CN116462579A - 一种螺芴蒽酮化合物的制备方法 - Google Patents
一种螺芴蒽酮化合物的制备方法 Download PDFInfo
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- -1 anthrone compound Chemical class 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- ABEVIHIQUUXDMS-UHFFFAOYSA-N (2-bromophenyl)-phenylmethanone Chemical compound BrC1=CC=CC=C1C(=O)C1=CC=CC=C1 ABEVIHIQUUXDMS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000654 additive Substances 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 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 10
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 8
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 7
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- LGVUAXNPXVXCCW-UHFFFAOYSA-M cesium;2,2-dimethylpropanoate Chemical group [Cs+].CC(C)(C)C([O-])=O LGVUAXNPXVXCCW-UHFFFAOYSA-M 0.000 claims description 4
- 150000002431 hydrogen Chemical group 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- WXAZIUYTQHYBFW-UHFFFAOYSA-N tris(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WXAZIUYTQHYBFW-UHFFFAOYSA-N 0.000 claims description 4
- WFMNHCSATCWAAQ-UHFFFAOYSA-M potassium;2,2-dimethylpropanoate Chemical compound [K+].CC(C)(C)C([O-])=O WFMNHCSATCWAAQ-UHFFFAOYSA-M 0.000 claims description 3
- SJRDNQOIQZOVQD-UHFFFAOYSA-M sodium;2,2-dimethylpropanoate Chemical compound [Na+].CC(C)(C)C([O-])=O SJRDNQOIQZOVQD-UHFFFAOYSA-M 0.000 claims description 3
- BCJVBDBJSMFBRW-UHFFFAOYSA-N 4-diphenylphosphanylbutyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCCP(C=1C=CC=CC=1)C1=CC=CC=C1 BCJVBDBJSMFBRW-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- QZUPHAGRBBOLTB-UHFFFAOYSA-N NSC 244302 Chemical compound C=1C=CC=CC=1P(C(C)(C)C)C1=CC=CC=C1 QZUPHAGRBBOLTB-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- ZOAIGCHJWKDIPJ-UHFFFAOYSA-M caesium acetate Chemical compound [Cs+].CC([O-])=O ZOAIGCHJWKDIPJ-UHFFFAOYSA-M 0.000 claims description 2
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims description 2
- DLQYXUGCCKQSRJ-UHFFFAOYSA-N tris(furan-2-yl)phosphane Chemical compound C1=COC(P(C=2OC=CC=2)C=2OC=CC=2)=C1 DLQYXUGCCKQSRJ-UHFFFAOYSA-N 0.000 claims description 2
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 claims 1
- 239000002585 base Substances 0.000 claims 1
