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Hydroxyl-substituted phenanthrene derivative synthesis method

A synthesis method and technology of derivatives, which are applied in chemical instruments and methods, preparation of organic compounds, organic compounds/hydrides/coordination complex catalysts, etc., can solve the problem of low yield and limited universality of substrates, etc. The problem is that the reaction time is short, the catalyst is cheap and easy to obtain, and the reaction yield is high.

Inactive Publication Date: 2019-04-05
EAST CHINA UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the substrate universality of these synthetic methods is very limited, only suitable for the synthesis of individual 9-hydroxyphenanthrene compounds, and the yield is not high (Organic Letters, 2006, 8, 3951-3954)
Moreover, the use of methanesulfonic acid catalysis usually requires the addition of a large excess of methanesulfonic acid to promote the smooth progress of the reaction, and it is easy to generate ethers and mesylate by-products in the reaction process

Method used

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  • Hydroxyl-substituted phenanthrene derivative synthesis method
  • Hydroxyl-substituted phenanthrene derivative synthesis method
  • Hydroxyl-substituted phenanthrene derivative synthesis method

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0034] Synthesis of 2-carboxymethylbiphenyl

[0035]

[0036] Add 2-bromophenylacetic acid (430mg, 2mmol), phenylboronic acid (366mg, 3mmol), palladium acetate (1mol%, 4.5mg, 0.02mmol), sodium carbonate (636mg, 6mmol), DMF ( 2mL), water (2mL), and reacted in an oil bath at 100°C for 1h; after the reaction was completed, 10ml of saturated saline was added, and acidified to weak acidity with dilute hydrochloric acid; extracted with ethyl acetate (3×10mL), and desolvated under reduced pressure Afterwards, the target compound 2-carboxymethylbiphenyl was purified and separated by column chromatography as a white solid with a yield of 98%, m.p.114-115°C. 1 H NMR (400MHz, CDCl 3 )δ9.76(s,1H),7.43–7.24(m,9H),3.62(s,2H); 13 C NMR (101MHz, CDCl 3 )δ 178.39, 142.65, 140.94, 131.07, 130.42, 130.31, 129.25 (2C), 128.31 (2C), 127.63, 127.45, 127.30, 38.57.

[0037] According to the method of Example 1, different starting materials can be used to prepare different 2-carboxymethylbiphe...

Embodiment 2

[0091] Synthesis of 9-Hydroxyphenanthrene

[0092]

[0093] In a 10 mL round bottom flask, to a solution of 2-carboxymethylbiphenyl (106 mg, 0.5 mmol) and phosphorus pentoxide (213 mg, 1.5 mmol) in dichloromethane (2 mL) was added trifluoromethanesulfonic acid (375 mg , 2.5mmol), stirred at room temperature for 2h; after the reaction, the reaction solution was added dropwise to a mixed solution of water (10mL) and ethyl acetate (10mL) to quench; then extracted with ethyl acetate (3 × 10mL) , spin off the solvent, and purified by column chromatography to obtain the target compound 9-hydroxyphenanthrene as a white solid with a yield of 91%, m.p.150-151°C. 1 H NMR (400MHz, CDCl 3 )δ8.67(dd, J=8.4,0.8Hz,1H),8.58(dd,J=8.4,6.7Hz,1H),8.31(dd,J=8.0,1.2Hz,1H),7.79–7.60(m ,3H),7.60–7.45(m,2H),6.99(s,1H),5.21(s,1H). 13 C NMR (101MHz, CDCl 3 )δ149.50, 132.68, 131.58, 127.26, 126.98, 126.76 (2C), 126.45, 125.56, 124.32, 122.74, 122.61, 122.36, 106.14; HRMS (EI) calcd forC 14 h 10 ...

Embodiment 3

[0095] Synthesis of 9-Hydroxyphenanthrene

[0096] In a 10 mL round bottom flask, to 2-carboxymethylbiphenyl (106 mg, 0.5 mmol), phosphorus pentoxide (282 mg, 2 mmol), phenylacetic acid (102 mg, 0.75 mmol) was added methanesulfonic acid (2 mL) , reacted at room temperature for 2h; after the reaction, the reaction solution was added dropwise to a mixed solution of water (10mL) and ethyl acetate (10mL) to quench; then extracted with ethyl acetate (3×10mL), decompressed to Put the solvent in a 10mL round bottom flask, add sodium hydroxide (100mg, 25mmol), water (1mL) and ethanol (1mL), stir at room temperature for 2 hours, add saturated saline 10mL after the reaction, and extract with ethyl acetate (3×10mL), the solvent was spun off, and the synthesis of the target compound 9-hydroxyphenanthrene was obtained by purification and separation by column chromatography, the yield was 84%, and the characterization data were as in Example 2.

[0097] According to the method of Example 2...

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Abstract

The invention relates to a hydroxyl-substituted phenanthrene derivative synthesis method, which includes taking a 2-carboxymethyl biphenyl compound as a raw material; and reacting under the action ofa catalyst to obtain a hydroxyl-substituted phenanthrene derivative, wherein the catalyst comprises one or two of trifluoromethanesulfonic acid or phosphorus pentoxide. Compared with the prior art, the synthesis method has the advantages of the cheap and easily-available catalyst, good universality of functional groups, simple and convenient operation, short reaction time, high reaction yield, mild reaction conditions and the like.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and relates to a method for synthesizing hydroxyl-substituted phenanthrene derivatives. Background technique [0002] Hydroxyl-substituted phenanthrene derivatives are an important class of polycyclic aromatic hydrocarbons, which widely exist in natural substances and have important biological and pharmaceutical activities. At the same time, as a class of organic synthesis intermediates, phenanthrene compounds have a wide range of application values ​​in the fields of organic synthetic chemistry, medicinal chemistry, materials chemistry, and electrochemistry. At present, there are two main synthetic methods of hydroxyl-substituted phenanthrene derivatives: 1) chlorination by thionyl chloride, and then Friedel-Crafts acylation under the catalysis of aluminum trichloride; Sulphonic acid acts as a catalyst to catalyze the reaction. However, the substrate universality of these synthetic m...

Claims

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Application Information

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IPC IPC(8): C07C37/00C07C39/40C07C41/26C07C43/23C07D317/70C07C39/15B01J31/02
CPCB01J31/0225C07C37/00C07C41/26C07C2603/26C07D317/70C07C39/40C07C43/23C07C39/15
Inventor 宋恭华王佳毅张娟彭延庆夏琦吴国栋
Owner EAST CHINA UNIV OF SCI & TECH
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