CN103435542B - 2-biaryl-6-arylquinazoline and preparation method thereof - Google Patents
2-biaryl-6-arylquinazoline and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 82
- 238000006243 chemical reaction Methods 0.000 claims abstract description 70
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 150000001875 compounds Chemical class 0.000 claims abstract description 47
- WYECURVXVYPVAT-UHFFFAOYSA-N 1-(4-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Br)C=C1 WYECURVXVYPVAT-UHFFFAOYSA-N 0.000 claims abstract description 26
- GDCWZYRWKSOYGQ-UHFFFAOYSA-N (2-amino-5-bromophenyl)methanol Chemical compound NC1=CC=C(Br)C=C1CO GDCWZYRWKSOYGQ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011261 inert gas Substances 0.000 claims abstract description 21
- 238000010992 reflux Methods 0.000 claims abstract description 18
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- 150000002940 palladium Chemical class 0.000 claims abstract description 8
- 150000001543 aryl boronic acids Chemical class 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 238000000746 purification Methods 0.000 claims abstract description 3
- 238000000926 separation method Methods 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 120
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 26
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 12
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical group Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 3
- 125000000532 dioxanyl group Chemical group 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims 1
- 235000015320 potassium carbonate Nutrition 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 72
- 239000000047 product Substances 0.000 description 39
- 229910052757 nitrogen Inorganic materials 0.000 description 36
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 23
- 238000005481 NMR spectroscopy Methods 0.000 description 20
- 239000007787 solid Substances 0.000 description 19
- 238000004458 analytical method Methods 0.000 description 18
- 239000000706 filtrate Substances 0.000 description 18
- 238000003760 magnetic stirring Methods 0.000 description 18
- 239000012074 organic phase Substances 0.000 description 18
- 238000001953 recrystallisation Methods 0.000 description 18
- 239000002904 solvent Substances 0.000 description 18
- 239000011521 glass Substances 0.000 description 11
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 9
- -1 iridium triphenylphosphine metal organic compounds Chemical class 0.000 description 8
- 229940027991 antiseptic and disinfectant quinoline derivative Drugs 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 150000003248 quinolines Chemical class 0.000 description 7
- BJQCPCFFYBKRLM-UHFFFAOYSA-N (3-methylphenyl)boronic acid Chemical compound CC1=CC=CC(B(O)O)=C1 BJQCPCFFYBKRLM-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical class CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- BIWQNIMLAISTBV-UHFFFAOYSA-N (4-methylphenyl)boronic acid Chemical compound CC1=CC=C(B(O)O)C=C1 BIWQNIMLAISTBV-UHFFFAOYSA-N 0.000 description 2
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- NSJVYHOPHZMZPN-UHFFFAOYSA-N (2-methylphenyl)boronic acid Chemical compound CC1=CC=CC=C1B(O)O NSJVYHOPHZMZPN-UHFFFAOYSA-N 0.000 description 1
- CEBAHYWORUOILU-UHFFFAOYSA-N (4-cyanophenyl)boronic acid Chemical compound OB(O)C1=CC=C(C#N)C=C1 CEBAHYWORUOILU-UHFFFAOYSA-N 0.000 description 1
- RZCPLOMUUCFPQA-UHFFFAOYSA-N (4-ethylphenyl)boronic acid Chemical compound CCC1=CC=C(B(O)O)C=C1 RZCPLOMUUCFPQA-UHFFFAOYSA-N 0.000 description 1
- VXWBQOJISHAKKM-UHFFFAOYSA-N (4-formylphenyl)boronic acid Chemical compound OB(O)C1=CC=C(C=O)C=C1 VXWBQOJISHAKKM-UHFFFAOYSA-N 0.000 description 1
- VOAAEKKFGLPLLU-UHFFFAOYSA-N (4-methoxyphenyl)boronic acid Chemical compound COC1=CC=C(B(O)O)C=C1 VOAAEKKFGLPLLU-UHFFFAOYSA-N 0.000 description 1
- JHVQEUGNYSVSDH-UHFFFAOYSA-N (4-methylnaphthalen-1-yl)boronic acid Chemical compound C1=CC=C2C(C)=CC=C(B(O)O)C2=C1 JHVQEUGNYSVSDH-UHFFFAOYSA-N 0.000 description 1
- WIKBZUXHNPONPP-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoro-2-iodo-2-(trifluoromethyl)propane Chemical compound FC(F)(F)C(I)(C(F)(F)F)C(F)(F)F WIKBZUXHNPONPP-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- ZNRGSYUVFVNSAW-UHFFFAOYSA-N 3-nitrophenylboronic acid Chemical compound OB(O)C1=CC=CC([N+]([O-])=O)=C1 ZNRGSYUVFVNSAW-UHFFFAOYSA-N 0.000 description 1
- LBUNNMJLXWQQBY-UHFFFAOYSA-N 4-fluorophenylboronic acid Chemical compound OB(O)C1=CC=C(F)C=C1 LBUNNMJLXWQQBY-UHFFFAOYSA-N 0.000 description 1
- XQYQEUHCQSNIPJ-UHFFFAOYSA-N 6-naphthalen-1-yl-2-(4-naphthalen-1-ylphenyl)quinoline Chemical compound C1=CC=C2C(=C1)C=CC=C2C3=CC=C(C=C3)C4=NC5=C(C=C4)C=C(C=C5)C6=CC=CC7=CC=CC=C76 XQYQEUHCQSNIPJ-UHFFFAOYSA-N 0.000 description 1
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- LXNAVEXFUKBNMK-UHFFFAOYSA-N acetic acid;palladium Chemical compound [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OOPSAZSKOMIGFX-UHFFFAOYSA-N boric acid;toluene Chemical compound OB(O)O.CC1=CC=CC=C1 OOPSAZSKOMIGFX-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 150000002504 iridium compounds Chemical class 0.000 description 1
- NPDIDUXTRAITDE-UHFFFAOYSA-N meta-methylbiphenyl Natural products CC1=CC=CC(C=2C=CC=CC=2)=C1 NPDIDUXTRAITDE-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000006452 multicomponent reaction Methods 0.000 description 1
- HUMMCEUVDBVXTQ-UHFFFAOYSA-N naphthalen-1-ylboronic acid Chemical compound C1=CC=C2C(B(O)O)=CC=CC2=C1 HUMMCEUVDBVXTQ-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- ZZLCFHIKESPLTH-UHFFFAOYSA-N p-methylbiphenyl Natural products C1=CC(C)=CC=C1C1=CC=CC=C1 ZZLCFHIKESPLTH-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010490 three component reaction Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
Landscapes
- Quinoline Compounds (AREA)
Abstract
2-联芳基-6-芳基喹啉及其制备方法,属于有机合成领域,采用了如下技术方案:2-联芳基-6-芳基喹啉,通式为:其中Aryl为芳基。该化合物的制备步骤为:取对溴苯乙酮、2-氨基-5-溴苯甲醇、芳基硼酸、RuCl2(DMSO)4、钯盐、三苯基膦和碱加入到有机溶剂中,在惰性气体保护下加热回流,反应结束后经分离、提纯即得2-联芳基-6-芳基喹啉。该方法一步合成2-联芳基-6-芳基喹啉,反应条件温和、产率高,反应经济高效,应用前景广阔。2-biaryl-6-arylquinoline and a preparation method thereof belong to the field of organic synthesis, and adopt the following technical scheme: 2-biaryl-6-arylquinoline, the general formula is: Wherein Aryl is an aryl group. The preparation steps of the compound are as follows: taking p-bromoacetophenone, 2-amino-5-bromobenzyl alcohol, aryl boronic acid, RuCl 2 (DMSO) 4 , palladium salt, triphenylphosphine and base into an organic solvent, Heating to reflux under the protection of an inert gas, separation and purification after the reaction to obtain 2-biaryl-6-arylquinoline. The method synthesizes 2-biaryl-6-arylquinoline in one step, has mild reaction conditions, high yield, economical and efficient reaction, and broad application prospect.
Description
技术领域technical field
本发明属于有机合成领域,具体涉及一类2-联芳基-6-芳基喹啉化合物,以及该类化合物的合成方法。The invention belongs to the field of organic synthesis, and in particular relates to a class of 2-biaryl-6-aryl quinoline compounds and a synthesis method of the compounds.