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 9
- RJGDLRCDCYRQOQ-UHFFFAOYSA-N anthrone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3CC2=C1 RJGDLRCDCYRQOQ-UHFFFAOYSA-N 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 3
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 238000005580 one pot reaction Methods 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ACRRNRKTRULOKX-UHFFFAOYSA-N 3-methylspiro[9h-anthracene-10,9'-fluorene] Chemical compound C12=CC=CC=C2C2=CC=CC=C2C21C1=CC=CC=C1CC1=CC=C(C)C=C12 ACRRNRKTRULOKX-UHFFFAOYSA-N 0.000 description 3
- YDBLFISDFDCYCC-UHFFFAOYSA-N spiro[9h-anthracene-10,9'-fluorene] Chemical compound C12=CC=CC=C2CC2=CC=CC=C2C11C2=CC=CC=C2C2=CC=CC=C21 YDBLFISDFDCYCC-UHFFFAOYSA-N 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- WXMZPPIDLJRXNK-UHFFFAOYSA-N butyl(diphenyl)phosphane Chemical group C=1C=CC=CC=1P(CCCC)C1=CC=CC=C1 WXMZPPIDLJRXNK-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 125000001979 organolithium group Chemical group 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- WJCGUPWVAISGFI-UHFFFAOYSA-N (2-bromophenyl)-(3-methylphenyl)methanone Chemical compound CC1=CC=CC(C(=O)C=2C(=CC=CC=2)Br)=C1 WJCGUPWVAISGFI-UHFFFAOYSA-N 0.000 description 1
- PGNXIGKGMHOQCA-UHFFFAOYSA-N (2-bromophenyl)-(4-methylphenyl)methanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=CC=C1Br PGNXIGKGMHOQCA-UHFFFAOYSA-N 0.000 description 1
- OEXSQPUVQPGIIN-UHFFFAOYSA-N (2-bromophenyl)-(4-phenylphenyl)methanone Chemical compound BrC1=CC=CC=C1C(=O)C1=CC=C(C=2C=CC=CC=2)C=C1 OEXSQPUVQPGIIN-UHFFFAOYSA-N 0.000 description 1
- CTGNTZJXOMWGQZ-UHFFFAOYSA-N (2-bromophenyl)-(4-tert-butylphenyl)methanone Chemical compound C1=CC(C(C)(C)C)=CC=C1C(=O)C1=CC=CC=C1Br CTGNTZJXOMWGQZ-UHFFFAOYSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- IBXMKLPFLZYRQZ-UHFFFAOYSA-N 1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1C=CC(=O)C=CC1=CC=CC=C1 IBXMKLPFLZYRQZ-UHFFFAOYSA-N 0.000 description 1
- KTADSLDAUJLZGL-UHFFFAOYSA-N 1-bromo-2-phenylbenzene Chemical group BrC1=CC=CC=C1C1=CC=CC=C1 KTADSLDAUJLZGL-UHFFFAOYSA-N 0.000 description 1
- APWAMQGDVJNMRK-UHFFFAOYSA-N 2-methoxy-9h-fluorene Chemical compound C1=CC=C2C3=CC=C(OC)C=C3CC2=C1 APWAMQGDVJNMRK-UHFFFAOYSA-N 0.000 description 1
