CN109608488A - 一种2-苯基邻位取代三乙基硅喹啉类化合物的合成方法 - Google Patents
一种2-苯基邻位取代三乙基硅喹啉类化合物的合成方法 Download PDFInfo
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- -1 silicon quinolines Chemical class 0.000 title claims abstract description 46
- 238000006467 substitution reaction Methods 0.000 title claims abstract description 29
- 238000010189 synthetic method Methods 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 22
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 11
- 150000001336 alkenes Chemical class 0.000 claims abstract description 9
- 150000007529 inorganic bases Chemical class 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- 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 description 20
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 8
- 235000011056 potassium acetate Nutrition 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 6
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 6
- 150000001805 chlorine compounds Chemical class 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 claims description 3
- WPTCSQBWLUUYDV-UHFFFAOYSA-N 2-quinolin-2-ylquinoline Chemical compound C1=CC=CC2=NC(C3=NC4=CC=CC=C4C=C3)=CC=C21 WPTCSQBWLUUYDV-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- LAXRNWSASWOFOT-UHFFFAOYSA-J (cymene)ruthenium dichloride dimer Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Ru+2].[Ru+2].CC(C)C1=CC=C(C)C=C1.CC(C)C1=CC=C(C)C=C1 LAXRNWSASWOFOT-UHFFFAOYSA-J 0.000 claims description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 1
- FSEXLNMNADBYJU-UHFFFAOYSA-N 2-phenylquinoline Chemical class C1=CC=CC=C1C1=CC=C(C=CC=C2)C2=N1 FSEXLNMNADBYJU-UHFFFAOYSA-N 0.000 abstract description 5
- 238000003756 stirring Methods 0.000 abstract description 3
- 239000012467 final product Substances 0.000 abstract description 2
- 150000003303 ruthenium Chemical class 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000005580 one pot reaction Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 15
- 238000001228 spectrum Methods 0.000 description 13
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- 230000003595 spectral effect Effects 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000001208 nuclear magnetic resonance pulse sequence Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 238000013019 agitation Methods 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 3
- 235000011613 Pinus brutia Nutrition 0.000 description 3
- 241000018646 Pinus brutia Species 0.000 description 3
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 3