背景技术Background technique
喹啉衍生物具有生物活性和药理活性,广泛应用于医药、农药等工业生产。喹啉衍生物最早从煤焦油中提取,技术路线工艺复杂,其产品种类有限,一些重要的喹啉衍生物通过该方法不能获得。近年来,在传统合成路线基础上,发展了以过渡金属络合物为催化剂的新的合成路线,是目前研究最多和最有前途的一种方法。为提高反应的原子经济性和合成效率,一锅法多组分反应构建多个共价键的反应引起化学家们的广泛兴趣。在醇参与的反应中,研究较多的催化剂是Ru、Ir等金属络合物;其中RuCl2(DMSO)4(DMSO=二甲基亚砜)结构简单、易于合成、现已商品化,是用于催化此反应效率和催化效果较好的催化剂之一。Quinoline derivatives have biological activity and pharmacological activity, and are widely used in industrial production such as medicine and pesticide. Quinoline derivatives were first extracted from coal tar. The technical route is complex and the product types are limited. Some important quinoline derivatives cannot be obtained by this method. In recent years, on the basis of traditional synthetic routes, a new synthetic route using transition metal complexes as catalysts has been developed, which is currently the most studied and most promising method. In order to improve the atom economy and synthetic efficiency of the reaction, the one-pot multicomponent reaction to construct multiple covalent bonds has attracted widespread interest among chemists. In the reaction involving alcohol, metal complexes such as Ru and Ir are the most studied catalysts; among them, RuCl 2 (DMSO) 4 (DMSO=dimethyl sulfoxide) has a simple structure, is easy to synthesize, and is now commercialized. It is one of the catalysts with better efficiency and catalytic effect for catalyzing this reaction.
近年来,以芳基取代的喹啉衍生物为配体的金属有机化合物在材料化学等领域的广泛应用前景,引起人们的极大兴趣。而芳基取代的喹啉衍生物,特别是联芳基的喹啉衍生物还很少有报道。In recent years, metal-organic compounds with aryl-substituted quinoline derivatives as ligands have aroused great interest for their wide application prospects in materials chemistry and other fields. However, aryl-substituted quinoline derivatives, especially biaryl-substituted quinoline derivatives, are rarely reported.
发明内容Contents of the invention
本发明的目的在于提供一类2-联芳基-6-芳基喹啉化合物及其制备方法。The object of the present invention is to provide a class of 2-biaryl-6-arylquinoline compounds and a preparation method thereof.
基于上述目的,本发明采用了如下技术方案:Based on above-mentioned purpose, the present invention adopts following technical scheme:
2-联芳基-6-芳基喹啉化合物,该化合物具有如下通式:2-biaryl-6-arylquinoline compound, the compound has the following general formula:
其中Aryl为芳基。 Wherein Aryl is an aryl group.
所述芳基R是-H、-CH3、-C2H5、-CN、-NO2、-CHO、-COOCH3、-OCH3或-F;R可以在芳环上任一位置。The aryl R is -H, -CH 3 , -C 2 H 5 , -CN, -NO 2 , -CHO, -COOCH 3 , -OCH 3 or -F; R can be at any position on the aromatic ring.
2-联芳基-6-芳基喹啉化合物的制备方法:取对溴苯乙酮、2-氨基-5-溴苯甲醇、芳基硼酸、RuCl2(DMSO)4(DMSO=二甲基亚砜)、钯盐、三苯基膦和碱加入到有机溶剂中,在惰性气体保护下加热回流反应,反应结束后经分离、提纯即得2-联芳基-6-芳基喹啉;反应路线如下:The preparation method of 2-biaryl-6-aryl quinoline compound: take p-bromoacetophenone, 2-amino-5-bromobenzyl alcohol, aryl boronic acid, RuCl 2 (DMSO) 4 (DMSO=dimethyl sulfoxide), palladium salt, triphenylphosphine and alkali are added to the organic solvent, and heated to reflux under the protection of an inert gas for reaction. After the reaction is completed, it is separated and purified to obtain 2-biaryl-6-arylquinoline; The reaction scheme is as follows:
芳基硼酸中的芳基与2-联芳基-6-芳基喹啉中的芳基相同。The aryl group in arylboronic acid is the same as the aryl group in 2-biaryl-6-arylquinoline.
对溴苯乙酮、2-氨基-5-溴苯甲醇、芳基硼酸、RuCl2(DMSO)4、钯盐、三苯基膦和碱的摩尔为1:1~2:2~6:0.01~0.1:0.02~0.1:0.05~0.2:2~8;有机溶剂的添加量为5~10ml/mmol对溴苯乙酮。The molar ratio of p-bromoacetophenone, 2-amino-5-bromobenzyl alcohol, arylboronic acid, RuCl 2 (DMSO) 4 , palladium salt, triphenylphosphine and base is 1:1~2:2~6:0.01 ~0.1: 0.02~0.1: 0.05~0.2: 2~8; the amount of organic solvent added is 5~10ml/mmol p-bromoacetophenone.
所述有机溶剂为二氧六环、苯、甲苯或四氢呋喃。The organic solvent is dioxane, benzene, toluene or tetrahydrofuran.
所述碱为氢氧化钠、氢氧化钾、碳酸钠或碳酸钾。The alkali is sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate.
所述钯盐为氯化钯或醋酸钯。The palladium salt is palladium chloride or palladium acetate.
所述回流反应的温度为80~120℃,时间为8~48h。The temperature of the reflux reaction is 80-120° C., and the time is 8-48 hours.
所述分离、提纯过程为:反应液中加水,用二氯甲烷萃取,萃取后经干燥、过滤、浓缩,再用二氯甲烷重结晶提纯。The separation and purification process is as follows: adding water to the reaction solution, extracting with dichloromethane, drying, filtering, concentrating after extraction, and then recrystallizing and purifying with dichloromethane.
本发明利用商品可得的钌催化剂和钯盐,共同催化对溴苯乙酮、2-氨基-5-溴苯甲醇和芳基硼酸的三组分反应,通过氢转移反应和Suzuki偶联反应,一锅法制备得到2-联芳基-6-芳基喹啉化合物,为合成芳基取代喹啉衍生物提供了一个实用的方法。该方法所用催化剂简单易得,反应条件温和、底物范围广、产率高等优势,具有重要的应用价值。2-联芳基-6-芳基喹啉化合物可用于合成环铱三苯基膦金属有机化合物,该金属有机化合物可以作为催化和发光材料。The present invention utilizes commercially available ruthenium catalysts and palladium salts to jointly catalyze the three-component reaction of p-bromoacetophenone, 2-amino-5-bromobenzyl alcohol and arylboronic acid, through hydrogen transfer reactions and Suzuki coupling reactions, The one-pot preparation of 2-biaryl-6-arylquinoline compounds provides a practical method for the synthesis of aryl-substituted quinoline derivatives. The catalyst used in the method is simple and easy to obtain, the reaction conditions are mild, the substrate range is wide, the yield is high, and the like, which has important application value. The 2-biaryl-6-arylquinoline compound can be used to synthesize ring iridium triphenylphosphine metal organic compounds, and the metal organic compounds can be used as catalysts and luminescent materials.
具体实施方式Detailed ways
下面结合具体实施例对本发明做进一步说明。The present invention will be further described below in conjunction with specific embodiments.