- MHVNUMRNTNTZJH-UHFFFAOYSA-N 2-phenyl-9h-fluorene Chemical compound C1=C2CC3=CC=CC=C3C2=CC=C1C1=CC=CC=C1 MHVNUMRNTNTZJH-UHFFFAOYSA-N 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- OAYLNYINCPYISS-UHFFFAOYSA-N ethyl acetate;hexane Chemical compound CCCCCC.CCOC(C)=O OAYLNYINCPYISS-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- UEMZDMHKFUFYCN-UHFFFAOYSA-N spiro[anthracene-10,9'-fluorene]-9-one Chemical compound C12=CC=CC=C2C(=O)C2=CC=CC=C2C11C2=CC=CC=C2C2=CC=CC=C21 UEMZDMHKFUFYCN-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/93—Spiro compounds
- C07C2603/94—Spiro compounds containing "free" spiro atoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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Abstract
本发明属于精细化学品及相关化学技术领域,提供了一种螺芴蒽酮化合物的制备方法,以芴及其衍生物和2‑溴二苯甲酮及其衍生物为原料,在催化剂存在的情况下,在碱、添加剂存在的情况下,在无水有机溶剂条件下,在130℃下反应24小时,即可得到相应的螺芴蒽酮结构的化合物。本发明的制备方法是一步法反应、反应条件温和、操作简便、收率高;利用该方法所合成的高效的螺芴蒽酮结构的化合物可以进一步官能化得到各类化合物,应用于有机光电材料的开发与研究。
Description
技术领域
本发明属于精细化学品及相关化学技术领域,提供了一种含螺芴蒽酮结构的化合物的高效制备方法。
背景技术
螺芴蒽酮是一类极其重要的螺环化合物,因具有π共轭效应使其具有很强的空穴传输能力,因此在有机光电材料领域中含螺芴蒽酮结构的化合物有着重要的用处。
已经报道的螺芴蒽酮结构的化合物的合成方法采用2-溴联苯与有机锂试剂作用后与蒽酮反应,之后在酸的催化下环合,制备螺芴蒽酮化合物[Angew.Chem.Int.Ed.,2019,58(33):11301-11305],然而这种方法需要大量的有机锂试剂和过量的酸,对环境不太友好,操作不便,条件苛刻。
近年来,过渡金属催化的构筑螺环的反应因其具有操作简单,反应条件温和等优点被越来越多的人所看好[ACS Catal.,2018,8(12):11029-11034;Chem.Sci.,2020,11(37):10198-10203]。而如今以过渡金属作为催化剂直接获得螺芴蒽酮结构的化合物的合成方法还未见报道。
发明内容
本发明提供了一种螺芴蒽酮结构的化合物的新颖制备方法,该合成方法能一步得到螺芴蒽酮结构的化合物、反应条件温和、操作简便、收率高。
本发明的技术方案:
一种螺芴蒽酮化合物的制备方法,以芴及其衍生物和2-溴二苯甲酮及其衍生物为原料,在钯催化剂、膦配体、碱、添加剂存在的情况下,于无水有机溶剂中,在130℃下反应24小时,即得到相应的螺芴蒽酮化合物,合成路线如下:
R1选自氢、芳基、杂芳基、烷氧基;
R2选自氢、烷基;
R3选自氢、甲基、烷氧基、芳基、酯基;
芴及其衍生物与2-溴二苯甲酮及其衍生物的摩尔比为1:1.2;
芴及其衍生物与催化剂的摩尔比为1:0.05;
芴及其衍生物与碱的摩尔比为1:4;
芴及其衍生物与添加剂的摩尔比为1:0.3;
芴及其衍生物在反应体系中的摩尔浓度为0.06mmol/mL;
2-溴二苯甲酮及其衍生物在反应体系中的摩尔浓度为0.08mmol/mL;
所述的无水有机溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、甲苯、乙腈、二甲基亚砜、四氢呋喃、N-甲基吡咯烷酮等中的一种或两种以上混合,优选N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜。
所述的钯催化剂为四(三苯基膦)钯、醋酸钯、氯化钯、二(乙酰丙酮)钯、三(二亚苄基丙酮)二钯中的一种或两种以上混合,优选为氯化钯、醋酸钯。
所述的膦配体为三苯基膦、三对甲苯基膦、三对甲氧基苯基膦、三对氟苯基膦、叔丁基二苯基膦、三环己基膦、三(2-呋喃基)膦、1,4-双(二苯膦)丁烷、1,1'-双(二苯基膦)二茂铁中的一种或两种以上混合,优选为三苯基膦、三对甲苯基膦、叔丁基二苯基膦;
所述的碱为氟化铯、乙酸铯、碳酸钾、碳酸钠、碳酸铯中的一种或两种以上混合,优选为碳酸铯、氟化铯。
