CN107090008B - 一种自负载双膦-钯催化剂及其制备方法和用途 - Google Patents
一种自负载双膦-钯催化剂及其制备方法和用途 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims abstract description 12
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 5
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 16
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 239000011777 magnesium Substances 0.000 claims description 11
- 229910052749 magnesium Inorganic materials 0.000 claims description 11
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 9
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- 238000004519 manufacturing process Methods 0.000 claims 1
- BHIIGRBMZRSDRI-UHFFFAOYSA-N [chloro(phenoxy)phosphoryl]oxybenzene Chemical compound C=1C=CC=CC=1OP(=O)(Cl)OC1=CC=CC=C1 BHIIGRBMZRSDRI-UHFFFAOYSA-N 0.000 abstract description 7
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- 239000007787 solid Substances 0.000 description 15
- -1 1, 4-dibromobenzene (4, 4-dibromobiphenyl) Chemical group 0.000 description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
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- ZZLCFHIKESPLTH-UHFFFAOYSA-N 4-Methylbiphenyl Chemical group C1=CC(C)=CC=C1C1=CC=CC=C1 ZZLCFHIKESPLTH-UHFFFAOYSA-N 0.000 description 2
- FTDZECHQBVIHKZ-UHFFFAOYSA-N 5,5-dibromo-2-phenylcyclohexa-1,3-diene Chemical group C1=CC(Br)(Br)CC=C1C1=CC=CC=C1 FTDZECHQBVIHKZ-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
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- QCZZSANNLWPGEA-UHFFFAOYSA-N 1-(4-phenylphenyl)ethanone Chemical group C1=CC(C(=O)C)=CC=C1C1=CC=CC=C1 QCZZSANNLWPGEA-UHFFFAOYSA-N 0.000 description 1
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- ZBTMRBYMKUEVEU-UHFFFAOYSA-N 1-bromo-4-methylbenzene Chemical compound CC1=CC=C(Br)C=C1 ZBTMRBYMKUEVEU-UHFFFAOYSA-N 0.000 description 1
- NLWCWEGVNJVLAX-UHFFFAOYSA-N 1-methoxy-2-phenylbenzene Chemical group COC1=CC=CC=C1C1=CC=CC=C1 NLWCWEGVNJVLAX-UHFFFAOYSA-N 0.000 description 1