产品例Product example
实施例1Example 1
2-联芳基-6-芳基喹啉化合物,通式为:2-biaryl-6-arylquinoline compounds, the general formula is:
具体结构可以是: The specific structure can be:
制备例Preparation example
实施例2Example 2
2-联苯基-6-苯基喹啉即化合物(1)的制备:在惰性气体(如高纯氮气)保护下,向10ml的Schlek反应管(无水无氧操作时常用的一种玻璃仪器)加入1.0mmol对溴苯乙酮、1.2mmol2-氨基-5-溴苯甲醇、2.0mmol苯基硼酸、0.01mmol RuCl2(DMSO)4、0.02mmol醋酸钯、0.05mmol三苯基膦和2.0mmol氢氧化钠和5ml二氧六环,用氮气置换反应管3次,然后在磁力搅拌下用油浴加热至110℃,反应回流8小时。去掉油浴,水浴降到室温;向反应液加3ml水,用5ml的二氯甲烷萃取三次,合并有机相并用无水MgSO4干燥30分钟,过滤;滤液用旋转蒸发器浓缩,浓缩后的固体以二氯甲烷为溶剂,重结晶得到纯产品化合物(1),产率85%。该产品的核磁分析数据如下:1H NMR.(400MHz,CDCl3):δ8.17(d,1H),7.84-8.09(m,6H),7.78(d,1H),7.42-7.51(m,5H),7.16-7.35(m,6H)。The preparation of 2-biphenyl-6-phenylquinoline, that is, compound (1): under the protection of inert gas (such as high-purity nitrogen), pour 10ml of Schlek reaction tube (a kind of glass commonly used in anhydrous and oxygen-free operation) instrument) by adding 1.0mmol p-bromoacetophenone, 1.2mmol 2-amino-5-bromobenzyl alcohol, 2.0mmol phenylboronic acid, 0.01mmol RuCl 2 (DMSO) 4 , 0.02mmol palladium acetate, 0.05mmol triphenylphosphine and 2.0 Mmol sodium hydroxide and 5ml dioxane were used to replace the reaction tube with nitrogen for 3 times, then heated to 110°C in an oil bath under magnetic stirring, and the reaction was refluxed for 8 hours. Remove the oil bath, and the water bath is down to room temperature; add 3ml of water to the reaction solution, extract three times with 5ml of dichloromethane, combine the organic phases and use anhydrous MgSO Dry for 30 minutes, filter; the filtrate is concentrated with a rotary evaporator, and the concentrated solid Using dichloromethane as solvent, the pure product compound (1) was obtained by recrystallization with a yield of 85%. The nuclear magnetic analysis data of this product are as follows: 1 H NMR.(400MHz, CDCl 3 ):δ8.17(d,1H),7.84-8.09(m,6H),7.78(d,1H),7.42-7.51(m, 5H), 7.16-7.35 (m, 6H).
实施例3Example 3
2-(4-甲基联苯基)-6-(4-甲基苯基)喹啉即化合物(2)的制备:在惰性气体(如高纯氮气)保护下,向10ml的Schlek反应管(无水无氧操作时常用的一种玻璃仪器)加入1.0mmol对溴苯乙酮、1.3mmol2-氨基-5-溴苯甲醇、3.0mmol对甲基苯硼酸、0.01mmol RuCl2(DMSO)4、0.03mmol醋酸钯、0.1mmol三苯基膦和5.0mmol氢氧化钾和5ml二氧六环,用氮气置换反应管3次,然后在磁力搅拌下用油浴加热至110℃,反应回流16小时。去掉油浴,水浴降到室温;向反应液加3ml水,用5ml的二氯甲烷萃取三次,合并有机相并用无水MgSO4干燥30分钟,过滤;滤液用旋转蒸发器浓缩,浓缩后的固体以二氯甲烷为溶剂,重结晶得到纯产品化合物(2),产率95%。该产品的核磁分析数据如下:1H NMR.(400MHz,CDCl3):δ8.16(d,1H),8.08(d,2H),7.74-7.97(m,4H),7.63(d,2H),7.40-7.46(m,4H),7.15(d,4H),2.37(s,6H)。The preparation of 2-(4-methylbiphenyl)-6-(4-methylphenyl)quinoline, that is, compound (2): under the protection of an inert gas (such as high-purity nitrogen), add a 10ml Schlek reaction tube (A glass instrument commonly used in anhydrous and oxygen-free operation) Add 1.0mmol p-bromoacetophenone, 1.3mmol 2-amino-5-bromobenzyl alcohol, 3.0mmol p-tolueneboronic acid, 0.01mmol RuCl 2 (DMSO) 4 , 0.03mmol palladium acetate, 0.1mmol triphenylphosphine, 5.0mmol potassium hydroxide and 5ml dioxane, replace the reaction tube with nitrogen for 3 times, then heat to 110°C with an oil bath under magnetic stirring, and reflux for 16 hours . Remove the oil bath, and the water bath is down to room temperature; add 3ml of water to the reaction solution, extract three times with 5ml of dichloromethane, combine the organic phases and use anhydrous MgSO Dry for 30 minutes, filter; the filtrate is concentrated with a rotary evaporator, and the concentrated solid Using dichloromethane as solvent, the pure product compound (2) was obtained by recrystallization with a yield of 95%. The NMR analysis data of this product are as follows: 1 H NMR.(400MHz, CDCl 3 ):δ8.16(d,1H),8.08(d,2H),7.74-7.97(m,4H),7.63(d,2H) , 7.40-7.46 (m, 4H), 7.15 (d, 4H), 2.37 (s, 6H).
实施例4Example 4
2-(3-甲基联苯基)-6-(3-甲基苯基)喹啉即化合物(3)的制备:在惰性气体(如高纯氮气)保护下,向10ml的Schlek反应管(无水无氧操作时常用的一种玻璃仪器)加入1.0mmol对溴苯乙酮、1.5mmol2-氨基-5-溴苯甲醇、3.5mmol3-甲基苯硼酸、0.02mmol RuCl2(DMSO)4、0.05mmol醋酸钯、0.12mmol三苯基膦和6.0mmol碳酸钠和5ml甲苯,用氮气置换反应管3次,然后在磁力搅拌下用油浴加热至110℃,反应回流24小时。去掉油浴,水浴降到室温;向反应液加3ml水,用5ml的二氯甲烷萃取三次,合并有机相并用无水MgSO4干燥30分钟,过滤;滤液用旋转蒸发器浓缩,浓缩后的固体以二氯甲烷为溶剂,重结晶得到纯产品化合物(3),产率92%。该产品的核磁分析数据如下:1H NMR.(400MHz,CDCl3):δ8.15(d,1H),7.69-7.93(m,5H),7.60(d,2H),7.05-7.41(m,9H),2.33(s,6H)。The preparation of 2-(3-methylbiphenyl)-6-(3-methylphenyl)quinoline, that is, compound (3): under the protection of inert gas (such as high-purity nitrogen), add 10ml of Schlek reaction tube (A glass instrument commonly used in anhydrous and oxygen-free operation) Add 1.0mmol p-bromoacetophenone, 1.5mmol 2-amino-5-bromobenzyl alcohol, 3.5mmol 3-methylphenylboronic acid, 0.02mmol RuCl 2 (DMSO) 4 , 0.05mmol palladium acetate, 0.12mmol triphenylphosphine, 6.0mmol sodium carbonate and 5ml toluene, replace the reaction tube with nitrogen for 3 times, then heat to 110° C. in an oil bath under magnetic stirring, and react at reflux for 24 hours. Remove the oil bath, and the water bath is down to room temperature; add 3ml of water to the reaction solution, extract three times with 5ml of dichloromethane, combine the organic phases and use anhydrous MgSO Dry for 30 minutes, filter; the filtrate is concentrated with a rotary evaporator, and the concentrated solid Using dichloromethane as solvent, the pure product compound (3) was obtained by recrystallization with a yield of 92%. The nuclear magnetic analysis data of this product are as follows: 1 H NMR.(400MHz, CDCl 3 ):δ8.15(d,1H),7.69-7.93(m,5H),7.60(d,2H),7.05-7.41(m, 9H), 2.33(s, 6H).
