Method for preparing polyaryl substituted naphthalene derivative by ruthenium-catalyzing aromatic ketone and diphenylacetylene cyclization reaction and application

A technology of naphthalene derivatives and tolanylacetylene, which is applied in the field of preparation of polyaromatic substituted naphthalene derivatives, can solve problems such as increasing production costs, and achieve the effect of simple and easy synthesis method

Active Publication Date: 2018-05-01
DALIAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, there are defects in this method. These reactions require a certain amount of ligand or an equivalent metal salt as an oxidant to complete the catalytic cycle, which not only increases the production cost, but also the metal salts are mostly heavy metal (copper, silver, etc.) salts that pollute the environment.

Method used

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  • Method for preparing polyaryl substituted naphthalene derivative by ruthenium-catalyzing aromatic ketone and diphenylacetylene cyclization reaction and application
  • Method for preparing polyaryl substituted naphthalene derivative by ruthenium-catalyzing aromatic ketone and diphenylacetylene cyclization reaction and application
  • Method for preparing polyaryl substituted naphthalene derivative by ruthenium-catalyzing aromatic ketone and diphenylacetylene cyclization reaction and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0019]

[0020] To a 25mL sealed tube with a magnet, add toluene (18mg, 0.1mmol), the corresponding aromatic ketone (0.2mmol), catalyst [RuCl 2 (p-cymene)] 2 (9mg, 15% mol), 0.5mL toluene, then add dry sodium carbonate (21mg, 0.2mmol) and potassium acetate (19mg, 0.2mmol), replace nitrogen three times, react at 100°C for 24 hours, then pass column chromatography Separation (eluent: petroleum ether) to obtain the target compound. Characterization is as follows.

[0021] 7-Methyl-3-(4-methylbenzyl)-1,2-diphenylnaphthalene: yield: 58%, melting point: 124-125°C. 1 H NMR (CDCl 3 ,400MHz)δ7.71(d,J=8.0Hz,1H),7.61(s,1H),7.28(dd,J 1 = 1.2Hz; J 2 =8.4Hz,1H),7.14-7.23(m,4H),7.05-7.10(m,5H),7.00(d,J=8.0Hz,2H),6.90-6.93(m,2H),6.85(d, J=7.6Hz,2H),3.86(s,2H),2.35(s,3H),2.29(s,3H). 13 C NMR (CDCl 3 ,100MHz)δ140.2,139.9,139.6,138.4,137.9,136.7,135.2,135.2,131.6,131.1,130.5,129.1,128.8,128.0,127.6,127.4,127.4,127.3,126.1,2,125.2,125.6 .HRMS(EI-TOF)calcd for C 31 h 26 (M + ):398.2...

Embodiment 2

[0023]

[0024] To a 25mL sealed tube with a magnet, add toluene (18mg, 0.1mmol), the corresponding aromatic ketone (0.2mmol), catalyst [RuCl 2 (p-cymene)] 2 (9mg, 15% mol), 0.5mL toluene, then add dry sodium carbonate (21mg, 0.2mmol) and potassium acetate (19mg, 0.2mmol), replace nitrogen three times, react at 100°C for 24 hours, then pass column chromatography Separation (eluent: petroleum ether) to obtain the target compound. Characterization is as follows.

[0025] 7-Methoxy-3-(4-methoxybenzyl)-1,2-diphenylnaphthalene: yield: 45%, melting point: 137-139°C. 1 HNMR (CDCl 3 ,400MHz)δ7.72(d,J=8.8Hz,1H),7.59(s,1H),7.16-7.18(m,2H),7.07-7.14(m,7H),6.90-6.92(m,2H) ,6.86(d,J=8.8Hz,2H),6.76(d,J=2.8Hz,1H),6.72-6.74(m,2H),3.83(s,2H),3.76(s,3H),3.64( s,3H). 13 C NMR (CDCl 3 ,100MHz)δ157.7,157.4,140.2,139.6,138.1,135.5,133.2,132.5,130.9,130.4,130.1,129.1,128.4,127.5,127.3,126.3,126.1,118.55,113.5,105.3MS (EI-TOF) calcd for C 31 h 26 o 2 (M + ):430.1933,found:430.1937.

Embodiment 3

[0027]

[0028] To a 25mL sealed tube with a magnet, add toluene (18mg, 0.1mmol), the corresponding aromatic ketone (0.2mmol), catalyst [RuCl 2 (p-cymene)] 2 (9mg, 15% mol), 0.5mL toluene, then add dry sodium carbonate (21mg, 0.2mmol) and potassium acetate (19mg, 0.2mmol), replace nitrogen three times, react at 100°C for 24 hours, then pass column chromatography Separation (eluent: petroleum ether) to obtain the target compound. Characterization is as follows.

[0029] 7-Fluoro-3-(4-fluorobenzyl)-1,2-diphenylnaphthalene: yield: 60%, melting point: 107-108°C. 1 H NMR (CDCl 3 ,400MHz)δ7.81(dd,J 1 = 5.6Hz; J 2 =9.2Hz,1H),7.65(s,1H),7.15-7.25(m,4H),7.04-7.10(m,6H),6.85-6.88(m,6H),3.89(s,2H). 13C NMR (CDCl 3 ,100MHz)δ162.5,161.9,160.1,159.5,140.6,139.6,138.9(d,J C-F =5.6Hz), 138.8, 136.6(d, J C-F =3.3Hz), 136.3(d, J C-F =4.3Hz), 132.5(d, J C-F =7.6Hz), 130.8, 130.4(d, J C-F =7.2Hz), 130.3, 129.9, 129.8, 127.7 (d, J C-F =6.4Hz), 127.4, 126.7, 126.4, 116.4, 116.1, 115...

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Abstract

The invnetion relates to a method for preparing a polyaryl substituted naphthalene derivative by ruthenium-catalyzing aromatic ketone and diphenylacetylene cyclization reaction and application. According to the method provided by the invention, the ruthenium which is relatively cheap is used as a catalyst and aromatic ketone beta-H is activated to synthesize a six-membered ring, i.e., the polyarylsubstituted naphthalene derivative; in a reaction process, an additive and an oxidant do not need to be added and only simple alkali is utilized; the reaction is carried out under moderate reaction conditions. The synthesis method provided by the invention is simple and feasible, scientific and reasonable, green and environmentally friendly and economical and practical and is suitable for being produced in a large scale.

Description

technical field [0001] The invention relates to the fields of medical technology and photoelectric materials, and mainly relates to a preparation method and application of polyaromatic substituted naphthalene derivatives. Background technique [0002] Due to their unique electrochemical and photochemical properties and their application in n-conjugated functional materials, polyaromatic substituted naphthalene derivatives are more and more widely used in organic fluorescent materials, semiconductor materials, etc., and polyaromatic substitution Naphthalene derivatives also have important applications in drug synthesis. The preparation method adopted in the prior art has made a great breakthrough compared with the relatively harsh conditions of the previous cyclometallation, aryl halide, aryl acid and the like. At present, under mild conditions, polyaromatic substituted naphthalene derivatives are prepared by the cyclization reaction of the C-H bond (even double C-H bond) of...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C15/24C07C1/207C07C43/205C07C41/30C07C25/22C07C17/263C09K11/06
CPCC07C1/2076C07C15/24C07C17/2637C07C25/22C07C41/30C07C43/2055C09K11/06C09K2211/1007C09K2211/1011
Inventor 张殊佳高杰
Owner DALIAN UNIV
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