CN112209956B - 一种制备2,6-二取代芳基硼酸酯类化合物的方法 - Google Patents
一种制备2,6-二取代芳基硼酸酯类化合物的方法 Download PDFInfo
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- -1 6-disubstituted aryl borate compound Chemical class 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000007529 inorganic bases Chemical class 0.000 claims abstract description 18
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 11
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 239000003446 ligand Substances 0.000 claims abstract description 7
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000011736 potassium bicarbonate Substances 0.000 claims description 9
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 9
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 9
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- 235000011181 potassium carbonates Nutrition 0.000 claims description 8
- 239000004327 boric acid Substances 0.000 claims description 7
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical group [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 7
- GEPJPYNDFSOARB-UHFFFAOYSA-N tris(4-fluorophenyl)phosphane Chemical compound C1=CC(F)=CC=C1P(C=1C=CC(F)=CC=1)C1=CC=C(F)C=C1 GEPJPYNDFSOARB-UHFFFAOYSA-N 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- 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 4
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
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- UKSZBOKPHAQOMP-SVLSSHOZSA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [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 UKSZBOKPHAQOMP-SVLSSHOZSA-N 0.000 claims description 2
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 claims description 2
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-Bis(diphenylphosphino)propane Substances C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 claims description 2
- IQHSSYROJYPFDV-UHFFFAOYSA-N 2-bromo-1,3-dichloro-5-(trifluoromethyl)benzene Chemical group FC(F)(F)C1=CC(Cl)=C(Br)C(Cl)=C1 IQHSSYROJYPFDV-UHFFFAOYSA-N 0.000 claims description 2
- 125000006201 3-phenylpropyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- CVICEEPAFUYBJG-UHFFFAOYSA-N 5-chloro-2,2-difluoro-1,3-benzodioxole Chemical group C1=C(Cl)C=C2OC(F)(F)OC2=C1 CVICEEPAFUYBJG-UHFFFAOYSA-N 0.000 claims description 2
- ICMAFTSLXCXHRK-UHFFFAOYSA-N Ethyl pentanoate Chemical compound CCCCC(=O)OCC ICMAFTSLXCXHRK-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 claims description 2