实施例5Example 5
2-(2-甲基联苯基)-6-(2-甲基苯基)喹啉即化合物(4)的制备:在惰性气体(如高纯氮气)保护下,向10ml的Schlek反应管(无水无氧操作时常用的一种玻璃仪器)加入1.0mmol对溴苯乙酮、1.8mmol2-氨基-5-溴苯甲醇、5.0mmol2-甲基苯硼酸、0.03mmol RuCl2(DMSO)4、0.1mmol醋酸钯、0.15mmol三苯基膦和8.0mmol碳酸钾和8ml苯,用氮气置换反应管3次,然后在磁力搅拌下用油浴加热至100℃,反应回流48小时。去掉油浴,水浴降到室温;向反应液加3ml水,用5ml的二氯甲烷萃取三次,合并有机相并用无水MgSO4干燥30分钟,过滤;滤液用旋转蒸发器浓缩,浓缩后的固体以二氯甲烷为溶剂,重结晶得到纯产品化合物(4),产率89%。该产品的核磁分析数据如下:1H NMR.(400MHz,CDCl3):δ8.18(d,1H),7.79-8.06(m,5H),7.62(d,2H),7.14-7.45(m,9H),2.39(s,6H)。The preparation of 2-(2-methylbiphenyl)-6-(2-methylphenyl)quinoline, that is, compound (4): under the protection of inert gas (such as high-purity nitrogen), add 10ml of Schlek reaction tube (A glass instrument commonly used in anhydrous and oxygen-free operation) Add 1.0mmol p-bromoacetophenone, 1.8mmol 2-amino-5-bromobenzyl alcohol, 5.0mmol 2-methylphenylboronic acid, 0.03mmol RuCl 2 (DMSO) 4 , 0.1mmol palladium acetate, 0.15mmol triphenylphosphine, 8.0mmol potassium carbonate and 8ml benzene, replace the reaction tube with nitrogen for 3 times, then heat to 100° C. in an oil bath under magnetic stirring, and reflux for 48 hours. Remove the oil bath, and the water bath is down to room temperature; add 3ml of water to the reaction solution, extract three times with 5ml of dichloromethane, combine the organic phases and use anhydrous MgSO Dry for 30 minutes, filter; the filtrate is concentrated with a rotary evaporator, and the concentrated solid Using dichloromethane as solvent, the pure product compound (4) was obtained by recrystallization with a yield of 89%. The nuclear magnetic analysis data of this product are as follows: 1 H NMR.(400MHz, CDCl 3 ):δ8.18(d,1H),7.79-8.06(m,5H),7.62(d,2H),7.14-7.45(m, 9H), 2.39(s, 6H).
实施例6Example 6
2-(4-甲氧基联苯基)-6-(4-甲氧基苯基)喹啉即化合物(5)的制备:在惰性气体(如高纯氮气)保护下,向10ml的Schlek反应管(无水无氧操作时常用的一种玻璃仪器)加入1.0mmol对溴苯乙酮、2.0mmol2-氨基-5-溴苯甲醇、4.5mmol对甲氧基苯硼酸、0.05mmol RuCl2(DMSO)4、0.05mmol醋酸钯、0.1mmol三苯基膦和7.0mmol氢氧化钠和5ml四氢呋喃,用氮气置换反应管3次,然后在磁力搅拌下用油浴加热至80℃,反应回流36小时。去掉油浴,水浴降到室温;向反应液加3ml水,用5ml的二氯甲烷萃取三次,合并有机相并用无水MgSO4干燥30分钟,过滤;滤液用旋转蒸发器浓缩,浓缩后的固体以二氯甲烷为溶剂,重结晶得到纯产品化合物(5),产率92%。该产品的核磁分析数据如下:1H NMR.(400MHz,CDCl3):δ8.09(d,1H),7.71-8.04(m,5H),7.60(d,2H),7.42-7.48(m,5H),6.86(d,4H),3.71(s,6H)。2-(4-methoxybiphenyl)-6-(4-methoxyphenyl)quinoline is the preparation of compound (5): under the protection of inert gas (such as high-purity nitrogen), add 10ml of Schlek Add 1.0mmol p-bromoacetophenone, 2.0mmol 2-amino-5-bromobenzyl alcohol, 4.5mmol p-methoxyphenylboronic acid, 0.05mmol RuCl 2 ( DMSO) 4 , 0.05mmol palladium acetate, 0.1mmol triphenylphosphine, 7.0mmol sodium hydroxide and 5ml tetrahydrofuran, replace the reaction tube with nitrogen for 3 times, then heat to 80°C with an oil bath under magnetic stirring, and reflux for 36 hours . Remove the oil bath, and the water bath is down to room temperature; add 3ml of water to the reaction solution, extract three times with 5ml of dichloromethane, combine the organic phases and use anhydrous MgSO Dry for 30 minutes, filter; the filtrate is concentrated with a rotary evaporator, and the concentrated solid Using dichloromethane as solvent, the pure product compound (5) was obtained by recrystallization with a yield of 92%. The nuclear magnetic analysis data of this product are as follows: 1 H NMR.(400MHz, CDCl 3 ):δ8.09(d,1H),7.71-8.04(m,5H),7.60(d,2H),7.42-7.48(m, 5H), 6.86(d, 4H), 3.71(s, 6H).
实施例7Example 7
2-(3-甲氧基联苯基)-6-(3-甲氧基苯基)喹啉即化合物(6)的制备:在惰性气体(如高纯氮气)保护下,向10ml的Schlek反应管(无水无氧操作时常用的一种玻璃仪器)加入1.0mmol对溴苯乙酮、1.1mmol2-氨基-5-溴苯甲醇、4mmol3-甲基苯硼酸、0.06mmol RuCl2(DMSO)4、0.08mmol氯化钯、0.16mmol三苯基膦和8.0mmol碳酸钠和7ml二氧六环,用氮气置换反应管3次,然后在磁力搅拌下用油浴加热至110℃,反应回流24小时。去掉油浴,水浴降到室温;向反应液加3ml水,用5ml的二氯甲烷萃取三次,合并有机相并用无水MgSO4干燥30分钟,过滤;滤液用旋转蒸发器浓缩,浓缩后的固体以二氯甲烷为溶剂,重结晶得到纯产品化合物(6),产率90%。该产品的核磁分析数据如下:1H NMR.(400MHz,CDCl3):δ8.10(d,1H),7.72-8.04(m,5H),7.62(d,2H),6.78-7.43(m,9H),3.75(s,6H)。2-(3-methoxybiphenyl)-6-(3-methoxyphenyl)quinoline is the preparation of compound (6): under the protection of inert gas (such as high-purity nitrogen), add 10ml of Schlek Add 1.0mmol p-bromoacetophenone, 1.1mmol 2-amino-5-bromobenzyl alcohol, 4mmol 3-methylphenylboronic acid, 0.06mmol RuCl 2 (DMSO) to the reaction tube (a glass instrument commonly used in anhydrous and oxygen-free operation) 4. 0.08mmol palladium chloride, 0.16mmol triphenylphosphine, 8.0mmol sodium carbonate and 7ml dioxane, replace the reaction tube with nitrogen for 3 times, then heat to 110°C with an oil bath under magnetic stirring, and reflux for 24 Hour. Remove the oil bath, and the water bath is down to room temperature; add 3ml of water to the reaction solution, extract three times with 5ml of dichloromethane, combine the organic phases and use anhydrous MgSO Dry for 30 minutes, filter; the filtrate is concentrated with a rotary evaporator, and the concentrated solid Using dichloromethane as solvent, the pure product compound (6) was obtained by recrystallization with a yield of 90%. The nuclear magnetic analysis data of this product are as follows: 1 H NMR.(400MHz, CDCl 3 ):δ8.10(d,1H),7.72-8.04(m,5H),7.62(d,2H),6.78-7.43(m, 9H), 3.75(s, 6H).
