Preparation method of phenanthrenequinone and derivatives of phenanthrenequinone

A derivative, the technology of phenanthrenequinone, which is applied in the field of synthesis of phenanthrenequinone and its derivatives, can solve the problems of harsh reaction conditions, harmful oxidants, complicated operation, etc., and achieve the effects of mild reaction temperature, simple operation and simple reaction

Inactive Publication Date: 2018-02-06

ZHEJIANG UNIV OF TECH

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AI-Extracted Technical Summary

Problems solved by technology

The raw materials of this method are not easy to prepare, which greatly limits its development, and some oxidants used are harmful; (2) the intramolecular oxidative coupling method of dibenzoyl and 1,1'-diformylbiphenyl (for example: Tamarkin, D .; Benny, D.; Rabinovitz, M. Angew. Chem. 1984, 96, 594-5; Enders, D.; Niemeier, O. Synlett 2004, 2111-2114)

The main disadvantage of...

Abstract

The invention provides a preparation method of phenanthrenequinone and derivatives of the phenanthrenequinone. O-aryl acetophenone compounds shown as the formula (I) are used as raw materials; in an organic solvent, reaction is performed for 12 to 36h at 60 to 100 DEG C in a pressure-proof sealing tube under the effects of catalysts and oxidizing agents; obtained reaction liquid is separated and purified to prepare the phenanthrenequinone and derivatives of the derivatives shown as the formula (II); the catalysts are selenium and selenium oxide. The preparation method has the advantages that the raw materials are simple and can be easily obtained; the reaction conditions are mild; the functional group tolerance is good; the operation is simple and achieves an environment-friendly effect; anovel method for synthetizing the phenanthrenequinone containing various substituent groups is provided.

Application Domain

Quinone preparation by oxidation

Technology Topic

ChemistryAcetophenone +8

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Examples

Experimental program(17)

Example Embodiment

[0025] Embodiment 1: take o-phenylacetophenone as raw material, prepare phenanthrenequinone

[0026]

[0027] Add 58.8mg (0.30mmol) of o-phenylacetophenone, 2.4mg (0.03mmol) of selenium powder, and 318.6mg (0.9mmol) of Selectfluor into a 25mL pressure-resistant sealed container in sequence, and then add 3mL of acetonitrile. The mixture was stirred and reacted at 80°C, followed by TLC detection, and the reaction was completed after 24 hours. The reaction solution was diluted with 10 mL of dichloromethane, and the clear liquid was obtained by filtration. After the organic solvent was evaporated, it was purified with a silica gel column, and then column chromatography (Eluant ratio: volume ratio of petroleum ether to ethyl acetate 10:1) Separation, collecting the eluate and evaporating the solvent to obtain 48 mg of reddish-brown solid phenanthrenequinone (76% yield).

[0028] Reddish-brown solid; m.p.218–220°C; IR(neat):1673(C=O)cm -1; 1 H NMR (400MHz, CDCl 3 ):δ8.16(dd,J 1 =8.0Hz,J 2 =1.6Hz, 2H), 7.99(d, J=8.0Hz, 2H), 7.73–7.67(m, 2H), 7.45(t, J=8.0Hz, 2H); 13 C NMR (100MHz, CDCl 3 ): δ180.3, 136.0, 135.8, 131.0, 130.5, 129.6, 124.0.

Example Embodiment

[0029] Embodiment 2: take o-phenylacetophenone as raw material, prepare phenanthrenequinone

[0030]

[0031] Add 58.8mg (0.30mmol) of o-phenylacetophenone, 4.8mg (0.06mmol) of selenium powder, and 159.3mg (0.45mmol) of Selectfluor into a 25mL pressure-resistant sealed container in sequence, and then add 1.5mL of nitromethane. The mixture was stirred and reacted at 100°C, followed by TLC detection, and the reaction was completed after 24 hours. The reaction liquid was diluted with 10 mL of dichloromethane, and the clear liquid was obtained by filtration. After the organic solvent was evaporated, it was purified with a silica gel column, and then column chromatography (Eluant ratio: volume ratio of petroleum ether to ethyl acetate 10:1) Separation, collecting the eluate and evaporating the solvent to obtain 40 mg of reddish-brown solid phenanthrenequinone (65% yield).

[0032] Reddish-brown solid; m.p.218–220°C; IR(neat):1673(C=O)cm -1; 1 H NMR (400MHz, CDCl 3 ):δ8.16(dd,J 1 =8.0Hz,J 2 =1.6Hz, 2H), 7.99(d, J=8.0Hz, 2H), 7.73–7.67(m, 2H), 7.45(t, J=8.0Hz, 2H); 13 C NMR (100MHz, CDCl 3 ): δ180.3, 136.0, 135.8, 131.0, 130.5, 129.6, 124.0.

Example Embodiment

[0033] Embodiment 3: take o-phenylacetophenone as raw material, prepare phenanthrenequinone

[0034]

[0035]Add 58.8mg (0.30mmol) of o-phenylacetophenone, 1.2mg (0.015mmol) of selenium powder, and 371.7mg (1.05mmol) of Selectfluor into a 25mL pressure-resistant sealed container, and then add 4.5mL of acetonitrile. The mixture was stirred and reacted at 100°C, followed by TLC detection, and the reaction was completed after 12 hours. The reaction solution was diluted with 10 mL of dichloromethane, and the clear liquid was obtained by filtration. After the organic solvent was evaporated, it was purified with a silica gel column, and then column chromatography (Eluant ratio: volume ratio of petroleum ether to ethyl acetate 10:1) separation, collecting the eluate and evaporating the solvent to obtain 44 mg of reddish-brown solid phenanthrenequinone (70% yield).

[0036] Reddish-brown solid; m.p.218–220°C; IR(neat):1673(C=O)cm -1; 1 H NMR (400MHz, CDCl 3 ):δ8.16(dd,J 1 =8.0Hz,J 2 =1.6Hz, 2H), 7.99(d, J=8.0Hz, 2H), 7.73–7.67(m, 2H), 7.45(t, J=8.0Hz, 2H); 13 C NMR (100MHz, CDCl 3 ): δ180.3, 136.0, 135.8, 131.0, 130.5, 129.6, 124.0.

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Classification and recommendation of technical efficacy words

mild reaction temperature
Strong tolerance

Preparation method of phenanthrenequinone and derivatives of phenanthrenequinone

AI-Extracted Technical Summary

Problems solved by technology

Abstract

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Examples

Example Embodiment

Example Embodiment

Example Embodiment

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Description & Claims & Application Information

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