- KQMIWCAOEFUBQK-UHFFFAOYSA-N 1-methoxy-3-phenylbenzene Chemical group COC1=CC=CC(C=2C=CC=CC=2)=C1 KQMIWCAOEFUBQK-UHFFFAOYSA-N 0.000 description 1
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- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
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- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
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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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/006—Palladium compounds
- C07F15/0066—Palladium compounds without a metal-carbon linkage
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
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- C07—ORGANIC CHEMISTRY
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- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
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- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
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- 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
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Abstract
本发明涉及一种自负载双膦‑钯催化剂的制备方法和用途。以二苯基磷氯为原料,经格式试剂取代氯后与二氯化钯配位形成催化剂。本发明所述催化剂具有如下优点:(1)所述催化剂具有较高的热稳定性;(2)所述催化剂可用于温和条件下催化Suzuki‑Miyaura偶联反应并取得优异的催化效果;(3)所述催化剂在催化反应完成后通过简单的离心过滤即可重复使用,解决了均相催化剂回收重复利用的难题。该方法反应路线简单可行,可作为高效催化剂运用于医药、香料、农药及功能性材料的合成中。
Description
技术领域
本发明涉及一种自负载双膦-钯催化剂及其制备方法和用途。
背景技术
钯催化的芳基卤代物与芳基硼酸的Suzuki-Miyaura偶联反应是构建精细化学品、药物和农业化学品最有效的合成转化途径。通常,偶联反应可以在均相钯催化剂的存在下有效地进行,然而均相钯催化仍存在一些缺点,包括催化剂的分离回收和再利用,以及金属催化剂的不完全分离导致的产物污染等诸多问题。解决这些问题的典型方法是将钯催化剂锚定在合适的载体上以制成相应的非均相钯催化剂,然而其中一些非均相钯催化剂与均相对应物相比显示出较低的催化活性,因此在非均相钯催化剂活性的增强上仍然需要更深层次的进展。
在非均相催化剂的领域里,一种通过活性金属中心和有机配体之间的配位键来用于催化剂的固定的自支持策略已经发展起来,此方法所得到的有机金属聚合物通常具有不易水解以及高的热稳定性的特点。因其金属-配体单元均匀地分布在聚合物主链中,使得反应底物更容易接近催化位点,增强了传质作用以及具有良好的反应效率。由于金属和配体的多样性,有机金属聚合物的催化性能可以通过精细地调节以满足具体要求,因此这类有机-无机混合材料已经可以较容易获得并成功地用作非均相催化剂的制备当中。
膦因具有强的σ供体能力和易于制备等特点已发展成为了一类通用的配体并被广泛用作非均相过渡金属催化剂中的官能团,通过适当设计,二膦-金属聚合物应该具有作为有效的非均相催化剂的能力。
