콕시, (C6~C20)아릴에서 선택되며, 상기 알킬, 알콕시 및 아릴은 할로겐, (C1~C8)알킬, (C1~C8)알콕시, (C6~C20)아릴, (C3~C20)헤테로아릴, (C1~C8)알콕시카르보닐, 하이드록시, 니트로에서 선택되는 하나 이상으로 치환될 수 있다.] R 1 to R 6 are each independently selected from hydrogen, halogen, (C 1 -C 8) alkyl, (C 1 -C 8) alkoxy, (C 6 -C 20) aryl, and the alkyl, alkoxy and aryl are halogen, (C 1- It may be substituted with one or more selected from C8) alkyl, (C1-C8) alkoxy, (C6-C20) aryl, (C3-C20) heteroaryl, (C1-C8) alkoxycarbonyl, hydroxy, nitro. ]

구체적으로 상기 화학식 1에서, R1과 R4는 서로 독립적으로 수소, 할로겐, (C1~C8)알킬, (C1~C8)알콕시, (C6~C20)아릴에서 선택되며;Specifically in Formula 1, R 1 and R 4 are each independently selected from hydrogen, halogen, (C1 ~ C8) alkyl, (C1 ~ C8) alkoxy, (C6 ~ C20) aryl;

R2와 R5는 서로 독립적으로 수소, (C1~C8)알콕시에서 선택되며;R 2 and R 5 are each independently selected from hydrogen, (C 1 -C 8) alkoxy;

R3와 R6는 서로 독립적으로 수소, 할로겐, (C1~C8)알킬, (C1~C8)알콕시에서 선택될 수 있다.R 3 and R 6 may be independently selected from hydrogen, halogen, (C 1 -C 8) alkyl, (C 1 -C 8) alkoxy.

보다 구체적으로, 화학식 1은 하기 화합물에서 선택될 수 있다. More specifically, Formula 1 may be selected from the following compounds.

Figure 112012044607020-pat00002
Figure 112012044607020-pat00002

Figure 112012044607020-pat00003
Figure 112012044607020-pat00003

Figure 112012044607020-pat00004
Figure 112012044607020-pat00004

또한 본 발명은 산 존재하에 하기 화학식 2로 표시되는 화합물로부터 상기 화학식 1로 표시되는 플루오로란센 유도체를 제조하는 방법을 제공한다.In another aspect, the present invention provides a method for producing a fluororansen derivative represented by the formula (1) from the compound represented by the formula (2) in the presence of an acid.

[화학식 2][Formula 2]

Figure 112012044607020-pat00005
Figure 112012044607020-pat00005

[상기 화학식 2 에서,[In Formula 2,

X는 CH2 또는 O를 나타내며;X represents CH 2 or O;

R1 내지 R6는 서로 독립적으로, 수소, 할로겐, (C1~C8)알킬, (C1~C8)알콕시, (C6~C20)아릴에서 선택되며, 상기 알킬, 알콕시 및 아릴은 할로겐, (C1~C8)알킬, (C1~C8)알콕시, (C6~C20)아릴, (C3~C20)헤테로아릴, (C1~C8)알콕시카르보닐, 하이드록시, 니트로에서 선택되는 하나 이상으로 치환될 수 있다.]R 1 to R 6 are each independently selected from hydrogen, halogen, (C 1 -C 8) alkyl, (C 1 -C 8) alkoxy, (C 6 -C 20) aryl, and the alkyl, alkoxy and aryl are halogen, (C 1- It may be substituted with one or more selected from C8) alkyl, (C1-C8) alkoxy, (C6-C20) aryl, (C3-C20) heteroaryl, (C1-C8) alkoxycarbonyl, hydroxy, nitro. ]

본 발명의 일 실시예에 따른 화학식 2는 촉매 존재하에서 하기 화학식 3으로부터 제조될 수 있다.Formula 2 according to an embodiment of the present invention may be prepared from the following formula (3) in the presence of a catalyst.

[화학식 3](3)

Figure 112012044607020-pat00006
Figure 112012044607020-pat00006

[상기 화학식 1 에서,[In Formula 1,

X는 CH2 또는 O를 나타내며;X represents CH 2 or O;

R1 내지 R6는 서로 독립적으로, 수소, 할로겐, (C1~C8)알킬, (C1~C8)알콕시, (C6~C20)아릴에서 선택되며, 상기 알킬, 알콕시 및 아릴은 할로겐, (C1~C8)알킬, (C1~C8)알콕시, (C6~C20)아릴, (C3~C20)헤테로아릴, (C1~C8)알콕시카르보닐, 하이드록시, 니트로에서 선택되는 하나 이상으로 치환될 수 있다.]R 1 to R 6 are each independently selected from hydrogen, halogen, (C 1 -C 8) alkyl, (C 1 -C 8) alkoxy, (C 6 -C 20) aryl, and the alkyl, alkoxy and aryl are halogen, (C 1- It may be substituted with one or more selected from C8) alkyl, (C1-C8) alkoxy, (C6-C20) aryl, (C3-C20) heteroaryl, (C1-C8) alkoxycarbonyl, hydroxy, nitro. ]

본 발명의 일 실시예에 따른 산은 염산, 인산, 황산, 질산 및 트리플루오로메탄설폰산에서 선택되는 하나 이상을 사용할 수 있으며, 화학식 2의 화합물, 1몰을 기준으로 0.01 ~ 0.50몰을 사용할 수 있다.Acid according to an embodiment of the present invention may be used at least one selected from hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid and trifluoromethanesulfonic acid, 0.01 to 0.50 moles based on 1 mole of the compound of formula (2) have.

본 발명에 따른 플루오란센 유도체들은 의약품이나 OLED에 이용할 수 있는 중요한 원료물질 또는 중간체로 이용될 수 있을 뿐만 아니라, 천연물 합성에도 이용될 수 있다. Fluoranthene derivatives according to the present invention can be used not only as important raw materials or intermediates that can be used in medicines or OLEDs, but also in natural product synthesis.

또한 본 발명에 따른 플루오란센 유도체의 제조방법은 산 존재 하에 간단한 공정, 짧은 반응시간, 높은 수율로 다양한 플루오란센 유도체를 제조할 수 있는 매우 효율적인 방법이다.In addition, the method for preparing a fluoranthene derivative according to the present invention is a very efficient method for preparing various fluoranthene derivatives in a simple process, short reaction time, and high yield in the presence of an acid.

본 발명은 다양한 용도의 원료물질 또는 중간물질로 사용 가능한 플루오란센 유도체를 제공하는 것으로, 본 발명에 따른 플루오란센 유도체는 하기 화학식 1로 표시된다.The present invention provides a fluoranthene derivative which can be used as a raw material or intermediate for various purposes, and the fluoranthene derivative according to the present invention is represented by the following Chemical Formula 1.

[화학식 1][Formula 1]

Figure 112012044607020-pat00007
Figure 112012044607020-pat00007

[상기 화학식 1 에서,[In Formula 1,

X는 CH2 또는 O를 나타내며;X represents CH 2 or O;

R1 내지 R6는 서로 독립적으로, 수소, 할로겐, (C1~C8)알킬, (C1~C8)알콕시, (C6~C20)아릴에서 선택되며, 상기 알킬, 알콕시 및 아릴은 할로겐, (C1~C8)알킬, (C1~C8)알콕시, (C6~C20)아릴, (C3~C20)헤테로아릴, (C1~C8)알콕시카르보닐, 하이드록시, 니트로에서 선택되는 하나 이상으로 치환될 수 있다.] R 1 to R 6 are each independently selected from hydrogen, halogen, (C 1 -C 8) alkyl, (C 1 -C 8) alkoxy, (C 6 -C 20) aryl, and the alkyl, alkoxy and aryl are halogen, (C 1- It may be substituted with one or more selected from C8) alkyl, (C1-C8) alkoxy, (C6-C20) aryl, (C3-C20) heteroaryl, (C1-C8) alkoxycarbonyl, hydroxy, nitro. ]

구체적으로 상기 화학식 1에서, R1과 R4는 서로독립적으로, 수소, 할로겐, (C1~C8)알킬, (C1~C8)알콕시, (C6~C20)아릴에서 선택되며;Specifically in Formula 1, R 1 and R 4 are each independently selected from hydrogen, halogen, (C1 ~ C8) alkyl, (C1 ~ C8) alkoxy, (C6 ~ C20) aryl;

R2와 R5는 서로독립적으로, 수소, (C1~C8)알콕시에서 선택되며;R 2 and R 5 are independently of each other selected from hydrogen, (C 1 -C 8) alkoxy;

R3와 R6는 서로독립적으로, 수소, 할로겐, (C1~C8)알킬, (C1~C8)알콕시에서 선택될 수 있다.R 3 and R 6 may be independently selected from hydrogen, halogen, (C 1 -C 8) alkyl, (C 1 -C 8) alkoxy.

