CN107935812B - Method for preparing polyaryl substituted naphthalene derivative by reaction of alkyl aryl ketone and tolane under catalysis of ruthenium - Google Patents

Method for preparing polyaryl substituted naphthalene derivative by reaction of alkyl aryl ketone and tolane under catalysis of ruthenium Download PDF

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CN107935812B
CN107935812B CN201711358009.XA CN201711358009A CN107935812B CN 107935812 B CN107935812 B CN 107935812B CN 201711358009 A CN201711358009 A CN 201711358009A CN 107935812 B CN107935812 B CN 107935812B
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tolane
substituted naphthalene
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张殊佳
高杰
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Dalian University
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Abstract

The invention uses cheap ruthenium as a catalyst, and activates aromatic ketone β -H to synthesize a six-membered ring to generate the polyaromatic substituted naphthalene derivative, and the synthesis process does not need additives and oxidants, only uses simple alkali and is carried out under mild reaction conditions.

Description

Method for preparing polyaryl substituted naphthalene derivative by reaction of alkyl aryl ketone and tolane under catalysis of ruthenium
The application is a divisional application with the application number of 2017113298008, the application date of 2017, 12 months and 13 days, and the invention name of the divisional application is ' a method for preparing polyaryl substituted naphthalene derivatives by a cyclization reaction of aromatic ketone and tolane catalyzed by ruthenium ' and an application thereof '.
Technical Field
The invention relates to the field of medical technology and photoelectric materials, and mainly relates to a preparation method and application of polyaromatic substituted naphthalene derivatives.
Background
Due to the unique electrochemical and photochemical properties of the polyaromatic substituted naphthalene derivatives and the application of the polyaromatic substituted naphthalene derivatives in n-conjugated functional materials, the polyaromatic substituted naphthalene derivatives are more and more widely applied in the aspects of organic fluorescent materials, semiconductor materials and the like, and have important application in the aspect of drug synthesis. Compared with the prior preparation method of cyclometallation, aryl halide, aryl acid and other harsh conditions, the preparation method adopted in the prior art has great breakthrough. At present, the C-H bond (even double C-H bonds) of an aromatic benzene ring is catalyzed by transition metal under mild conditions to be activated and carry out cyclization reaction with alkyne to prepare the polyaromatic substituted naphthalene derivative. However, the method has the defects that the reactions can only complete catalytic circulation by using a certain amount of ligand or equivalent metal salt as an oxidant, so that the production cost is increased, and the metal salt is mostly heavy metal (such as copper, silver and the like) salt which pollutes the environment. Based on this, there is a need in the art for more environmentally friendly, green, and economical methods for synthesizing polyaromatic substituted naphthalene derivatives.
Disclosure of Invention
To overcome the disadvantages of the prior art, the present invention provides a method for preparing ruthenium ([ RuCl ]) with low cost under mild conditions without additives and oxidants2(p-cymene)]2) A method for synthesizing a derivative of polyaromatic substituted naphthalene as a catalyst.
The invention adopts the following technical scheme: a polyaromatic substituted naphthalene derivative has a structure shown as a general formula I:
Figure BDA0001511407060000011
wherein R is1Is composed of
Figure BDA0001511407060000012
One of-H or-F, R2Is composed of
Figure BDA0001511407060000013
-CH3、-CH2CH3、-CH3、
Figure BDA0001511407060000014
or-CF3One kind of (1).
Preferably, the derivative of the polyaromatic substituted naphthalene is:
Figure BDA0001511407060000015
Figure BDA0001511407060000021
another subject of the invention is a process for the preparation of the derivatives of polyaromatic substituted naphthalenes mentioned above, which comprises: diphenylacetylene and aromatic ketone are used as raw materials, and [ RuCl ] is added2(p-cymene)]2Heating alkali and a nonpolar organic solvent to 80-100 ℃ in a nitrogen environment to react for 12-24h, and performing column chromatography separation to obtain a polyaromatic substituted naphthalene derivative; the molar ratio of the tolane to the aromatic ketone is 1:2, [ RuCl2(p-cymene)]2Accounts for 15mol percent of the tolane, and the molar ratio of the alkali to the aromatic ketone is 1: 1.