本发明中,我们设计合成了两种二膦配体,并将其用作钯配体以构建有机金属聚合物催化剂。该催化剂具有较高的热稳定性,并在温和条件下催化Suzuki-Miyaura偶联反应取得了优异的催化效果,在催化反应完成后通过简单的离心过滤即可重复使用,解决了均相催化剂回收重复利用的难题。
发明内容
本发明所要解决的问题是提供能高效催化Suzuki-Miyaura偶联反应且易于回收循环使用的双膦-钯催化剂及其制备方法和用途,本发明原料及试剂简单易得,路线可行,反应后处理简单。
本发明提供的技术方案是两种双膦-钯催化剂,其结构如下述式3或式4:
本发明还提供了上述两种双膦-钯催化剂的制备方法,该方法包括下述步骤:
(a)室温下将氯化钯加入到盐酸中,盐酸的用量是氯化钯物质的量的3~10倍,加乙醇稀释,乙醇体积是盐酸的1~4倍。
(b)在干燥的有机溶剂中,同时加入镁屑,1粒(35 mg)碘及1,4-二溴苯(4,4-二溴联苯)反应,之后加入二苯基磷氯室温下搅拌8 h得到化合物1(2),反应时间为1~10 h,反应温度为20~60 ℃,上述三种物质的摩尔比为镁屑:1,4-二溴苯(4,4-二溴联苯):二苯基膦氯=3~6:1:2。
(c)将与氯化钯等物质的量的1(2)加入到1,2-二氯乙烷和乙醇的混合溶剂中,加热至60 ℃溶解,两种溶剂的体积比为1,2-二氯乙烷:乙醇=1:1~6。
(d)将步骤(a)得到的溶液加到步骤(c)得到的溶液中,在40~80 ℃保温反应12~72h,然后冷却,过滤,洗涤,干燥得到自聚合双膦-钯催化剂3(4)。
上述化合物1,2具有如下结构式:
所述盐酸浓度为12N,有机溶剂为甲苯,乙腈,四氢呋喃或N,N’-二甲基甲酰胺,镁屑为处理掉表面氧化层后干燥的镁屑。
上述反应过程由如下反应式表示:
本发明提供的两种双膦-钯催化剂的用途,是用于催化Suzuki-Miyaura偶联反应,由如下反应式表示:
其中:
R1为H、p-CH3O、m-CH3O、o-CH3O、p-CH3、p-CF3、p-CN、p-NO2;
R2为H、p-CH3O、p-CH3、p-COCH3;
X为I、Br、Cl;
碱为碳酸钾,乙酸钾,氢氧化钠,碳酸铯等。
本发明提供一种自负载双膦-钯催化剂的制备方法和用途。以二苯基磷氯为原料,经格式试剂取代氯后与二氯化钯配位形成催化剂。该催化剂具有较高的热稳定性,并在温和条件下催化Suzuki-Miyaura偶联反应取得了优异的催化效果,在催化反应完成后通过简单的离心过滤即可重复使用,解决了均相催化剂回收重复利用的难题。该方法反应路线简单可行,可作为高效催化剂应用于医药、香料、农药及功能性材料的合成中。
具体实施方式
通过以下实施例将有助于理解本发明,但并不限制本发明的内容。
实施例1-8:双膦-钯催化剂的制备方法。
实施例 1
镁屑(144 mg, 6 mmol),1粒(约35 mg,以下皆同)碘及1,4-二溴苯(468 mg, 2mmol)溶于干燥的N,N’-二甲基甲酰胺(6 mL)中,40 ℃反应6 h,加入二苯基磷氯(880 mg,4 mmol),室温下搅拌8 h,反应结束后氯化铵水溶液洗涤,乙酸乙酯萃取,干燥,通过柱层析(展开剂为石油醚)得白色固体1(268 mg,60%)。M.p. 166-167 °C;IR(KBr):υ 3053, 1478,1433, 1092, 821, 741, 694, 552, 513, 483 cm-1;1H-NMR (600 MHz, CDCl3, 25 ℃,TMS): δ = 7.22-7.24 (m, 4H), 7.31-7.33 (m, 20H);13C-NMR (150 MHz, CDCl3, 25℃, TMS): δ = 128.49, 128.82, 133.34, 133.80, 136.71, 137.93; 31P-NMR (240MHz,CDCl3, 25 ℃, TMS): δ = -6.64。
实施例 2
镁屑(288 mg, 12 mmol),1粒碘及1,4-二溴苯(624 mg, 2 mmol)溶于干燥的四氢呋喃(6 mL)中,60 ℃反应8 h,加入二苯基磷氯(880 mg, 4 mmol),室温下搅拌8 h,反应结束后氯化铵水溶液洗涤,乙酸乙酯萃取,干燥,通过柱层析(展开剂为石油醚)得白色固体1(335 mg,75%)。M.p. 166-167 °C;IR(KBr):υ 3053, 1478, 1433, 1092, 821, 741, 694,552, 513, 483 cm-1;1H-NMR (600 MHz, CDCl3, 25 ℃, TMS): δ = 7.22-7.24 (m, 4H), 7.31-7.33 (m, 20 H);13C-NMR (150 MHz, CDCl3, 25 ℃, TMS): δ= 128.49,128.82, 133.34, 133.80, 136.71, 137.93; 31P-NMR (240 MHz,CDCl3, 25 ℃, TMS): δ=-6.64。