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims description 2
- IIOSDXGZLBPOHD-UHFFFAOYSA-N tris(2-methoxyphenyl)phosphane Chemical compound COC1=CC=CC=C1P(C=1C(=CC=CC=1)OC)C1=CC=CC=C1OC IIOSDXGZLBPOHD-UHFFFAOYSA-N 0.000 claims description 2
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 claims description 2
- UYUUAUOYLFIRJG-UHFFFAOYSA-N tris(4-methoxyphenyl)phosphane Chemical compound C1=CC(OC)=CC=C1P(C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 UYUUAUOYLFIRJG-UHFFFAOYSA-N 0.000 claims description 2
- 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 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
- PXYCJKZSCDFXLR-UHFFFAOYSA-N tris[4-(trifluoromethyl)phenyl]phosphane Chemical compound C1=CC(C(F)(F)F)=CC=C1P(C=1C=CC(=CC=1)C(F)(F)F)C1=CC=C(C(F)(F)F)C=C1 PXYCJKZSCDFXLR-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 6
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- 238000001308 synthesis method Methods 0.000 abstract description 3
- 150000001298 alcohols Chemical class 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 abstract description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 34
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 30
- 239000000047 product Substances 0.000 description 23
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 20
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 18
- 239000011734 sodium Substances 0.000 description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 10
- 239000000741 silica gel Substances 0.000 description 10
- 229910002027 silica gel Inorganic materials 0.000 description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
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- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 5
- 238000012746 preparative thin layer chromatography Methods 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- RINOYHWVBUKAQE-UHFFFAOYSA-N 1-iodo-2-methylbenzene Chemical compound CC1=CC=CC=C1I RINOYHWVBUKAQE-UHFFFAOYSA-N 0.000 description 4
- 239000004292 methyl p-hydroxybenzoate Substances 0.000 description 4
- 229960002216 methylparaben Drugs 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- IVDFJHOHABJVEH-UHFFFAOYSA-N HOCMe2CMe2OH Natural products CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
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Classifications