보다 구체적으로 R1과 R4는 서로독립적으로, 수소, 클로라이드, 브로마이드, 아이오다이드, 메틸, 에틸, 프로필, 이소프로필, n-부틸, t-부틸, 메톡시, 에톡시, 프로폭시, 부톡시, 페닐, 나프틸 또는 안트라센에서 선택되며;More specifically R 1 and R 4 are independently of each other hydrogen, chloride, bromide, iodide, methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, methoxy, ethoxy, propoxy, Selected from oxy, phenyl, naphthyl or anthracene;

R2와 R5는 서로독립적으로, 수소, 메톡시, 에톡시, 프로폭시, 부톡시에서 선택되며;R 2 and R 5 are independently of each other selected from hydrogen, methoxy, ethoxy, propoxy, butoxy;

R3와 R6는 서로독립적으로, 수소, 클로라이드, 브로마이드, 아이오다이드, 메틸, 에틸, 프로필, 이소프로필, n-부틸, t-부틸, 메톡시, 에톡시, 프로폭시, 부톡시 에서 선택될 수 있다.R 3 and R 6 are independently of each other selected from hydrogen, chloride, bromide, iodide, methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, methoxy, ethoxy, propoxy, butoxy Can be.

본 발명의 화학식 1은 하기 화합물에서 선택될 수 있으나 이에 한정이 있는 것은 아니다. Formula 1 of the present invention may be selected from the following compounds, but is not limited thereto.

Figure 112012044607020-pat00008
Figure 112012044607020-pat00008

Figure 112012044607020-pat00009
Figure 112012044607020-pat00009

Figure 112012044607020-pat00010
Figure 112012044607020-pat00010

또한 본 발명은 산 존재하에 하기 화학식 2로 표시되는 화합물로부터 상기 화학식 1로 표시되는 플루오로란센 유도체를 제조하는 방법을 제공한다.In another aspect, the present invention provides a method for producing a fluororansen derivative represented by the formula (1) from the compound represented by the formula (2) in the presence of an acid.

[화학식 2][Formula 2]

Figure 112012044607020-pat00011
Figure 112012044607020-pat00011

[상기 화학식 1 또는 화학식 2 에서,[In Formula 1 or Formula 2,

X는 CH2 또는 O를 나타내며;X represents CH 2 or O;

R1 내지 R6는 서로 독립적으로, 수소, 할로겐, (C1~C8)알킬, (C1~C8)알콕시, (C6~C20)아릴에서 선택되며, 상기 알킬, 알콕시 및 아릴은 할로겐, (C1~C8)알킬, (C1~C8)알콕시, (C6~C20)아릴, (C3~C20)헤테로아릴, (C1~C8)알콕시카르보닐, 하이드록시, 니트로에서 선택되는 하나 이상으로 치환될 수 있다.]R 1 to R 6 are each independently selected from hydrogen, halogen, (C 1 -C 8) alkyl, (C 1 -C 8) alkoxy, (C 6 -C 20) aryl, and the alkyl, alkoxy and aryl are halogen, (C 1- It may be substituted with one or more selected from C8) alkyl, (C1-C8) alkoxy, (C6-C20) aryl, (C3-C20) heteroaryl, (C1-C8) alkoxycarbonyl, hydroxy, nitro. ]

본 발명의 일 실시예에 따른 촉매는 화학식 3, 1몰을 기준으로 0.01 ~ 0.1몰을 사용할 수 있으며 보다 바람직하게는 반응의 효율성 측면에서 0.025~0.05몰 일 수 있다.The catalyst according to an embodiment of the present invention may use 0.01 to 0.1 moles based on 1 mole of Formula 3, and more preferably 0.025 to 0.05 mole in terms of efficiency of the reaction.

본 발명의 일 실시예에 따른 산은 한정이 있는 것은 아니나, 염산, 인산, 황산, 질산 및 트리플루오로메탄설폰산에서 선택되는 하나이상을 사용할 수 있으며, 촉매의 효율성 측면에서 트리플루오로메탄술폰산(TfOH)이 보다 바람직하다.Acid according to an embodiment of the present invention is not limited, but one or more selected from hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid and trifluoromethanesulfonic acid may be used, and trifluoromethanesulfonic acid ( TfOH) is more preferred.

본 발명의 일 실시예에 따른 산은 화학식 2의 화합물, 1몰을 기준으로 0.01 0.50몰을 사용할 수 있으며, 부생성물을 줄이기 위해 0.05 ~ 0.30 몰이 보다 바람직하다.Acid according to an embodiment of the present invention may use 0.01 0.50 moles based on 1 mole of the compound of Formula 2, more preferably 0.05 ~ 0.30 moles to reduce by-products.

본 발명의 일 실시예에 따른 화학식 2는 촉매 존재하에서 하기 화학식 3으로부터 제조될 수 있다.Formula 2 according to an embodiment of the present invention may be prepared from the following formula (3) in the presence of a catalyst.

[화학식 3] (3)

[상기 화학식 1 에서, [In Formula 1,

X는 CH2 또는 O를 나타내며;X represents CH 2 or O;

R1 내지 R6는 서로 독립적으로, 수소, 할로겐, (C1~C8)알킬, (C1~C8)알콕시, (C6~C20)아릴에서 선택되며, 상기 알킬, 알콕시 및 아릴은 할로겐, (C1~C8)알킬, (C1~C8)알콕시, (C6~C20)아릴, (C3~C20)헤테로아릴, (C1~C8)알콕시카르보닐, 하이드록시, 니트로에서 선택되는 하나 이상으로 치환될 수 있다.]R 1 to R 6 are each independently selected from hydrogen, halogen, (C 1 -C 8) alkyl, (C 1 -C 8) alkoxy, (C 6 -C 20) aryl, and the alkyl, alkoxy and aryl are halogen, (C 1- It may be substituted with one or more selected from C8) alkyl, (C1-C8) alkoxy, (C6-C20) aryl, (C3-C20) heteroaryl, (C1-C8) alkoxycarbonyl, hydroxy, nitro. ]

본 발명의 일 실시예에 따른 화학식 3으로부터 화학식 2를 제조할 시 사용되는 촉매는 한정이 있는 것은 아니나, 금(Au)촉매, 은(Ag)촉매 또는 이들의 혼합촉매일 수 있으며, 금(Au)촉매는 AuCl, AuCl3, Ph3PAuCl, (C6F5)3PAuCl, (4-CF3-C6H4)3PAuCl, IMesAuCl [IMes : 1,3-bis(2,4,6-trimethylphenyl)imidazol-2- ylidene], IPrAuCl [IPr : 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene], Au(JohnPhos)Cl [JohnPhos : (2-biphenyl)di-tert-butylphosphine]에서 선택되는 하나이상이며, 은(Ag)촉매는 AgOTf, AgNTf2, AgSbF6, AgAsF6, AgBF4, AgNO3 에서 선택되는 하나 이상일 수 있다.The catalyst used in preparing Formula 2 from Formula 3 according to an embodiment of the present invention is not limited, but may be a gold (Au) catalyst, a silver (Ag) catalyst, or a mixed catalyst thereof, and gold (Au). The catalyst is AuCl, AuCl 3 , Ph 3 PAuCl, (C 6 F 5 ) 3 PAuCl, (4-CF 3 -C 6 H 4 ) 3 PAuCl, IMesAuCl [IMes: 1,3-bis (2,4,6) -trimethylphenyl) imidazol-2- ylidene], IPrAuCl [IPr: 1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene], Au (JohnPhos) Cl [JohnPhos: (2-biphenyl) di- tert - butylphosphine] at least one selected from, and silver (Ag) catalyst may be at least one selected from AgOTf, AgNTf 2 , AgSbF 6 , AgAsF 6 , AgBF 4 , AgNO 3 .