Preferably, the aromatic ketone is:
Figure BDA0001511407060000022
wherein R is1Is composed of
Figure BDA0001511407060000023
One of-H or-F, R2Is composed of
Figure BDA0001511407060000024
-CH3、-CH2CH3、-CH3、
Figure BDA0001511407060000025
or-CF3One kind of (1).
Preferably, the aromatic ketone is
Figure BDA0001511407060000026
Figure BDA0001511407060000027
One kind of (1).
Further, the non-polar organic solvent is any one of benzene, toluene, dichloroethane, chloroform, styrene, cyclohexane or hexane. Toluene is preferred.
Further, the alkali is KOAc or Na2CO3、Cs2CO3、K2CO3、Li2CO3NaOAc or LiOAcOr more than one. KOAc and Na are preferred2CO3。
As a preferred embodiment of the present invention, the polyaromatic substituted naphthalene derivative is prepared by: placing aromatic ketone and tolane in a sealed tube, adding [ RuCl ]2(p-cymene)]2And toluene, adding dried sodium carbonate and potassium acetate, heating to 100 ℃ in a nitrogen environment, reacting for 24 hours, and separating by column chromatography to obtain the polyaryl substituted naphthalene derivative.
The third purpose of the invention is to protect the application of the derivative of the polyaromatic substituted naphthalene in the fields of medicine preparation and photoelectric materials.
Such as for novel tyrosine protein kinase inhibitors
Figure BDA0001511407060000032
Or blue light emitting materials
Figure BDA0001511407060000033
And (4) preparing.
Compared with the prior art, the invention has the beneficial effects that:
the present invention uses relatively inexpensive ruthenium ([ RuCl ]2(p-cymene)]2) The method is simple, feasible, scientific, reasonable, environment-friendly, economical and practical, and is suitable for large-scale production.
Detailed Description
The invention is described in more detail below with reference to specific examples, without limiting the scope of the invention. Unless otherwise specified, the experimental methods adopted by the invention are all conventional methods, and experimental equipment, materials, reagents and the like used in the experimental method can be purchased from chemical companies.
Example 1
Figure BDA0001511407060000031
To the beltA25 mL sealed tube of magneton was charged with tolane (18mg, 0.1mmol), the corresponding aromatic ketone (0.2mmol), and the catalyst [ RuCl ]2(p-cymene)]2(9mg, 15% mol), 0.5mL of toluene, followed by addition of dried sodium carbonate (21mg, 0.2mmol) and potassium acetate (19mg, 0.2mmol), nitrogen purging three times, reaction at 100 ℃ for 24 hours, and separation by column chromatography (eluent: petroleum ether) to give the title compound. The characterization is as follows.
4, 5-diphenyl-6- (thiophene-2-methylene) benzo [ b]Thiophene: yield: 40 percent.1H NMR(CDCl3,400MHz)δ7.81(s,1H),7.33(d,J＝5.2Hz,1H),7.10-7.18(m,9H),7.00-7.02(m,3H),6.87(dd,J1＝3.6Hz；J2＝5.2Hz,1H),6.59-6.60(m,1H),4.07(s,2H).13C NMR(CDCl3,100MHz)δ144.1,139.7,139.4,135.7,130.8,130.4,127.5,126.7,126.5,126.4,125.9,124.2,123.8,122.1,34.5.HRMS(EI-TOF)calcd for C25H18S2(M+):382.0850,found:382.0847.
Example 2
Figure BDA0001511407060000041
To a 25mL stopcock with magnetons was added tolane (18mg, 0.1mmol), the corresponding aromatic ketone (0.2mmol), the catalyst [ RuCl ]2(p-cymene)]2(9mg, 15% mol), 0.5mL of toluene, followed by addition of dried sodium carbonate (21mg, 0.2mmol) and potassium acetate (19mg, 0.2mmol), nitrogen purging three times, reaction at 100 ℃ for 24 hours, and separation by column chromatography (eluent: petroleum ether) to give the title compound. The characterization is as follows.
3-methyl-1, 2, 7-triphenylnaphthalene: yield: 65 percent. Melting point: 163 ℃ and 165 ℃.1H NMR(CDCl3,400MHz)δ7.91(d,J＝8.4Hz,1H),7.79(s,1H),7.69-7.73(m,2H),7.52(d,J＝7.2Hz,2H),7.37(t,J＝8.0Hz,2H),7.29(d,J＝7.2Hz,1H),7.10-7.23(m,8H),7.02-7.05(m,2H),2.26(s,3H).13CNMR(CDCl3,100MHz)δ141.5,140.6,140.4,139.2,139.0,137.9,134.7,132.1,131.5,131.1,130.1,128.8,127.7,127.6,127.5,127.4,127.2,127.1,126.4,126.2,125.5,124.9,22.0.HRMS(EI-TOF)calcdfor C29H22(M+):370.1722,found:370.1723.
Example 3
Figure BDA0001511407060000042
To a 25mL stopcock with magnetons was added tolane (18mg, 0.1mmol), the corresponding aromatic ketone (0.2mmol), the catalyst [ RuCl ]2(p-cymene)]2(9mg, 15% mol), 0.5mL of toluene, followed by addition of dried sodium carbonate (21mg, 0.2mmol) and potassium acetate (19mg, 0.2mmol), nitrogen purging three times, reaction at 100 ℃ for 24 hours, and separation by column chromatography (eluent: petroleum ether) to give the title compound. The characterization is as follows.
