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CN107935812A - Ruthenium is catalyzed the method that alkyl arone prepares more virtue substitution naphthalene derivativeses with tolans reaction - Google Patents

Ruthenium is catalyzed the method that alkyl arone prepares more virtue substitution naphthalene derivativeses with tolans reaction Download PDF

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CN107935812A
CN107935812A CN201711358009.XA CN201711358009A CN107935812A CN 107935812 A CN107935812 A CN 107935812A CN 201711358009 A CN201711358009 A CN 201711358009A CN 107935812 A CN107935812 A CN 107935812A
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张殊佳
高杰
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Abstract

本分案申请涉及钌催化烷基芳酮与二苯乙炔反应制备多芳取代萘衍生物的方法。本发明使用较廉价的钌作为催化剂，将芳香酮β‑H活化合成六元环即生成多芳取代萘衍生物；反应过程中无需添加剂及氧化剂，仅使用简单的碱，在温和反应条件下进行。本发明提供的合成方法简单易行、科学合理、绿色环保、经济实用，适合规模化生产。This divisional application relates to a method for preparing polyaromatic substituted naphthalene derivatives through the reaction of ruthenium-catalyzed alkyl aryl ketones and toluene acetylenes. The present invention uses relatively cheap ruthenium as a catalyst to activate the aromatic ketone β-H to synthesize a six-membered ring to generate polyaromatic substituted naphthalene derivatives; no additives and oxidants are required during the reaction, and only a simple base is used, and the reaction is carried out under mild reaction conditions . The synthesis method provided by the invention is simple, feasible, scientific and reasonable, environmentally friendly, economical and practical, and suitable for large-scale production.

Description

钌催化烷基芳酮与二苯乙炔反应制备多芳取代萘衍生物的 方法Ruthenium-Catalyzed Reaction of Alkylaryl Ketones with Tolanylacetylene to Prepare Polyaryl-Substituted Naphthalene Derivatives method

本申请为申请号为2017113298008、申请日为2017年12月13日、发明名称为“一种钌催化芳香酮与二苯乙炔环化反应制备多芳取代萘衍生物的方法及应用”的分案申请。This application is a divisional application with the application number 2017113298008, the application date is December 13, 2017, and the title of the invention is "a method and application for the preparation of polyaromatic substituted naphthalene derivatives by ruthenium-catalyzed cyclization of aromatic ketones and tolanylacetylenes" Application.

技术领域technical field

本发明涉及医药技术及光电材料领域，主要涉及多芳取代萘衍生物的制备方法及应用。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.

背景技术Background technique

多芳取代萘衍生物由于其独特的电化学，光化学性能以及它们在n共轭的功能材料上的应用，使其在有机荧光材料、半导体材料等方面的应用越来越广泛，并且多芳取代萘衍生物在药物合成方面也有重要应用。现有技术中已采用的制备方法相比以前的环金属化、芳基卤、芳基酸等比较苛刻的条件有了很大的突破。目前，多采用在温和条件下通过过渡金属催化芳香苯环的C-H键(甚至双C-H键)活化与炔烃发生环化反应制备多芳取代的萘衍生物。但该方法存在缺陷，这些反应需要一定量的配体或者当量的金属盐做氧化剂才能完成催化循环，不仅提高了生产成本，而且金属盐多为对环境污染的重金属(铜、银等)盐类。基于此，本领域需要更加环保、绿色、经济的方法来合成多芳取代萘衍生物。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 the aromatic benzene ring and alkyne under mild conditions. 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. . Based on this, more environmentally friendly, green and economical methods are needed in this field to synthesize polyaromatic substituted naphthalene derivatives.

发明内容Contents of the invention

为弥补现有技术的不足，本发明提供了一种无需添加剂及氧化剂在温和条件下以较廉价的钌([RuCl2(p-cymene)]2)作为催化剂合成了多芳取代萘的衍生物的方法。In order to make up for the deficiencies of the prior art, the present invention provides a derivative of polyaromatic substituted naphthalene synthesized under mild conditions with relatively cheap ruthenium ([RuCl 2 (p-cymene)] 2 ) as a catalyst without the need for additives and oxidants Methods.