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- 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/04—Esters of boric acids
-
- 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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
一种制备2,6‑二取代芳基硼酸酯类化合物的方法,包括以下步骤:在反应管中,加入钯催化剂和膦配体,加入降冰片烯,加入第一无机碱以及第二无机碱,加入醇类,加入有机溶剂,体系置换为惰性气体保护,加热,恒温反应,然后分离纯化得到2,6‑二取代芳基硼酸酯类化合物。本发明的合成方法具有原料廉价易得,反应条件温和,底物适应性好,操作简单,且产品质量稳定,纯度高等特点。本发明合成一系列2,6‑二取代芳基硼酸酯类产物作为有机合成中间体有着广泛的应用价值。
Description
技术领域
本发明属于有机合成化学技术领域,涉及制备成2,6-二取代芳基硼酸酯类化合物的方法。
背景技术
芳基硼酸酯类化合物是一类具有重要应用价值的含硼化合物,广泛应用于具有重要生物活性的药物分子和天然产物的合成中,一直以来都是有机化学和药物化学领域的研究热点。其中由于芳基硼酸酯类化合物可被广泛应用于Suzuki偶联反应中,该类反应是药物合成中重要的合成步骤,所以合成一系列具有不同取代的芳基硼酸酯类化合物具有重要的意义。目前合成含有多取代的芳基硼酸酯类化合物的方法,主要通过Miyaura硼酸酯化反应获得相应的反应产物。尽管该方法可以以较高收率获得相应的芳基硼酸酯类产物,但其原料通常比较复杂(需提前制备相对应的碘代芳烃底物),操作繁琐(从基础原料到产物需要多步反应),要求反应条件复杂,底物适应性不好。因此设计和开发反应条件简单温和的合成多取代芳基硼酸酯类化合物的新方法,有很大潜在应用的价值。
发明内容
本发明的目的在于提供一种简便、高效的2,6-二取代芳基硼酸酯类化合物的合成方法,实现反应原料易得,反应条件温和,操作简易,高效地制备出目标产物。
为了达到上述目的,本发明所采用的技术方案为:
一种制备2,6-二取代芳基硼酸酯类化合物的方法,其合成反应式为:
进一步,所述的反应式中的R1包括甲基、乙基、异丙基或苯基,R2包括氢、4-溴、5-苯基、4-甲基、5-氯或5-氟或4-甲酸甲酯基,R3包括正丙基、正丁基、正戊基、仲丁基、3-甲氧基丙基、4-甲氧基丁基、3-苯基丙基、戊酸乙酯基、5-乙酰氧基戊基或正戊氰基、乙基、己基。
一种制备2,6-二取代芳基硼酸酯类化合物的方法,包括以下步骤:在反应管中,加入钯催化剂和膦配体,加入降冰片烯,加入第一无机碱以及第二无机碱,加入醇类,加入有机溶剂,体系置换为惰性气体保护,加热,恒温反应,然后分离纯化得到2,6-二取代芳基硼酸酯类化合物。
可选地,其中1-取代2-碘代芳烃类化合物、1-溴代烃类化合物、联频哪醇硼酸酯、钯催化剂、膦配体、降冰片烯、第一无机碱、第二无机碱、醇类的摩尔比依次为1:(2~3):(1~2):(0.05~0.2):(0.1~0.4):(1~1.5):(2~6):(1~3):(1~2);优选地,1-取代2-碘代芳烃类化合物与联频哪醇硼酸酯的摩尔比为1:1。
可选地,所述的钯催化剂为乙酸钯、氯化钯、四三苯基膦钯、二(三苯基膦)二氯化钯、三(二亚苄基丙酮)二钯或二(二亚苄基丙酮)钯。
可选地,所述的膦配体为三苯基膦、三(邻甲基苯基)膦、三(对甲基苯基)膦、三(邻甲氧基苯基)膦、三(对甲氧基苯基)膦、三(4-氟苯基)膦、三(4-三氟甲基苯基)膦、三环己基膦、三叔丁基膦、三(2-呋喃基)膦、x-phos、s-phos、dppe或dppp。
可选地,第一无机碱、第二无机碱可选项包括碳酸氢钾、碳酸氢钠、醋酸钾、醋酸钠、碳酸锂、碳酸铯或氢氧化钠;第一无机碱或第二无机碱中至少包括碳酸钾、碳酸氢钾、碳酸钠其中之一。
可选地,所述的有机溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲亚砜或N-甲基吡咯烷酮。
可选地,所述的醇类为含有α-氢的醇类。
可选地,所述的醇类为异丙醇、苄醇、甲醇或乙醇,优选异丙醇。
可选地,所述加热的温度为90~120℃,优选100℃;或,恒温反应时间为3~48h,优选12h。
本发明的合成方法具有原料廉价易得,反应条件温和,底物适应性好,操作简单,且产品质量稳定,纯度高等特点。本发明合成一系列2,6-二取代芳基硼酸酯类产物作为有机合成中间体有着广泛的应用价值。
具体实施方式
下面通过实施例对本发明作进一步的描述。
实施例1
在25ml使用聚四氟乙烯塞的Schlenk管中,加入小号搅拌子,将醋酸钯4.5mg(0.02mmol)、三(4-氟苯基)膦(0.04mmol)、联频哪醇硼酸酯(0.2mmol)加入后,加入干燥过的碳酸钾(0.8mmol)、碳酸氢钾40mg(0.4mmol)。之后迅速加入降冰片烯(0.3mmol)、2-碘甲苯(0.2mmol)、正溴丁烷(0.4mmol)、异丙醇(0.2mmol)以及N,N-二甲基甲酰胺0.5mL。将反应管于液氮下冷冻30s,取出后抽真空并充入氩气,该操作循环5次直至反应管中充满氩气,后将反应管在油浴100℃下反应12小时。冷却至室温后反应混合物中加入乙酸乙酯10mL稀释,用饱和食盐水(饱和氯化钠溶液,下同)洗涤3次,无水硫酸钠干燥后旋干,通过制备TLC硅胶板纯化(硅胶板厚度1mm,载样量应小于0.5mmol,展开剂比例,石油醚:乙酸乙酯=40:1,比例调节以及分离效果与实际环境温度湿度有关,实例实施温度为25℃,相对湿度50%)一到两次,即得到2-丁基6-甲基频哪醇硼酸酯基苯。
