KR101932740B1 - Naphthoquinone Derivatives, Benzoquinone Derivatives, and Anthracenedione Derivatives, Their Use and Novel Method for Preparation - Google Patents

Abstract

The present invention relates to a novel process for preparing a quinone derivative or an anthracenedione derivative by a copper-catalyzed cross-dehydrogenation coupling reaction of a naphthoquinone, a benzoquinone or an anthracenedione compound with various cycloalkanes, a naphthoquinone derivative , A benzoquinone derivative, an anthracenedione derivative, and a use thereof. According to the novel production method of the present invention, a naphthoquinone derivative, a benzoquinone derivative or an anthracenedione derivative can be prepared in one step, And the cost and time can be reduced, and the derivatives according to the present invention can be variously used as an animal medicine.

Description

TECHNICAL FIELD The present invention relates to a naphthoquinone derivative, a benzoquinone derivative and an anthracenedione derivative, a use thereof,

The present invention relates to a naphthoquinone derivative, a benzoquinone derivative and an anthracenedione derivative, a use thereof, and a novel process for producing the same.

Coupling reactions are important synthetic tools that have been widely used in organic and natural product synthesis. In recent years, direct functionalization of CH bonds has emerged as an important cross-coupling strategy for the production of various CC bonds due to its economic advantages, which avoids the mixing of the necessary substituents. This cross-dehydrogenative coupling (CDC) of CH bonds has the advantage of reducing the synthesis step and producing the product at low cost and environmentally friendly. Recently, many methods for CDC reaction have been reported to form various CC bonds. Among these, reports related to Csp ² -Csp ³ bond formation include direct activation of a Csp ³ -H bond adjacent to a heteroatom, a carbonyl group, or an allyl group and a benzyl group.

Quinone compounds, including 1,4-benzoquinone and 1,4-naphthoquinone, are interesting and important compounds found in many natural products and pharmaceuticals. These quinone-based molecules exhibit a wide range of biological properties including anticancer, antibacterial, antimicrobial, antiviral, antigenic, antiinflammatory, antiplasmoid, neuroactive and radiolabeling activities. Some of these compounds are currently used as drugs. For example, parvaquone, designated as Clexon, is used for the treatment of a disease of theileria parva, a micro-parasite causing the East Coast Fever (theileriosis) . It is also used for the treatment of malaria. In addition, Atovaquone has been approved for the treatment of pneumocystis pneumonia, toxoplasmosis, and malaria. In addition, quinone-based molecules are also widely used as building blocks for the synthesis of bioactive natural products, molecular electronics, drugs, dyes, and ligands.

Due to their importance and usefulness, several synthesis methods for the functionalization of quinones have been tested based on transition metal-catalyzed reactions. Typical methods include the first introduction of a halogen to quinone followed by a palladium-catalyzed cross-coupling reaction. Further, recently, direct CH functionalization of benzoquinone has been carried out by a silver catalyst, palladium catalyst or iron-mediated reaction using boronic acid in the presence of a co-oxidant to avoid prefunctionalization There is a bar. However, as described above, although there are many methods for the functionalization of benzoquinone in the presence of boronic acid, easier and more efficient tools still need to be developed.

Also, tert- butyl hydroperoxide hydroxide (TBHP), Pd (OAc) together with ether and phenol or naphthol derivatives in the presence ₂ / Cu (OTf) ₂ - dehydrogenation catalyst cross coupling reaction, by the ring with the adjacent oxygen Csp ³ - H bond has been developed and a tertiary-butyl peroxide (TBHP) -mediated free radical reaction of 2-hydroxy-1,4-naphthoquinone and a hydrocarbon has been disclosed, No direct coupling reaction of quinone with an inactivated cycloalkane has been reported.

Korean Registered Patent No. 10-1079140 (registered on October 27, 2011)

An object of the present invention is to provide a novel naphthoquinone derivative.

Another object of the present invention is to provide a benzoquinone derivative.

It is still another object of the present invention to provide an anthracenedione derivative.

Another object of the present invention is to provide an animal medicine composition which can effectively lower the heat of livestock.

Another object of the present invention is to provide a novel process for synthesizing a naphthoquinone derivative, a benzoquinone derivative and an anthracenedione derivative which can increase the yield and reduce the reaction time.

In order to accomplish the above object, the present invention provides a naphthoquinone derivative represented by the following formula 1:

[Chemical Formula 1]

Wherein R ₁ is selected from the group consisting of hydrogen, (C ₁ -C 4) alkyl, aryl and hydroxy, R ₂ is (C ₃ -C 13) cycloalkyl and R ₃ is hydrogen or (C 1 -C 4) Lt; / RTI >

According to another aspect of the present invention, there is provided a benzoquinone derivative represented by Formula 2 below:

(2)

In the above formula (2), R ₄ is (C 3 -C 13) cycloalkyl.

According to another aspect of the present invention, there is provided an anthracenedione derivative represented by the following general formula (3) or (4);

(3)

In Formula 3, R < ₅ > is (C3-C13) cycloalkyl;

[Chemical Formula 4]

In the above formula (4), R < ₆ > is (C3-C13) cycloalkyl.

In order to accomplish still another object of the present invention, the present invention provides a method for producing a naphthoquinone derivative represented by Formula 1, a benzoquinone derivative represented by Formula 2, and an anthracenedione derivative represented by Formula 3 or 4, Or a pharmaceutically acceptable salt thereof.

In order to accomplish the above-mentioned further object, the present invention provides a process for producing a reaction product comprising (a) reacting 1,4-naphthoquinone, 1,4-dihydroxynaphthalene, anthracene- Dihydroxyanthracene-9,10-dione, (b) (C3-C13) cycloalkyl as a catalyst, Cu (OTf) ₂ as a catalyst, and tertiary- butyl Wherein the reaction is carried out at 60 ° C to 100 ° C for 4 hours to 10 hours together with hydroperoxides (TBHP).

The present invention relates to a novel naphthoquinone derivative, a benzoquinone derivative and an anthracenedione derivative, an animal pharmaceutical composition containing the same, and a novel process for producing the same, and the derivative has an activity of reducing heat and is useful as a pharmaceutical composition for animals In addition, since the novel process according to the present invention can synthesize the compound in a single step by using copper as a catalyst which is easy to obtain and cheap, the desired product can be obtained with high efficiency while reducing cost and reaction time can do.

Figures 1 and 2 show the structures of the compounds prepared according to the novel process of the invention.
Figures 3 and 4 show schematically the mechanism of the process for preparing the novel compounds disclosed in the present invention.

As a continuing study in this field, the inventors of the present invention have found that there is a direct copper-catalyzed Csp ² -Csp ³ bond in the presence of an oxidizing agent between the various quinone compounds and the cycloalkanes containing middle and large size rings Forming reaction. Recently, a mechanism of the role of the transition metal in the TBHP oxidation reaction has been studied, and it has been found that the metals effectively initiate the radical formation process by effecting single-electron transfer from the metal salt to TBHP, Indicate that the use of metal increases the rate of radical reaction. Of the transition metals, copper salts are relatively inexpensive compared to others, so it is efficient to couple Csp ² -Csp ³ coupling between quinone and cycloalkane with a combination of copper salt and TBHP to increase product yield and reduce reaction time As an application of such a reaction, the inventors of the present invention have confirmed the one-step synthesis reaction of a naphthoquinone derivative, anthracenedione derivative, benzoquinone derivative and derivatives thereof containing a pharquione derivative to complete the present invention Respectively.

Accordingly, the present invention provides a naphthoquinone derivative represented by the following formula (1);

[Chemical Formula 1]

Wherein R ₁ is selected from the group consisting of hydrogen, (C ₁ -C 4) alkyl, aryl and hydroxy, R ₂ is (C ₃ -C 13) cycloalkyl and R ₃ is hydrogen or (C 1 -C 4) Lt; / RTI >

Preferably, R ₁ is selected from the group consisting of hydrogen, methyl, aryl and hydroxy, R ₂ is selected from the group consisting of cyclohexane, cycloheptane, cyclooctane and cyclododecane, R ₃ May be hydrogen or methoxy.