实施例 3
镁屑(144 mg, 6 mmol),1粒碘及4,4-二溴联苯(624 mg, 2 mmol)溶于干燥的N,N’-二甲基甲酰胺(6 mL)中,40 ℃反应6 h,加入二苯基磷氯(880 mg, 4 mmol),室温下搅拌8 h,反应结束后氯化铵水溶液洗涤,乙酸乙酯萃取,干燥,通过柱层析(展开剂为石油醚)得白色固体2(235 mg,45%)。M.p. 192.5-194.0 °C;IR(KBr):υ 3053, 3012, 1584, 1475,1432, 1092, 818, 745, 695, 508, 492 cm-1;1H-NMR (600 MHz, CDCl3, 25 ℃, TMS):δ = 7.34-7.38 (m, 24H), 7.55-7.57 (m, 4H);13C-NMR (150 MHz, CDCl3, 25 ℃,TMS): δ = 127.25, 128.75, 129.01, 133.97, 134.38, 136.72 137.23, 140.92; 31P-NMR (240 MHz, CDCl3, 25 ℃, TMS): δ = -6.97。
实施例 4
镁屑(288 mg, 12 mmol),1粒碘及4,4-二溴联苯(624 mg, 2 mmol)溶于干燥的四氢呋喃(6 mL)中,60 ℃反应8 h,加入二苯基磷氯(880 mg, 4 mmol),室温下搅拌8 h,反应结束后氯化铵水溶液洗涤,乙酸乙酯萃取,干燥,通过柱层析(展开剂为石油醚)得白色固体2(366 mg,70%)。M.p. 192.5-194.0 °C;IR(KBr):υ 3053, 3012, 1584, 1475, 1432,1092, 818, 745, 695, 508, 492 cm-1;1H-NMR (600 MHz, CDCl3, 25 ℃, TMS): δ =7.34-7.38 (m, 24H), 7.55-7.57 (m, 4H);13C-NMR (150 MHz, CDCl3, 25 ℃, TMS): δ= 127.25, 128.75, 129.01, 133.97, 134.38, 136.72 137.23, 140.92; 31P-NMR (240MHz,CDCl3, 25 ℃, TMS): δ = -6.97。
实施例 5
将化合物1(223 mg, 0.5 mmol)溶解于60℃的25 mL1,2-二氯乙烷和乙醇的混合溶剂(V1,2-二氯乙烷:V乙醇=1:4)中,室温下将氯化钯(89 mg, 0.5 mmol)加入到浓盐酸(0.25 mL)中溶解,再加乙醇(0.5 mL)稀释,之后将其逐滴加入到上述溶液中,40 ℃反应24 h,离心,沉淀干燥得亮黄色固体化合物,即为双膦-钯催化剂3(225 mg)。M.p.>300℃;IR(KBr):υ3054, 1480, 1435, 1097, 743, 692, 543, 534 cm-1;13C CP/MAS NMR: δ = 127.3,129.7, 134.3, 137.5;31P CP/MAS NMR: δ =4.2, 17.2, 23.8。
实施例 6
将化合物1(223 mg, 0.5 mmol)溶解于60℃的25 mL混合溶剂(V1,2-二氯乙烷:V乙醇=1:6)中,室温下将氯化钯(89 mg, 0.5 mmol)加入到浓盐酸(0.25 mL)中溶解,再加乙醇(0.5 mL)稀释,之后将其逐滴加入到上述溶液中,80 ℃反应48 h,离心,沉淀干燥得亮黄色固体化合物,即为双膦-钯催化剂3(270 mg)。M.p.>300℃;IR(KBr):υ 3054, 1480,1435, 1097, 743, 692, 543, 534 cm-1。13C CP/MAS NMR: δ = 127.3, 129.7, 134.3,137.5;31P CP/MAS NMR: δ = 4.2, 17.2, 23.8。
实施例 7
将化合物2(261 mg, 0.5 mmol)溶解于60℃的30 mL混合溶剂(V1,2-二氯乙烷:V乙醇=1:2)中,室温下将氯化钯(89 mg, 0.5 mmol)加入到浓盐酸(0.25 mL)中溶解,再加乙醇(0.5mL)稀释,之后将其逐滴加入到上述溶液中,40 ℃反应24 h,离心,沉淀干燥得黄棕色固体化合物,即为双膦-钯催化剂4(206 mg)。M.p.>300℃;IR(KBr):υ 3052, 1481, 1434,1097, 743, 703, 691, 510 cm-1。13C CP/MAS NMR: δ = 124.7, 127.3, 129.1, 132.9,135.3, 139.4;31P CP/MAS NMR: δ = 4.6, 23.4。