实施例2
在25ml使用聚四氟乙烯塞的Schlenk管中,加入小号搅拌子,将醋酸钯4.5mg(0.02mmol)、三(4-氟苯基)膦(0.04mmol)、联频哪醇硼酸酯(0.2mmol)加入后,加入干燥过的碳酸钾(1.2mmol)、碳酸氢钾40mg(0.6mmol)。之后迅速加入降冰片烯(0.3mmol)、2-碘甲苯(0.2mmol)、正溴丁烷(0.4mmol)、异丙醇(0.2mmol)以及N,N-二甲基甲酰胺0.5mL。将反应管于液氮下冷冻30s,取出后抽真空并充入氩气,该操作循环5次直至反应管中充满氩气,后将反应管在油浴100℃下反应12小时。冷却至室温后反应混合物中加入乙酸乙酯10mL稀释,用饱和食盐水洗涤3次,无水硫酸钠干燥后旋干,通过制备TLC硅胶板纯化(硅胶板厚度1mm,载样量应小于0.5mmol,展开剂比例,石油醚:乙酸乙酯=40:1,比例调节以及分离效果与实际环境温度湿度有关,实例实施温度为25℃,相对湿度50%)一到两次,即得到2-丁基6-甲基频哪醇硼酸酯基苯。
实施例3
在25ml使用聚四氟乙烯塞的Schlenk管中,加入小号搅拌子,将醋酸钯2.3mg(0.01mmol)、三(4-氟苯基)膦(0.04mmol)、联频哪醇硼酸酯(0.2mmol)加入后,加入干燥过的碳酸钾(0.8mmol)、碳酸氢钾40mg(0.4mmol)。之后迅速加入降冰片烯(0.3mmol)、2-碘甲苯(0.2mmol)、正溴丁烷(0.4mmol)、异丙醇(0.2mmol)以及N,N-二甲基甲酰胺0.5mL。将反应管于液氮下冷冻30s,取出后抽真空并充入氩气,该操作循环5次直至反应管中充满氩气,后将反应管在油浴100℃下反应12小时。冷却至室温后反应混合物中加入乙酸乙酯10mL稀释,用饱和食盐水洗涤3次,无水硫酸钠干燥后旋干,通过制备TLC硅胶板纯化(硅胶板厚度1mm,载样量应小于0.5mmol,展开剂比例,石油醚:乙酸乙酯=40:1,比例调节以及分离效果与实际环境温度湿度有关,实例实施温度为25℃,相对湿度50%)一到两次,即得到2-丁基6-甲基频哪醇硼酸酯基苯。
实施例4
在25ml使用聚四氟乙烯塞的Schlenk管中,加入小号搅拌子,将醋酸钯4.5mg(0.02mmol)、三(4-氟苯基)膦(0.04mmol)、联频哪醇硼酸酯(0.2mmol)加入后,加入干燥过的碳酸钾(0.8mmol)、碳酸氢钾40mg(0.4mmol)。之后迅速加入降冰片烯(0.3mmol)、2-碘甲苯(0.2mmol)、正溴丁烷(0.4mmol)、异丙醇(0.2mmol)以及N,N-二甲基甲酰胺0.5mL。将反应管于液氮下冷冻30s,取出后抽真空并充入氩气,该操作循环5次直至反应管中充满氩气,后将反应管在油浴100℃下反应6小时。冷却至室温后反应混合物中加入乙酸乙酯10mL稀释,用饱和食盐水洗涤3次,无水硫酸钠干燥后旋干,通过制备TLC硅胶板纯化(硅胶板厚度1mm,载样量应小于0.5mmol,展开剂比例,石油醚:乙酸乙酯=40:1,比例调节以及分离效果与实际环境温度湿度有关,实例实施温度为25℃,相对湿度50%)一到两次,即得到2-丁基6-甲基频哪醇硼酸酯基苯。
实施例5~20
实施例2~17中除了使用的2-取代碘带芳烃和(或)溴代烃类化合物不同外,其它反应条件相同,具体反应条件为:在25ml使用聚四氟乙烯塞的Schlenk管中,加入小号搅拌子,将醋酸钯4.5mg(0.02mmol)、三(4-氟苯基)膦(0.04mmol)、联频哪醇硼酸酯(0.2mmol)加入后,加入干燥过的碳酸钾(0.8mmol)、碳酸氢钾(0.4mmol)。之后迅速加入降冰片烯(0.3mmol)、相对应的2-取代碘代芳烃(0.2mmol)、溴代烷烃(0.4mmol)、异丙醇(0.2mmol)以及N,N-二甲基甲酰胺0.5mL。将反应管于液氮下冷冻30s,取出后抽真空并充入氩气,该操作循环5次直至反应管中充满氩气,后将反应管在油浴100℃下反应12小时。冷却至室温后反应混合物中加入乙酸乙酯10mL稀释,用饱和食盐水洗涤3次,无水硫酸钠干燥后旋干,通过制备TLC硅胶板纯化(硅胶板厚度1mm,载样量应小于0.5mmol,展开剂比例,石油醚:乙酸乙酯=40:1~20:1,视底物类型决定,实例15、16、17使用30:1进行分离,实例18、19、20使用20:1分离,其余使用40:1进行分离,比例调节以及分离效果与实际环境温度湿度有关,实例实施温度为25℃,相对湿度50%)一到两次,即得到2-取代6-取代频哪醇硼酸酯基芳烃底物。。
所有实施例所使用的2-取代碘代芳烃、溴代烃类化合物和产物,以及核磁产率如表1所示:
表1.钯催化制备2-取代6-取代频哪醇硼酸酯基芳烃类化合物
续表1.钯催化制备2-取代6-取代频哪醇硼酸酯基芳烃类化合物
所有实施例所得到的2-取代6-取代频哪醇硼酸酯基芳烃类化合物均通过核磁共振图谱确认结构,具体如下:
实施例1产物核磁共振谱图数据:1H NMR(600MHz,CDCl3)δ7.15(t,J=7.6Hz,1H),6.97–6.93(m,2H),2.67–2.62(m,2H),2.39(s,3H),1.56–1.56(m,2H),1.39(s,12H),1.38–1.32(m,2H),0.92(t,J=7.4Hz,3H).13C NMR(151MHz,CDCl3)δ146.89,141.48,129.03,126.49,125.64,83.65,36.36,35.08,25.01,22.79,22.22,14.06.HRMS(ESI-TOF)m/z:calculated for C17H27BNaO2 +:297.2002(M+Na)+,found:297.2000.