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 238000004983 proton decoupled 13C NMR spectroscopy Methods 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- FTVLMFQEYACZNP-UHFFFAOYSA-N trimethylsilyl trifluoromethanesulfonate Chemical compound C[Si](C)(C)OS(=O)(=O)C(F)(F)F FTVLMFQEYACZNP-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- MAZOHJVAXBNBPX-UHFFFAOYSA-N ruthenium hydrochloride Chemical compound Cl.[Ru] MAZOHJVAXBNBPX-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- VDULMXJUOWIPGE-UHFFFAOYSA-N 1-phenylisoquinoline quinoline Chemical class N1=CC=CC2=CC=CC=C12.C1(=CC=CC=C1)C1=NC=CC2=CC=CC=C12 VDULMXJUOWIPGE-UHFFFAOYSA-N 0.000 description 1
- UTFRXHNWUFPRPQ-UHFFFAOYSA-N 2,3-dichloro-1-methyl-4-propan-2-ylbenzene;ruthenium(2+) Chemical class [Ru+2].CC(C)C1=CC=C(C)C(Cl)=C1Cl UTFRXHNWUFPRPQ-UHFFFAOYSA-N 0.000 description 1
- XYIYPANMBGCDAQ-UHFFFAOYSA-N 3-chloro-2-phenylquinoline Chemical compound ClC1=CC2=CC=CC=C2N=C1C1=CC=CC=C1 XYIYPANMBGCDAQ-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229940027991 antiseptic and disinfectant quinoline derivative Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002512 chemotherapy Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000007336 electrophilic substitution reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 238000004896 high resolution mass spectrometry Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
本发明公开了一种2‑苯基邻位取代三乙基硅喹啉类化合物的合成方法,包括以下步骤:将三乙基硅烷、2‑苯基喹啉类化合物、无机碱、不饱和烯烃和钌催化剂加入到盛有溶剂的反应容器中,加热条件下一锅法制得所述2‑苯基邻位取代三乙基硅喹啉类化合物。本发明创造性地由相对低廉的钌配合物催化催化剂,在添加无机碱和烯烃的条件下,催化2‑苯基喹啉衍生物与三乙基硅烷加热搅拌下一锅法合成2‑苯基邻位取代三乙基硅喹啉类化合物,除终产物外,一系列转化过程中的中间体均无需分离和纯化,只需要一个反应步骤,使用的钌催化剂量较少,且价格较为低廉,为工业生产减少了资金和劳动力的投入量。
Description
技术领域
本发明涉及有机合成技术领域,具体涉及一种2-苯基邻位取代三乙基硅喹啉类化合物的合成方法。
背景技术
含硅喹啉类衍生物是一类极为重要的有机化合物,被广泛应用于新型材料的合成,且其中大多具有生物活性和药理活性,尤其是2-苯基邻位取代三乙基硅喹啉类化合物在抗病毒、抗肿瘤等方面具有良好的应用,因此受到了人们的广泛关注。这类化合物通常具有连接喹啉环的硅基骨架结构单元,往往通过喹啉环化合物与三氟甲基磺酸三甲基硅酯(trimethylsilyl trifluoromethanesulfonate,TMSOTf)或三甲基氯硅烷(trimethylchlorosilane,TMSCl)等硅基化试剂发生亲电取代反应而得,但是这些合成方法往往具有需要多步合成、化学选择性低、官能团兼容性低及会产生大量的无机盐类等缺点。近年来开发了由贵金属铑、铱配合物通过碳-氢键活化的方式可大大提高该类骨架化合物的合成效率,这种方式得到了有机化学家们的青睐(如J.Am.Chem.Soc.2015,137,6742;J.Am.Chem.Soc.2017,139,4879;J.Am.Chem.Soc.2017,139,12137;ACS Catal.2016,6,1493等)。然而,目前的合成方法中铑、铱等金属配合物的价格比较昂贵,影响了合成方法的工业化。
基于此,找出一种更适合于工业应用的2-苯基邻位取代三乙基硅喹啉类化合物的合成方法具有重要意义。
发明内容
本发明所要解决的技术问题是:提供一种更适合于工业应用的2-苯基邻位取代三乙基硅喹啉类化合物的合成方法。
为了解决上述技术问题,本发明采用的技术方案为:一种2-苯基邻位取代三乙基硅喹啉类化合物的合成方法,包括以下步骤:将三乙基硅烷、2-苯基喹啉类化合物、无机碱、不饱和烯烃和钌催化剂加入到盛有溶剂的反应容器中,加热条件下一锅法制得所述2-苯基邻位取代三乙基硅喹啉类化合物。
进一步地,所述2-苯基类喹啉化合物的结构式如下:
式中:R为H、单取代基或多取代基。
优选地,若R为单取代基时,取代基可为喹啉环的3位、4位、5位、6位、7位或8位上独立取代的氯、溴、甲基、甲氧基或三氟甲基等。