实施例8Example 8
2-(2-甲氧基联苯基)-6-(2-甲氧基苯基)喹啉即化合物(7)的制备:在惰性气体(如高纯氮气)保护下,向10ml的Schlek反应管(无水无氧操作时常用的一种玻璃仪器)加入1.0mmol对溴苯乙酮、2mmol2-氨基-5-溴苯甲醇、6mmol3-甲基苯硼酸、0.1mmol RuCl2(DMSO)4、0.1mmol醋酸钯、0.2mmol三苯基膦和8.0mmol碳酸钠和5ml二氧六环,用氮气置换反应管3次,然后在磁力搅拌下用油浴加热至110℃,反应回流48小时。去掉油浴,水浴降到室温;向反应液加3ml水,用5ml的二氯甲烷萃取三次,合并有机相并用无水MgSO4干燥30分钟,过滤;滤液用旋转蒸发器浓缩,浓缩后的固体以二氯甲烷为溶剂,重结晶得到纯产品化合物(7),产率84%。该产品的核磁分析数据如下:1H NMR.(400MHz,CDCl3):δ8.09(d,1H),7.70-8.04(m,5H),7.56(d,2H),6.87-7.42(m,9H),3.81(s,6H)。2-(2-methoxybiphenyl)-6-(2-methoxyphenyl)quinoline is the preparation of compound (7): under the protection of inert gas (such as high-purity nitrogen), add 10ml of Schlek Add 1.0mmol p-bromoacetophenone, 2mmol 2-amino-5-bromobenzyl alcohol, 6mmol 3-methylphenylboronic acid, 0.1mmol RuCl 2 (DMSO) 4 , 0.1mmol palladium acetate, 0.2mmol triphenylphosphine, 8.0mmol sodium carbonate and 5ml dioxane, replace the reaction tube with nitrogen for 3 times, then heat to 110° C. in an oil bath under magnetic stirring, and react at reflux for 48 hours. Remove the oil bath, and the water bath is down to room temperature; add 3ml of water to the reaction solution, extract three times with 5ml of dichloromethane, combine the organic phases and use anhydrous MgSO Dry for 30 minutes, filter; the filtrate is concentrated with a rotary evaporator, and the concentrated solid Using dichloromethane as a solvent, the pure product compound (7) was obtained by recrystallization with a yield of 84%. The nuclear magnetic analysis data of this product are as follows: 1 H NMR.(400MHz, CDCl 3 ):δ8.09(d,1H),7.70-8.04(m,5H),7.56(d,2H),6.87-7.42(m, 9H), 3.81(s, 6H).
实施例9Example 9
2-(3-甲酸甲酯基联苯基)-6-(3-甲酸甲酯基苯基)喹啉即化合物(8)的制备:在惰性气体(如高纯氮气)保护下,向10ml的Schlek反应管(无水无氧操作时常用的一种玻璃仪器)加入1.0mmol对溴苯乙酮、1.6mmol2-氨基-5-溴苯甲醇、4.5mmol3-甲酸甲酯苯硼酸、0.08mmol RuCl2(DMSO)4、0.09mmol醋酸钯、0.18mmol三苯基膦和7.0mmol氢氧化钾和6ml苯,用氮气置换反应管3次,然后在磁力搅拌下用油浴加热至100℃,反应回流24小时。去掉油浴,水浴降到室温;向反应液加3ml水,用5ml的二氯甲烷萃取三次,合并有机相并用无水MgSO4干燥30分钟,过滤;滤液用旋转蒸发器浓缩,浓缩后的固体以二氯甲烷为溶剂,重结晶得到纯产品化合物(8),产率92%。该产品的核磁分析数据如下:1H NMR.(400MHz,CDCl3):δ8.07-8.21(m,5H),7.42-7.95(m,12H),3.86(s,6H)。The preparation of 2-(3-methylcarboxybiphenyl)-6-(3-methylcarboxyphenyl)quinoline, compound (8): under the protection of inert gas (such as high-purity nitrogen), add 10ml Add 1.0mmol of p-bromoacetophenone, 1.6mmol of 2-amino-5-bromobenzyl alcohol, 4.5mmol of 3-methyl phenylboronic acid, 0.08mmol of RuCl 2 (DMSO) 4 , 0.09mmol palladium acetate, 0.18mmol triphenylphosphine, 7.0mmol potassium hydroxide and 6ml benzene, replace the reaction tube with nitrogen for 3 times, then heat to 100°C with an oil bath under magnetic stirring, and react to reflux 24 hours. Remove the oil bath, and the water bath is down to room temperature; add 3ml of water to the reaction solution, extract three times with 5ml of dichloromethane, combine the organic phases and use anhydrous MgSO Dry for 30 minutes, filter; the filtrate is concentrated with a rotary evaporator, and the concentrated solid Using dichloromethane as solvent, the pure product compound (8) was obtained by recrystallization with a yield of 92%. The nuclear magnetic analysis data of this product are as follows: 1 H NMR. (400MHz, CDCl 3 ): δ8.07-8.21 (m, 5H), 7.42-7.95 (m, 12H), 3.86 (s, 6H).
实施例10Example 10
2-(4-甲酸甲酯基联苯基)-6-(4-甲酸甲酯基苯基)喹啉即化合物(9)的制备:在惰性气体(如高纯氮气)保护下,向10ml的Schlek反应管(无水无氧操作时常用的一种玻璃仪器)加入1.0mmol对溴苯乙酮、1.3mmol2-氨基-5-溴苯甲醇、5.5mmol4-甲酸甲酯苯硼酸、0.04mmol RuCl2(DMSO)4、0.06mmol氯化钯、0.15mmol三苯基膦和7.0mmol碳酸钠和10ml甲苯,用氮气置换反应管3次,然后在磁力搅拌下用油浴加热至120℃,反应回流30小时。去掉油浴,水浴降到室温;向反应液加3ml水,用5ml的二氯甲烷萃取三次,合并有机相并用无水MgSO4干燥30分钟,过滤;滤液用旋转蒸发器浓缩,浓缩后的固体以二氯甲烷为溶剂,重结晶得到纯产品化合物(9),产率93%。该产品的核磁分析数据如下:1H NMR.(400MHz,CDCl3):δ8.06-8.13(m,7H),7.74-7.91(m,3H),7.45-7.62(m,7H),3.89(s,6H)。The preparation of 2-(4-methylcarboxybiphenyl)-6-(4-methylcarboxyphenyl)quinoline, compound (9): under the protection of inert gas (such as high-purity nitrogen), add 10ml Add 1.0mmol of p-bromoacetophenone, 1.3mmol of 2-amino-5-bromobenzyl alcohol, 5.5mmol of 4-methyl phenylboronic acid, 0.04mmol of RuCl 2 (DMSO) 4 , 0.06mmol palladium chloride, 0.15mmol triphenylphosphine, 7.0mmol sodium carbonate and 10ml toluene, replace the reaction tube with nitrogen for 3 times, then heat to 120°C with an oil bath under magnetic stirring, and react to reflux 30 hours. Remove the oil bath, and the water bath is down to room temperature; add 3ml of water to the reaction solution, extract three times with 5ml of dichloromethane, combine the organic phases and use anhydrous MgSO Dry for 30 minutes, filter; the filtrate is concentrated with a rotary evaporator, and the concentrated solid Using dichloromethane as solvent, the pure product compound (9) was obtained by recrystallization with a yield of 93%. The nuclear magnetic analysis data of this product are as follows: 1 H NMR.(400MHz, CDCl 3 ):δ8.06-8.13(m,7H),7.74-7.91(m,3H),7.45-7.62(m,7H),3.89( s, 6H).
实施例11Example 11
2-(4-乙基联苯基)-6-(4-乙基苯基)喹啉即化合物(10)的制备:在惰性气体(如高纯氮气)保护下,向10ml的Schlek反应管(无水无氧操作时常用的一种玻璃仪器)加入1.0mmol对溴苯乙酮、1.7mmol2-氨基-5-溴苯甲醇、4.5mmol4-乙基苯硼酸、0.03mmol RuCl2(DMSO)4、0.04mmol氯化钯、0.16mmol三苯基膦和6.0mmol碳酸钠和5ml二氧六环,用氮气置换反应管3次,然后在磁力搅拌下用油浴加热至110℃,反应回流36小时。去掉油浴,水浴降到室温;向反应液加3ml水,用5ml的二氯甲烷萃取三次,合并有机相并用无水MgSO4干燥30分钟,过滤;滤液用旋转蒸发器浓缩,浓缩后的固体以二氯甲烷为溶剂,重结晶得到纯产品化合物(10),产率91%。该产品的核磁分析数据如下:1H NMR.(400MHz,CDCl3):δ8.04-8.10(m,3H),7.70-7.89(m,3H),7.41-7.56(m,7H),7.17(d,4H),2.58(m,4H),1.25(t,6H)。2-(4-Ethylbiphenyl)-6-(4-ethylphenyl)quinoline is the preparation of compound (10): under the protection of inert gas (such as high-purity nitrogen), add 10ml Schlek reaction tube (A glass instrument commonly used in anhydrous and oxygen-free operation) Add 1.0mmol p-bromoacetophenone, 1.7mmol 2-amino-5-bromobenzyl alcohol, 4.5mmol 4-ethylphenylboronic acid, 0.03mmol RuCl 2 (DMSO) 4 , 0.04mmol palladium chloride, 0.16mmol triphenylphosphine, 6.0mmol sodium carbonate and 5ml dioxane, replace the reaction tube with nitrogen for 3 times, then heat to 110°C with an oil bath under magnetic stirring, and react at reflux for 36 hours . Remove the oil bath, and the water bath is down to room temperature; add 3ml of water to the reaction solution, extract three times with 5ml of dichloromethane, combine the organic phases and use anhydrous MgSO Dry for 30 minutes, filter; the filtrate is concentrated with a rotary evaporator, and the concentrated solid Using dichloromethane as solvent, the pure product compound (10) was obtained by recrystallization with a yield of 91%. The nuclear magnetic analysis data of this product are as follows: 1 H NMR.(400MHz, CDCl 3 ): δ8.04-8.10(m,3H),7.70-7.89(m,3H),7.41-7.56(m,7H),7.17( d, 4H), 2.58(m, 4H), 1.25(t, 6H).