实施例2产物核磁共振谱图数据:1H NMR(600MHz,CDCl3)δ7.04(s,2H),2.58–2.51(m,2H),2.29(s,3H),1.49–1.45(m,2H),1.31(s,12H),1.28(m,2H),0.85(t,J=7.4Hz,3H).13C NMR(151MHz,CDCl3)δ149.19,143.84,129.42,128.61,123.49,83.91,36.06,34.80,24.99,22.73,22.00,14.02.HRMS(ESI-TOF)m/z:calculated for C17H26BNaO2 +:375.1107(M+Na)+,found:375.1140.
实施例3产物核磁共振谱图数据:1H NMR(600MHz,CDCl3)δ7.44–7.40(m,2H),7.37–7.33(m,2H),7.32–7.28(m,2H),7.11–7.16(m,2H),2.72–2.67(m,2H),1.67–1.60(m,2H),1.43–1.37(m,2H),1.13(s,12H),0.94(t,J=7.3Hz,3H).13C NMR(151MHz,CDCl3)δ146.58,146.43,143.96,129.20,128.69,127.92,127.01,126.83,126.03,83.76,36.43,34.89,24.99,22.91,14.14.HRMS(ESI-TOF)m/z:calculated for C22H29BNaO2 +:359.2158(M+Na)+,found:359.2151.
实施例4产物核磁共振谱图数据:1H NMR(600MHz,CDCl3)δ6.78(s,2H),2.66–2.59(m,2H),2.36(s,3H),2.25(s,3H),1.55–1.51(m,2H),1.37(s,12H),1.37–1.33(m,2H),0.92(t,J=7.4Hz,3H).13C NMR(151MHz,CDCl3)δ147.30,141.80,138.73,127.58,126.64,83.47,36.30,35.27,25.01,22.90,22.20,21.32,14.10.HRMS(ESI-TOF)m/z:calculatedfor C18H29BNaO2 +:311.2158(M+Na)+,found:311.2164.
实施例5产物核磁共振谱图数据:1H NMR(600MHz,CDCl3)δ7.30(t,J=7.6Hz,1H),6.99–6.95(m,2H).,3.77(s,3H),2.71–2.67(m,2H),2.67–2.62(m,2H),1.57–1.54(m,2H),1.39(s,12H),1.36(m,2H),0.92(t,J=7.4Hz,3H).13C NMR(151MHz,CDCl3)δ160.73,151.74,129.67,124.16,112.42,82.90,56.36,34.37,30.80,24.60,22.85,13.68.HRMS(ESI-TOF)m/z:calculated for C17H27BNaO2 +:311.2158(M+Na)+,found:311.2155.