进一步地,所述钌催化剂选自六水三(2,2'-联喹啉)二氯化钌、二氯(p-甲基异丙苯)钌(II)二聚体、三(三苯基磷)二氯化钌、三(三苯基膦)羰基氢化钌或三(三苯基膦)羰基氢氯化钌中的一种或多种;优选为三(三苯基膦)羰基氢氯化钌。
进一步地,所述无机碱选自碳酸钾、氢氧化钾、醋酸钾、磷酸钾、六氟磷酸钾、碳酸氢钾、四氟硼酸钾或叔丁醇钾中的一种或多种;优选为醋酸钾。
进一步地,所述不饱和烯烃选自环己烯、苯乙烯、丙烯酸甲酯或降冰片烯中的一种或多种;优选为降冰片烯。
进一步地,所述溶剂选自正己烷、1,2-二氯乙烷、甲苯、四氯化碳、三氯甲烷、四氢呋喃、乙腈或乙醇中的一种或多种;优选为甲苯。
进一步地,所述加热的温度为50-150℃,维持加热时间为16-36小时;优选为120℃,维持加热16小时。
进一步地,反应中各物质的摩尔量比为:2-苯基喹啉类化合物:三乙基硅烷:无机碱:不饱和烯烃:钌催化剂=1:4:0.1-0.5:4:0.01-0.20。
进一步地,反应过程在无氧条件下进行;优选为在氮气保护下进行。
优选地,所述合成方法的反应式如下式(1)所示:
式中:R为H、单取代基或多取代基。
本发明的有益效果在于:与现有技术比,本发明方案具有起始原料简单易制备、合成收率高且合成过程操作方便等优点;本发明创造性地由相对低廉的钌配合物催化催化剂,在添加无机碱和烯烃的条件下,催化2-苯基喹啉衍生物与三乙基硅烷加热搅拌下一锅法合成2-苯基邻位取代三乙基硅喹啉类化合物,除终产物外,一系列转化过程中的中间体均无需分离和纯化,只需要一个反应步骤,使用的钌催化剂量较少,且价格较为低廉,为工业生产减少了资金和劳动力的投入量;本发明方案为2-苯基邻位取代三乙基硅喹啉类化合物提供了一种简洁高效的制备方法。因此,本发明方案具有良好的实用价值和社会经济效率,对同类产品及下游产品的工艺开发具有良好的借鉴意义。
附图说明
图1为本发明实施例1~5制得的产物的核磁共振氢谱;
图2为本发明实施例1~5制得的产物的核磁共振碳谱;
图3为本发明实施例6制得的产物的核磁共振氢谱;
图4为本发明实施例6制得的产物的核磁共振碳谱;
图5为本发明实施例7制得的产物的核磁共振氢谱;
图6为本发明实施例7制得的产物的核磁共振碳谱。
具体实施方式
为详细说明本发明的技术内容、所实现目的及效果,以下结合实施方式并配合附图予以说明。
本发明实施例1为:一种2-苯基邻位取代三乙基硅喹啉的合成方法,反应过程如下式(2)所示:
在20mL史莱克管中,依次加入2-苯基喹啉(103mg,0.5mmo1)、三乙基硅烷(232mg,2.0mmo1)、六氟磷酸钾(0.15mmo1)、环己烯(2.0mmo1)、三(三苯基膦)羰基氢氯化钌(23.8mg,0.025mmol),在甲苯(1mL)和氮气条件下,反应温度为120℃情况下电磁搅拌(转数500-800rpm/min)反应,反应时间为16小时,经气相色谱-质谱联用仪检测,产率为27%。
本发明实施例2为:一种2-苯基邻位取代三乙基硅喹啉的合成方法,其与实施例1的区别仅在于:无机碱为叔丁醇钾,产率为27%。
本发明实施例3为:一种2-苯基邻位取代三乙基硅喹啉的合成方法:在20mL史莱克管中,依次加入2-苯基喹啉(103mg,0.5mmo1)、三乙基硅烷(232mg,2.0mmo1)、醋酸钾(15mg,0.15mmo1),降冰片烯(200μL,2.0mmo1)、六水三(2,2'-联喹啉)二氯化钌(0.025mmol),在甲苯(1mL)和氮气条件下,反应温度为120℃情况下电磁搅拌(转数500-800rpm/min)反应,反应时间为16小时,经气相色谱-质谱联用仪检测,产率为43%。
本发明实施例4为:一种2-苯基邻位取代三乙基硅喹啉的合成方法,其与实施例1的区别仅在于:钌催化剂为二氯(p-甲基异丙苯)钌(II)二聚体,产率为43%。
本发明实施例5为:一种2-苯基邻位取代三乙基硅喹啉的合成方法:在20mL史莱克管中,依次加入2-苯基喹啉(103mg,0.5mmo1)、三乙基硅烷(232mg,2.0mmo1)、醋酸钾(15mg,0.15mmo1),降冰片烯(200μL,2.0mmo1)、三(三苯基膦)羰基氢氯化钌(23.8mg,0.025mmol),在甲苯(1mL)和氮气条件下,反应温度为120℃情况下电磁搅拌(转数500-800rpm/min)反应,反应时间为16小时。反应完成后,将溶剂(甲苯)用旋转蒸发去除,混合物用柱层析分离,洗脱剂为乙酸乙酯和石油醚,分离后得到淡黄色液体(123mg,77%)。
取实施例1-5制得的产物分别进行核磁共振(Nuclear Magnetic ResonanceSpectroscopy,NMR)及高分辨率质谱(high resolution mass spectrometry,HRMS)定性检测,结果发现产物检测数据一致(为避免冗余,仅示出实施例5制得的产物的测试数据),具体如下:
1H NMR(300MHz,CDCl3):如图1所示,δ=8.26-8.18(m,2H),7.92-7.89(m,1H),7.81-7.74(m,2H),7.67-7.66(m,5H),0.89-0.84(m,9H),0.68-0.60(m,6H).
测试过程中其他参数如下:温度(temperature):294.8;脉冲序列(pulsesequence):zg30;扫描次数(number of scans):16;接收增益(receiver gain):70;松弛延迟(relaxation delay):1.0000;脉冲宽度(pulse width):15.0000;扫描频率(spctrometer frequency):300.13;频谱宽度(spectral width):6009.6;最低频率(lowest frequency):-1151.4;核(nucleus):1H;获得尺寸(acquired size):32768;光谱尺寸(spectral size):65536。
13C{1H}NMR(75MHz,CDCl3):如图2所示,δ=161.9,148.3,147.5,136.7,136.5,129.9,129.7,129.6,128.8,127.8,127.6,127.5,127.0,126.5,121.9,7.8,4.7.