More preferably, the naphthoquinone derivative is selected from the group consisting of 2-cyclohexyl-3-hydroxynaphthalene-1,4-dione, 2-cyclohexylnaphthalene- 1,4-dione, 2-cycloheptyl-3-methylnaphthalene-1,4-dione, 2-cyclooctyl-3-methylnaphthalene- 2-cyclohexyl-3-phenylnaphthalene-1, 4-dione, 2-cyclohexyl-3- 4-dione, 2-cycloheptylnaphthalene-1,4-dione, 2-cyclooctyl-3-hydroxynaphthalene- 3-hydroxynaphthalene-1,4-dione, 2-cyclododecylnaphthalene-1,4-dione, 3-cyclohexyl- Cycloheptyl-3-methylnaphthalene-1,4-dione, 2-cyclooctyl-3-methylnaphthalene-1 , 4-dione and 2-cyclododecyl-3-methylnaphthalene-1,4-dione.

The present invention also provides a benzoquinone derivative represented by the following general formula (2);

(2)

In the above formula (2), R < ₄ > is (C3-C13) cycloalkyl.

Preferably, R ₄ in the formula (2) may be selected from the group consisting of cyclohexane, cycloheptane, cyclooctane and cyclododecane.

More preferably, the benzoquinone derivative is selected from the group consisting of [1,1'-bi (cyclohexane)] -3,6-diene-2,5-dione, 2-cycloheptylcyclohexa-2,5- Diene, 2-cyclooctylcyclohexa-2,5-diene-1,4-dione and 2-cyclododecylcyclohexa-2,5-diene-1,4-dione have.

Further, the present invention provides an anthracenedione derivative represented by the following general formula (3) or (4);

(3)

In Formula 3, R < ₅ > is (C3-C13) cycloalkyl;

[Chemical Formula 4]

In Formula 4, R ₆ is (C3-C13) cycloalkyl.

Preferably, in Formula 3, R < ₅ > is any one selected from cyclohexane, cycloheptane, and cyclooctane; In Formula 4, R ₆ may be cyclohexane or cyclooctane.

More preferably, the anthracenedione derivative is selected from the group consisting of 2-cyclohexyl-3-hydroxyanthracene-1,4-dione, 2-cycloheptyl-3-hydroxyanthracene- -Hydroxyanthracene-1,4-dione, 2-cyclohexyl-1,4-dihydroxyanthracene-9,10-dione and 2-cyclooctyl-1,4-dihydroxyanthracene- ≪ / RTI >

In addition, the present invention provides an animal pharmaceutical composition comprising an naphthoquinone derivative represented by the following general formula (1), a benzoquinone derivative represented by the general formula (2) and an anthracenedione derivative represented by the general formula (3) Lt; / RTI >

[Chemical Formula 1]

Wherein R ₁ is selected from the group consisting of hydrogen, (C ₁ -C 4) alkyl, aryl and hydroxy, R ₂ is (C ₃ -C 13) cycloalkyl and R ₃ is hydrogen or (C 1 -C 4) Alkoxy;

(2)

In the above formula (2), R < ₄ > is (C3-C13) cycloalkyl;

(3)

In Formula 3, R < ₅ > is (C3-C13) cycloalkyl;

[Chemical Formula 4]

In Formula 4, R ₆ is (C3-C13) cycloalkyl.

Preferably, R ₁ is selected from the group consisting of hydrogen, methyl, aryl and hydroxy, R ₂ is selected from the group consisting of cyclohexane, cycloheptane, cyclooctane and cyclododecane, R ₃ is hydrogen or methoxy; In Formula 2, R ₄ is any one selected from the group consisting of cyclohexane, cycloheptane, cyclooctane, and cyclododecane; In Formula 3, R ₅ is any one selected from cyclohexane, cycloheptane, and cyclooctane; In Formula 4, R ₆ may be cyclohexane or cyclooctane.

More preferably, the naphthoquinone derivative is selected from the group consisting of 2-cyclohexyl-3-hydroxynaphthalene-1,4-dione, 2-cyclohexylnaphthalene- 1,4-dione, 2-cycloheptyl-3-methylnaphthalene-1,4-dione, 2-cyclooctyl-3-methylnaphthalene- 2-cyclohexyl-3-phenylnaphthalene-1, 4-dione, 2-cyclohexyl-3- 4-dione, 2-cycloheptylnaphthalene-1,4-dione, 2-cyclooctyl-3-hydroxynaphthalene- 3-hydroxynaphthalene-1,4-dione, 2-cyclododecylnaphthalene-1,4-dione, 3-cyclohexyl- Cycloheptyl-3-methylnaphthalene-1,4-dione, 2-cyclooctyl-3-methylnaphthalene-1 , 4-dione and 2-cyclododecyl-3-methylnaphthalene-1,4-dione, and the benzoquinone derivative may be selected from the group consisting of [1,1'-bicyclohexane] Diene-2,5-dione, 2-cycloheptylcyclohexa-2,5-diene-1,4-dione, 2-cyclooctylcyclohexa-2,5-diene- -Cyclododecylcyclohexa-2,5-diene-1,4-dione.

Further, the anthracenedione derivative may be at least one selected from the group consisting of 2-cyclohexyl-3-hydroxyanthracene-1,4-dione, 2-cycloheptyl-3-hydroxyanthracene- Anthracene-1,4-dione, 2-cyclohexyl-1,4-dihydroxyanthracene-9,10-dione and 2-cyclooctyl-1,4-dihydroxyanthracene-9,10- ≪ / RTI >

The naphthoquinone derivative, the benzoquinone derivative and the anthracenedione derivative have an activity of reducing the heat of an animal. Accordingly, the animal pharmaceutical composition of the present invention containing the derivatives as an active ingredient is useful for lowering the heat of livestock Can be used.

Furthermore, the present invention relates to a process for the preparation of (a) 1,4-naphthoquinone, 1,4-dihydroxynaphthalene, anthracene-1,4-dione, 1,4-benzoquinone and 1,4- -9,10-dione and (b) (C3-C13) cycloalkyl as a catalyst, Cu (OTf) ₂ as a catalyst, and tertiary butyl hydroperoxide (TBHP) At a temperature of 60 ° C to 100 ° C for 4 hours to 10 hours. The present invention also provides a process for producing a naphthoquinone derivative, a benzoquinone derivative and an anthracenedione derivative.

In this case, the 1,4-naphthoquinone may be a compound represented by the following general formula (5);

[Chemical Formula 5]

In Formula 5, R ₇ is any one selected from the group consisting of hydrogen, (C 1 -C 4) alkyl, aryl, hydroxy and halogen, and R ₈ is hydrogen or (C 1 -C 4) alkoxy.

More preferably, in Formula 5, R ₇ may be any one selected from the group consisting of hydrogen, methyl, aryl, hydroxy, bromine and chlorine, and R ₈ may be hydrogen or methoxy.

The (C3-C13) cycloalkyl may also be cyclohexane, cycloheptane, cyclooctane or cyclododecane.

More preferably, the reaction of the compound with the catalyst and the oxidizing agent can be carried out at 80 DEG C for 6 hours, but is not limited thereto.

In one embodiment of the present invention, the naphthoquinone derivative prepared by the above process can be represented by the following formula (1);

[Chemical Formula 1]

Wherein R ₁ is selected from the group consisting of hydrogen, (C ₁ -C 4) alkyl, aryl and hydroxy, R ₂ is (C ₃ -C 13) cycloalkyl and R ₃ is hydrogen or (C 1 -C 4) Lt; / RTI >

More preferably, R ₁ is selected from the group consisting of hydrogen, methyl, aryl and hydroxy, R ₂ is selected from the group consisting of cyclohexane, cycloheptane, cyclooctane and cyclododecane, R ₃ may be hydrogen or methoxy.

The benzoquinone derivative prepared by the above process may be represented by the following general formula (2);

(2)

In the above formula (2), R < ₄ > is (C3-C13) cycloalkyl.