实施例6产物核磁共振谱图数据:1H NMR(600MHz,CDCl3)δ7.15(t,J=7.7Hz,1H),7.00(d,J=7.8Hz,1H),6.89(d,J=7.7Hz,1H),2.96–2.89(m,1H),2.54(t,J=8.1Hz,2H),1.50(d,J=8.8Hz,4H),1.32(s,12H),1.17(m,6H),0.85(t,J=7.6Hz,3H).13C NMR(151MHz,CDCl3)δ152.31,146.09,129.10,125.74,121.27,83.78,36.50,34.82,33.97,25.06,24.42,22.88,14.10.HRMS(ESI-TOF)m/z:calculated for C12H31BNaO2 +:325.2315(M+Na)+,found:325.2308.
实施例7产物核磁共振谱图数据:1H NMR(600MHz,CDCl3)δ7.22(d,J=8.2Hz,1H),6.91(d,J=8.1Hz,1H),2.59(t,J=8.0Hz,2H),2.41(s,3H),1.57–1.52(m,2H),1.40(s,12H),1.38–1.32(m,2H),0.91(t,J=7.4Hz,3H).13C NMR(151MHz,CDCl3)δ145.15,138.35,131.60,129.71,127.36,84.10,35.83,34.77,25.06,22.69,19.79,14.04.HRMS(ESI-TOF)m/z:calculated for C17H26BClNaO2 +:331.1612(M+Na)+,found:331.1613.
实施例8产物核磁共振谱图数据:1H NMR(600MHz,CDCl3)δ6.94–6.86(m,2H),2.63–2.58(m,2H),2.29(d,J=2.3Hz,3H),1.55–1.51(m,2H),1.40(s,12H),1.36–1.33(m,2H),0.91(t,J=7.4Hz,3H).13C NMR(151MHz,CDCl3)δ159.25(d,J=241.8Hz),142.24(d,J=3.6Hz),127.56(d,J=15.2Hz),127.38(d,J=7.6Hz),115.58(d,J=22.7Hz),84.01,35.64,35.12,25.04,22.69,14.05,14.00(d,J=4.9Hz).HRMS(ESI-TOF)m/z:calculatedfor C17H27BFNaO2 +:315.1908(M+Na)+,found:315.1903.
实施例9产物核磁共振谱图数据:1H NMR(600MHz,CDCl3)δ7.15(t,J=7.6Hz,1H),6.95(d,J=7.6Hz,2H),2.65–2.60(m,2H),2.39(s,3H),1.62–1.59(m,2H),1.39(s,12H),0.94(d,J=7.3Hz,3H).13C NMR(151MHz,CDCl3)δ146.71,141.51,129.03,126.57,125.77,83.68,38.69,26.00,25.02,24.79,22.24.HRMS(ESI-TOF)m/z:calculated for C16H25BNaO2 +:283.1845(M+Na)+,found:283.1840.
实施例10产物核磁共振谱图数据:1H NMR(600MHz,CDCl3)δ7.14(t,J=7.6Hz,1H),6.96–6.92(m,2H),2.66–2.60(m,2H),2.39(s,3H),1.57–1.54(m,2H),1.39(s,12H),1.32(m,4H),0.90–0.87(m,3H).13C NMR(151MHz,CDCl3)δ146.98,141.52,129.07,126.53,125.67,83.68,36.70,32.68,31.99,25.04,22.65,22.25,14.10.HRMS(ESI-TOF)m/z:calculated for C18H29BNaO2 +:311.2158(M+Na)+,found:311.2165.
实施例11产物核磁共振谱图数据:1H NMR(600MHz,CDCl3)δ7.07(t,J=7.6Hz,1H),6.88(d,J=7.5Hz,1H),6.84(d,J=7.6Hz,1H),2.46(d,J=7.4Hz,2H),2.33(s,3H),1.80–1.72(m,1H),1.32(s,12H),0.81(d,J=6.6Hz,6H).13C NMR(151MHz,CDCl3)δ145.62,141.53,128.72,126.67,126.64,83.67,45.63,30.89,25.11,22.48,22.31.HRMS(ESI-TOF)m/z:calculated for C17H27BNaO2 +:297.2002(M+Na)+,found:297.2005.