实施例 8
将化合物2(261 mg, 0.5 mmol)溶解于60℃的30 mL混合溶剂(V1,2-二氯乙烷:V乙醇=1:3)中,室温下将氯化钯(89 mg, 0.5 mmol)加入到浓盐酸(0.25 mL)中溶解,再加乙醇(0.5mL)稀释,之后将其逐滴加入到上述溶液中,80 ℃反应48 h,离心,沉淀干燥得黄棕色固体化合物,即为双膦-钯催化剂4(285 mg)。M.p.>300℃;IR(KBr):υ 3052, 1481, 1434,1097, 743, 703, 691, 510 cm-1。13C CP/MAS NMR: δ = 124.7, 127.3, 129.1, 132.9,135.3, 139.4;31P CP/MAS NMR: δ = 4.6, 23.4。
实施例9-15:双膦-钯催化剂的用途。
实施例 9
2-溴苯甲醚(0.126 mL,1.0 mmol),苯硼酸(0.170 g,1.5 mmol),碳酸钾(0.277g,2.0 mmol),催化剂3(1.9 mg,0.003 mmol)加入乙醇和水(1/1,体积比)的混合溶液(3mL)中,25 ℃反应3.5 h。反应结束后加入二氯甲烷(5 mL),离心,沉淀干燥得到回收催化剂3(1.9 mg,回收率100%)。上清液用饱和食盐水洗涤(5 mL×3),无水硫酸镁干燥,过滤,滤液浓缩,柱层析(展开剂为石油醚)得白色固体2-甲氧基联苯(0.176 g,96%)。M.p.:30~32 ℃;1H NMR(400 MHz,CDCl3):δ = 3.78 (s, 3H), 6.97 (d, J = 8.5 Hz, 1H), 7.02 (t, J = 7.5 Hz,1H), 7.30(t, J = 7.1 Hz, 3H), 7.39 (t, J =7.6 Hz, 2H), 7.52 (d, J =7.6 Hz, 2H)。
实施例 10
3-溴苯甲醚(0.125 mL,1.0 mmol),苯硼酸(0.170 g,1.5 mmol),碳酸钾(0.277g,2.0 mmol),催化剂3(1.9 mg,0.003 mmol)加入乙醇和水(1/1,体积比)的混合溶液(3mL)中,25 ℃反应3.5 h。反应结束后加入二氯甲烷(5 mL),离心,沉淀干燥得到回收催化剂3(1.9 mg,回收率100%)。上清液用饱和食盐水洗涤(5 mL×3),无水硫酸镁干燥,过滤,滤液浓缩,柱层析(展开剂为石油醚)得白色固体3-甲氧基联苯(0.180 g,98%)。M.p.:30~32 ℃;1H NMR(400 MHz,CDCl3):δ = 3.78 (s, 3H), 6.86 (d, J = 8.2 Hz, 1H), 7.11 (s,1H), 7.15 (d, J = 7.7 Hz, 1H), 7.28-7.32 (m, 2H), 7.38 (t, J = 7.5 Hz, 2H),7.56 (d, J = 8.0 Hz, 2H)。
实施例 11
4-溴苯甲醚(0.125 mL,1.0 mmol),苯硼酸(0.170 g,1.5 mmol),碳酸钾(0.277g,2.0 mmol),催化剂3(1.9 mg,0.003 mmol)加入乙醇和水(1/1,体积比)的混合溶液(3mL)中,25 ℃反应3.5 h。反应结束后加入二氯甲烷(5 mL),离心,沉淀干燥得到回收催化剂3(1.9 mg,回收率100%)。上清液用饱和食盐水洗涤(5 mL×3),无水硫酸镁干燥,过滤,滤液浓缩,柱层析(展开剂为石油醚)得白色固体4-甲氧基联苯(0.180 g,98%)。M.p.:85~87 ℃;1H NMR(400 MHz,CDCl3):δ = 3.85 (s, 3H), 6.98 (d, J = 8.4 Hz, 2H), 7.30 (t, J = 7.4 Hz, 1H), 7.41 (t, J = 15 Hz, 2H), 7.52-7.56 (m, 4H)。
实施例 12