보다 바람직하게 반응의 수율 증가와 반응 시간의 단축을 위해 금촉매는Ph3PAuCl일 수 있으며, 은촉매는 AgSbF6 일 수 있으며 금촉매인 Ph3PAuCl와 은촉매인 AgSbF6의 혼합촉매가 보다 바람직하다.More preferably, the gold catalyst may be Ph 3 PAuCl, the silver catalyst may be AgSbF 6 , and the mixed catalyst of the gold catalyst Ph 3 PAuCl and the silver catalyst AgSbF 6 is more preferable in order to increase the yield of the reaction and shorten the reaction time.

본발명의 일 실시예에 따른 금촉매와 은촉매의 혼합촉매는 금촉매와 은촉매의 혼합비율이 촉매로써의 효율을 가장 높일 수 있는 범위로 금촉매 1몰을 기준으로 은촉매 0.5 ~ 1.5몰일 수 있으며 보다 바람직한 경우 0.8 ~ 1.2몰일 수 있다.The mixed catalyst of the gold catalyst and the silver catalyst according to an embodiment of the present invention is 0.5 to 1.5 moles of silver catalyst based on 1 mole of the gold catalyst in a range in which the mixing ratio of the gold catalyst and the silver catalyst can increase the efficiency as a catalyst. And more preferably 0.8 to 1.2 moles.

본 발명의 일 실시예에 따른 촉매는 화학식 3, 1몰을 기준으로 0.01 ~ 0.1몰을 사용할 수 있으며 보다 바람직하게는 반응의 효율성 측면에서 0.025 ~ 0.05몰 일 수 있다.The catalyst according to an embodiment of the present invention may use 0.01 to 0.1 moles based on 1 mole of Formula 3, and more preferably 0.025 to 0.05 mole in terms of efficiency of the reaction.

본 발명의 제조방법에서 사용되는 용매는 통상의 유기용매이면 모두 가능하나, 다이클로로메탄(DCM), 다이클로로에탄(DCE), 톨루엔(Toluene), 아세토나이트릴(MeCN), 나이트로 메탄(Nitromethan), 테트라하이드로퓨란(THF), N,N-다이메틸 포름아마이드 (DMF) 및 N,N-다이메틸아세트아마이드(DMA)로 이루어진 군으로부터 선택되는 1종 이상을 사용하는 것이 바람직하며 (보다 용이한 제거를 위해) 다이클로로메탄(DCM)를 용매로 사용하는 것이 더욱 바람직하다.The solvent used in the preparation method of the present invention may be any organic solvent, but may be dichloromethane (DCM), dichloroethane (DCE), toluene (Toluene), acetonitrile (MeCN), nitromethane (Nitromethan). ), Tetrahydrofuran (THF), N, N -dimethyl formamide (DMF) and N, N -dimethylacetamide (DMA) are preferably used (more easily More preferably) using dichloromethane (DCM) as solvent.

반응온도는 실온에서 상기 반응을 수행하며, 반응시간은 반응물질, 촉매의 종류 및 출발물질의 양에 따라 달라질 수 있으며, TLC 등을 통하여 출발물질이 완전히 소모됨을 확인한 후 반응을 완결시키도록 한다. 반응이 완결되면 추출과정 후 감압 하에서 용매를 증류시킨 후 관 크로마토그래피 등의 통상적인 방법을 통하여 목적물을 분리 정제할 수도 있다.
The reaction temperature is carried out at room temperature, the reaction time may vary depending on the reactants, the type of catalyst and the amount of starting material, and complete the reaction after confirming that the starting material is completely consumed through TLC. After the reaction is completed, the solvent may be distilled off under reduced pressure after the extraction process, and the desired product may be separated and purified through conventional methods such as column chromatography.

이하, 실시예를 통하여 본 발명의 구성을 보다 구체적으로 설명하지만, 하기의 실시예들은 본 발명에 대한 이해를 돕기 위한 것으로서, 본 발명의 범위가 여기에 국한된 것은 아니다.
Hereinafter, the configuration of the present invention in more detail through examples, the following examples are provided to help the understanding of the present invention, the scope of the present invention is not limited thereto.

[실시예 1] 4,5,6,11,12,12a-Hexahydrobenzo[j]fluoranthene (4,5,6, 11,12,12a-hexahydrobenzo[j]fluoranthene)의 제조.Example 1 4,5,6,11,12,12a-Hexahydrobenzo [j] fluoranthene Preparation of (4,5,6, 11,12,12a-hexahydrobenzo [j] fluoranthene).

Figure 112012044607020-pat00013
Figure 112012044607020-pat00013

3,3',4,4'-테트라하이드로-1,1'-바이타프틸 (3,3',4,4'-Tetrahydro-1,1'-binaphthyl)(51.7 mg, 0.2 mmol)이 들어있는 4 mL의 반응 용기에 다이클로로메탄(0.8 mL)을 주입한 후, 트리플루오로메탄설폰 산(1.5 mg, 0.01 mmol)을 넣고, 실온에서 5분간 교반 시킨 후, 별도의 과정 없이 여과하였다. 용매를 제거한 후 관 크로마토그래피로 분리하여, 표제 화합물인 4,5,6,11,12,12a-헥사하이드로벤조[j]플루오란센 (4,5,6,11,12,12a-hexahydrobenzo[j]fluoranthene) (48.6 mg, 94%)을 얻었다.Contains 3,3 ', 4,4'-tetrahydro-1,1'-vitaphthyl (3,3', 4,4'-Tetrahydro-1,1'-binaphthyl) (51.7 mg, 0.2 mmol) After dichloromethane (0.8 mL) was injected into the reaction vessel of 4 mL, trifluoromethanesulfonic acid (1.5 mg, 0.01 mmol) was added thereto, stirred at room temperature for 5 minutes, and filtered without any further process. The solvent was removed and the residue was separated by column chromatography to obtain the title compound 4,5,6,11,12,12a-hexahydrobenzo [j] fluoranthene (4,5,6,11,12,12a-hexahydrobenzo [ j] fluoranthene) (48.6 mg, 94%).

1H NMR (400 MHz, CDCl3): δ 7.63 (d, J = 7.7 Hz, 1H), 7.30 (d, J = 7.2, 1H), 7.25-7.22 (m, 2H), 7.17-7.05 (m, 3H), 3.52 (d, J = 13.5 Hz, 1H), 3.20-3.01 (m, 3H), 2.94-2.76 (m, 3H), 2.64-2.58 (m, 1H), 2.17-2.09 (m, 1H), 1.89-1.78 (m, 1H), 1.50-1.39 (m, 1H).
 1 H NMR (400 MHz, CDCl 3 ): δ 7.63 (d, J = 7.7 Hz, 1H), 7.30 (d, J = 7.2, 1H), 7.25-7.22 (m, 2H), 7.17-7.05 (m, 3H), 3.52 (d, J = 13.5 Hz, 1H), 3.20-3.01 (m, 3H), 2.94-2.76 (m, 3H), 2.64-2.58 (m, 1H), 2.17-2.09 (m, 1H) , 1.89-1.78 (m, 1 H), 1.50-1.39 (m, 1 H).

[실시예 2] 1,3,8,10-테트라메틸-4,5,6,11,12,12a-헥사하이드로벤조 [j]플루오란센 (1,3,8,10-Tetramethyl-4,5,6,11,12,12a-hexahydrobenzo[j] fluoranthene)의 제조.Example 2 1,3,8,10-tetramethyl-4,5,6,11,12,12a-hexahydrobenzo [j] fluoranthene (1,3,8,10-Tetramethyl-4, 5,6,11,12,12a-hexahydrobenzo [j] fluoranthene).