所述的添加剂为新戊酸铯、新戊酸钾、新戊酸钠。
分离方法为柱层析。
用柱层析方法进行产物分离时,可以使用硅胶或者中性氧化铝作为固定相,展开剂一般为极性与非极性的混合溶剂,如乙酸乙酯-石油醚、乙酸乙酯-正己烷、二氯甲烷-石油醚、甲醇-石油醚。
本发明的有益效果:本发明方法为一步合成法、反应条件温和、操作简便、收率高;利用该方法所合成的螺芴蒽酮结构的化合物可以进一步官能化得到各类化合物[J.Am.Chem.Soc.2017,139(1),245–254]、[Org.Lett.2018,20(14),4354-4357]、[J.Am.Chem.Soc.2004,126(6),1688–1698],应用于有机光电材料的开发与研究。
附图说明
图1是实施例1中10H-螺[蒽-9,9'-芴]-10-酮的1H核磁谱图。
图2是实施例1中10H-螺[蒽-9,9'-芴]-10-酮的13C核磁谱图。
图3是实施例2中2'-苯基-10H-螺[蒽-9,9'-芴]-10-酮的1H核磁谱图。
图4是实施例2中2'-苯基-10H-螺[蒽-9,9'-芴]-10-酮的13C核磁谱图。
图5是实施例3中2-甲基-10H-螺[蒽-9,9'-芴]-10-酮的1H核磁谱图。
图6是实施例3中2-甲基-10H-螺[蒽-9,9'-芴]-10-酮的13C核磁谱图。
图7是实施例4中3-甲基-10H-螺[蒽-9,9'-芴]-10-酮的1H核磁谱图。
图8是实施例4中3-甲基-10H-螺[蒽-9,9'-芴]-10-酮的13C核磁谱图。
图9是实施例5中2-叔丁基-10H-螺[蒽-9,9'-芴]-10-酮的1H核磁谱图。
图10是实施例5中2-叔丁基-10H-螺[蒽-9,9'-芴]-10-酮的13C核磁谱图。
图11是实施例6中2-苯基-10H-螺[蒽-9,9'-芴]-10-酮的1H核磁谱图。
图12是实施例6中2-苯基-10H-螺[蒽-9,9'-芴]-10-酮的13C核磁谱图。
图13是实施例7中2'-甲氧基-10H-螺[蒽-9,9'-芴]-10-酮的1H核磁谱图。
图14是实施例7中2'-甲氧基-10H-螺[蒽-9,9'-芴]-10-酮的13C核磁谱图。
具体实施方式
本发明所述的螺芴蒽酮结构的化合物的制备方法,具有反应步骤少、反应条件温和、便于操作和反应收率高等优点。
下面结合具体实施例,进一步阐述本发明。这些实施例仅用于说明本发明而不用于限制本发明的范围。在本领域内的技术人员对本发明所做的简单替换或改进均属于本发明所保护的技术方案之内。
实施例1:10H-螺[蒽-9,9'-芴]-10-酮的合成
在25mL反应器中,加入芴(0.033g,0.2mmol),2-溴二苯甲酮(0.063g,0.24mmol),氯化钯(0.002g,0.01mmol),三苯基膦(0.005g,0.02mmol),碳酸铯(0.196g,0.8mmol),新戊酸铯(0.014g,0.06mmol),加入无水N,N-二甲基甲酰胺3mL,130℃、氮气条件下搅拌24h。柱层析分离(硅胶,200-300目;展开剂,石油醚:乙酸乙酯=50:1)得到10H-螺[蒽-9,9'-芴]-10-酮0.062g,产率90%。
白色固体;熔点241-242℃,1H NMR(400MHz,CDCl3):δ8.42(dd,J=7.9,1.2Hz,2H),7.87(d,J=7.6Hz,2H),7.45–7.34(m,4H),7.28(d,J=1.5Hz,1H),7.27–7.26(m,1H),7.17(td,J=7.5,1.1Hz,2H),6.87(d,J=7.6Hz,2H),6.61–6.52(m,2H);13C NMR(101MHz,CDCl3):δ152.4,144.9,141.0,133.6,131.3,128.7,128.1,128.0,127.5,127.4,125.1,120.4,58.1.IR(KBr):υmax3068,2920,1656,1601,1454,1323,1263,1086,935,814,750,730cm-1;HRMS(EI)m/zcalcd for C26H16O+[M+]:344.1201;found:344.1191。
实施例2:2'-苯基-10H-螺[蒽-9,9'-芴]-10-酮的合成
操作同实施例1,由2-苯基-9H-芴与2-溴二苯甲酮反应24小时得到2'-苯基-10H-螺[蒽-9,9'-芴]-10-酮0.061g,产率72%。
白色固体;熔点288-289℃,1H NMR(400MHz,CDCl3):δ8.44(d,J=7.9Hz,2H),7.91(dd,J=18.4,7.8Hz,2H),7.65(d,J=8.0Hz,1H),7.39(q,J=7.7Hz,5H),7.28(dq,J=12.9,6.8,6.3Hz,5H),7.16(t,J=7.5Hz,1H),7.09(s,1H),6.62(d,J=8.0Hz,2H);13C NMR(101MHz,CDCl3):δ184.4,152.7,144.8,141.8,140.7,140.5,140.3,133.7,131.3,128.8,128.7,128.1,127.5,127.5,127.2,127.0,125.2,123.8,120.8,120.5,58.2.IR(KBr):υmax3064,2921,1665,1463,1453,1320,1262,1150,931,754,698,681cm-1;HRMS(EI)m/zcalcdfor C32H20O+[M+]:420.1514;found:420.1510。