实施例12Example 12
2-(4-醛基联苯基)-6-(4-醛基苯基)喹啉即化合物(11)的制备:在惰性气体(如高纯氮气)保护下,向10ml的Schlek反应管(无水无氧操作时常用的一种玻璃仪器)加入1.0mmol对溴苯乙酮、1.6mmol2-氨基-5-溴苯甲醇、5mmol4-醛基苯硼酸、0.02mmol RuCl2(DMSO)4、0.09mmol醋酸钯、0.19mmol三苯基膦和8.0mmol碳酸钠和8ml二氧六环,用氮气置换反应管3次,然后在磁力搅拌下用油浴加热至110℃,反应回流8小时。去掉油浴,水浴降到室温;向反应液加3ml水,用5ml的二氯甲烷萃取三次,合并有机相并用无水MgSO4干燥30分钟,过滤;滤液用旋转蒸发器浓缩,浓缩后的固体以二氯甲烷为溶剂,重结晶得到纯产品化合物(11),产率82%。该产品的核磁分析数据如下:1H NMR.(400MHz,CDCl3):δ9.90(s,2H),8.07-8.14(m,3H),7.73-7.91(m,6H),7.45-7.68(m,8H)。The preparation of 2-(4-formyl biphenyl)-6-(4-formylphenyl)quinoline, that is, compound (11): under the protection of inert gas (such as high-purity nitrogen), transfer to a 10ml Schlek reaction tube (A glass instrument commonly used in anhydrous and oxygen-free operation) Add 1.0mmol p-bromoacetophenone, 1.6mmol 2-amino-5-bromobenzyl alcohol, 5mmol 4-formyl phenylboronic acid, 0.02mmol RuCl 2 (DMSO) 4 , 0.09mmol palladium acetate, 0.19mmol triphenylphosphine, 8.0mmol sodium carbonate and 8ml dioxane, the reaction tube was replaced with nitrogen for 3 times, then heated to 110°C in an oil bath under magnetic stirring, and the reaction was refluxed for 8 hours. Remove the oil bath, and the water bath is down to room temperature; add 3ml of water to the reaction solution, extract three times with 5ml of dichloromethane, combine the organic phases and use anhydrous MgSO Dry for 30 minutes, filter; the filtrate is concentrated with a rotary evaporator, and the concentrated solid Using dichloromethane as solvent, the pure product compound (11) was obtained by recrystallization with a yield of 82%. The nuclear magnetic analysis data of this product are as follows: 1 H NMR.(400MHz, CDCl 3 ): δ9.90(s, 2H), 8.07-8.14(m, 3H), 7.73-7.91(m, 6H), 7.45-7.68( m, 8H).
实施例13Example 13
2-(4-氰基联苯基)-6-(4-氰基苯基)喹啉即化合物(12)的制备:在惰性气体(如高纯氮气)保护下,向10ml的Schlek反应管(无水无氧操作时常用的一种玻璃仪器)加入1.0mmol对溴苯乙酮、1.5mmol2-氨基-5-溴苯甲醇、4.5mmol4-氰基苯硼酸、0.04mmol RuCl2(DMSO)4、0.07mmol氯化钯、0.15mmol三苯基膦和8.0mmol氢氧化钾和9ml甲苯,用氮气置换反应管3次,然后在磁力搅拌下用油浴加热至110℃,反应回流18小时。去掉油浴,水浴降到室温;向反应液加3ml水,用5ml的二氯甲烷萃取三次,合并有机相并用无水MgSO4干燥30分钟,过滤;滤液用旋转蒸发器浓缩,浓缩后的固体以二氯甲烷为溶剂,重结晶得到纯产品化合物(12),产率87%。该产品的核磁分析数据如下:1H NMR.(400MHz,CDCl3):δ8.08-8.16(m,3H),7.75-7.94(m,6H),7.47-7.69(m,8H)。2-(4-cyanobiphenyl)-6-(4-cyanophenyl)quinoline is the preparation of compound (12): under the protection of inert gas (such as high-purity nitrogen), add 10ml Schlek reaction tube (A glass instrument commonly used in anhydrous and oxygen-free operation) Add 1.0mmol p-bromoacetophenone, 1.5mmol 2-amino-5-bromobenzyl alcohol, 4.5mmol 4-cyanophenylboronic acid, 0.04mmol RuCl 2 (DMSO) 4 , 0.07mmol palladium chloride, 0.15mmol triphenylphosphine, 8.0mmol potassium hydroxide and 9ml toluene, replace the reaction tube with nitrogen for 3 times, then heat to 110° C. in an oil bath under magnetic stirring, and reflux for 18 hours. Remove the oil bath, and the water bath is down to room temperature; add 3ml of water to the reaction solution, extract three times with 5ml of dichloromethane, combine the organic phases and use anhydrous MgSO Dry for 30 minutes, filter; the filtrate is concentrated with a rotary evaporator, and the concentrated solid Using dichloromethane as solvent, the pure product compound (12) was obtained by recrystallization with a yield of 87%. The nuclear magnetic analysis data of this product are as follows: 1 H NMR. (400MHz, CDCl 3 ): δ8.08-8.16 (m, 3H), 7.75-7.94 (m, 6H), 7.47-7.69 (m, 8H).
实施例14Example 14
2-(4-硝基联苯基)-6-(4-硝基苯基)喹啉即化合物(13)的制备:在惰性气体(如高纯氮气)保护下,向10ml的Schlek反应管(无水无氧操作时常用的一种玻璃仪器)加入1.0mmol对溴苯乙酮、1.6mmol2-氨基-5-溴苯甲醇、3.5mmol4-硝基苯硼酸、0.08mmol RuCl2(DMSO)4、0.1mmol醋酸钯、0.2mmol三苯基膦和8.0mmol碳酸钠和5ml二氧六环,用氮气置换反应管3次,然后在磁力搅拌下用油浴加热至110℃,反应回流30小时。去掉油浴,水浴降到室温;向反应液加3ml水,用5ml的二氯甲烷萃取三次,合并有机相并用无水MgSO4干燥30分钟,过滤;滤液用旋转蒸发器浓缩,浓缩后的固体以二氯甲烷为溶剂,重结晶得到纯产品化合物(13),产率84%。该产品的核磁分析数据如下:1H NMR.(400MHz,CDCl3):δ8.07-8.29(m,7H),7.74-7.95(m,7H),7.46-7.61(m,3H)。The preparation of 2-(4-nitrobiphenyl)-6-(4-nitrophenyl)quinoline, that is, compound (13): under the protection of an inert gas (such as high-purity nitrogen), add a 10ml Schlek reaction tube (A glass instrument commonly used in anhydrous and oxygen-free operation) Add 1.0mmol p-bromoacetophenone, 1.6mmol 2-amino-5-bromobenzyl alcohol, 3.5mmol 4-nitrophenylboronic acid, 0.08mmol RuCl 2 (DMSO) 4 , 0.1mmol palladium acetate, 0.2mmol triphenylphosphine, 8.0mmol sodium carbonate and 5ml dioxane, replace the reaction tube with nitrogen for 3 times, then heat to 110°C with an oil bath under magnetic stirring, and react at reflux for 30 hours. Remove the oil bath, and the water bath is down to room temperature; add 3ml of water to the reaction solution, extract three times with 5ml of dichloromethane, combine the organic phases and use anhydrous MgSO Dry for 30 minutes, filter; the filtrate is concentrated with a rotary evaporator, and the concentrated solid Using dichloromethane as solvent, the pure product compound (13) was obtained by recrystallization with a yield of 84%. The nuclear magnetic analysis data of the product are as follows: 1 H NMR. (400MHz, CDCl 3 ): δ8.07-8.29 (m, 7H), 7.74-7.95 (m, 7H), 7.46-7.61 (m, 3H).