More preferably, R ₄ in Formula 2 may be selected from the group consisting of cyclohexane, cycloheptane, cyclooctane, and cyclododecane.

Furthermore, the anthracenedione derivative produced by the above production method can be represented by the following formula 3 or 4;

(3)

In Formula 3, R < ₅ > is (C3-C13) cycloalkyl;

[Chemical Formula 4]

In Formula 4, R ₆ is (C3-C13) cycloalkyl.

More preferably, in Formula 3, R ₅ is any one selected from cyclohexane, cycloheptane, and cyclooctane; In Formula 4, R ₆ may be cyclohexane or cyclooctane.

In one embodiment of the present invention, the naphthoquinone derivative, the benzoquinone derivative and the anthracenedione derivative produced by the above-mentioned production method are 2-cyclohexyl-3-hydroxynaphthalene-1,4-dione, 2-cyclohexylnaphthalene- Cyclohexyl-3-methylnaphthalene-1, 4-dione, 2-cyclohexyl-3-methylnaphthalene- 4-dione, 2-cyclododecyl-3-methylnaphthalene-1,4-dione, 2-cyclohexyl-3-phenylnaphthalene- 2-cycloheptyl-3-hydroxynaphthalene-1,4-dione, 2-cycloheptylnaphthalene-1,4-dione, 2-cyclooctyl- 2-cyclododecylnaphthalene-1,4-dione, 3-cyclohexyl-2-hydroxynaphthalene-1,4-dione, 6-methoxynaphthalene-1,4-dione, 2-cycloheptyl-3-methylnaphthalene-1, 4-dione, 2-cycloheptyl-3-methylnaphthalene- 2-cycloheptyl-3-hydroxyanthracene-1,4-dione, 2-cyclooctyl-3-hydroxyanthracene-1,4-dione, Diene-2,5-dione, 2-cycloheptylcyclohexa-2,5-diene-1,4-dione, 2-cyclooctylcyclo Diene-1,4-dione, 2-cyclododecylcyclohexa-2,5-diene-1,4-dione, 2-cyclohexyl-1,4-dihydroxyanthracene- 10-dione, and 2-cyclooctyl-1,4-dihydroxyanthracene-9,10-dione.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to the following examples. It is to be understood that both the foregoing description and the following detailed description are exemplary and explanatory and are intended to provide further explanation of the invention as claimed. no.

< Preparation Example  1> Preparation of reagents and compounds

All experiments according to the invention were carried out in air contact. TLC for analysis was performed using a pre-coated silica gel plate (Art. 5554) with a fluorescence indicator from Merck, and silica gel 9385 (Merck) was used for flash column chromatography. The melting point of each compound was measured using a Fisher-Johns melting point apparatus containing a micro-cover glass and not calibrated, ¹ H NMR analysis was performed in CDCl ₃ as a solvent chemical shift at 7.24 ppm, and at 0.00 ppm &Lt; / RTI &gt; using a Varian-VNS (600 MHz) spectrometer at TMS as solvent chemistry shifts. ¹³ C NMR spectra were measured with a 77.0 ppm using a Varian-VNS (150 MHz) spectrometer in CDCl ₃ as solvent and chemical shifts. IR analysis (infrared analysis) was recorded with FTIR (BIO-RAD), and high-resolution mass spectra were performed using a JOEL JMS-700 spectrometer (Korea Basic Science Institute).

< Example  1> Compound synthesis based on various reaction conditions based on copper catalyst

Using various catalysts and antioxidants, a direct cross-reaction of 2-methyl-1,4-naphthoquinone (compound 6a; 1.0 mmol) and cyclohexane (7a; 10.0 mmol) - Experiments were conducted to optimize the coupling reaction.

That is, the product 8 was obtained under various reaction time conditions using various catalysts and oxidizing agents through the reaction as shown in the following Reaction Scheme 1, and the product was purified by column chromatography to obtain the yield. Data and a compound already reported.

[Reaction Scheme 1]

(b: separation yield after column chromatography, c: incomplete reaction proceeds, d: d: compound 6a is decomposed)

As shown in Table 1, the reaction was carried out at various temperatures by combining various catalysts and antioxidants. In the first experiment (Entry 1), TBHP (3 equiv) was used without copper for 24 hours at 80 ° C. The reaction proceeded, resulting in a very small amount of coupled product 8 and did not undergo complete reaction. When the reaction proceeded in the presence of CuI (5 mol%) (Entry 2), the reactant, 6a, was decomposed without forming any product. In addition, reaction with TBHP in the presence of a catalyst, 5 mol% CuO or CuCl ₂ , produced Product 8 with yields of 7% and 16%, respectively (Entry 3 and Entry 4, respectively). On the other hand, under the conditions where 5 mol% of CuCl (PPh ₃ ) ₃ or Cu (acac) ₂ was used as a catalyst, Compound 8 was obtained with a yield of 26% and 28% respectively (Entry 5 and Entry 6).

In this reaction, the yield was very low, so that another copper catalyst was screened and the reaction was carried out using Cu (OTf) ₂ . That is, when 5 mol% of Cu (OTf) ₂ was used as a catalyst, the yield of the compound 8 was increased to 64% (Entry 7) within 6 hours after the start of the reaction and the loading amount of the catalyst was reduced to 2 mol% And 10 mol%, respectively (Entry 8 and Entry 9). In addition, when TBHP was reduced to 1 or 2 equivalents, the yield was low (Entry 10 and Entry 11, respectively).

This time, the experiment was carried out by replacing the oxidizing agent with di-tertiary-butyl peroxide (DTBP), and the yield was reduced as shown in Entry 12 and no product was produced when tested in the presence of H ₂ O ₂ Entry 13). Other metal catalysts such as FeCl ₂ , FeCl ₃ or Pd (OAc) ₂ also did not increase yields (Entry 14, 15 and 16, respectively).

Based on the above results, the reaction using 5 mol% of Cu (OTf) ₂ as a catalyst and TBHP as an oxidizing agent was further studied.

< Example  2 > Cu ( OTf ₂ ) And TBHP  Variety in existence Naphthoquinone  Synthesis of derivatives

Based on the results in Example 1 above, the reaction of variously substituted 1,4-naphthoquinone with various cycloalkanes including medium or large size rings was carried out to extend the utility and generality of the reaction Respectively. The reaction was as shown in Reaction Scheme 2 below.

That is, Cu (OTf) ₂ (5 mol%) was added to the quinone solvent, and 3 equivalents of TBHP was added using a syringe. Then, heat was applied to 80 DEG C or refluxed under air for 6-7 hours, and the solvent was evaporated under reduced pressure with a rotary evaporator. The product was then purified by flash column chromatography on silica gel.

[Reaction Scheme 2]

As a result, the compounds as shown in Fig. 1 could be prepared. Specifically, the reaction of compound 6a with cycloheptane (7b), cyclooctane (7c) and cyclododecane (7d) at 80 ° C for 7 hours resulted in products 9-11 respectively 62, 61, 58 %. &Lt; / RTI &gt; In addition, the reaction of 1,4-naphthoquinone 6b and 6c, each containing a phenyl or hydroxyl group at position 2, has also been successfully accomplished. Also, in the reaction of compound 6b with 7a or 7c, compounds 12 and 13 were obtained with yields of 62% and 57%, respectively.

On the other hand, the reaction of compounds 6c and 7a provided the biocon and pharmacologically interesting pharquione compound 4 with a yield of 72%. Similarly, the reaction of 6c with 7b-7d yielded compounds 14-16 at yields of 64, 66 and 62%, respectively, and the reaction of compound 6d with OMe group at position 6 of the ring with 7a-7d gave compound 17- 20 was produced with a yield of 65 to 70%. Functional groups such as methyl, phenyl, hydroxyl, and methoxy except the bromide and chloride of the 1,4-naphthoquinone ring proceeded well. Interestingly, when the 1,4-naphthoquinone 6e and 6f compounds containing bromine and chlorine atoms at the 2-position of the ring are coupled with cyclohexane, 4 were produced with yields of 64% and 63%, respectively.