实施例12产物核磁共振谱图数据:1H NMR(600MHz,CDCl3)δ7.16(t,J=7.6Hz,1H),6.98–6.94(m,2H),3.37(t,J=5.8Hz,2H),3.33(s,3H),2.74–2.70(m,2H),2.40(s,3H),1.88–1.83(m,2H),1.39(s,12H).13C NMR(151MHz,CDCl3)δ145.99,141.74,129.15,126.76,125.85,83.75,72.18,58.51,32.87,32.39,25.03,22.27.HRMS(ESI-TOF)m/z:calculatedfor C17H27BNaO3 +:313.1951(M+Na)+,found:313.1968.
实施例13产物核磁共振谱图数据:1H NMR(600MHz,CDCl3)δ7.08(t,J=7.6Hz,1H),6.91–6.86(m,2H),3.31(d,J=6.2Hz,2H),3.25(s,3H),2.60(t,J=7.3Hz,2H),2.32(s,3H),1.57–1.54(m,4H),1.32(s,12H).13C NMR(151MHz,CDCl3)δ146.47,141.63,129.12,126.68,125.69,83.71,72.83,58.55,36.33,29.62,29.23,25.04,22.26.HRMS(ESI-TOF)m/z:calculated for C18H29BNaO3 +:327.2107(M+Na)+,found:327.2115.
实施例14产物核磁共振谱图数据:1H NMR(600MHz,CDCl3)δ7.28–7.24(m,2H),7.18(d,J=6.7Hz,2H),7.15(t,J=7.6Hz,2H),6.98–6.94(m,2H),2.72–2.65(m,4H),2.39(s,3H),1.95–1.90(m,2H),1.36(s,12H).13C NMR(151MHz,CDCl3)δ146.36,142.47,141.66,129.14,128.45,128.26,126.71,125.67,125.64,83.70,36.31,36.00,34.33,25.03,22.27.HRMS(ESI-TOF)m/z:calculated for C22H29BNaO2 +:359.2158(M+Na)+,found:359.2163.
实施例15产物核磁共振谱图数据:1H NMR(600MHz,CDCl3)δ7.15(t,J=7.6Hz,1H),6.97–6.93(dd,J=7.6,4.9Hz,2H),4.11(q,J=7.2Hz,2H),2.70–2.64(m,2H),2.39(s,3H),2.30(d,J=7.6Hz,2H),1.69–1.65(m,2H),1.64–1.60(m,2H),1.39(s,12H),1.24(m 3H)13CNMR(151MHz,CDCl3)δ173.75,146.28,141.73,129.17,126.75,125.69,83.73,60.20,36.25,34.34,32.35,25.04,24.97,22.27,14.26.HRMS(ESI-TOF)m/z:calculated forC21H32BNaO4 +:369.2213,found:369.2220.
实施例16产物核磁共振谱图数据:1H NMR(600MHz,CDCl3)δ7.15(t,J=7.6Hz,1H),6.95(t,J=7.5Hz,2H),4.05(t,J=6.8Hz,2H),2.68–2.62(m,2H),2.39(s,3H),2.04(s,3H),1.68–1.57(m,6H),1.39(s,12H)13C NMR(151MHz,CDCl3)δ171.24,146.48,141.70,129.14,126.71,125.69,83.70,64.58,36.50,32.48,28.58,25.94,25.04,22.27,21.04.HRMS(ESI-TOF)m/z:calculated for C21H32BNaO4 +:369.2213,found:369.2221.
实施例17产物核磁共振谱图数据:1H NMR(600MHz,CDCl3)δ7.17(t,J=7.6Hz,1H),6.98(d,J=7.6Hz,1H),6.94(d,J=7.6Hz,1H),2.70(t,J=7.5Hz,2H),2.40(s,3H),2.33(t,J=7.0Hz,2H),1.75(m,2H),1.70–1.66(m,2H),1.39(s,12H).13C NMR(151MHz,CDCl3)δ145.34,142.08,129.32,127.09,125.69,119.79,83.81,35.49,31.45,25.06,22.33,17.10.HRMS(ESI-TOF)m/z:calculated for C18H26BNNaO2 +:322.1954(M+Na)+,found:322.1970.