实施例15Example 15
2-(3-硝基联苯基)-6-(3-硝基苯基)喹啉即化合物(14)的制备:在惰性气体(如高纯氮气)保护下,向10ml的Schlek反应管(无水无氧操作时常用的一种玻璃仪器)加入1.0mmol对溴苯乙酮、1.4mmol2-氨基-5-溴苯甲醇、3.5mmol3-硝基苯硼酸、0.09mmol RuCl2(DMSO)4、0.08mmol氯化钯、0.16mmol三苯基膦和7.0mmol碳酸钠和10ml苯,用氮气置换反应管3次,然后在磁力搅拌下用油浴加热至100℃,反应回流36小时。去掉油浴,水浴降到室温;向反应液加3ml水,用5ml的二氯甲烷萃取三次,合并有机相并用无水MgSO4干燥30分钟,过滤;滤液用旋转蒸发器浓缩,浓缩后的固体以二氯甲烷为溶剂,重结晶得到纯产品化合物(14),产率80%。该产品的核磁分析数据如下:1H NMR.(400MHz,CDCl3):δ8.09-8.42(m,7H),7.76-7.98(m,5H),7.46-7.64(m,5H)。The preparation of 2-(3-nitrobiphenyl)-6-(3-nitrophenyl)quinoline, that is, compound (14): under the protection of an inert gas (such as high-purity nitrogen), add a 10ml Schlek reaction tube (A glass instrument commonly used in anhydrous and oxygen-free operation) Add 1.0mmol p-bromoacetophenone, 1.4mmol 2-amino-5-bromobenzyl alcohol, 3.5mmol 3-nitrophenylboronic acid, 0.09mmol RuCl 2 (DMSO) 4 , 0.08mmol palladium chloride, 0.16mmol triphenylphosphine, 7.0mmol sodium carbonate and 10ml benzene, replace the reaction tube with nitrogen for 3 times, then heat to 100° C. in an oil bath under magnetic stirring, and reflux for 36 hours. Remove the oil bath, and the water bath is down to room temperature; add 3ml of water to the reaction solution, extract three times with 5ml of dichloromethane, combine the organic phases and use anhydrous MgSO Dry for 30 minutes, filter; the filtrate is concentrated with a rotary evaporator, and the concentrated solid Using dichloromethane as solvent, the pure product compound (14) was obtained by recrystallization with a yield of 80%. The nuclear magnetic analysis data of this product are as follows: 1 H NMR. (400MHz, CDCl 3 ): δ8.09-8.42 (m, 7H), 7.76-7.98 (m, 5H), 7.46-7.64 (m, 5H).
实施例16Example 16
2-(4-氟联苯基)-6-(4-氟苯基)喹啉即化合物(15)的制备:在惰性气体(如高纯氮气)保护下,向10ml的Schlek反应管(无水无氧操作时常用的一种玻璃仪器)加入1.0mmol对溴苯乙酮、1.6mmol2-氨基-5-溴苯甲醇、3mmol4-氟苯硼酸、0.06mmol RuCl2(DMSO)4、0.1mmol醋酸钯、0.2mmol三苯基膦和8.0mmol氢氧化钾和5ml四氢呋喃,用氮气置换反应管3次,然后在磁力搅拌下用油浴加热至80℃,反应回流48小时。去掉油浴,水浴降到室温;向反应液加3ml水,用5ml的二氯甲烷萃取三次,合并有机相并用无水MgSO4干燥30分钟,过滤;滤液用旋转蒸发器浓缩,浓缩后的固体以二氯甲烷为溶剂,重结晶得到纯产品化合物(15),产率87%。该产品的核磁分析数据如下:1H NMR.(400MHz,CDCl3):δ8.15(d,1H),8.07(d,2H),7.76-7.94(m,3H),7.45-7.62(m,7H),7.09(d,4H)。The preparation of 2-(4-fluorobiphenyl)-6-(4-fluorophenyl)quinoline, that is, compound (15): under the protection of inert gas (such as high-purity nitrogen), transfer to a 10ml Schlek reaction tube (without A glass instrument commonly used in water anaerobic operation) add 1.0mmol p-bromoacetophenone, 1.6mmol 2-amino-5-bromobenzyl alcohol, 3mmol 4-fluorophenylboronic acid, 0.06mmol RuCl 2 (DMSO) 4 , 0.1mmol acetic acid Palladium, 0.2mmol triphenylphosphine, 8.0mmol potassium hydroxide and 5ml tetrahydrofuran were used to replace the reaction tube with nitrogen for 3 times, then heated to 80°C with an oil bath under magnetic stirring, and the reaction was refluxed for 48 hours. Remove the oil bath, and the water bath is down to room temperature; add 3ml of water to the reaction solution, extract three times with 5ml of dichloromethane, combine the organic phases and use anhydrous MgSO Dry for 30 minutes, filter; the filtrate is concentrated with a rotary evaporator, and the concentrated solid Using dichloromethane as solvent, the pure product compound (15) was obtained by recrystallization with a yield of 87%. The nuclear magnetic analysis data of this product are as follows: 1 H NMR.(400MHz, CDCl 3 ): δ8.15(d,1H),8.07(d,2H),7.76-7.94(m,3H),7.45-7.62(m, 7H), 7.09(d, 4H).
实施例17Example 17
2-[4-(1-萘基)苯基]-6-(1-萘基)喹啉即化合物(16)的制备:在惰性气体(如高纯氮气)保护下,向10ml的Schlek反应管(无水无氧操作时常用的一种玻璃仪器)加入1.0mmol对溴苯乙酮、1.8mmol2-氨基-5-溴苯甲醇、4mmol1-萘基硼酸、0.05mmol RuCl2(DMSO)4、0.08mmol氯化钯、0.16mmol三苯基膦和8.0mmol碳酸钠和10ml二氧六环,用氮气置换反应管3次,然后在磁力搅拌下用油浴加热至110℃,反应回流12小时。去掉油浴,水浴降到室温;向反应液加3ml水,用5ml的二氯甲烷萃取三次,合并有机相并用无水MgSO4干燥30分钟,过滤;滤液用旋转蒸发器浓缩,浓缩后的固体以二氯甲烷为溶剂,重结晶得到纯产品化合物(16),产率91%。该产品的核磁分析数据如下:1H NMR.(400MHz,CDCl3):δ8.13(d,1H),8.07(d,2H),7.71-7.95(m,3H),7.62-7.69(m,10H),7.33-7.54(m,7H)。2-[4-(1-naphthyl)phenyl]-6-(1-naphthyl)quinoline is the preparation of compound (16): under the protection of inert gas (such as high-purity nitrogen), react with 10ml of Schlek Add 1.0 mmol p-bromoacetophenone, 1.8 mmol 2-amino-5-bromobenzyl alcohol, 4 mmol 1-naphthylboronic acid, 0.05 mmol RuCl 2 (DMSO) 4 , 0.08mmol of palladium chloride, 0.16mmol of triphenylphosphine, 8.0mmol of sodium carbonate and 10ml of dioxane were used to replace the reaction tube with nitrogen for 3 times, then heated to 110°C in an oil bath under magnetic stirring, and the reaction was refluxed for 12 hours. Remove the oil bath, and the water bath is down to room temperature; add 3ml of water to the reaction solution, extract three times with 5ml of dichloromethane, combine the organic phases and use anhydrous MgSO Dry for 30 minutes, filter; the filtrate is concentrated with a rotary evaporator, and the concentrated solid Using dichloromethane as solvent, the pure product compound (16) was obtained by recrystallization with a yield of 91%. The nuclear magnetic analysis data of this product are as follows: 1 H NMR.(400MHz, CDCl 3 ): δ8.13(d,1H),8.07(d,2H),7.71-7.95(m,3H),7.62-7.69(m, 10H), 7.33-7.54 (m, 7H).