As described above, in consideration of general application of the protocol using substituted 1,4-naphthoquinone, unsubstituted 1,4-naphthoquinone (6 g), anthracene-1,4-dion (6h) , 4-benzoquinone (6i) and a cyclic alkane. At this time, the reagent and the reaction formula used were as shown in Reaction Scheme 3 below.

[Reaction Scheme 3]

The resulting structure of the resulting compounds was as shown in Fig.

First, the direct oxidative CH activity in the reaction of 6 g of unsubstituted 1,4-naphthoquinone with the cycloalkane was confirmed. As a result, the coupled product of unexpected 1,4-naphthoquinone (6 g) A derivative containing a hydroxy group was produced. For example, the 6-hour reaction of 6 g with cyclohexane yielded compounds 4 and 4 'with yields of 59% and 16%, respectively, in reaction with cycloheptane the products 14 and 14' 16%. &Lt; / RTI &gt; Similarly, reaction with cyclooctane produced products 15 and 15 'respectively at yields of 60% and 14%, and reaction with cyclododecane produced products 16 and 16' respectively at yields of 50% and 24% Respectively.

Thus, from the above results, it has been found that the process according to the present invention allows direct introduction of OH or cycloalkyl groups as the main components in the 2 and 3-positions of unsubstituted 1,4-naphthoquinones.

On the other hand, the reaction of anthracene-1,4-dione (6h) with 7a, 7b or 7c produced products 21-23 with yields of 62, 60 and 59%. Also, in the reaction of 1,4-benzoquinone (6i), the product 24-27 was produced as a sole compound, respectively, at a yield of 56 to 61%.

According to the above results, it was confirmed whether the direct oxidative coupling reaction as described above was applied to other structures. Specifically, naphthalene-1,4-diol (6j) and 1,4-dihydroxyanthracene-9,10-dione (6k) were subjected to the reaction scheme as shown in Reaction Scheme 4 below. At this time, Cu (OTf) ₂ (5 mol%) was added to the naphthalene-1,4-diol or 1,4-dihydroxyanthracene-9,10-dione solvent, and 3 equivalents of TBHP Respectively. Then, heat was applied to 80 DEG C or refluxed under air for 6-7 hours, and the solvent was evaporated under reduced pressure with a rotary evaporator. The product was then purified by flash column chromatography on silica gel.

[Reaction Scheme 4]

As a result, the structures of the prepared compounds were the same as the compounds 28 and 29 shown in the above-mentioned Reaction Scheme 4. Specifically, the coupled product of naphthalene-l, 4-diol (6j) with cyclohexane and cyclooctane provides the unexpected wave quinone compound (4) and the 1,4-naphthoquinone compound 66 and 62%, respectively. In the reaction with 1,4-dihydroxyanthracene-9,10-dione (6k), products 28 and 29 were produced with yields of 54% and 52%, respectively.

Finally, in order to clarify the mechanism of the reaction, a control experiment was carried out, wherein the reactants, the reaction conditions, the products and the like were as shown in the following Reaction Scheme 5, and the amounts of the reactants were the same as those in the above experiment.

[Reaction Scheme 5]

Specifically, under the absence of TBHP as a radical material, the desired product, Compound 8, was not produced (Eq. (1)). When TEMPO was added as a radical trapping reagent, Compound 8 was not produced as a coupling product. Instead, Compound 30, a compound added with cyclohexane and TEMPO, was detected by GC-MS (Eq. (2)). These results indicate that the reaction according to the present invention proceeds through the radical pathway.

In addition, another control experiment was carried out using compound 4 'under standard conditions (Eq. (3)) in order to confirm the mechanism of formation of 4 in compound 6g. However, in this case, product 4 was not produced, which means that the formation of 4 does not proceed through compound 4 '.

Based on the control experiment as described above, the mechanism of the coupling reaction is illustrated in FIG. That is, according to FIG. 3, in the first step of the catalytic cycle, the copper (II) salt ligand is exchanged with TBHP through homogeneous decomposition of the OO bond to form the tert-butoxide radical and the copper (III) -OH salt . The tert-butoxyl radical then draws hydrogen atoms from the cyclohexane to produce the radical intermediate 31, which reacts with compound 6a to yield intermediate 32. [ Oxidation by the single electron transfer between compound 32 and copper (III) -OOtBu produces copper (II) -OOtBu species and carbon cation intermediate 33, and after the deprotonation of compound 33, Resulting in final product 8 and TBHP production. Alternatively, the final product, Compound 8, may be generated by direct hydrogen from compound 32 via tert-butylperoxy radical.

The proposed final mechanism for the formation of compound 4 from 6g of such a compound is shown in FIG. That is, the radical intermediate product 34 prepared from the compounds 6g and 7a can be prepared by transferring the tert-butylperoxy radical from copper (III) -OOtBu to form the tert-butylperoxide species 35, and the peroxide decomposition of the compound 35, Compound 36 is generated to give the final product 4 through an enolization reaction.

< Synthetic example  1> Synthesis of Compound 4, 8-29

Dihydroxyanthracene-9,10-dione, substituted or unsubstituted &lt; RTI ID = 0.0 &gt; 1 &lt; / RTI &gt; Cu (OTf) ₂ (5 mol%) was added to a solution of 4-naphthoquinone (6; 1.0 mmol) and cycloalkane (7; 10.0 mmol), followed by the addition of 3 equivalents of TBHP using a syringe Respectively. Then, the reaction was carried out by raising the temperature to 80 ° C for 6-7 hours or refluxing at atmospheric pressure. To obtain the residue, the solvent was evaporated in a rotary evaporator under reduced pressure, and the residue was then purified by silica gel flash column chromatography to give the desired product (4, 9-29).

(1) 2- Cyclohexyl -3- Hydroxy naphthalene -1,4- Dion (2- Cyclohexyl -3-hydroxynaphthalene-1,4-dione; 4)

The above compound was obtained as a solid having a melting point of 133-135 DEG C through a general reaction. Yield: 72% (184 mg). ^{1 H NMR (600 MHz, CDCl} 3): d = 8.07 (1 H, d, J = 8.4 Hz), 8.01 (1 H, d, J = 7.8 Hz), 7.70 (1 H, t, J = 7.8 Hz ), 7.62 (1H, t, J = 7.8 Hz), 7.46 (1H, s), 3.06-3.02 (1H, m), 1.97-1.91 m), 1.70-1.68 (1H, m), 1.59-1.77 (2H, m), 1.37-1.23 ppm (3 H, m); ¹³ C NMR (150 MHz, CDCl ₃ ): d = 184.5, 181.9, 152.8, 134.8, 133.1, 132.6, 129.2, 127.8, 126.8, 125.5, 35.1, 29.2, 26.7, 25.9 ppm; IR (ATR):? = 3346, 2922, 2854, 1649, 1590, 1339, 1272, 1240, 938 cm ^-1 ; ^{HRMS m / z [M +]} calcd for C 16 H 16 O 3: 256.1099; found: 256.1097.

(2) 2- Cyclohexylnaphthalene -1,4- Dion (2- Cyclohexylnaphthalene -1,4- dione; 4 ')

The above compound was obtained as a solid having melting point of 86-88 DEG C through a general reaction. Yield: 16% (38 mg). ¹ H NMR (600 MHz, CDCl ₃ ): d = 8.06-8.04 (1 H, m), 8.00-7.99 (1H, m), 7.69-7.66 , 2.88-2.84 (1H, m), 1.82-1.80 (4H, m), 1.75-1.72 (1H, m), 1.44-1.37 ); ¹³ C NMR (150 MHz, CDCl ₃ ): d = 185.5, 184.7, 156.2, 133.5, 133.4, 132.9, 132.4, 131.8, 126.6, 125.8, 36.6, 32.2, 26.3, 25.9 ppm; IR (ATR): ν = 1925, 2851, 1652, 1590, 1301, 1255, 934 cm ^-1 ; ^{HRMS m / z [M +]} calcd for C 16 H 16 O 2: 240.1150; found: 240.1148.