Figure 112012044607020-pat00014
Figure 112012044607020-pat00014

5,5',7,7'-테트라메틸-3,3',4,4'-테트라하이드로-1,1'-바이나프틸 [5,5',7, 7'-Tetramethyl-3,3',4,4'-tetrahydro-1,1'-binaphthyl] (62.9 mg, 0.2 mmol)이 들어있는 4 mL의 반응 용기에 다이클로로메탄(0.8 mL)을 주입한 후, 트리플루오로메탄설폰 산(1.5 mg, 0.01 mmol)을 넣고, 실온에서 5분간 교반시킨 후, 별도의 과정 없이 여과하였다. 용매를 제거한 후 관 크로마토그래피로 분리하여, 표제 화합물인1,3,8,10-테트라메틸-4,5,6,11,12,12a-헥사하이드로벤조[j]플루오란센 (1,3,8,10-tetramethyl-4,5,6,11,12,12a-hexahydrobenzo[j]fluoranthene) (59.8 mg, 95%)을 얻었다.5,5 ', 7,7'-tetramethyl-3,3', 4,4'-tetrahydro-1,1'-binafryl [5,5 ', 7,7'-Tetramethyl-3,3 Dichloromethane (0.8 mL) was injected into a 4 mL reaction vessel containing ', 4,4'-tetrahydro-1,1'-binaphthyl] (62.9 mg, 0.2 mmol), followed by trifluoromethanesulfonic acid. (1.5 mg, 0.01 mmol) was added thereto, stirred at room temperature for 5 minutes, and filtered without additional processing. The solvent was removed and the residue was separated by column chromatography to obtain the title compound 1,3,8,10-tetramethyl-4,5,6,11,12,12a-hexahydrobenzo [j] fluoranthene (1,3 , 8,10-tetramethyl-4,5,6,11,12,12a-hexahydrobenzo [j] fluoranthene) (59.8 mg, 95%) was obtained.

1H NMR (400 MHz, CDCl3): δ 7.27 (s, 1H), 6.89 (s, 1H), 6.78 (s, 1H), 3.46 (d, J = 13.4 Hz, 1H), 3.05-2.95 (m, 2H), 2.87-2.77 (m, 4H), 2.69-2.58 (m, 1H), 2.40 (s, 3H), 2.34 (s, 3H), 2.27 (s, 3H), 2.25 (s, 3H), 2.19-2.11 (m, 1H), 1.82-1.73 (m, 1H), 1.39-1.30 (m, 1H).
 1 H NMR (400 MHz, CDCl 3 ): δ 7.27 (s, 1H), 6.89 (s, 1H), 6.78 (s, 1H), 3.46 (d, J = 13.4 Hz, 1H), 3.05-2.95 (m , 2H), 2.87-2.77 (m, 4H), 2.69-2.58 (m, 1H), 2.40 (s, 3H), 2.34 (s, 3H), 2.27 (s, 3H), 2.25 (s, 3H), 2.19-2.11 (m, 1 H), 1.82-1.73 (m, 1 H), 1.39-1.30 (m, 1 H).

[실시예 3] 3,10-다이메톡시-4,5,6,11,12,12a-헥사하이드로벤조[j] 플루오란센 (3,10-Dimethoxy-4,5,6,11,12,12a-hexahydrobenzo[j]fluoranth -ene)의 제조.Example 3 3,10-Dimethoxy-4,5,6,11,12,12a-hexahydrobenzo [j] fluoranthene (3,10-Dimethoxy-4,5,6,11,12 , 12a-hexahydrobenzo [j] fluoranth-ene).

Figure 112012044607020-pat00015
Figure 112012044607020-pat00015

7,7'-다이메톡시-3,3',4,4'-테트라하이드로-1,1'-바이나프틸 (7,7'-Dime thoxy-3,3',4,4'-tetrahydro-1,1'-binaphthyl) (63.6 mg, 0.2 mmol)이 들어있는 4 mL의 반응 용기에 다이클로로메탄(0.8 mL)을 주입한 후, 트리플루오로메탄설폰 산(1.5 mg, 0.01 mmol)을 넣고, 실온에서 10분간 교반 시킨 후, 별도의 과정 없이 여과하였다. 용매를 제거한 후 관 크로마토그래피로 분리하여, 표제 화합물인 3,10-다이메톡시-4,5,6,11,12,12a-헥사하이드로 벤조[j]플루오란센 (3,10-dimethoxy-4,5,6,11,12,12a-hexahydrobenzo[j] fluoranthene) (61.7 mg, 97%)을 얻었다.7,7'-dimethoxy-3,3 ', 4,4'-tetrahydro-1,1'-binaphthyl (7,7'-Dime thoxy-3,3', 4,4'-tetrahydro Dichloromethane (0.8 mL) was injected into a 4 mL reaction vessel containing -1,1'-binaphthyl) (63.6 mg, 0.2 mmol), followed by trifluoromethanesulfonic acid (1.5 mg, 0.01 mmol). The mixture was stirred at room temperature for 10 minutes, and then filtered without further processing. The solvent was removed and the residue was separated by column chromatography to obtain the title compound 3,10-dimethoxy-4,5,6,11,12,12a-hexahydro benzo [j] fluoranthene (3,10-dimethoxy- 4,5,6,11,12,12a-hexahydrobenzo [j] fluoranthene) (61.7 mg, 97%) was obtained.

1H NMR (300 MHz, CDCl3): δ 7.15 (dd, J = 2.8 Hz, J = 5.5 Hz, 2H), 7.04 (d, J = 8.1 Hz, 1H), 5.07 (dd, J = 3.7 Hz, J = 8.4 Hz, 1H), 6.67 (d, J = 8.1 Hz, 1H), 3.89 (s, 3H), 3.85 (s, 3H), 3.62-3.58 (m, 1H), 3.15-2.95 (m, 3H), 2.93-2.82 (m, 2H), 2.80-2.76 (m, 2H), 2.18-2.08 (m, 1H), 1.88-1.73 (m, 1H), 1.41-1.27 (m, 1H).
 1 H NMR (300 MHz, CDCl 3 ): δ 7.15 (dd, J = 2.8 Hz, J = 5.5 Hz, 2H), 7.04 (d, J = 8.1 Hz, 1H), 5.07 (dd, J = 3.7 Hz, J = 8.4 Hz, 1H), 6.67 (d, J = 8.1 Hz, 1H), 3.89 (s, 3H), 3.85 (s, 3H), 3.62-3.58 (m, 1H), 3.15-2.95 (m, 3H ), 2.93-2.82 (m, 2H), 2.80-2.76 (m, 2H), 2.18-2.08 (m, 1H), 1.88-1.73 (m, 1H), 1.41-1.27 (m, 1H).

[실시예 4] 1,8-다이메톡시-4,5,6,11,12,12a-헥사하이드로벤조 [j]플루오란센 (1,8-Dimethoxy-4,5,6,11,12,12a-hexahydrobenzo[j]fluoranthene)의 제조.Example 4 1,8-dimethoxy-4,5,6,11,12,12a-hexahydrobenzo [j] fluoranthene (1,8-Dimethoxy-4,5,6,11,12 , 12a-hexahydrobenzo [j] fluoranthene).

Figure 112012044607020-pat00016
Figure 112012044607020-pat00016

5,5'-다이메톡시-3,3',4,4'-테트라하이드로-1,1'-바이나프틸 (5,5'-Dimeth -oxy-3,3',4,4'-tetrahydro-1,1'-binaphthyl) (63.6 mg, 0.2 mmol)이 들어있는 4 mL의 반응 용기에 다이클로로메탄(0.8 mL)을 주입한 후, 트리플루오로메탄설폰 산(1.5 mg, 0.01 mmol)을 넣고, 실온에서 10분간 교반 시킨 후, 별도의 과정 없이 여과하였다. 용매를 제거한 후 관 크로마토그래피로 분리하여, 표제 화합물인 1,8-다이메톡시-4,5,6,11,12,12a-헥사하이드로 벤조[j]플루오란센 (1,8-dimethoxy-4,5,6,11,12,12a-hexahydrobenzo[j] fluoranthene) (61.1 mg, 96%)을 얻었다.5,5'-dimethoxy-3,3 ', 4,4'-tetrahydro-1,1'-binapryl (5,5'-Dimeth -oxy-3,3', 4,4'- Dichloromethane (0.8 mL) was injected into a 4 mL reaction vessel containing tetrahydro-1,1'-binaphthyl) (63.6 mg, 0.2 mmol), followed by trifluoromethanesulfonic acid (1.5 mg, 0.01 mmol). After the addition, the mixture was stirred at room temperature for 10 minutes, and filtered without any further process. The solvent was removed and the residue was separated by column chromatography to obtain the title compound 1,8-dimethoxy-4,5,6,11,12,12a-hexahydro benzo [j] fluoranthene (1,8-dimethoxy- 4,5,6,11,12,12a-hexahydrobenzo [j] fluoranthene) (61.1 mg, 96%) was obtained.