实施例18Example 18
2-[4-(4-甲基-1-萘基)苯基]-6-(4-甲基-1-萘基)喹啉即化合物(17)的制备:在惰性气体(如高纯氮气)保护下,向10ml的Schlek反应管(无水无氧操作时常用的一种玻璃仪器)加入1.0mmol对溴苯乙酮、1.4mmol2-氨基-5-溴苯甲醇、6mmol4-甲基-1-萘基硼酸、0.07mmol RuCl2(DMSO)4、0.08mmol醋酸钯、0.2mmol三苯基膦和8.0mmol碳酸钠和5ml甲苯,用氮气置换反应管3次,然后在磁力搅拌下用油浴加热至120℃,反应回流30小时。去掉油浴,水浴降到室温;向反应液加3ml水,用5ml的二氯甲烷萃取三次,合并有机相并用无水MgSO4干燥30分钟,过滤;滤液用旋转蒸发器浓缩,浓缩后的固体以二氯甲烷为溶剂,重结晶得到纯产品化合物(17),产率94%。该产品的核磁分析数据如下:1H NMR.(400MHz,CDCl3):δ8.10(d,1H),8.04(d,2H),7.73-7.92(m,5H),7.42-7.65(m,7H),7.15-7.33(m,6H),2.66(s,6H)。2-[4-(4-methyl-1-naphthyl)phenyl]-6-(4-methyl-1-naphthyl)quinoline is the preparation of compound (17): in an inert gas (such as high-purity Under the protection of nitrogen), add 1.0mmol of p-bromoacetophenone, 1.4mmol of 2-amino-5-bromobenzyl alcohol, 6mmol of 4-methyl- 1-Naphthylboronic acid, 0.07mmol RuCl 2 (DMSO) 4 , 0.08mmol palladium acetate, 0.2mmol triphenylphosphine and 8.0mmol sodium carbonate and 5ml toluene, replace the reaction tube with nitrogen 3 times, then wash with oil under magnetic stirring The bath was heated to 120°C and the reaction was refluxed for 30 hours. Remove the oil bath, and the water bath is down to room temperature; add 3ml of water to the reaction solution, extract three times with 5ml of dichloromethane, combine the organic phases and use anhydrous MgSO Dry for 30 minutes, filter; the filtrate is concentrated with a rotary evaporator, and the concentrated solid Using dichloromethane as solvent, the pure product compound (17) was obtained by recrystallization with a yield of 94%. The nuclear magnetic analysis data of this product are as follows: 1 H NMR.(400MHz, CDCl 3 ): δ8.10(d,1H),8.04(d,2H),7.73-7.92(m,5H),7.42-7.65(m, 7H), 7.15-7.33 (m, 6H), 2.66 (s, 6H).
实施例19Example 19
2-[4-(5-甲基-1-萘基)苯基]-6-(5-甲基-1-萘基)喹啉即化合物(18)的制备:在惰性气体(如高纯氮气)保护下,向10ml的Schlek反应管(无水无氧操作时常用的一种玻璃仪器)加入1.0mmol对溴苯乙酮、1.7mmol2-氨基-5-溴苯甲醇、6mmol3-甲基苯硼酸、0.05mmol RuCl2(DMSO)4、0.07mmol氯化钯、0.16mmol三苯基膦和7.0mmol碳酸钠和8ml二氧六环,用氮气置换反应管3次,然后在磁力搅拌下用油浴加热至110℃,反应回流20小时。去掉油浴,水浴降到室温;向反应液加3ml水,用5ml的二氯甲烷萃取三次,合并有机相并用无水MgSO4干燥30分钟,过滤;滤液用旋转蒸发器浓缩,浓缩后的固体以二氯甲烷为溶剂,重结晶得到纯产品化合物(18),产率87%。该产品的核磁分析数据如下:1H NMR.(400MHz,CDCl3):δ8.15(d,1H),8.06(d,2H),7.74-7.92(m,5H),7.44-7.58(m,7H),7.11-7.39(m,6H),2.69(s,6H)。2-[4-(5-methyl-1-naphthyl)phenyl]-6-(5-methyl-1-naphthyl)quinoline is the preparation of compound (18): in an inert gas (such as high-purity Under the protection of nitrogen), add 1.0mmol of p-bromoacetophenone, 1.7mmol of 2-amino-5-bromobenzyl alcohol, 6mmol of 3-methylbenzene Boric acid, 0.05mmol RuCl 2 (DMSO) 4 , 0.07mmol palladium chloride, 0.16mmol triphenylphosphine and 7.0mmol sodium carbonate and 8ml dioxane, replace the reaction tube with nitrogen gas 3 times, then wash with oil under magnetic stirring The bath was heated to 110°C and the reaction was refluxed for 20 hours. Remove the oil bath, and the water bath is down to room temperature; add 3ml of water to the reaction solution, extract three times with 5ml of dichloromethane, combine the organic phases and use anhydrous MgSO Dry for 30 minutes, filter; the filtrate is concentrated with a rotary evaporator, and the concentrated solid Using dichloromethane as solvent, the pure product compound (18) was obtained by recrystallization with a yield of 87%. The nuclear magnetic analysis data of this product are as follows: 1 H NMR.(400MHz, CDCl 3 ): δ8.15(d,1H),8.06(d,2H),7.74-7.92(m,5H),7.44-7.58(m, 7H), 7.11-7.39 (m, 6H), 2.69 (s, 6H).
应用例Application example
实施例20Example 20
2-联苯基-6-苯基喹啉即化合物(1)的用途:它可用于合成环铱三苯基膦金属有机化合物(19)化合物(19)可以作为催化剂和发光材料。2-biphenyl-6-phenylquinoline is the use of compound (1): it can be used to synthesize ring iridium triphenylphosphine organometallic compound (19) Compound (19) can be used as catalyst and luminescent material.
取1mmol配体即化合物(1),三苯基磷2.5mmol,0.5mmol三氯化铱,加入50mL三口烧瓶中,加15mL乙二醇独乙醚及5mL水溶解,在氮气保护下加热回流12小时。反应完成冷却至室温,抽滤,用水和乙醇洗涤沉淀数次,真空干燥,即得环铱化合物(19),黄色固体,产率83%。该产品的核磁分析数据如下:1H NMR.(400MHz,CDCl3):δ8.12-8.15(m,2H),7.71-7.93(m,6H),7.49-7.61(m,22H),7.25-7.37(m,18H)。Take 1mmol of the ligand compound (1), 2.5mmol of triphenylphosphine, and 0.5mmol of iridium trichloride, add it to a 50mL three-neck flask, add 15mL of ethylene glycol monoethyl ether and 5mL of water to dissolve, and heat to reflux for 12 hours under the protection of nitrogen . After the reaction was completed, it was cooled to room temperature, filtered with suction, washed with water and ethanol several times, and dried in vacuo to obtain ring iridium compound (19) as a yellow solid with a yield of 83%. The nuclear magnetic analysis data of this product are as follows: 1 H NMR.(400MHz, CDCl 3 ):δ8.12-8.15(m,2H),7.71-7.93(m,6H),7.49-7.61(m,22H),7.25- 7.37 (m, 18H).
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EP0145337A2 (en) * | 1983-11-21 | 1985-06-19 | Chevron Research And Technology Company | Electrochromic devices |
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EP0145337A2 (en) * | 1983-11-21 | 1985-06-19 | Chevron Research And Technology Company | Electrochromic devices |
KR20120027600A (en) * | 2010-09-13 | 2012-03-22 | 덕산하이메탈(주) | Compound containing quinoline derivatives and organic electronic element using the same, terminal thereof |
CN103242379A (en) * | 2013-05-20 | 2013-08-14 | 洛阳师范学院 | 2-ferrocenyl-arylquinoline and preparation method thereof |
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RuCl2(dmso)4 Catalyzes the Solvent-Free Indirect Friedländer Synthesi Polysubstituted Quinolines from Alcohols;Ricardo Martínez等;《Eur. J. Org. Chem.》;20071231;1599–1605 * |
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