(3) 2- Cyclohexyl -3-methylnaphthalene-1,4- Dion (2- Cyclohexyl -3-methylnaphthalene-1,4-dione; 8)

The above compound was obtained as a solid having melting point of 78-80 占 폚 through a general reaction. Yield: 64% (163 mg). ¹ H NMR (600 MHz, CDCl ₃ ): d = 7.99-7.96 (2 H, m), 7.63-7.59 (2 H, m), 2.86-2.82 , 2.05-1.99 (2 H, m), 1.81-1.80 (2 H, m), 1.74-1.70 (1 H, m), 1.58-1.56 (2 H, m), 1.33-1.28 ppm ); ¹³ C NMR (150 MHz, CDCl ₃ ): d = 185.6, 185.0, 150.4, 142.9, 133.3, 132.9, 132.7, 131.7, 126.1, 125.9, 40.7, 29.8, 26.9, 25.7, 12.5 ppm; IR (ATR): ν = 2929, 2849, 1654, 1589, 1288, 1240, 1239, 920 cm ^-1 ; ^{HRMS m / z [M +]} calcd for C 17 H 18 O 2: 254.1307; found: 254.1306.

(4) 2- Cycloheptyl -3-methylnaphthalene-1,4- Dion (2- Cycloheptyl -3-methylnaphthalene-1,4-dione; 9)

The above compound was obtained as a solid having melting point of 40-42 DEG C through a general reaction. Yield: 62% (166 mg). ¹ H NMR (600 MHz, CDCl ₃ ): d = 8.01-7.99 (2 H, m), 7.66-7.61 (2 H, m), 3.05 2.03-1.85 (2H, m), 1.84-1.80 (2H, m), 1.64-1.57 (6H, m), 1.53-1.47 ppm (2H, m); ¹³ C NMR (150 MHz, CDCl ₃ ): d = 185.8, 184.9, 152.5, 141.7, 133.3, 133.0, 132.6, 131.8, 126.1, 125.9, 41.1, 32.3, 28.8, 28.2, 28.1, 12.7 ppm; IR (ATR): ν = 2918, 2854, 1653, 1594, 1451, 1286, 954 cm ^-1 ; ^{HRMS m / z [M +]} calcd for C 18 H 20 O 2: 268.1463; found: 68.1465.

(5) 2- Cyclooctyl -3-methylnaphthalene-1,4- Dion (2- Cyclooctyl -3-methylnaphthalene-1,4-dione; 10):

This compound was obtained as a solid with melting point 43-45 캜 by a general reaction. Yield: 61% (172 mg). ¹ H NMR (600 MHz, CDCl ₃ ): d = 7.91-7.89 (2 H, m), 7.57-7.52 (2 H, m), 3.11 -1.92 (2 H, m), 1.76-1.70 (2 H, m), 1.67-1.53 (3 H, m), 1.52-1.46 (5 H, m), 1.44-1.38 ppm (2 H, m); ¹³ C NMR (150 MHz, CDCl ₃ ): d = 185.5, 184.5, 153.4, 141.3, 133.0, 132.8, 132.4, 131.6, 125.9, 125.7, 38.5, 32.2, 26.9, 26.5, 26.2, 12.7 ppm; IR (ATR): ν = 2917, 2851, 1652, 1594, 1325, 1257, 949 cm ^-1 ; ^{HRMS m / z [M +]} calcd for C 19 H 22 O 2: 282.1620; found: 282.1617.

(6) 2- Cyclododecyl -3-methylnaphthalene-1,4- Dion (2- Cyclododecyl -3-methylnaphthalene-1,4-dione; 11)

The above compound was obtained as a solid having melting point of 110-112 DEG C through a general reaction. Yield: 58% (196 mg). ¹ H NMR (600 MHz, CDCl _{3 )} : d = 8.04-8.01 (2 H, m), 7.66-7.63 (2 H, m), 3.19 (1 H, br s), 2.23 2.02-1.99 (2 H, m), 1.56-1.54 (3 H, m), 1.46-1.40 (5 H, m), 1.36-1.35 ppm (12 H, m); ¹³ C NMR (150 MHz, CDCl ₃ ): d = 185.6, 185.0, 150.9, 143.9, 133.3, 133.0, 132.7, 131.8, 126.3, 126.0, 29.1, 24.3, 24.2, 23.9, 22.8, 22.2, 12.9 ppm; IR (ATR): ν = 2929, 2856, 1654, 1594, 1464, 1326, 1287, 957 cm ^-1 ; HRMS m / z [M ⁺ ] calcd for C ₂₃ H ₃₀ O ₂ : 338.2246; found: 338.2243.

(7) 2- Cyclohexyl -3- Phenyl naphthalene -1,4- Dion (2- Cyclohexyl -3-phenylnaphthalene-1,4-dione; 12)

This compound was obtained as a solid having melting point of 136-138 DEG C through a general reaction. Yield: 62% (196 mg). ¹ H NMR (600 MHz, CDCl ₃ ): d = 8.08 (1 H, d, J = 7.8 Hz), 8.04 (1H, d, J = 6.6 Hz), 7.72-7.67 (1H, d, J = 6.6 Hz), 2.48 (1H, tt, J = 12.6, 3.0 Hz), 2.01 ), 1.70-1.68 (2 H, m), 1.59-1.55 (4 H, m), 1.28-1.20 ppm (2 H, m); ¹³ C NMR (150 MHz, CDCl ₃ ): d = 185.6, 185.0, 151.0, 146.5, 134.2, 133.5, 133.3, 132.8, 131.6, 128.7, 128.2, 128.0, 126.2, 42.5, 30.6, 26.6, 25.7 ppm; IR (ATR): ν = 2924, 2854, 1656, 1591, 1447, 1324, 1255, 945 cm ^-1 ; ^{HRMS m / z [M +]} calcd for C 22 H 20 O 2: 316.1463; found: 316.1465.

(8) 2- Cyclooctyl -3- Phenyl naphthalene -1,4- Dion (2- Cyclooctyl -3-phenylnaphthalene-1,4-dione; 13)

This compound was obtained as a solid having a melting point of 141-143 DEG C through a general reaction. Yield: 57% (196 mg). ^{1 H NMR (600 MHz, CDCl} 3): d = 8.07 (1 H, d, J = 7.2 Hz), 8.04 (1 H, d, J = 7.2 Hz), 7.72-7.67 (2 H, m), 7.46 (1H, m), 7.41-7.39 (1H, m), 7.17 (2H, d, J = 7.2 Hz) ), 1.69-1.64 (2 H, m), 1.56-1.51 (3 H, m), 1.49-1.45 (1 H, m), 1.42-1.36 m); ^{13 C NMR (150 MHz, CDCl} 3): d = 185.4, 185.1, 153.7, 144.9, 134.2, 133.5, 133.4, 132.8, 131.7, 128.7, 128.2, 128.1, 126.2, 126.1, 40.1, 32.6, 29.6, 26.5, 26.1 ppm; IR (ATR): ν = 2917, 2858, 1658, 1595, 1445, 1287, 970 cm ^-1 ; HRMS m / z [M ⁺ ] calcd for C ₂₄ H ₂₄ O ₂ : 344.1776; found: 344.1779.

(9) 2- Cycloheptyl -3- Hydroxy naphthalene -1,4- Dion (2- Cycloheptyl -3-hydroxynaphthalene-1,4-dione; 14)

This compound was obtained as a solid with melting point of 213-215 [deg.] C through a general reaction. Yield: 64% (173 mg). ^{1 H NMR (600 MHz, CDCl} 3): d = 8.06 (1 H, d, J = 7.8 Hz), 8.00 (1 H, d, J = 7.8 Hz), 7.69 (1 H, d, J = 7.8 Hz ), 7.61 (1H, d, J = 7.2 Hz), 7.42 (1H, s), 3.16 (1H, t, J = 11.4, 3.6 Hz), 2.00-1.94 1.75 (2 H, m), 1.67-1.59 (4 H, m), 1.58-1.47 ppm (4 H, m); ¹³ C NMR (150 MHz, CDCl ₃ ): d = 184.3, 181.9, 152.1, 134.8, 133.1, 132.6, 129.9, 129.2, 126.8, 125.8, 36.5, 32.0, 28.1, 27.9 ppm; IR (ATR): ν = 3347, 2923, 2853, 1654, 1591, 1328, 1278, 1245, 901 cm ^-1 ; ^{HRMS m / z [M +]} calcd for C 17 H 18 O 3: 270.1256; found: 270.1255.