1H NMR (400 MHz, CDCl3): δ 7.24 (m, 3H), 6.75 (dd, J = 0.7 Hz, J = 8.0 Hz, 1H), 6.69 (d, J = 8.0 Hz, 1H), 3.86 (s, 6H), 3.47-3.43 (m, 1H), 3.21 (dd, J = 5.0 Hz, J = 17.6 Hz, 1H), 3.01 (td, J = 4.0 Hz, J = 16.6 Hz, 1H), 2.95-2.83 (m, 2H), 2.82-2.71 (m, 1H), 2.66-2.59 (m, 2H), 2.18-2.09 (m, 1H), 1.86-1.71 (m, 1H), 1.43-1.28 (m, 1H).
 1 H NMR (400 MHz, CDCl 3 ): δ 7.24 (m, 3H), 6.75 (dd, J = 0.7 Hz, J = 8.0 Hz, 1H), 6.69 (d, J = 8.0 Hz, 1H), 3.86 ( s, 6H), 3.47-3.43 (m, 1H), 3.21 (dd, J = 5.0 Hz, J = 17.6 Hz, 1H), 3.01 (td, J = 4.0 Hz, J = 16.6 Hz, 1H), 2.95- 2.83 (m, 2H), 2.82-2.71 (m, 1H), 2.66-2.59 (m, 2H), 2.18-2.09 (m, 1H), 1.86-1.71 (m, 1H), 1.43-1.28 (m, 1H ).

[실시예 5] 1,2,8,9-테트라메톡시-4,5,6,11,12,12a-헥사하이드로벤조 [j]플루오로란센 (1,2,8,9-Tetramethoxy-4,5,6,11,12,12a-hexahydrobenzo [j]fluoranthene)의 제조.Example 5 1,2,8,9-tetramethoxy-4,5,6,11,12,12a-hexahydrobenzo [j] fluorolancene (1,2,8,9-Tetramethoxy- 4,5,6,11,12,12a-hexahydrobenzo [j] fluoranthene).

Figure 112012044607020-pat00017
Figure 112012044607020-pat00017

7,7'-다이메톡시-3,3',4,4'-테트라하이드로-1,1'-바이나프틸 (7,7'-Dimethoxy-3,3',4,4'-tetrahydro-1,1'-binaphthyl) (75.6 mg, 0.2 mmol)이 들어있는 4 mL의 반응 용기에 다이클로로메탄(0.8 mL)을 주입한 후, 트리플루오로메탄설폰 산(1.5 mg, 0.01 mmol)을 넣고, 실온에서 30분간 교반 시킨 후, 별도의 과정 없이 여과하였다. 용매를 제거한 후 관 크로마토그래피로 분리하여, 표제 화합물인 1,2,8,9-테트라메톡시-4,5,6,11,12,12a-헥사하이드로벤조[j]플루오로란센 (1,2,8,9-tetramethoxy-4,5,6,11,12,12a-hexahydrobenzo[j]fluoranthene) (67.3 mg, 89%)을 얻었다.7,7'-dimethoxy-3,3 ', 4,4'-tetrahydro-1,1'-binaphthyl (7,7'-Dimethoxy-3,3', 4,4'-tetrahydro- Inject dichloromethane (0.8 mL) into a 4 mL reaction vessel containing 1,1'-binaphthyl) (75.6 mg, 0.2 mmol), add trifluoromethanesulfonic acid (1.5 mg, 0.01 mmol) After stirring for 30 minutes at room temperature, the mixture was filtered without further processing. The solvent was removed and the residue was separated by column chromatography to obtain the title compound 1,2,8,9-tetramethoxy-4,5,6,11,12,12a-hexahydrobenzo [j] fluorolancene (1 , 2,8,9-tetramethoxy-4,5,6,11,12,12a-hexahydrobenzo [j] fluoranthene) (67.3 mg, 89%) was obtained.

1H NMR (400 MHz, CDCl3): δ 7.12 (s, 1H), 6.74 (s, 1H), 6.68 (s, 1H), 3.934 (s, 3H), 3.927 (s, 3H), 3.89 (s, 3H), 3.88 (s, 3H) 3.62 (d, J = 13.3, 1H), 3.13-3.08 (m, 1H), 3.00-2.95 (m, 2H), 2.89-2.70 (m, 4H), 2.14-2.09 (m, 1H), 1.93-1.80 (m, 1H), 1.52-1.38 (m, 1H). 1 H NMR (400 MHz, CDCl 3 ): δ 7.12 (s, 1H), 6.74 (s, 1H), 6.68 (s, 1H), 3.934 (s, 3H), 3.927 (s, 3H), 3.89 (s , 3H), 3.88 (s, 3H) 3.62 (d, J = 13.3, 1H), 3.13-3.08 (m, 1H), 3.00-2.95 (m, 2H), 2.89-2.70 (m, 4H), 2.14- 2.09 (m, 1 H), 1.93-1.80 (m, 1 H), 1.52-1.38 (m, 1 H).

[실시예 6] 4,11-다이옥사-5,6,12,12a-테트라하이드로벤조[j] 플루오로란센 (4,11-Dioxa-5,6,12,12a-tetrahydrobenzo[j]fluoranthene)의 제조.Example 6 4,11- di oxa -5,6,12,12a- tetrahydro-benzo [j] fluoro-field sensor (4,11-Dioxa-5,6,12,12a-tetrahydrobenzo [j] fluoranthene Manufacture).

Figure 112012044607020-pat00018
Figure 112012044607020-pat00018

2H,2'H-4,4'-바이크로멘 [2H,2'H-4,4'-Bichromene] (52.4 mg, 0.2 mmol)이 들어있는 4 mL의 반응 용기에 다이클로로메탄(0.8 mL)을 주입한 후, 트리플루오로메탄설폰 산(9.0 mg, 0.06 mmol)을 넣고, 실온에서 20 분간 교반 시킨 후, 별도의 과정 없이 여과하였다. 용매를 제거한 후 관 크로마토그래피로 분리하여, 표제 화합물인 4,11-다이옥사-5,6,12,12a-테트라하이드로벤조[j]플루오로란센 (4,11-dioxa-5,6,12,12a-tetrahydro benzo[j]fluoranthene) (40.0 mg, 76%)을 얻었다.Dichloromethane (0.8 mL) in a 4 mL reaction vessel containing 2H, 2'H-4,4'-bichromene [2H, 2'H-4,4'-Bichromene] (52.4 mg, 0.2 mmol) ) Was injected, trifluoromethanesulfonic acid (9.0 mg, 0.06 mmol) was added thereto, stirred at room temperature for 20 minutes, and filtered without additional processing. The solvent was removed and the residue was separated by column chromatography to obtain the title compound 4,11-dioxa-5,6,12,12a-tetrahydrobenzo [ j ] fluorolancene (4,11-dioxa-5,6, 12,12a-tetrahydro benzo [ j ] fluoranthene) (40.0 mg, 76%) was obtained.

1H NMR (300 MHz, CDCl3): δ 7.48 (d, J = 7.6 Hz, 1H), 7.17 (dt, J = 7.6 Hz, 1.6 Hz, 1H), 7.11 (t, J = 7.6 Hz, 1H), 7.04 (d, J = 7.1 Hz, 1H), 7.00-6.96 (m, 2H), 6.84 (d, J = 8.0 Hz, 1H), 4.92-4.87 (m, 1H), 4.46-4.41 (m, 1H), 4.28-4.22 (m, 1H), 3.92-3.87 (m, 1H), 3.81-3.75 (m, 1H), 3.25-3.18 (m, 1H), 3.11-3.04 (m, 1H).
 1 H NMR (300 MHz, CDCl 3 ): δ 7.48 (d, J = 7.6 Hz, 1H), 7.17 (dt, J = 7.6 Hz, 1.6 Hz, 1H), 7.11 (t, J = 7.6 Hz, 1H) , 7.04 (d, J = 7.1 Hz, 1H), 7.00-6.96 (m, 2H), 6.84 (d, J = 8.0 Hz, 1H), 4.92-4.87 (m, 1H), 4.46-4.41 (m, 1H ), 4.28-4.22 (m, 1H), 3.92-3.87 (m, 1H), 3.81-3.75 (m, 1H), 3.25-3.18 (m, 1H), 3.11-3.04 (m, 1H).