4-乙酰基溴苯(0.20 g,1.0 mmol),苯硼酸(0.170 g,1.5 mmol),碳酸钾(0.277g,2.0 mmol),催化剂4(2.2 mg,0.003 mmol)加入乙醇和水(1/1,体积比)的混合溶液(3mL)中,25 ℃反应3 h。反应结束后加入二氯甲烷(5 mL),离心,沉淀干燥得到回收催化剂4(2.2 mg,回收率100%)。上清液用饱和食盐水洗涤(5 mL×3),无水硫酸镁干燥,过滤,滤液浓缩,柱层析(展开剂为石油醚)得白色固体4-乙酰基联苯(0.194g,99%)。M.p.:152~154℃;1H NMR(400 MHz,CDCl3):δ = 2.62 (s, 3H), 7.39 (t, J =7.3 Hz, 1H), 7.46 (t, J =7.3 Hz, 2H), 7.62 (d, J = 7.2 Hz, 2H), 7.67 (d, J = 7.2 Hz, 2H), 8.02 (d, J = 6.8 Hz, 2H)。
实施例 13
4-甲基溴苯(0.123 mL,1.0 mmol),苯硼酸(0.170 g,1.5 mmol),碳酸钾(0.277g,2.0 mmol),催化剂4(2.2 mg,0.003 mmol)加入乙醇和水(1/1,体积比)的混合溶液(3mL)中,25 ℃反应3 h。反应结束后加入二氯甲烷(5 mL),离心,沉淀干燥得到回收催化剂4(2.2 mg,回收率100%)。上清液用饱和食盐水洗涤(5 mL×3),无水硫酸镁干燥,过滤,滤液浓缩,柱层析(展开剂为石油醚)得白色固体4-甲基联苯(0.165g,98%)。M.p.:45~47 ℃;1HNMR(400 MHz,CDCl3):δ = 2.34 (s, 3H), 7.19 (d, J = 8.0 Hz, 2H), 7.25-7.39 (m,1H), 7.37 (t, J =7.5 Hz, 2H), 7.45 (d, J = 8.0 Hz, 2H), 7.54 (d, J = 7.2Hz,2H)。
实施例 14
碘苯(0.111 mL,1.0 mmol),苯硼酸(0.170 g,1.5 mmol),碳酸钾(0.277 g,2.0mmol),催化剂4(2.2 mg,0.003 mmol)加入乙醇和水(1/1,体积比)的混合溶液(3 mL)中,25℃反应3 h。反应结束后加入二氯甲烷(5 mL),离心,沉淀干燥得到回收催化剂4(2.2 mg,回收率100%)。上清液用饱和食盐水洗涤(5 mL×3),无水硫酸镁干燥,过滤,滤液浓缩,柱层析(展开剂为石油醚)得白色固体联苯(0.153g,99%)。M.p.:67~69 ℃;1H NMR (400 MHz,CDCl3): δ 7.32-7.36 (m, 2H), 7.42-7.46 (m, 4H), 7.58-7.60 (m, 4H)。
实施例 15
溴苯(0.112 mL,1.0 mmol),4-甲氧基苯硼酸(0.228 g,1.5 mmol),碳酸钾(0.277g,2.0 mmol),催化剂3(1.9 mg,0.003 mmol)加入乙醇和水(1/1,体积比)的混合溶液(3mL)中,25 ℃反应3.5 h。反应结束后加入二氯甲烷(5 mL),离心,沉淀干燥得到回收催化剂3(1.9 mg,回收率100%)。上清液用饱和食盐水洗涤(5 mL×3),无水硫酸镁干燥,过滤,滤液浓缩,柱层析(展开剂为石油醚)得白色固体4-甲氧基联苯(0.180g,98%)。M.p.:85~87 ℃;1H NMR (400 MHz, CDCl3): δ = 3.85 (s, 3H), 6.98 (d, J = 8.4 Hz, 2H), 7.30 (t,J = 7.4 Hz, 1H), 7.41 (t, J = 15 Hz, 2H), 7.52-7.56 (m, 4H)。
Claims (4)
2.一种制备权利要求1所述的自负载双膦-钯催化剂的方法,该方法包括下述步骤:
(a)室温下将氯化钯加入到盐酸中,盐酸的用量是氯化钯物质的量的3~10倍,加乙醇稀释,乙醇体积是盐酸的1~4倍;
(b)在干燥的有机溶剂中,同时加入镁屑,1粒碘及1,4-二溴苯或4,4’-二溴联苯反应,反应时间为1~10 h,反应温度为20~60 ℃,之后加入二苯基氯化膦室温下搅拌8 h得到化合物1或化合物2,上述三种物质的摩尔比为镁屑:1,4-二溴苯或4,4’ -二溴联苯:二苯基氯化膦=3~6:1:2;
(c)将与氯化钯等物质的量的化合物1或化合物2加入到1,2-二氯乙烷和乙醇的混合溶剂中,加热至60 ℃溶解,两种溶剂的体积比为1,2-二氯乙烷:乙醇=1:1~6;
(d)将步骤(a)得到的溶液加到步骤(c)得到的溶液中,在40~80 ℃保温反应12~72 h,然后冷却,过滤,洗涤,干燥得到如式3或式4所述自负载双膦-钯催化剂;
上述化合物1,2具有如下结构式:
3.根据权利要求2所述的方法,其特征在于所述步骤(a)中盐酸浓度为12 N,步骤(b)中有机溶剂为甲苯,乙腈,四氢呋喃或N,N-二甲基甲酰胺,镁屑为处理掉表面氧化层后干燥的镁屑。
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