(10) 2- Cycloheptyl naphthalene -1,4- Dion (2- Cycloheptylnaphthalene -1,4-dione; 14 ')

The above compound was obtained as a solid with melting point 47-49 캜 through a general reaction. Yield: 16% (41 mg). ¹ H NMR (600 MHz, CDCl ₃ ): d = 8.02-8.00 (1H, m), 7.97-7.95 (1H, m), 7.65-7.62 , 2.99 (1H, tt, J = 10.2, 3.6 Hz), 1.80-1.78 (2H, m), 1.75-1.70 (2H, m), 1.66-1.62 4 H, m), 1.45-1.39 ppm (2 H, m); ¹³ C NMR (150 MHz, CDCl ₃ ): d = 185.4, 184.6, 157.6, 133.4, 133.3, 132.6, 132.3, 131.7, 126.5, 125.7, 38.1, 38.0, 34.1, 27.7, 26.9 ppm; IR (ATR): ν = 2918, 2859, 1635, 1589, 1337, 1255 cm ^-1 ; ^{HRMS m / z [M +]} calcd for C 17 H 18 O 2: 254.1307; found: 254.1310.

(11) 2- Cyclooctyl -3- Hydroxy naphthalene -1,4- Dion (2- Cyclooctyl -3-hydroxynaphthalene-1,4-dione; 15)

This compound was obtained as a solid having a melting point of 50-52 DEG C through a general reaction. Yield: 66% (187 mg). ¹ H NMR (600 MHz, CDCl ₃ ): d = 8.07 (1H, dd, J = 7.2, 1.2 Hz), 8.02 J = 7.2, 1.2 Hz), 7.62 (1H, td, J = 7.2, 1.2 Hz), 7.35 (1H, s), 3.16 (1H, tt, J = 10.8, 3.6 Hz), 2.06-1.99 2 H, m), 1.80-1.74 (2 H, m), 1.70-1.64 (3 H, m), 1.63-1.53 ppm (7 H, m); ¹³ C NMR (150 MHz, CDCl ₃ ): d = 184.4, 182.0, 151.9, 134.8, 133.0, 132.7, 130.9, 126.8, 125.8, 34.2, 31.3, 26.6, 26.4, 26.3 ppm; IR (ATR):? = 3365, 2919, 2852, 1645, 1592, 1366, 1340, 1263 cm ^-1 ; ^{HRMS m / z [M +]} calcd for C 18 H 20 O 3: 284.1412; found: 284.1411.

(12) 2- Cyclooctylnaphthalene -1,4- Dion (2- Cyclooctylnaphthalene -1,4- dione ; 15 ')

This compound was obtained as a solid with melting point of 44-46 캜 by a general reaction. Yield: 14% (37 mg). ¹ H NMR (600 MHz, CDCl ₃ ): d = 8.07-8.05 (1 H, m), 8.02-8.00 (1H, m), 7.70-7.67 , 3.16-3.14 (1H, m), 1.74-1.69 (4H, m), 1.65-1.62 (2H, m), 1.60-1.56 ppm (8H, m); ¹³ C NMR (150 MHz, CDCl ₃ ): d = 185.6, 184.8, 157.9, 133.5, 133.4, 133.0, 132.5, 131.8, 126.6, 125.8, 36.0, 31.9, 26.5, 26.3, 25.6 ppm; IR (ATR): ν = 2916, 2853, 1659, 1593, 1326, 1298, 1251, 901 cm ^-1 ; ^{HRMS m / z [M +]} calcd for C 18 H 20 O 3: 268.1463; found: 268.1465.

(13) 2- Cyclododecyl -3- Hydroxy naphthalene -1,4- Dion (2- Cyclododecyl -3-hydroxynaphthalene-1,4-dione; 16)

The above compound was obtained as a solid having a melting point of 160-162 DEG C through a general reaction. Yield: 62% (211 mg). ^{1 H NMR (600 MHz, CDCl} 3): d = 8.08 (1 H, d, J = 7.8 Hz), 8.02 (1 H, d, J = 7.2 Hz), 7.71 (1 H, td, J = 7.2, 1.2 Hz), 7.63 (1H, td, J = 7.2,1.2 Hz), 7.43 (1H, s), 3.39-3.35 (1H, m), 1.98-1.92 (5 H, m), 1.44-1.35 (6 H, m), 1.34-1.22 ppm (9 H, m); ¹³ C NMR (150 MHz, CDCl ₃ ): d = 184.7, 181.7, 153.3, 134.8, 133.1, 132.6, 129.2, 128.2, 126.9, 125.6, 29.4, 28.1, 24.4, 24.1, 23.7, 22.8, 22.4 ppm; IR (ATR): ν = 3327, 2928, 2860, 1692, 1635, 1592, 1466, 1336, 1261, 1238 cm ^-1 ; ^{HRMS m / z [M +]} calcd for C 22 H 28 O 3: 340.2038; found: 340.2036.

(14) 2- Cyclododecylnaphthalene -1,4- Dion (2- Cyclododecylnaphthalene -1,4-dione; 16 ')

This compound was obtained as a solid having a melting point of 130-132 deg. C through a general reaction. Yield: 24% (84 mg). ¹ H NMR (600 MHz, CDCl ₃ ): d = 8.07-8.05 (1 H, m), 8.02-8.00 (1H, m), 7.69-7.66 , 3.24-3.22 (1H, m), 1.68-1.63 (2H, m), 1.49-1.41 (5H, m), 1.39-1.24 ppm (15H, m); ¹³ C NMR (150 MHz, CDCl ₃ ): d = 185.3, 184.9, 156.1, 133.9, 133.5, 133.4, 132.4, 131.8, 126.3, 125.8, 32.4, 29.0, 23.6, 23.5, 23.3, 22.3 ppm; IR (ATR): ν = 2925, 2858, 1654, 1597, 1468, 1305, 1253, 905 cm ^-1 ; ^{HRMS m / z [M +]} calcd for C 22 H 28 O 2: 324.2089; found: 324.2085.

(15) 3- Cyclohexyl -2- Hydroxy -6- Methoxynaphthalene -1,4- Dion (3-Cyclohexyl-2-hydroxy-6-methoxynaphthalene-1,4-dione; 17)

The above compound was obtained as a solid having melting point of 110-112 DEG C through a general reaction. Yield: 70% (200 mg). ¹ H NMR (600 MHz, CDCl ₃ ): d = 8.01 (1 H, d, J = 9.0 Hz), 7.46 (1H, s), 7.30 ), 3.90 (3 H, s), 3.06-3.02 (1 H, m), 1.97-1.90 (2 H, m), 1.79-1.77 1.59-1.57 (2 H, m), 1.38-1.24 ppm (3 H, m); ¹³ C NMR (150 MHz, CDCl ₃ ): d = 184.0, 182.1, 163.2, 152.6, 130.9, 129.2, 127.6, 126.5, 120.9, 109.5, 55.9, 35.0, 29.2, 26.7, 25.9 ppm; IR (ATR):? = 3360, 2920, 2862, 1644, 1596, 1459, 1324, 1278, 1230, 916 cm ^-1 ; ^{HRMS m / z [M +]} calcd for C 17 H 18 O 4: 286.1205; found: 286.1205.