[실시예 7] 1,8-터트-부틸-4,11-다이옥사-5,6,12,12a-테트라 하이드로벤조[j]플루오로란센 (1,8-tert-Butyl-4,11-dioxa-5,6,12,12a-tetra hydrobenzo[j]fluoranthene)의 제조.Example 7 1,8- tert -butyl-4,11-dioxa-5,6,12,12a-tetrahydrobenzo [ j ] fluorolancene (1,8- tert- Butyl-4,11 -dioxa-5,6,12,12a-tetra hydrobenzo [ j ] fluoranthene).

Figure 112012044607020-pat00019
Figure 112012044607020-pat00019

6,6'-다이-터트-부틸-2H,2'H-4,4'-바이크로멘 [6,6'-Di-tert-butyl-2H,2'H-4,4'-bichromene] (74.8 mg, 0.2 mmol)이 들어있는 4 mL의 반응 용기에 다이클로로메탄(0.8 mL)을 주입한 후, 트리플루오로메탄설폰 산(9.0 mg, 0.06 mmol)을 넣고, 실온에서 2시간 교반 시킨 후, 별도의 과정 없이 여과하였다. 용매를 제거한 후 관 크로마토그래피로 분리하여, 표제 화합물인 3,10-다이메톡시-4,5,6,11,12,12a-헥사하이드로 벤조[j]플루오란센 (3,10-dimethoxy-4,5,6,11,12,12a-hexahydrobenzo[j]fluoranthene) (66.6 mg, 89%)을 얻었다.6,6'-di-tert-butyl-2H, 2'H-4,4'-bichromen [6,6'-Di-tert-butyl-2H, 2'H-4,4'-bichromene] After dichloromethane (0.8 mL) was injected into a 4 mL reaction vessel containing (74.8 mg, 0.2 mmol), trifluoromethanesulfonic acid (9.0 mg, 0.06 mmol) was added thereto, followed by stirring at room temperature for 2 hours. After that, it was filtered without any further process. The solvent was removed and the residue was separated by column chromatography to obtain the title compound 3,10-dimethoxy-4,5,6,11,12,12a-hexahydro benzo [j] fluoranthene (3,10-dimethoxy- 4,5,6,11,12,12a-hexahydrobenzo [j] fluoranthene) (66.6 mg, 89%) was obtained.

1H NMR (400 MHz, CDCl3) δ 7.45 (d, J = 2.4 Hz, 1H), 7.21 (dd, J = 8.6, 2.4 Hz, 1H), 7.18 (d, J = 8.3 Hz, 1H), 6.90 (d, J = 8.6 Hz, 1H), 6.81 (d, J = 8.3 Hz, 1H), 5.24-5.20 (m, 1H), 4.48-4.43 (m, 1H), 4.17-4.03 (m, 2H), 3.83-3.77(m, 1H), 3.20-3.04(m, 2H), 1.44(s, 9H), 1.35 (s, 9H).
 1 H NMR (400 MHz, CDCl 3 ) δ 7.45 (d, J = 2.4 Hz, 1H), 7.21 (dd, J = 8.6, 2.4 Hz, 1H), 7.18 (d, J = 8.3 Hz, 1H), 6.90 (d, J = 8.6 Hz, 1H), 6.81 (d, J = 8.3 Hz, 1H), 5.24-5.20 (m, 1H), 4.48-4.43 (m, 1H), 4.17-4.03 (m, 2H), 3.83-3.77 (m, 1H), 3.20-3.04 (m, 2H), 1.44 (s, 9H), 1.35 (s, 9H).

[실시예 8] 1,8-다이메톡시-4,11-다이옥사-5,6,12,12a-테트라 하이드로벤조[j]플루오란센 (1,8-Dimethoxy-4,11-dioxa-5,6,12,12a-tetra hydrobenzo[j]fluoranthene)의 제조.Example 8 1,8-Dimethoxy-4,11-dioxa-5,6,12,12a-tetrahydrobenzo [ j ] fluoranthene (1,8-Dimethoxy-4,11-dioxa- Preparation of 5,6,12,12a-tetra hydrobenzo [ j ] fluoranthene).

Figure 112012044607020-pat00020
Figure 112012044607020-pat00020

6,6'-다이메톡시-2H,2'H-4,4'-바이크로멘 [6,6'-Dimethoxy-2H,2'H-4,4'-bichromene] (64.4 mg, 0.2 mmol)이 들어있는 4 mL의 반응 용기에 다이클로로메탄(0.8 mL)을 주입한 후, 트리플루오로메탄설폰 산(9.0 mg, 0.06 mmol)을 넣고, 실온에서 40분간 교반 시킨 후, 별도의 과정 없이 여과하였다. 용매를 제거한 후 관 크로마토그래피로 분리하여, 표제 화합물을 1,8-다이메톡시-4,11-다이옥사-5,6,12,12a-테트라 하이드로벤조 [j]플루오란센 (1,8-dimethoxy-4,11-dioxa-5,6,12,12a-tetra hydrobenzo [j]fluoranthene) (49.0 mg, 76%)을 얻었다.6,6'-dimethoxy-2H, 2'H-4,4'-bichromen [6,6'-Dimethoxy-2H, 2'H-4,4'-bichromene] (64.4 mg, 0.2 mmol Inject dichloromethane (0.8 mL) into a 4 mL reaction vessel containing), add trifluoromethanesulfonic acid (9.0 mg, 0.06 mmol), stir at room temperature for 40 minutes, and then Filtered. The solvent was removed and then separated by column chromatography to give the title compound as 1,8-dimethoxy-4,11-dioxa-5,6,12,12a-tetrahydrobenzo [ j ] fluoranthene (1,8 -dimethoxy-4,11-dioxa-5,6,12,12a-tetra hydrobenzo [ j ] fluoranthene) (49.0 mg, 76%) was obtained.

1H NMR (400 MHz, CDCl3) δ 6.99 (d, J = 3.0 Hz, 1H), 6.90 (d, J = 8.9 Hz, 1H), 6.82-6.74 (m, 2H), 6.62 (d, J = 8.6 Hz, 1H), 5.07-5.04 (m, 1H), 4.42-4.38 (m, 1H), 4.21-4.16 (m, 1H), 3.92-3.89 (m, 1H), 3.84 (s, 3H), 3.81 (s, 3H), 3.72-3.60 (m, 1H), 3.25-3.12 (m, 1H), 3.10-2.96 (m, 1H).
 1 H NMR (400 MHz, CDCl 3 ) δ 6.99 (d, J = 3.0 Hz, 1H), 6.90 (d, J = 8.9 Hz, 1H), 6.82-6.74 (m, 2H), 6.62 (d, J = 8.6 Hz, 1H), 5.07-5.04 (m, 1H), 4.42-4.38 (m, 1H), 4.21-4.16 (m, 1H), 3.92-3.89 (m, 1H), 3.84 (s, 3H), 3.81 (s, 3H), 3.72-3.60 (m, 1H), 3.25-3.12 (m, 1H), 3.10-2.96 (m, 1H).

[실시예 9] 3,10-다이페닐-4,11-다이옥사-5,6,12,12a-테트라 하이드로벤조[j]플루오란센 (3,10-Diphenyl-4,11-dioxa-5,6,12,12a-tetra hydrobenzo[j]fluoranthene)의 제조.Example 9 3,10-Diphenyl-4,11-dioxa-5,6,12,12a-tetrahydrobenzo [ j ] fluoranthene (3,10-Diphenyl-4,11-dioxa-5 , 6,12,12a-tetra hydrobenzo [ j ] fluoranthene).

