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Manganese dioxide or m-chloroperoxybenzoic acid-participated oxidative coupling-prepared phenanthrene, dinaphthol and biphenyl derivative

A technology of m-chloroperoxybenzoic acid and manganese dioxide, applied in chemical instruments and methods, organic cyclization, organic chemistry and other directions, can solve the problems of low reaction yield, harsh reaction conditions, high toxicity and the like

Inactive Publication Date: 2010-06-23
NANKAI UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The above methods have the following defects: high toxicity, harsh reaction conditions, difficult separation of catalyst and product, long reaction steps, and low reaction yield

Method used

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  • Manganese dioxide or m-chloroperoxybenzoic acid-participated oxidative coupling-prepared phenanthrene, dinaphthol and biphenyl derivative
  • Manganese dioxide or m-chloroperoxybenzoic acid-participated oxidative coupling-prepared phenanthrene, dinaphthol and biphenyl derivative
  • Manganese dioxide or m-chloroperoxybenzoic acid-participated oxidative coupling-prepared phenanthrene, dinaphthol and biphenyl derivative

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] Embodiment 1: 2,3,6, the synthesis of 7-tetramethoxy-9-phenanthrene acid methyl ester:

[0030] Add 0.179g (0.5mmol) (E)-2,3-bis(3',4'-dimethoxyphenyl)methyl acrylate and 5mL trifluoroacetic acid into a 25mL four-neck flask, stir at room temperature to dissolve the raw materials, Add 0.044g (0.5mmol) MnO 2 , the mixture was stirred at room temperature for 2 hours, 50 mL of dichloromethane was added, washed with water, dried, filtered, and precipitated to obtain 2,3,6,7-tetramethoxy-9-phenanthrene carboxylate methyl ester. Conversion (100%) and yield (100%) were determined by HPLC. m.p.202-203℃ 1 H NMR (CDCl 3 , 400MHz) δ: 8.65(s, 1H), 8.43(s, 1H), 7.81(s, 1H), 7.77(s, 1H), 7.27(s, 1H), 4.14(s, 3H), 4.13(s , 3H), 4.08(s, 3H), 4.04(s, 3H), 4.02(s, 3H).

[0031] The following phenanthrene derivatives can be synthesized by the same method, but this does not limit the present invention.

[0032] 2,3,6,7-Tetramethoxy-9-phenanthrenemethylnitrile: Yield 99%, mp 266-268°C;...

Embodiment 2

[0044] Embodiment 2: 2,3,6, the synthesis of 7-tetramethoxy-9-phenanthrene acid:

[0045] Add 0.5mmol (E)-2,3-bis(3′,4′-dimethoxyphenyl)acrylic acid and 5mL trifluoroacetic acid to a 25mL four-neck flask, stir at room temperature to dissolve the raw materials, add 0.5mmol MnO 2 , the mixture was stirred at room temperature for 2 hours, 50 mL of dichloromethane was added, washed with water, dried, filtered, and precipitated to obtain 2,3,6,7-tetramethoxy-9-phenanthrene carboxylate methyl ester. Conversion (100%) and yield (100%) were determined by HPLC. m.p.285-287℃; 1 H NMR (DMSO, 300MHz) δ: 8.58(s, 1H), 8.43(s, 1H), 8.03(s, 1H), 7.99(s, 1H), 7.54(s, 1H), 4.08(s, 3H) , 4.07(s, 3H), 3.94(s, 3H), 3.93(s, 3H).

Embodiment 3

[0046] Example 3: Synthesis of 2,3,6,7-tetramethoxy-9-phenanthrene acid methyl ester:

[0047] Weigh 0.5 mmol of E, Z formula mixed 2,3-bis-(3',4'-dimethoxyphenyl)methyl acrylate with a molar ratio of 1:1 in a 25 mL four-necked flask, 5 mL of trifluoroacetic acid , stir at room temperature to dissolve the raw material, add 0.044g (0.5mmol) MnO 2 , the mixture was stirred at room temperature for 2 hours, 50 mL of dichloromethane was added, washed with water, dried, filtered, and precipitated to obtain 2,3,6,7-tetramethoxy-9-phenanthrene carboxylate methyl ester. Conversion (100%) and yield (100%) were determined by HPLC. m.p.202-203℃

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Abstract

The invention relates to manganese dioxide or m-chloroperoxybenzoic acid-participated oxidative coupling-prepared phenanthrene, dinaphthol and biphenyl derivative. The preparation method comprises the steps of: adding (E)-1, 2-di (phenyl-substituted) ethylene derivative or (z)-1, 2-di (phenyl-substituted) ethylene derivative or mixture of E / Z with any proportions into organic solvent to be dissolved; adding the manganese dioxide or the m-chloroperoxybenzoic acid (m-CPBA) again; stirring within the range from -30 DEG C to 80 DEG C, so that raw materials are completely reacted; adding water; separating liquid; drying an organic layer; evaporating the solvent to obtain a product phenanthrene derivative; and recrystallizing the product to obtain a pure product. The same method can be used forpreparing the dinaphthol derivative with 2-naphthol and preparing the biphenyl derivative with substituted benzene.

Description

technical field [0001] The invention relates to the preparation of phenanthrene, binaphthol and biphenyl derivatives through oxidative coupling involving manganese dioxide or m-chloroperoxybenzoic acid. Background technique [0002] WO03070166 discloses the preparation method of phenanthroquinolizidine and phenanthrenequinolizidine derivatives and their application in medicine. CN101189968 discloses the application of phenanthrene and quinolizidine derivatives and their salts in pesticides. Among them, the synthesis of phenanthrene ring is a key step in the synthesis of phenanthrene and quinolizidine derivatives. The methods reported in the literature mainly include: Pschorr cyclization method, light coupling method, iodine diacetate Benzene (PIDA), thallium trifluoroacetic acid coupling method, lead acetate coupling method, vanadium trifluoride and vanadyl trichloride coupling method (see literature: 1.Pschorr, R.Chem.Ber.1896, 29, 496- 501.2. Jin, Z.; Wang, Q.M.; Huang, ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B37/10C07C69/94C07C255/54C07D317/68
Inventor 汪清民王开亮呼艳娜吴萌李峥苏波
Owner NANKAI UNIV
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