(16) 2- Cycloheptyl -3-methylnaphthalene-1,4- Dion (2- Cycloheptyl -3-methylnaphthalene-1,4-dione; 18)

This compound was obtained as a solid having melting point of 136-138 DEG C through a general reaction. Yield: 68% (204 mg). ^{1 H NMR (600 MHz, CDCl} 3): d = 7.96 (1 H, d, J = 9.0 Hz), 7.42 (1 H, d, J = 3.0 Hz), 7.19 (1 H, d, J = 3.0 Hz ), 7.12 (1H, dd, J = 8.4,2.4 Hz), 3.86 (3 H, s), 3.11 (1H, tt, J = 11.4, 3.6 Hz), 1.96-1.89 -1.71 (2 H, m), 1.63-1.59 (4 H, m), 1.55-1.49 (3 H, m), 1.48-1.45 ppm (1 H, m); ¹³ C NMR (150 MHz, CDCl ₃ ): d = 183.9, 182.2, 163.2, 151.9, 130.9, 129.8, 129.1, 126.4, 120.8, 109.5, 55.9, 36.5, 32.1, 28.1, 27.9 ppm; IR (ATR):? = 3350, 2919, 2846, 1665, 1592, 1447, 1341, 1282, 1022, 954 cm ^-1 ; ^{HRMS m / z [M +]} calcd for C 18 H 20 O 4: 300.1362; found: 300.1364.

(17) 2- Cyclooctyl -3-methylnaphthalene-1,4- Dion (2- Cyclooctyl -3-methylnaphthalene-1,4-dione; 19)

The above compound was obtained as a solid having a melting point of 85-187 DEG C through a general reaction. Yield: 68% (213 mg). ¹ H NMR (600 MHz, CDCl ₃ ): d = 7.95 (1H, d, J = 9.0 Hz), 7.40 (1H, d, J = 3.0 Hz), 7.20-7.19 (1H, d, J = 9.0, 2.4 Hz), 3.85 (3H, s), 3.23-3.19 (1H, m), 1.99-1.94 , 1.62-1.58 (3 H, m), 1.57-1.44 ppm (7 H, m); ¹³ C NMR (150 MHz, CDCl ₃ ): d = 183.8, 182.2, 163.1, 151.8, 130.9, 129.0, 126.4, 120.8, 120.7, 55.8, 34.2, 31.4, 26.6, 26.4, 26.3 ppm; IR (ATR): ν = 3353, 2919, 2854, 1644, 1592, 1458, 1326, 1273, 1232, 1028, 915 cm ^-1 ; ^{HRMS m / z [M +]} calcd for C 19 H 22 O 4: 314.1518; found: 314.1521.

(18) 2- Cyclododecyl -3-methylnaphthalene-1,4- Dion (2- Cyclododecyl -3-methylnaphthalene-1,4-dione; 20)

The above compound was obtained as a solid having melting point of 97-99 DEG C through a general reaction. Yield: 65% (241 mg). ¹ H NMR (600 MHz, CDCl _{3 )} : d = 8.02 (1H, d, J = 9.0 Hz), 7.47 (1H, d, J = 2.4 Hz), 7.19 (2H, m), 1.63-1.52 (5H, m), 3.98-3.34 (1H, 1.44-1.37 (5 H, m), 1.35-1.23 ppm (10 H, m); ¹³ C NMR (150 MHz, CDCl ₃ ): d = 184.2, 182.9, 163.2, 153.1, 130.9, 129.2, 128.0, 126.5, 120.8, 109.5, 55.9, 29.3, 28.2, 24.4, 24.1, 23.7, 22.8. 22.5 ppm; IR (ATR):? = 3352, 2930, 2854, 1663, 1592, 1451, 1338, 1268, 1016, 892 cm ^-1 ; HRMS m / z [M ⁺ ] calcd for C ₂₃ H ₃₀ O ₄ : 370.2144; found: 370.2142.

(19) 2- Cyclohexyl -3- Hydroxyanthracene -1,4- Dion (2- Cyclohexyl -3-hydroxyanthracene-1,4-dione; 21)

The above compound was obtained as a solid having a melting point of 205-207 deg. C through a general reaction. Yield: 62% (190 mg). ¹ H NMR (600 MHz, CDCl ₃ ): d = 8.59 (2 H, s), 8.02 (2 H, t, J = 7.8 Hz), 7.68-7.63 ), 3.14 (1H, t, J = 12.0, 3.0 Hz), 2.04-1.97 (2H, m), 1.82-1.80 (2H, m), 1.74-1.72 (2 H, m), 1.42-1.29 ppm (4 H, m); ¹³ C NMR (150 MHz, CDCl ₃ ): d = 184.1, 181.4, 154.2, 135.6, 134.2, 130.2, 130.1, 129.9, 129.8, 129.2, 128.9, 128.7, 126.0, 35.3, 29.1, 26.8, 25.9 ppm; IR (ATR): ν = 3327, 2924, 2854, 1649, 1466, 1359, 1294, 1050, 921 cm ^-1 ; ^{HRMS m / z [M +]} calcd for C 20 H 18 O 3: 306.1256; found: 306.1260.

(20) 2- Cycloheptyl -3- Hydroxyanthracene -1,4- Dion (2- Cycloheptyl -3-hydroxyanthracene-1,4-dione; 22)

The above compound was obtained as a solid having a melting point of 178-180 DEG C through a general reaction. Yield: 60% (192 mg). ¹ H NMR (600 MHz, CDCl ₃ ): d = 8.57 (2 H, s), 8.00 (2 H, t, J = 7.8 Hz), 7.67-7.62 M), 1.84-1.79 (2H, m), 1.73-1.67 (4H, m), 1.63-1.54 (2H, m), 3.14 (1H, t, J = ppm (4 H, m); ¹³ C NMR (150 MHz, CDCl _{3 )} : d = 183.9, 181.5, 153.5, 135.6, 134.2, 131.9, 130.2, 130.1, 129.8, 129.2, 129.1, 128.8, 128.6, 36.8, 32.0, 28.2, 27.9 ppm; IR (ATR): ν = 3328, 2917, 2868, 1644, 1455, 1370, 1257, 1177, 1017, 915 cm ^-1 ; ^{HRMS m / z [M +]} calcd for C 21 H 20 O 3: 320.1412; found: 320.1415.

(21) 2- Cyclooctyl -3- Hydroxyanthracene -1,4- Dion (2- Cyclooctyl -3-hydroxyanthracene-1,4-dione; 23)

The above compound was obtained as a solid having a melting point of 173-175 DEG C through a general reaction. Yield: 61% (204 mg). ^{1 H NMR (600 MHz, CDCl} 3): d = 8.58 (2 H, d, J = 4.8 Hz), 8.01 (2 H, t, J = 7.8 Hz), 7.67-7.62 (2 H, m), 7.53 (1H, m), 2.11-1.05 (2H, m), 1.81-1.73 (2H, m), 1.71-1.63 (5H, m), 1.59-1.53 ppm (5 H, m); ¹³ C NMR (150 MHz, CDCl ₃ ): d = 183.9, 181.6, 153.4, 135.6, 134.2, 132.9, 130.2, 129.9, 129.8, 129.2, 129.1, 128.9, 128.6, 126.1, 34.6, 31.4, 26.7, ppm; IR (ATR): ν = 3321, 2920, 2852, 1647, 1457, 1368, 1265, 1176, 1008, 914 cm ^-1 ; ^{HRMS m / z [M +]} calcd for C 22 H 22 O 3: 334.1569; found: 334.1566.

(22) [1,1 ' -bis Cyclohexane )] - 3,6-dien-2,5- Dion ([1,1'-Bi (cyclohexane)] - 3,6-diene-2,5-dione; 24)

This compound was obtained as a solid with melting point of 52-54 DEG C through a general reaction. Yield: 61% (116 mg). ¹ H NMR (600 MHz, CDCl ₃ ): d = 6.73 (1H, d, J = 9.6 Hz), 6.67 (1H, dd, J = 10.2, 2.4 Hz), 6.49-6.48 , 2.69-2.65 (1H, m), 1.81-1.79 (2H, m), 1.76-1.73 (2H, m), 1.42-1.35 , 1.20-1.11 ppm (2 H, m); ¹³ C NMR (150 MHz, CDCl ₃ ): d = 188.2, 187.1, 153.9, 137.0, 135.9, 130.8, 36.4, 36.3, 31.9, 29.6, 26.3, 25.9 ppm; IR (ATR): ν = 2927, 2854, 1649, 1446, 1301, 1070, 993, 886 cm ^-1 ; HRMS m / z [M ⁺ ] calcd for C ₁₂ H ₁₄ O ₂ : 190.0994; found: 190.0995.