实施例3:2-甲基-10H-螺[蒽-9,9'-芴]-10-酮的合成
在25mL反应器中,加入芴(0.033g,0.2mmol),(2-溴苯基)(对甲苯基)甲酮(0.066g,0.24mmol),氯化钯(0.002g,0.01mmol),三苯基膦(0.005g,0.02mmol),碳酸铯(0.196g,0.8mmol),新戊酸铯(0.014g,0.06mmol),加入无水N,N-二甲基乙酰胺3mL,130℃、氮气条件下搅拌24h。柱层析分离(硅胶,200-300目;展开剂,石油醚:乙酸乙酯=50:1)得到2-甲基-10H-螺[蒽-9,9'-芴]-10-酮0.055g,产率77%。
白色固体;熔点255-257℃,1H NMR(400MHz,CDCl3):δ8.37(dd,J=32.9,7.9Hz,2H),7.86(d,J=7.6Hz,2H),7.36(dt,J=15.0,7.5Hz,3H),7.23(d,J=7.7Hz,1H),7.21–7.09(m,3H),6.86(d,J=7.6Hz,2H),6.52(d,J=7.9Hz,1H),6.33(s,1H),2.10(s,3H);13CNMR(101MHz,CDCl3):δ184.1,152.6,144.9,144.9,144.4,141.0,133.4,131.4,129.2,128.8,128.7,128.0,127.9,127.6,127.4,127.3,125.1,120.4,58.1,21.9.IR(KBr):υmax3051,2908,2843,1658,1605,1450,1317,1158,929,837,750,685cm-1;HRMS(EI)m/zcalcdfor C27H18O+[M+]:358.1358;found:358.1350。
实施例4:3-甲基-10H-螺[蒽-9,9'-芴]-10-酮
操作同实施例3,由芴与(2-溴苯基)(间甲苯基)甲酮反应24h得到3-甲基-10H-螺[蒽-9,9'-芴]-10-酮0.052g,产率72%。
白色固体;熔点256-258℃,1H NMR(400MHz,CDCl3):δ8.42(d,J=7.9Hz,1H),8.23(s,1H),7.85(d,J=7.6Hz,2H),7.37(q,J=7.1Hz,3H),7.24(t,J=7.5Hz,1H),7.15(t,J=7.5Hz,2H),7.08(d,J=8.0Hz,1H),6.85(d,J=7.6Hz,2H),6.55(d,J=7.9Hz,1H),6.45(d,J=8.1Hz,1H),2.37(s,3H);13C NMR(101MHz,CDCl3):δ184.5,152.5,144.9,142.1,141.0,137.2,134.8,133.5,131.5,131.1,128.7,128.0,127.9,127.5,127.4,127.3,125.1,120.4,57.9,21.1.IR(KBr):υmax3060,2917,1661,1600,1492,1311,1216,1029,922,830,750,692cm-1;HRMS(EI)m/zcalcd for C27H18O+[M+]:358.1358;found:358.1350。
实施例5:2-叔丁基-10H-螺[蒽-9,9'-芴]-10-酮的合成
在25mL反应器中,加入芴(0.033g,0.2mmol),(2-溴苯基)(4-(叔丁基)苯基)甲酮(0.076g,0.24mmol),醋酸钯(0.002g,0.01mmol),三对甲苯基膦(0.006g,0.02mmol),碳酸铯(0.196g,0.8mmol),新戊酸钠(0.007g,0.06mmol),加入无水N,N-二甲基甲酰胺3mL,130℃、氮气条件下搅拌24h。柱层析分离(硅胶,200-300目;展开剂,石油醚:乙酸乙酯=50:1)得到2-叔丁基-10H-螺[蒽-9,9'-芴]-10-酮0.047g,产率58%。
白色固体;熔点260-262℃,1H NMR(400MHz,CDCl3):δ8.38(dd,J=25.6,8.0Hz,2H),7.86(d,J=7.6Hz,2H),7.38(dq,J=15.9,8.3Hz,4H),7.23(t,J=7.2Hz,1H),7.15(t,J=7.3Hz,2H),6.87(d,J=7.6Hz,2H),6.59–6.50(m,2H),1.02(s,9H);13C NMR(101MHz,CDCl3):δ157.0,152.5,145.1,144.8,141.0,133.3,131.5,128.6,127.9,127.8,127.4,127.3,127.2,125.1,124.9,124.4,120.3,58.4,35.0,30.9.IR(KBr):υmax3064,2963,2859,1663,1604,1449,1318,1164,928,845,759,735cm-1;HRMS(EI)m/zcalcd for C30H24O+[M+]:400.1827;found:400.1822。