测试过程中其他参数如下:温度(temperature):295.7;脉冲序列(pulsesequence):zgpg30;扫描次数(number of scans):256;接收增益(receiver gain):195;松弛延迟(relaxation delay):2.0000;脉冲宽度(pulse width):10.0000;扫描频率(spctrometer frequency):75.47;频谱宽度(spectral width):18028.8;最低频率(lowest frequency):-1468.0;核(nucleus):13C;获得尺寸(acquired size):32768;光谱尺寸(spectral size):65536。
HRMS(采用EI源模式):m/z C21H25NSi[M+H]+的理论值(Calculated value,calcd.)为:320.1790,测定值(found)为:320.1799。
本发明实施例6为:一种4-氯-2-(2-(三乙基硅)苯基)喹啉的合成方法,反应方程式如下式(3)所示:
在20mL史莱克管中,依次加入4-氯-2苯基喹啉(120mg,0.5mmo1)、三乙基硅烷(232mg,2.0mmo1)、醋酸钾(15mg,0.15mmo1)、降冰片烯(200μL,2.0mmo1)、三(三苯基膦)羰基氢氯化钌(23.8mg,0.025mmol),在甲苯(1mL)和氮气条件下,反应温度为120℃情况下电磁搅拌(转数500-800rpm/min)反应,反应时间为16小时。反应完成后,将溶剂用旋转蒸发去除,混合物用柱层析分离,洗脱剂为乙酸乙酯和石油醚,分离后得到淡黄色液体(133mg,75%)。
取实施例6制得的产物分别进行NMR及HRMS定性检测,产物检测数据如下:
1H NMR(300MHz,CDCl3):如图3所示,δ=8.34-8.31(m,1H),8.23-8.20(m,1H),7.86-7.66(m,4H),7.59-7.46(m,3H),0.91-0.86(m,9H),0.71-0.63(m,6H).
测试过程中其他参数如下:温度(temperature):296.4;脉冲序列(pulsesequence):zg30;扫描次数(number of scans):16;接收增益(receiver gain):32;松弛延迟(relaxation delay):1.0000;脉冲宽度(pulse width):15.0000;扫描频率(spctrometer frequency):300.13;频谱宽度(spectral width):6009.6;最低频率(lowest frequency):-1054.0;核(nucleus):1H;获得尺寸(acquired size):32768;光谱尺寸(spectral size):65536。
13C{1H}NMR(75MHz,CDCl3):如图4所示,161.7,148.4,147.1,142.7,136.8,136.6,130.8,129.9,129.5,128.9,127.9,127.4,125.2,124.2,121.8,7.8,4.9.
测试过程中其他参数如下:温度(temperature):297.8;脉冲序列(pulsesequence):zgpg30;扫描次数(number of scans):196;接收增益(receiver gain):195;松弛延迟(relaxation delay):2.0000;脉冲宽度(pulse width):10.0000;扫描频率(spctrometer frequency):75.47;频谱宽度(spectral width):26315.8;最低频率(lowest frequency):-1837.7;核(nucleus):13C;获得尺寸(acquired size):32768;光谱尺寸(spectral size):65536。
HRMS(EI):m/z calcd for C21H24ClNSi[M+H]+355.1337,found 355.1449。
本发明实施例7为:一种1-(2-((三乙基)苯基)异喹啉的合成方法,反应方程式如下式(4)所示:
在20mL史莱克管中,依次加入2苯基异喹啉(103mg,0.5mmo1)、三乙基硅烷(232mg,2.0mmo1)、醋酸钾(15mg,0.15mmo1)、降冰片烯(200μL,2.0mmo1)、三(三苯基膦)羰基氢氯化钌(23.8mg,0.025mmol),在甲苯(1mL)和氮气条件下,反应温度为120℃情况下电磁搅拌(转数500-800rpm/min)反应,反应时间为16小时。反应完成后,将溶剂用旋转蒸发去除,混合物用柱层析分离,洗脱剂为乙酸乙酯和石油醚,分离后得到棕色液体(129mg,81%)。
取实施例7制得的产物分别进行NMR及HRMS定性检测,产物检测数据如下:
1H NMR(300MHz,CDCl3):如图5所示,δ=8.61(d,1H,J=2.7Hz),7.90-7.66(m,5H),7.51-7.39(m,4H),0.77(t,9H,J=7.8Hz),0.39-0.31(m,6H).