(23) 2- Cycloheptylcyclohexa -2,5- Dien -1,4- Dion (2-Cycloheptylcyclohexa-2,5-diene-1,4-dione; 25)

This compound was obtained as a solid having a melting point of 55-57 DEG C through a general reaction. Yield: 59% (120 mg). ¹ H NMR (600 MHz, CDCl ₃ ): d = 6.69 (1H, d, J = 10.2 Hz), 6.64 (1H, dd, J = M), 1.39-1.39 ppm (2 H, m), 1.63-1.59 (2 H, m), 1.53-1.45 (4 H, m) ; ¹³ C NMR (150 MHz, CDCl ₃ ): d = 188.2, 187.0, 153.4, 136.8, 135.7, 130.4, 37.8, 33.9, 27.6, 26.8 ppm; IR (ATR): ν = 2918, 2853, 1652, 1447, 1294, 1188, 906 cm ^-1 ; ^{HRMS m / z [M +]} calcd for C 13 H 16 O 2: 204.1150; found: 204.1147.

(24) 2- Cyclooctylcyclohexa -2,5- Dien -1,4- Dion (2-Cyclooctylcyclohexa-2,5-diene-1,4-dione; 26)

This compound was obtained as a solid with melting point of 58-60 [deg.] C through a general reaction. Yield: 58% (126 mg). ¹ H NMR (600 MHz, CDCl ₃ ): d = 6.70 (1H, d, J = 10.2 Hz), 6.65 (1H, dd, J = 1.8 Hz), 2.94-2.91 (1H, m), 1.69-1.62 (3 H, m), 1.62-1.59 (3 H, m), 1.56-1.49 ppm (8 H, m); ¹³ C NMR (150 MHz, CDCl ₃ ): d = 188.2, 187.2, 155.6, 136.9, 135.8, 130.7, 35.7, 31.6, 26.5, 26.2, 25.5 ppm; IR (ATR): ν = 2920, 2854, 1649, 1451, 1296, 1201, 1071, 907 cm ^-1 ; ^{HRMS m / z [M +]} calcd for C 14 H 18 O 2: 218.1307; found: 218.1308.

(25) 2- Cyclododecyl cyclohexa -2,5- Dien -1,4- Dion (2-Cyclododecylcyclohexa-2,5-diene-1,4-dione; 27)

The above compound was obtained as a solid having melting point of 104-106 DEG C through a general reaction. Yield: 56% (153 mg). ¹ H NMR (600 MHz, CDCl ₃ ): d = 6.72 (1H, d, J = 9.6 Hz), 6.67 (1H, dd, J = 1.8 Hz), 3.02-2.98 (1H, m), 1.62-1.56 (2H, m), 1.44-1.41 (3H, m), 1.37-1.29 H, m); ¹³ C NMR (150 MHz, CDCl ₃ ): d = 188.0, 187.3, 153.9, 137.0, 135.8, 131.8, 32.3, 28.7, 23.7, 23.6, 23.5, 23.3, 22.2 ppm; IR (ATR): ν = 2929, 2856, 1649, 1469, 1295, 1051, 922 cm ^-1 ; ^{HRMS m / z [M +]} calcd for C 18 H 26 O 2: 274.1933; found: 274.1932.

(26) 2- Cyclohexyl -1,4- Dihydroxyanthracene -9,10- Dion (2- Cyclohexyl -1,4-dihydroxyanthracene-9,10-dione; 28)

The above compound was obtained as a solid having melting point of 166-168 DEG C through a general reaction. Yield: 54% (174 mg). ¹ H NMR (600 MHz, CDCl ₃ ): d = 13.57 (1H, s), 12.99 (1H, s), 8.31-8.29 (2H, m), 7.79-7.78 (1H, s), 3.08 (1H, tt, J = 9.0, 3.0 Hz), 1.94-1.92 (2H, m), 1.87-1.85 (2H, m), 1.79-1.76 ), 1.49-1.42 (2H, m), 1.38-1.31 (2H, m), 1.31-1.27 ppm (1H, m); ¹³ C NMR (150 MHz, CDCl ₃ ): d = 187.2, 186.2, 158.2, 156.9, 134.3, 134.2, 133.6, 133.5, 129.9, 126.8, 125.7, 111.9, 110.7, 37.2, 32.4, 26.6, 26.1 ppm; IR (ATR):? = 3341, 2925, 2850, 1652, 1622, 1582, 1431, 1231, 1023, 952 cm ^-1 ; ^{HRMS m / z [M +]} calcd for C 20 H 18 O 4: 322.1205; found: 322.1204.

(27) 2- Cyclooctyl -1,4- Dihydroxyanthracene -9,10- Dion (2- Cyclooctyl -1,4-dihydroxyanthracene-9,10-dione; 29)

This compound was obtained as a solid having a melting point of 138-140 DEG C through a general reaction. Yield: 52% (182 mg). ¹ H NMR (600 MHz, CDCl ₃ ): d = 13.56 (1H, s), 12.97 (1H, s), 8.32-8.29 (2H, m), 7.78-7.77 (1H, s), 3.37-3.35 (1H, m), 1.82-1.70 (7H, m), 1.70-1.62 ppm (7H, m); ^{13 C NMR (150 MHz, CDCl} 3): d = 187.1, 186.1, 158.1, 156.5, 152.4, 134.2, 134.1, 133.6, 133.5, 126.9, 126.8, 126.0, 112.0, 110.6, 36.7, 32.5, 26.7, 26.4, 25.9 ppm; IR (ATR): ν = 3337, 2918, 2853, 1657, 1623, 1582, 1431, 1230, 1054, 959 cm ^-1 ; ^{HRMS m / z [M +]} calcd for C 22 H 22 O 4: 350.1518; found: 350.1516.

While the present invention has been particularly shown and described with reference to specific embodiments thereof, those skilled in the art will appreciate that such specific embodiments are merely preferred embodiments and that the scope of the present invention is not limited thereby. Do. That is, the practical scope of the present invention is defined by the appended claims and their equivalents.

Claims (12)

delete delete delete delete delete delete An anthracenedione derivative represented by the following general formula (3) or (4);
(3)

In Formula 3, R &lt; ₅ &gt; is (C3-C13) cycloalkyl;
[Chemical Formula 4]

In the above formula (4), R &lt; ₆ &gt; is (C3-C13) cycloalkyl. 8. The compound of claim 7, wherein in Formula 3, R &lt; ₅ &gt; is any one selected from cyclohexyl, cycloheptyl, and cyclooctyl;
In the formula (4), R ₆ is cyclohexyl or cyclooctyl. 8. The method of claim 7, wherein the anthracenedione derivative is selected from the group consisting of 2-cyclohexyl-3-hydroxyanthracene-1,4-dione, 2-cycloheptyl-3-hydroxyanthracene- 3-hydroxyanthracene-1,4-dione, 2-cyclohexyl-1,4-dihydroxyanthracene-9,10-dione and 2-cyclooctyl-1,4-dihydroxyanthracene- Wherein the anthracenedione derivative is selected from the group consisting of dione. delete delete (A) any compound selected from 2-hydroxyanthracene-1,4-dione or 1,4-dihydroxyanthracene-9,10-dione and (b) (C3-C13) cycloalkyl , as Cu (OTf) ₂ and the oxidizing agent as a catalyst, tertiary-butyl hydroperoxide hydroxide (TBHP), comprising a step of reacting at 60 ℃ to 100 ℃ for 4 hours to 10 hours with, claim 7, wherein the anthracene dione according &Lt; / RTI &gt;

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