实施例6:2-苯基-10H-螺[蒽-9,9'-芴]-10-酮的合成
在25mL反应器中,加入芴(0.033g,0.2mmol),[1,1'-联苯]-4-基(2-溴苯基)甲酮(0.081g,0.24mmol),氯化钯(0.002g,0.01mmol),叔丁基二苯基膦(0.005g,0.02mmol),碳酸铯(0.196g,0.8mmol),新戊酸钾(0.007g,0.06mmol),加入无水N,N-二甲基甲酰胺3mL,130℃、氮气条件下搅拌24h。柱层析分离(硅胶,200-300目;展开剂,石油醚:乙酸乙酯=50:1)得到2-苯基-10H-螺[蒽-9,9'-芴]-10-酮0.074g,产率88%。
白色固体;熔点288-289℃,1H NMR(400MHz,CDCl3):δ8.47(dd,J=23.8,8.0Hz,2H),7.86(d,J=7.6Hz,2H),7.60(d,J=8.2Hz,1H),7.37(q,J=7.1Hz,3H),7.26(d,J=7.8Hz,6H),7.16(t,J=7.5Hz,2H),6.92(d,J=7.6Hz,2H),6.75(s,1H),6.56(d,J=8.0Hz,1H);13C NMR(101MHz,CDCl3):δ184.1,152.4,146.1,145.5,145.1,141.1,139.8,133.6,131.4,130.3,128.8,128.7,128.2,128.1,128.0,127.5,127.4,127.3,126.5,126.4,125.2,120.6,58.4.IR(KBr):υmax3060,2921,1663,1604,1503,1474,1400,1315,1264,1151,927,890cm-1;HRMS(EI)m/zcalcd for C32H20O+[M+]:420.1514;found:420.1510。
实施例7:2'-甲氧基-10H-螺[蒽-9,9'-芴]-10-酮的合成
操作同实施例6,由2-甲氧基-9H-芴与2-溴二苯甲酮反应24小时得到2'-甲氧基-10H-螺[蒽-9,9'-芴]-10-酮0.056g,产率75%。
白色固体;熔点215-216℃,1H NMR(400MHz,CDCl3):δ8.47(d,J=7.8Hz,2H),7.92–7.75(m,2H),7.40(dt,J=13.5,7.6Hz,3H),7.31(t,J=7.5Hz,2H),7.11(t,J=7.5 Hz,1H),6.98(d,J=8.3 Hz,1H),6.85(d,J=7.6 Hz,1H),6.63(d,J=7.9 Hz,2H),6.43(s,1H),3.66(s,3H);13C NMR(101 MHz,CDCl3):δ184.3,160.6,154.2,152.1,145.0,141.0,134.0,133.6,131.3,128.1,128.0,127.5,127.4,125.0,121.3,119.6,114.4,110.2,58.1,55.5.IR(KBr):υmax3056,2831,1665,1601,1493,1320,1210,1038,931,824,755,687 cm-1;HRMS(ESI)m/zcalcd for C27H19O2 +[M+H+]:375.1380;found:375.1379。
Claims (5)
1.一种螺芴蒽酮化合物的制备方法,其特征在于,以芴及其衍生物和2-溴二苯甲酮及其衍生物为原料,在钯催化剂、膦配体、碱、添加剂存在的情况下,于无水有机溶剂中,在130℃下反应24小时,即得到相应的螺芴蒽酮化合物,合成路线如下:
其中,R1选自氢、芳基、杂芳基、烷氧基;
R2选自氢、烷基;
R3选自氢、甲基、烷氧基、芳基、酯基;
芴及其衍生物与2-溴二苯甲酮及其衍生物的摩尔比为1:1.2;
芴及其衍生物与催化剂的摩尔比为1:0.05;
芴及其衍生物与碱的摩尔比为1:4;
芴及其衍生物与添加剂的摩尔比为1:0.3;
芴及其衍生物在反应体系中的摩尔浓度为0.06mmol/mL;
2-溴二苯甲酮及其衍生物在反应体系中的摩尔浓度为0.08mmol/mL;
所述的添加剂为新戊酸铯、新戊酸钾、新戊酸钠。
2.根据权利要求1所述的制备方法,其特征在于,所述的无水有机溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、甲苯、乙腈、二甲基亚砜、四氢呋喃、N-甲基吡咯烷酮中的一种或两种以上混合。
3.根据权利要求1所述的制备方法,其特征在于,所述的钯催化剂为四(三苯基膦)钯、醋酸钯、氯化钯、二(乙酰丙酮)钯、三(二亚苄基丙酮)二钯中的一种或两种以上混合。
4.根据权利要求1所述的制备方法,其特征在于,所述的膦配体为三苯基膦、三对甲苯基膦、三对甲氧基苯基膦、三对氟苯基膦、叔丁基二苯基膦、三环己基膦、三(2-呋喃基)膦、1,4-双(二苯膦)丁烷、1,1'-双(二苯基膦)二茂铁中的一种或两种以上混合。
5.根据权利要求1所述的制备方法,其特征在于,所述的碱为氟化铯、乙酸铯、碳酸钾、碳酸钠、碳酸铯中的一种或两种以上混合。
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