3-ethyl-1, 2-diphenylnaphthalene: yield: 25 percent. Melting point: 124 ℃ and 125 ℃.1H NMR(CDCl3,400MHz)δ7.79-7.81(m,1H),7.72(s,1H),7.37-7.40(m,2H),7.22-7.26(m,1H),7.01-7.14(m,8H),6.96-6.98(m,2H),2.51(dd,J1＝7.6Hz；J2＝14.8Hz,2H),1.08(t,J＝7.6Hz,3H).13C NMR(CDCl3,100MHz)δ140.4,140.3,139.6,139.5,138.8,133.0,131.2,131.0,130.4,127.4,127.4,126.8,126.3,126.1,125.8,125.7,125.3,27.4,15.1.HRMS(EI-TOF)calcd forC24H20(M+):308.1565,found:308.1567.
Example 4
Figure BDA0001511407060000051
To a 25mL stopcock with magnetons was added tolane (18mg, 0.1mmol), the corresponding aromatic ketone (0.2mmol), the catalyst [ RuCl ]2(p-cymene)]2(9mg, 15% mol), 0.5mL of toluene, followed by addition of dried sodium carbonate (21mg, 0.2mmol) and potassium acetate (19mg, 0.2mmol), nitrogen purging three times, reaction at 100 ℃ for 24 hours, and separation by column chromatography (eluent: petroleum ether) to give the title compound. The characterization is as follows.
7-fluoro-3-methyl-1, 2-diphenylnaphthalene: yield: 30 percent. Fusion furnacePoint: 139 ℃ and 140 ℃.1H NMR(CDCl3,400MHz)δ7.81(dd,J1＝6.0Hz；J2＝8.8Hz,1H),7.75(s,1H),7.06-7.23(m,10H),7.01-7.03(m,2H),2.24(s,3H).13C NMR(CDCl3,100MHz)δ161.6,159.2,140.8,140.3,138.9,138.2(d,JC-F＝5.6Hz),133.7(d,JC-F＝2.3Hz),132.3,132.2,130.9,129.9(d,JC-F＝5.6Hz),129.4(d,JC-F＝8.6Hz),127.6(d,JC-F＝4.9Hz),127.3,126.6,126.3,116.2,115.9,110.3,110.1,21.8.HRMS(EI-TOF)calcdfor C23H17F(M+):312.1314,found:312.1312.
Example 5
Figure BDA0001511407060000052
To a 25mL stopcock with magnetons was added tolane (18mg, 0.1mmol), the corresponding aromatic ketone (0.2mmol), the catalyst [ RuCl ]2(p-cymene)]2(9mg, 15% mol), 0.5mL of toluene, followed by addition of dried sodium carbonate (21mg, 0.2mmol) and potassium acetate (19mg, 0.2mmol), nitrogen purging three times, reaction at 100 ℃ for 24 hours, and separation by column chromatography (eluent: petroleum ether) to give the title compound. The characterization is as follows.
3-isobutyl-1, 2-diphenylnaphthalene: yield: 35 percent. Melting point: 107-108 ℃.1H NMR(CDCl3,400MHz)δ7.85-7.87(m,1H),7.73(s,1H),7.43-7.47(m,2H),7.29-7.33(m,1H),7.07-7.21(m,8H),7.01-7.03(m,2H),2.48(d,J＝7.2Hz,2H),1.66-1.73(m,1H),0.76-0.78(d,J＝6.4Hz,6H).13C NMR(CDCl3,100MHz)δ140.3,140.0,139.6,138.9,137.9,132.7,131.3,131.1,130.7,127.7,127.4,127.4,127.2,126.8,126.3,126.1,125.6,125.3,43.5,29.8,29.1,22.6.HRMS(EI-TOF)calcd for C26H24(M+):336.1878,found:336.1882.
Example 6
Figure BDA0001511407060000061
To the magnetic ringA25 mL sealed tube was charged with tolane (18mg, 0.1mmol), the corresponding aromatic ketone (0.2mmol), and the catalyst [ RuCl ]2(p-cymene)]2(9mg, 15% mol), 0.5mL of toluene, followed by addition of dried sodium carbonate (21mg, 0.2mmol) and potassium acetate (19mg, 0.2mmol), nitrogen purging three times, reaction at 100 ℃ for 24 hours, and separation by column chromatography (eluent: petroleum ether) to give the title compound. The characterization is as follows.
1, 2-diphenyl-3- (trifluoromethyl) naphthalene: yield: 45 percent. Melting point: 118 ℃ and 119 ℃.1H NMR(CDCl3,400MHz)δ8.34(s,1H),8.02(d,J＝8.0Hz,1H),7.57-7.60(m,1H),7.94-7.50(m,2H),7.18-7.24(m,3H),7.13-7.16(m,3H),7.05-7.11(m,4H).13C NMR(CDCl3,100MHz)δ141.6,138.1,137.7,135.9,134.0,131.4,130.8(d,JC-F＝5.8Hz),129.4,128.9,128.4,128.3,128.2,127.6,127.1,126.9,126.9,126.8,126.2,126.2.HRMS(EI-TOF)calcd for C23H15F3(M+):348.1126,found:348.1124.
Comparative example:
adding 0.1mmol of tolane and aromatic ketone into 25mL sealed tube with magnetons
Figure BDA0001511407060000063
(0.2mmol), catalyst [ RuCl ]2(p-cymene)]20.01mol, adding 0.5mL organic solvent and dried alkali with equal mol of aromatic ketone, pumping nitrogen three times, reacting at 100 deg.C for 24 hr, and separating by column chromatography (eluent: petroleum ether) to obtain target compound
Figure BDA0001511407060000064
The yields were calculated and the results are shown in table 1.
TABLE 1
Figure BDA0001511407060000062
Figure BDA0001511407060000071
Yield of catalyst at 0.015mmol
As can be seen from the data in Table 1 and the comparison of the yields in examples 1 to 6, the highest yield is obtained when the organic solvent is toluene, the base is sodium carbonate and potassium acetate, and the amount of the catalyst is 15 mol%. Therefore, the optimal reaction conditions are adopted in the experimental process.
The above description is only for the purpose of creating a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can substitute or change the technical solution and the inventive concept of the present invention within the technical scope of the present invention.