Figure 112012044607020-pat00021
Figure 112012044607020-pat00021

8,8'-다이페닐-2H,2'H-4,4'-바이크로멘 [8,8'-Diphenyl-2H,2'H-4,4'-bichromene] (82.8 mg, 0.2 mmol)이 들어있는 4 mL의 반응 용기에 다이클로로메탄(0.8 mL)을 주입한 후, 트리플루오로메탄설폰 산(9.0 mg, 0.06 mmol)을 넣고, 실온에서 40분간 교반 시킨 후, 별도의 과정 없이 여과하였다. 용매를 제거한 후 관 크로마토그래피로 분리하여, 표제 화합물인 3,10-다이페닐-4,11-다이옥사-5,6,12,12a-테트라 하이드로벤조 [j]플루오란센 (3,10-diphenyl-4,11-dioxa-5,6,12,12a-tetrahydrobenzo [j]fluoranthene) (76.3 mg, 92%)을 얻었다.8,8'-diphenyl-2H, 2'H-4,4'-bichromen [8,8'-Diphenyl-2H, 2'H-4,4'-bichromene] (82.8 mg, 0.2 mmol) Dichloromethane (0.8 mL) was injected into a 4 mL reaction vessel containing trifluoromethanesulfonic acid (9.0 mg, 0.06 mmol), stirred at room temperature for 40 minutes, and filtered It was. The solvent was removed and the residue was separated by column chromatography to obtain the title compound 3,10-diphenyl-4,11-dioxa-5,6,12,12a-tetrahydrobenzo [ j ] fluoranthene (3,10- diphenyl-4,11-dioxa-5,6,12,12a-tetrahydrobenzo [ j ] fluoranthene) (76.3 mg, 92%) was obtained.

1H NMR (400 MHz, CDCl3) δ 7.64 (d, J = 7.1 Hz, 2H), 7.58 (d, J = 7.1 Hz, 2H), 7.51 (dd, J = 7.8, 1.6 Hz, 1H), 7.44 (t, J = 7.1 Hz, 4H), 7.38-7.32 (m, 2H), 7.25-7.22 (m, 2H), 7.11 (d, J = 7.5 Hz, 1H), 7.09-7.06 (m, 1H), 4.96-4.92 (m, 1H), 4.52-4.47 (m, 1H), 4.28-4.22 (m, 1H), 3.99-3.95 (m, 1H), 3.84-3.78 (m, 1H), 3.31-3.24 (m, 1H), 3.10-3.16 (m, 1H).
 1 H NMR (400 MHz, CDCl 3 ) δ 7.64 (d, J = 7.1 Hz, 2H), 7.58 (d, J = 7.1 Hz, 2H), 7.51 (dd, J = 7.8, 1.6 Hz, 1H), 7.44 (t, J = 7.1 Hz, 4H), 7.38-7.32 (m, 2H), 7.25-7.22 (m, 2H), 7.11 (d, J = 7.5 Hz, 1H), 7.09-7.06 (m, 1H), 4.96-4.92 (m, 1H), 4.52-4.47 (m, 1H), 4.28-4.22 (m, 1H), 3.99-3.95 (m, 1H), 3.84-3.78 (m, 1H), 3.31-3.24 (m , 1H), 3.10-3.16 (m, 1H).

[실시예 10] 3,10-다이브로모-4,11-다이옥사-5,6,12,12a-테트라 하이드로벤조[j]플루오란센 (3,10-Dibromo-4,11-dioxa-5,6,12,12a-tetra hydrobenzo[j]fluoranthene)의 제조.Example 10 3,10-Dibromo-4,11-dioxa-5,6,12,12a-tetrahydrobenzo [ j ] fluoranthene (3,10-Dibromo-4,11-dioxa-5 , 6,12,12a-tetra hydrobenzo [ j ] fluoranthene).

Figure 112012044607020-pat00022
Figure 112012044607020-pat00022

8,8'-다이브로모-2H,2'H-4,4'-바이크로멘 [8,8'-Dibromo-2H,2'H-4,4'-bichromene] (84.0 mg, 0.2 mmol)이 들어있는 4 mL의 반응 용기에 다이클로로메탄(0.8 mL)을 주입한 후, 트리플루오로메탄설폰 산(9.0 mg, 0.06 mmol)을 넣고, 실온에서 20분간 교반 시킨 후, 별도의 과정 없이 여과하였다. 용매를 제거한 후 관 크로마토그래피로 분리하여, 표제 화합물인 3,10-다이브로모-4,11-다이옥사-5,6,12,12a-테트라 하이드로벤조 [j]플루오란센 (3,10-dibromo-4,11-dioxa-5,6,12,12a-tetra hydrobenzo[j] fluoranthene) (72.2 mg, 86%)을 얻었다.8,8'-Dibromo-2H, 2'H-4,4'-bichromen [8,8'-Dibromo-2H, 2'H-4,4'-bichromene] (84.0 mg, 0.2 mmol) After dichloromethane (0.8 mL) was injected into a 4 mL reaction vessel containing trifluoromethanesulfonic acid (9.0 mg, 0.06 mmol), the mixture was stirred at room temperature for 20 minutes, and then filtered without further processing. It was. The solvent was removed and the residue was separated by column chromatography to obtain the title compound 3,10-dibromo-4,11-dioxa-5,6,12,12a-tetrahydrobenzo [ j ] fluoranthene (3,10- dibromo-4,11-dioxa-5,6,12,12a-tetra hydrobenzo [ j ] fluoranthene) (72.2 mg, 86%) was obtained.

1H NMR (400 MHz, CDCl3) δ 7.42 (t, J = 7.8 Hz, 2H), 7.32 (d, J = 7.8 Hz, 1H), 7.07 (d, J = 7.8 Hz, 1H), 6.86 (t, J = 7.8 Hz, 1H), 5.04-5.01 (m, 1H), 4.57-4.52 (m, 1H), 4.37-4.31 (m, 1H), 3.87-3.79 (m, 2H), 3.27-3.19 (m, 1H), 3.11-3.04 (m, 1H).
 1 H NMR (400 MHz, CDCl 3 ) δ 7.42 (t, J = 7.8 Hz, 2H), 7.32 (d, J = 7.8 Hz, 1H), 7.07 (d, J = 7.8 Hz, 1H), 6.86 (t , J = 7.8 Hz, 1H), 5.04-5.01 (m, 1H), 4.57-4.52 (m, 1H), 4.37-4.31 (m, 1H), 3.87-3.79 (m, 2H), 3.27-3.19 (m , 1H), 3.11-3.04 (m, 1H).

[실시예 11] 3,10-다이브로모-1,8-다이메틸-4,11-다이옥사-5,6,12,12a-테트라하이드로벤조[j]플루오란센 (3,10-Dibromo-1,8-dimethyl -4,11-dioxa-5,6,12,12a-tetrahydrobenzo[j]fluoranthene)의 제조.Example 11 3,10-Dibromo-1,8-dimethyl-4,11-dioxa-5,6,12,12a-tetrahydrobenzo [ j ] fluoranthene (3,10-Dibromo- Preparation of 1,8-dimethyl-4,11-dioxa-5,6,12,12a-tetrahydrobenzo [ j ] fluoranthene).

Figure 112012044607020-pat00023
Figure 112012044607020-pat00023

8,8'-다이브로모-6,6'-다이메틸-2H,2'H-4,4'-바이크로멘 [8,8'-Dibromo-6,6'-dimethyl-2H,2'H-4,4'-bichromene] (89.6 mg, 0.2 mmol)이 들어있는 4 mL의 반응 용기에 다이클로로메탄(0.8 mL)을 주입한 후, 트리플루오로메탄설폰 산(9.0 mg, 0.06 mmol)을 넣고, 실온에서 4시간 교반 시킨 후, 별도의 과정 없이 여과하였다. 용매를 제거한 후 관 크로마토그래피로 분리하여, 표제 화합물인 3,10-다이브로모-1,8-다이메틸-4,11-다이옥사-5,6,12,12a-테트라하이드로벤조[j]플루오란센 (3,10-dibromo-1,8-dimethy l-4,11-dioxa-5,6,12,12a-tetrahydrobenzo[j]fluoranthene) (79.8 mg, 89%)을 얻었다.8,8'-Dibromo-6,6'-dimethyl-2H, 2'H-4,4'-bichromen [8,8'-Dibromo-6,6'-dimethyl-2H, 2'H Dichloromethane (0.8 mL) was injected into a 4 mL reaction vessel containing -4,4'-bichromene] (89.6 mg, 0.2 mmol), followed by trifluoromethanesulfonic acid (9.0 mg, 0.06 mmol). The mixture was stirred at room temperature for 4 hours, and then filtered without any additional procedure. The solvent was removed and the residue was separated by column chromatography to obtain the title compound 3,10-dibromo-1,8-dimethyl-4,11-dioxa-5,6,12,12a-tetrahydrobenzo [ j ] fluoro Lansen (3,10-dibromo-1,8-dimethy l-4,11-dioxa-5,6,12,12a-tetrahydrobenzo [ j ] fluoranthene) (79.8 mg, 89%) was obtained.