本发明采用如下技术方案：多芳取代萘的衍生物，具有如通式Ⅰ所示的结构：The present invention adopts the following technical scheme: derivatives of polyaromatic substituted naphthalene have a structure as shown in general formula I:

其中，R1为-H或-F中的一种，R2为-CH3、-CH2CH3、-CH3、或-CF3中的一种。where R1 is One of -H or -F, R2 is -CH 3 , -CH 2 CH 3 , -CH 3 , or - one of CF 3 .

优选的，所述多芳取代萘的衍生物为： Preferably, the derivatives of polyaryl substituted naphthalene are:

本发明另一个目的是请求保护上述多芳取代萘的衍生物的制备方法，即：将二苯乙炔与芳香酮作为原料，加入[RuCl2(p-cymene)]2、碱和非极性有机溶剂，在氮气环境下加热至80-100℃反应12-24h，经柱层析分离得到多芳取代萘的衍生物；所述的二苯乙炔与芳香酮摩尔比为1:2，[RuCl2(p-cymene)]2占二苯乙炔的15mol％，碱与芳香酮的摩尔比为1:1。Another object of the present invention is to claim the preparation method of the above polyaromatic substituted naphthalene derivatives, namely: use toluene and aromatic ketones as raw materials, add [RuCl 2 (p-cymene)] 2 , alkali and non-polar organic Solvent, heated to 80-100°C for 12-24h under nitrogen atmosphere, and separated by column chromatography to obtain derivatives of polyaromatic substituted naphthalene; the molar ratio of toluene to aromatic ketone is 1:2, [RuCl 2 (p-cymene)] 2 accounts for 15 mol% of tolanyl acetylene, and the molar ratio of base to aromatic ketone is 1:1.

优选的，所述的芳香酮为：其中R1为-H或-F中的一种，R2为-CH3、-CH2CH3、-CH3、或-CF3中的一种。Preferably, the aromatic ketone is: where R1 is One of -H or -F, R2 is -CH 3 , -CH 2 CH 3 , -CH 3 , or - one of CF 3 .

优选的，芳香酮为 中的一种。Preferably, the aromatic ketone is One of.

进一步的，所述非极性有机溶剂为苯、甲苯、二氯乙烷、氯仿、苯乙烯、环乙烷或己烷中任一种。优选甲苯。Further, the non-polar organic solvent is any one of benzene, toluene, dichloroethane, chloroform, styrene, cycloethane or hexane. Toluene is preferred.

进一步的，所述的碱为KOAc、Na2CO3、Cs2CO3、K2CO3、Li2CO3、NaOAc、LiOAc中的一种或一种以上。优选KOAc和Na2CO3。Further, the base is one or more of KOAc, Na 2 CO 3 , Cs 2 CO 3 , K 2 CO 3 , Li 2 CO 3 , NaOAc, and LiOAc. KOAc and Na2CO3 are preferred.

作为本发明优选的实施方案，该多芳取代萘衍生物的制备方法为：将芳香酮和二苯乙炔置于封管中，加入[RuCl2(p-cymene)]2和甲苯，同时加入干燥的碳酸钠和醋酸钾在氮气环境下加热至100℃反应24小时，经柱层析分离得到多芳取代萘的衍生物。As a preferred embodiment of the present invention, the preparation method of the polyaromatic substituted naphthalene derivatives is: place aromatic ketones and toluene in sealed tubes, add [RuCl 2 (p-cymene)] 2 and toluene, and simultaneously add dry Sodium carbonate and potassium acetate were heated to 100°C for 24 hours under nitrogen atmosphere, and the derivatives of polyaromatic substituted naphthalene were obtained by column chromatography.

本发明第三个目的是请求保护上述多芳取代萘的衍生物在药物制备及光电材料领域上的应用。The third object of the present invention is to claim the application of the above-mentioned derivatives of polyaromatic substituted naphthalene in the fields of drug preparation and optoelectronic materials.

比如用于新型酪氨酸蛋白激酶抑制剂或蓝光材料的制备。For example, for novel tyrosine protein kinase inhibitors or Blu-ray material preparation.