上述的对实施例的描述是为了便于该技术领域的普通技术人员能理解和应用本发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改,并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此,本发明不限于这里的实施例,本领域技术人员根据本发明的揭示,对于本发明做出的改进和修改都应该在本发明的保护范围之内。
Claims (8)
1.一种制备2,6-二取代芳基硼酸酯类化合物的方法,其特征在于,其合成反应式为:
;
所述的反应式中的R1为甲基、乙基、异丙基或苯基,R2为氢、4-溴、5-苯基、4-甲基、5-氯或5-氟或4-甲酸甲酯基,R3为正丙基、正丁基、正戊基、仲丁基、3-甲氧基丙基、4-甲氧基丁基、3-苯基丙基、戊酸乙酯基、5-乙酰氧基戊基或正戊氰基、乙基、己基;
所述制备2,6-二取代芳基硼酸酯类化合物的方法,包括以下步骤:在反应管中,加入1-取代2-碘代芳烃类化合物、1-溴代烃类化合物、联频哪醇硼酸酯、钯催化剂和膦配体,加入降冰片烯,加入无机碱1以及无机碱2,加入醇,加入溶剂,体系置换为惰性气体保护,加热,恒温反应,然后分离纯化得到2,6-二取代芳基硼酸酯类化合物;其中,无机碱1、无机碱2为碳酸氢钾、碳酸氢钠、碳酸钾、碳酸钠、醋酸钾、醋酸钠、碳酸锂、碳酸铯或氢氧化钠;所述的醇为异丙醇、苄醇、甲醇或乙醇。
2.根据权利要求1所述的制备2,6-二取代芳基硼酸酯类化合物的方法,其特征在于:其中1-取代2-碘代芳烃类化合物、1-溴代烃类化合物、联频哪醇硼酸酯、钯催化剂、膦配体、降冰片烯、无机碱1、无机碱2、醇的摩尔比依次为1:(2 ~ 3):(1~2):(0.05 ~ 0.2):(0.1 ~0.4):(1 ~ 1.5):(2 ~ 6):(1 ~ 3):(1 ~ 2)。
3.根据权利要求1所述的制备2,6-二取代芳基硼酸酯类化合物的方法,其特征在于:
所述的钯催化剂为乙酸钯、氯化钯、四三苯基膦钯、二(三苯基膦)二氯化钯、三(二亚苄基丙酮)二钯或二(二亚苄基丙酮)钯。
4.根据权利要求1所述的制备2,6-二取代芳基硼酸酯类化合物的方法,其特征在于:
所述的膦配体为三苯基膦、三(邻甲基苯基)膦、三(对甲基苯基)膦、三(邻甲氧基苯基)膦、三(对甲氧基苯基)膦、三(4-氟苯基)膦、三(4-三氟甲基苯基)膦、三环己基膦、三叔丁基膦、三(2-呋喃基)膦、x-phos、s-phos、dppe或dppp。
5.根据权利要求1所述的制备2,6-二取代芳基硼酸酯类化合物的方法,其特征在于:
无机碱1或无机碱2中至少包括碳酸钾、碳酸氢钾、碳酸钠其中之一。
6.根据权利要求1所述的制备2,6-二取代芳基硼酸酯类化合物的方法,其特征在于:
所述的溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲亚砜或N-甲基吡咯烷酮。
7.根据权利要求1所述的制备2,6-二取代芳基硼酸酯类化合物的方法,其特征在于:加热的温度为90~120℃;或,恒温反应时间为3~48h。
8.根据权利要求1所述的制备2,6-二取代芳基硼酸酯类化合物的方法,其特征在于:
1-取代2-碘代芳烃类化合物与联频哪醇硼酸酯的摩尔比为1:1;加热的温度为100℃;恒温反应时间为12h。
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