1H NMR (400 MHz, CDCl3) δ 7.24 (s, 1H), 7.18 (s, 1H), 7.10 (s, 1H), 5.17-5.13 (m, 1H), 4.56-4.50 (m, 1H), 4.28-4.22 (m, 1H), 3.82-3.73 (m, 2H), 3.19-3.08 (m, 1H), 3.08-3.03 (m, 1H), 2.32 (s, 3H), 2.30 (s, 3H).
 1 H NMR (400 MHz, CDCl 3 ) δ 7.24 (s, 1H), 7.18 (s, 1H), 7.10 (s, 1H), 5.17-5.13 (m, 1H), 4.56-4.50 (m, 1H), 4.28-4.22 (m, 1H), 3.82-3.73 (m, 2H), 3.19-3.08 (m, 1H), 3.08-3.03 (m, 1H), 2.32 (s, 3H), 2.30 (s, 3H).

[실시예 12] 1,8-다이아이오도-4,11-다이옥사-5,6,12,12a-테트라 하이드로벤조[j]플루오로란센 (1,8-Diiodo-4,11-dioxa-5,6,12,12a-tetra hydrobenzo[j]fluoranthene)의 제조.Example 12 1,8-Diiodo-4,11-dioxa-5,6,12,12a-tetrahydrobenzo [ j ] fluorolancene (1,8-Diiodo-4,11-dioxa -5,6,12,12a-tetra hydrobenzo [ j ] fluoranthene).

Figure 112012044607020-pat00024
Figure 112012044607020-pat00024

6,6'-다이아이오도-2H,2'H-4,4'-바이크로멘 [6,6'-Diiodo-2H,2'H-4,4'-bichromene] (102.8 mg, 0.2 mmol)이 들어있는 4 mL의 반응 용기에 다이클로로메탄(0.8 mL)을 주입한 후, 트리플루오로메탄설폰 산(9.0 mg, 0.30 06 mmol)을 넣고, 실온에서 5시간 교반 시킨 후, 별도의 과정 없이 여과하였다. 용매를 제거한 후 관 크로마토그래피로 분리하여, 표제 화합물을 1,8-다이아이오도-4,11-다이옥사-5,6,12,12a-테트라 하이드로벤조 [j]플루오로란센 (1,8-diiodo-4,11-dioxa-5,6,12,12a-tetrahydrobenzo[j] fluoranthene) (76.1 mg, 74%)을 얻었다.6,6'-Diiodo-2H, 2'H-4,4'-bichromen [6,6'-Diiodo-2H, 2'H-4,4'-bichromene] (102.8 mg, 0.2 mmol Inject dichloromethane (0.8 mL) into a 4 mL reaction vessel containing), add trifluoromethanesulfonic acid (9.0 mg, 0.30 06 mmol), and stir at room temperature for 5 hours. Filter without. The solvent was removed and then separated by column chromatography to give the title compound as 1,8-dioio-4,11-dioxa-5,6,12,12a-tetrahydrobenzo [ j ] fluorolancene (1, 8-diiodo-4,11-dioxa-5,6,12,12a-tetrahydrobenzo [ j ] fluoranthene) (76.1 mg, 74%) was obtained.

1H NMR (400 MHz, CDCl3) δ 7.70 (d, J = 2.1 Hz, 1H), 7.43 (dd, J = 8.6, 2.1 Hz, 1H), 7.40 (d, J = 8.4 Hz, 1H), 6.74 (d, J = 8.6, 1.7 Hz, 1H), 6.64 (d, J = 8.6, 1.7 Hz, 1H), 5.46-4.52 (m, 1H), 4.48-4.42 (m, 1H), 4.22-4.15 (m, 1H), 3.85-3.79 (m, 1H), 3.73-3.67(m, 1H), 3.22-3.14 (m, 1H), 3.07-3.00 (m, 1H). 1 H NMR (400 MHz, CDCl 3 ) δ 7.70 (d, J = 2.1 Hz, 1H), 7.43 (dd, J = 8.6, 2.1 Hz, 1H), 7.40 (d, J = 8.4 Hz, 1H), 6.74 (d, J = 8.6, 1.7 Hz, 1H), 6.64 (d, J = 8.6, 1.7 Hz, 1H), 5.46-4.52 (m, 1H), 4.48-4.42 (m, 1H), 4.22-4.15 (m , 1H), 3.85-3.79 (m, 1H), 3.73-3.67 (m, 1H), 3.22-3.14 (m, 1H), 3.07-3.00 (m, 1H).

Claims (8)

삭제delete 삭제delete 삭제delete 트리플루오로메탄설폰산 존재하에 하기 화학식 2로 표시되는 화합물로부터 하기 화학식 1로 표시되는 플루오로란센 유도체를 제조하는 방법.
[화학식 1]
Figure 112012083049236-pat00029

[화학식 2]
Figure 112012083049236-pat00030

[상기 화학식 1 또는 화학식 2 에서,
X는 CH2 또는 O를 나타내며;
R1과 R4는 동일하며, 수소, 할로겐, (C1~C8)알킬, (C1~C8)알콕시 또는 (C6~C20)아릴에서 선택되며;
R2와 R5는 동일하며, 수소 또는 (C1~C8)알콕시에서 선택되며;
R3와 R6는 동일하며, 수소, 할로겐, (C1~C8)알킬 또는 (C1~C8)알콕시에서 선택된다. ]A method for preparing a fluorolancene derivative represented by the following formula (1) from a compound represented by the following formula (2) in the presence of trifluoromethanesulfonic acid.
[Formula 1]
Figure 112012083049236-pat00029

(2)
Figure 112012083049236-pat00030

[In Formula 1 or Formula 2,
X represents CH 2 or O;
R 1 and R 4 are the same and are selected from hydrogen, halogen, (C 1 -C 8) alkyl, (C 1 -C 8) alkoxy or (C 6 -C 20) aryl;
R 2 and R 5 are the same and are selected from hydrogen or (C 1 -C 8) alkoxy;
R 3 and R 6 are the same and are selected from hydrogen, halogen, (C 1 -C 8) alkyl or (C 1 -C 8) alkoxy. ] 제 4항에 있어서,
화학식 1은 하기 화합물에서 선택되는 것인 방법.
Figure 112012083049236-pat00032

Figure 112012083049236-pat00033

Figure 112012083049236-pat00034
5. The method of claim 4,
Formula 1 is selected from the following compounds.
Figure 112012083049236-pat00032

Figure 112012083049236-pat00033

Figure 112012083049236-pat00034
 제 4항에 있어서,
상기 화학식 1의 플루오란센 유도체의 제조는 상기 화학식 2로 표시되는 화합물에 트리플루오로메탄설폰산을 첨가하여 5분 내지 5시간동안 반응이 수행되는 것을 특징으로 하는 방법.5. The method of claim 4,
Preparation of the fluoranthene derivative of Formula 1 is characterized in that the reaction is carried out for 5 minutes to 5 hours by adding trifluoromethanesulfonic acid to the compound represented by the formula (2). 제 4항에 있어서,
트리플루오로메탄설폰산은 화학식 2의 화합물, 1몰을 기준으로 0.01 ~ 0.50몰을 사용하는 방법.5. The method of claim 4,
Trifluoromethanesulfonic acid is a method of using a compound of formula 2, 0.01 ~ 0.50 moles based on 1 mole. 제 6항에 있어서,
반응은 다이클로로메탄(DCM), 다이클로로에탄(DCE), 톨루엔(Toluene), 아세토나이트릴(MeCN), 나이트로메탄(nitromethan), 테트라하이드로퓨란(THF), N,N-다이메틸포름아마이드(DMF) 및 N,N-다이메틸아세트아마이드(DMA)에서 선택되는 하나이상의 용매하에서 수행되는 것을 특징으로 하는 방법.The method according to claim 6,
Reactions include dichloromethane (DCM), dichloroethane (DCE), toluene, toluene, acetonitrile (MeCN), nitromethan, tetrahydrofuran (THF), N, N -dimethylformamide (DMF) and N, N -dimethylacetamide (DMA).
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J. Org. Chem., Vol. 49, pp. 103-1033 (1984.).*

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