与现有技术相比，本发明的有益效果是：Compared with prior art, the beneficial effect of the present invention is:

本发明使用较廉价的钌([RuCl2(p-cymene)]2)作为催化剂，将芳香酮β-H活化合成六元环即生成多芳取代萘衍生物；反应过程中无需添加剂及氧化剂，仅使用简单的碱，在温和反应条件下进行。本发明提供的合成方法简单易行、科学合理、绿色环保、经济实用，适合规模化生产。The present invention uses relatively cheap ruthenium ([RuCl 2 (p-cymene)] 2 ) as a catalyst to activate aromatic ketone β-H to synthesize a six-membered ring to generate polyaromatic substituted naphthalene derivatives; no additives and oxidants are needed during the reaction, Use only simple bases and proceed under mild reaction conditions. The synthesis method provided by the invention is simple, feasible, scientific and reasonable, environmentally friendly, economical and practical, and suitable for large-scale production.

具体实施方式Detailed ways

下面通过具体实施例详述本发明，但不限制本发明的保护范围。如无特殊说明，本发明所采用的实验方法均为常规方法，所用实验器材、材料、试剂等均可从化学公司购买。The present invention is described in detail below through specific examples, but the protection scope of the present invention is not limited. Unless otherwise specified, the experimental methods used in the present invention are conventional methods, and the experimental equipment, materials, reagents, etc. used can be purchased from chemical companies.

实施例1Example 1

向带有磁子的25mL封管中加入二苯乙炔(18mg，0.1mmol)，相应的芳香酮(0.2mmol)，催化剂[RuCl2(p-cymene)]2(9mg，15％mol)，0.5mL甲苯，之后加入干燥的碳酸钠(21mg，0.2mmol)和醋酸钾(19mg，0.2mmol)，抽换氮气三次，100℃下反应24小时，然后经柱色谱分离(洗脱剂为：石油醚)从而得到目标化合物。表征如下。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), 0.5 mL of toluene, then added dry sodium carbonate (21mg, 0.2mmol) and potassium acetate (19mg, 0.2mmol), replaced nitrogen three times, reacted at 100°C for 24 hours, and then separated by column chromatography (eluent: petroleum ether ) to obtain the target compound. Characterization is as follows.

4,5-二苯基-6-(噻吩-2-亚甲基)苯并[b]噻吩：产率：40％。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:382.0847.4,5-Diphenyl-6-(thiophene-2-methylene)benzo[b]thiophene: Yield: 40%. 1 H NMR (CDCl 3 , 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,J 1 =3.6Hz; J 2 =5.2Hz,1H),6.59-6.60(m,1H),4.07(s,2H). 13 C NMR(CDCl 3 ,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 C 25 H 18 S 2 (M + ): 382.0850, found: 382.0847.

实施例2Example 2

向带有磁子的25mL封管中加入二苯乙炔(18mg，0.1mmol)，相应的芳香酮(0.2mmol)，催化剂[RuCl2(p-cymene)]2(9mg，15％mol)，0.5mL甲苯，之后加入干燥的碳酸钠(21mg，0.2mmol)和醋酸钾(19mg，0.2mmol)，抽换氮气三次，100℃下反应24小时，然后经柱色谱分离(洗脱剂为：石油醚)从而得到目标化合物。表征如下。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), 0.5 mL of toluene, then added dry sodium carbonate (21mg, 0.2mmol) and potassium acetate (19mg, 0.2mmol), replaced nitrogen three times, reacted at 100°C for 24 hours, and then separated by column chromatography (eluent: petroleum ether ) to obtain the target compound. Characterization is as follows.

3-甲基-1,2,7-三苯基萘：产率：65％。熔点：163-165℃。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:370.1723.3-Methyl-1,2,7-triphenylnaphthalene: Yield: 65%. Melting point: 163-165°C. 1 H NMR (CDCl 3 , 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). 13 CNMR (CDCl 3 , 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, 1267.4, 2, 1 124.9, 22.0. HRMS (EI-TOF) calcd for C 29 H 22 (M + ): 370.1722, found: 370.1723.

实施例3Example 3

向带有磁子的25mL封管中加入二苯乙炔(18mg，0.1mmol)，相应的芳香酮(0.2mmol)，催化剂[RuCl2(p-cymene)]2(9mg，15％mol)，0.5mL甲苯，之后加入干燥的碳酸钠(21mg，0.2mmol)和醋酸钾(19mg，0.2mmol)，抽换氮气三次，100℃下反应24小时，然后经柱色谱分离(洗脱剂为：石油醚)从而得到目标化合物。表征如下。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), 0.5 mL of toluene, then added dry sodium carbonate (21mg, 0.2mmol) and potassium acetate (19mg, 0.2mmol), replaced nitrogen three times, reacted at 100°C for 24 hours, and then separated by column chromatography (eluent: petroleum ether ) to obtain the target compound. Characterization is as follows.