测试过程中其他参数如下:温度(temperature):295.5;脉冲序列(pulsesequence):zg30;扫描次数(number of scans):16;接收增益(receiver gain):32;松弛延迟(relaxation delay):1.0000;脉冲宽度(pulse width):15.0000;扫描频率(spctrometer frequency):300.13;频谱宽度(spectral width):6009.6;最低频率(lowest frequency):-1151.4;核(nucleus):1H;获得尺寸(acquired size):32768;光谱尺寸(spectral size):65536。
13C{1H}NMR(75MHz,CDCl3):如图6所示,δ=163.1,146.0,141.7,137.0,136.4,136.2,130.1,129.9,128.1,128.0,127.2,126.9,126.8,120.2,7.5,3.8.
测试过程中其他参数如下:温度(temperature):296.3;脉冲序列(pulsesequence):zgpg30;扫描次数(number of scans):194;接收增益(receiver gain):195;松弛延迟(relaxation delay):2.0000;脉冲宽度(pulse width):10.0000;扫描频率(spctrometer frequency):75.47;频谱宽度(spectral width):18028.8;最低频率(lowest frequency):-1468.0;核(nucleus):13C;获得尺寸(acquired size):32768;光谱尺寸(spectral size):65536。
HRMS(EI):m/z calcd for C21H25NSi[M+H]+320.1790,found 320.1829。
上述实施例中核磁共振谱采用Bruker BioSpin GmbH的核磁共振波谱仪测得。
以上所述仅为本发明的实施例,并非因此限制本发明的专利范围,凡是利用本发明说明书及附图内容所作的等同变换,或直接或间接运用在相关的技术领域,均同理包括在本发明的专利保护范围内。
Claims (10)
1.一种2-苯基邻位取代三乙基硅喹啉类化合物的合成方法,其特征在于:包括以下步骤:将三乙基硅烷、2-苯基喹啉类化合物、无机碱、不饱和烯烃和钌催化剂加入到盛有溶剂的反应容器中,加热条件下一锅法制得所述2-苯基邻位取代三乙基硅喹啉类化合物。
2.根据权利要求1所述的2-苯基邻位取代三乙基硅喹啉类化合物的合成方法,其特征在于:所述2-苯基类喹啉化合物的结构式如下:
式中:R为H、单取代基或多取代基。
3.根据权利要求2所述的2-苯基邻位取代三乙基硅喹啉类化合物的合成方法,其特征在于:若R为单取代基时,取代基为喹啉环的3位、4位、5位、6位、7位或8位上独立取代的氯、溴、甲基、甲氧基或三氟甲基。
4.根据权利要求1-3任一项所述的2-苯基邻位取代三乙基硅喹啉类化合物的合成方法,其特征在于:所述钌催化剂选自六水三(2,2'-联喹啉)二氯化钌、二氯(p-甲基异丙苯)钌(II)二聚体、三(三苯基磷)二氯化钌、三(三苯基膦)羰基氢化钌或三(三苯基膦)羰基氢氯化钌中的一种或多种;优选为三(三苯基膦)羰基氢氯化钌。
5.根据权利要求1-3任一项所述的2-苯基邻位取代三乙基硅喹啉类化合物的合成方法,其特征在于:所述无机碱选自碳酸钾、氢氧化钾、醋酸钾、磷酸钾、六氟磷酸钾、碳酸氢钾、四氟硼酸钾或叔丁醇钾中的一种或多种;优选为醋酸钾。
6.根据权利要求1-3任一项所述的2-苯基邻位取代三乙基硅喹啉类化合物的合成方法,其特征在于:所述不饱和烯烃选自环己烯、苯乙烯、丙烯酸甲酯或降冰片烯中的一种或多种;优选为降冰片烯。
7.根据权利要求1-3任一项所述的2-苯基邻位取代三乙基硅喹啉类化合物的合成方法,其特征在于:所述溶剂选自正己烷、1,2-二氯乙烷、甲苯、四氯化碳、三氯甲烷、四氢呋喃、乙腈或乙醇中的一种或多种;优选为甲苯。
8.根据权利要求1-3任一项所述的2-苯基邻位取代三乙基硅喹啉类化合物的合成方法,其特征在于:所述加热的温度为50-150℃,维持加热时间为16-36小时;优选为120℃,维持加热16小时。
9.根据权利要求1-3任一项所述的2-苯基邻位取代三乙基硅喹啉类化合物的合成方法,其特征在于:反应中各物质的摩尔量比为:2-苯基喹啉类化合物:三乙基硅烷:无机碱:不饱和烯烃:钌催化剂=1:4:0.1-0.5:4:0.01-0.20。
10.根据权利要求1-3任一项所述的2-苯基邻位取代三乙基硅喹啉类化合物的合成方法,其特征在于:反应过程在无氧条件下进行;优选为在氮气保护下进行。
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