Claims (1)

1. The ruthenium catalyzed alkyl aryl ketone and diphenyl acetylene reaction process of preparing 3-isobutyl-1, 2-diphenyl naphthalene features that diphenyl acetylene and aromatic ketone are reacted
Figure FDA0002436553220000011
As raw material, adding diphenylacetylene 0.1mmol and aromatic ketone into 25mL sealed tube with magneton
Figure FDA0002436553220000012
0.2mmol, catalyst [ RuCl ]2(p-cymene)]2Accounting for 15mol percent of tolane, 0.5mL of toluene, then adding 0.2mmol of dried sodium carbonate and 0.2mmol of potassium acetate, pumping nitrogen for three times, reacting for 24 hours at 100 ℃, and separating by column chromatography, wherein an eluent is: petroleum ether to obtain the derivative 3-isobutyl-1, 2-diphenyl naphthalene of polyaromatic substituted naphthalene.
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CN201711358060.0A Active CN108017613B (en) 2017-12-13 2017-12-13 Method for preparing polyaryl substituted naphthalene derivative by ruthenium-catalyzed reaction of heterocyclic aromatic ketone and tolane
CN201711358055.XA Pending CN108101734A (en) 2017-12-13 2017-12-13 A kind of method that ruthenium catalysis fluorine-containing aromatic ketone prepares more virtue substitution naphthalene derivativeses with tolans reaction
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