3-乙基-1,2-二苯基萘：产率：25％。熔点：124-125℃。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:308.1567.3-Ethyl-1,2-diphenylnaphthalene: Yield: 25%. Melting point: 124-125°C. 1 H NMR(CDCl 3 ,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, J 1 =7.6Hz; J 2 =14.8Hz, 2H), 1.08(t, J=7.6Hz, 3H). 13 C NMR (CDCl 3 , 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. H 20 (M + ):308.1565,found:308.1567.

实施例4Example 4

向带有磁子的25mL封管中加入二苯乙炔(18mg，0.1mmol)，相应的芳香酮(0.2mmol)，催化剂[RuCl2(p-cymene)]2(9mg，15％mol)，0.5mL甲苯，之后加入干燥的碳酸钠(21mg，0.2mmol)和醋酸钾(19mg，0.2mmol)，抽换氮气三次，100℃下反应24小时，然后经柱色谱分离(洗脱剂为：石油醚)从而得到目标化合物。表征如下。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), 0.5 mL of toluene, then added dry sodium carbonate (21mg, 0.2mmol) and potassium acetate (19mg, 0.2mmol), replaced nitrogen three times, reacted at 100°C for 24 hours, and then separated by column chromatography (eluent: petroleum ether ) to obtain the target compound. Characterization is as follows.

7-氟-3-甲基-1,2-二苯基萘：产率：30％。熔点：139-140℃。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:312.1312.7-Fluoro-3-methyl-1,2-diphenylnaphthalene: Yield: 30%. Melting point: 139-140°C. 1 H NMR (CDCl 3 , 400MHz) δ7.81 (dd, J 1 =6.0Hz; J 2 =8.8Hz, 1H), 7.75(s, 1H), 7.06-7.23(m, 10H), 7.01-7.03( m,2H),2.24(s,3H). 13 C NMR(CDCl 3 ,100MHz)δ161.6,159.2,140.8,140.3,138.9,138.2(d,J CF ＝5.6Hz),133.7(d,J CF ＝2.3 Hz),132.3,132.2,130.9,129.9(d,J CF ＝5.6Hz),129.4(d,J CF ＝8.6Hz),127.6(d,J CF ＝4.9Hz),127.3,126.6,126.3,116.2, 115.9, 110.3, 110.1, 21.8. HRMS (EI-TOF) calcd for C 23 H 17 F (M + ): 312.1314, found: 312.1312.

实施例5Example 5

向带有磁子的25mL封管中加入二苯乙炔(18mg，0.1mmol)，相应的芳香酮(0.2mmol)，催化剂[RuCl2(p-cymene)]2(9mg，15％mol)，0.5mL甲苯，之后加入干燥的碳酸钠(21mg，0.2mmol)和醋酸钾(19mg，0.2mmol)，抽换氮气三次，100℃下反应24小时，然后经柱色谱分离(洗脱剂为：石油醚)从而得到目标化合物。表征如下。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), 0.5 mL of toluene, then added dry sodium carbonate (21mg, 0.2mmol) and potassium acetate (19mg, 0.2mmol), replaced nitrogen three times, reacted at 100°C for 24 hours, and then separated by column chromatography (eluent: petroleum ether ) to obtain the target compound. Characterization is as follows.

3-异丁基-1,2-二苯基萘：产率：35％。熔点：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:336.1882.3-Isobutyl-1,2-diphenylnaphthalene: Yield: 35%. Melting point: 107-108°C. 1 H NMR(CDCl 3 ,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 13 C NMR (CDCl 3 , 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, 125.9, 291.2, 291.2, 2 .HRMS(EI-TOF) calcd for C 26 H 24 (M + ):336.1878,found:336.1882.

实施例6Example 6

向带有磁子的25mL封管中加入二苯乙炔(18mg，0.1mmol)，相应的芳香酮(0.2mmol)，催化剂[RuCl2(p-cymene)]2(9mg，15％mol)，0.5mL甲苯，之后加入干燥的碳酸钠(21mg，0.2mmol)和醋酸钾(19mg，0.2mmol)，抽换氮气三次，100℃下反应24小时，然后经柱色谱分离(洗脱剂为：石油醚)从而得到目标化合物。表征如下。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), 0.5 mL of toluene, then added dry sodium carbonate (21mg, 0.2mmol) and potassium acetate (19mg, 0.2mmol), replaced nitrogen three times, reacted at 100°C for 24 hours, and then separated by column chromatography (eluent: petroleum ether ) to obtain the target compound. Characterization is as follows.

1,2-二苯基-3-(三氟甲基)萘：产率：45％。熔点：118-119℃。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:348.1124.1,2-Diphenyl-3-(trifluoromethyl)naphthalene: Yield: 45%. Melting point: 118-119°C. 1 H NMR (CDCl 3 , 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). 13 C NMR(CDCl 3 ,100MHz)δ141.6,138.1,137.7,135.9,134.0,131.4,130.8(d, J CF ＝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 C 23 H 15 F 3 (M + ): 348.1126,found: 348.1124.

对比例：Comparative example:

向带有磁子的25mL封管中加入二苯乙炔0.1mmol，芳香酮(0.2mmol)，催化剂[RuCl2(p-cymene)]20.01mol，之后加入0.5mL有机溶剂和与芳香酮等摩尔的干燥的碱，抽换氮气三次，100℃下反应24小时，然后经柱色谱分离(洗脱剂为：石油醚)从而得到目标化合物计算产率，结果如表1所示。Add 0.1 mmol of toluene acetylene, aromatic ketone (0.2mmol), catalyst [RuCl 2 (p-cymene)] 2 0.01mol, then add 0.5mL organic solvent and dry base equimolar with aromatic ketone, replace nitrogen three times, react at 100°C for 24 hours, then Column chromatographic separation (eluent is: petroleum ether) to obtain the target compound Calculate the yield, and the results are shown in Table 1.

表1Table 1

*催化剂为0.015mmol时的产率*The yield when the catalyst is 0.015mmol

由表1数据和对实施例1-6产率对比可知，当有机溶剂选择甲苯，碱为碳酸钠和醋酸钾时，催化剂用量为15mol％时，产率最高。故而，在实验过程中均采用此最佳反应条件进行。From the data in Table 1 and the comparison of the yields of Examples 1-6, it can be seen that when the organic solvent is selected toluene, and the alkali is sodium carbonate and potassium acetate, the catalyst consumption is 15mol%, and the yield is the highest. Therefore, the optimal reaction conditions were used in the experiment.

以上所述，仅为本发明创造较佳的具体实施方式，但本发明创造的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明创造披露的技术范围内，根据本发明创造的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明创造的保护范围之内。The above is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto, any person familiar with the technical field within the technical scope of the disclosure of the present invention, according to the present invention Any equivalent replacement or change of the created technical solution and its inventive concept shall be covered within the scope of protection of the present invention.

Claims (6)

1. ruthenium is catalyzed the method that alkyl arone prepares more virtue substitution naphthalene derivativeses with tolans reaction, it is characterised in that by two Phenylacetylene and aromatic ketoneAs raw material, [RuCl is added2(p-cymene)]2, alkali and non-polar organic solvent, 80-100 DEG C of reaction 12-24h is heated in a nitrogen environment, and more virtue substitution naphthalene derivatives are obtained through column chromatography for separation；It is described Tolans and aromatic ketone molar ratio be 1:2, [RuCl2(p-cymene)]2Account for the 15mol% of tolans, alkali and aromatic ketone Molar ratio be 1:1.
2. according to the method described in claim 1, it is characterized in that, the non-polar organic solvent is benzene, toluene, two chloroethenes It is any in alkane, chloroform, styrene, cyclohexane or hexane.
3. according to the method described in claim 2, it is characterized in that, organic solvent is toluene.
4. according to the method described in claim 1, it is characterized in that, the alkali is KOAc, Na2CO3、Cs2CO3、K2CO3、 Li2CO3, one or more in NaOAc, LiOAc.
5. according to the method described in claim 4, it is characterized in that the alkali is KOAc and Na2CO3。
A kind of 6. application of virtue substitution naphthalene derivatives more as claimed in claim 1 in medicine preparation and field of photovoltaic materials.
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CN108047198A (en) 2018-05-18
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