CN105396616A - 一种金属钯催化剂及其制备方法和应用 - Google Patents
一种金属钯催化剂及其制备方法和应用 Download PDFInfo
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 163
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 82
- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 29
- 239000002184 metal Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 7
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 28
- -1 phosphine small molecules Chemical class 0.000 claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 14
- 238000006069 Suzuki reaction reaction Methods 0.000 claims abstract description 9
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 75
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 39
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 30
- 238000001816 cooling Methods 0.000 claims description 24
- WDFQBORIUYODSI-UHFFFAOYSA-N 4-bromoaniline Chemical compound NC1=CC=C(Br)C=C1 WDFQBORIUYODSI-UHFFFAOYSA-N 0.000 claims description 16
- 150000001412 amines Chemical class 0.000 claims description 16
- 150000002940 palladium Chemical class 0.000 claims description 14
- 238000006555 catalytic reaction Methods 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 9
- VLVCDUSVTXIWGW-UHFFFAOYSA-N 4-iodoaniline Chemical compound NC1=CC=C(I)C=C1 VLVCDUSVTXIWGW-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 claims description 6
- WDIIYWASEVHBBT-UHFFFAOYSA-N di(propan-2-yl)phosphane Chemical compound CC(C)PC(C)C WDIIYWASEVHBBT-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- 239000011261 inert gas Substances 0.000 claims description 5
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000010668 complexation reaction Methods 0.000 claims description 3
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 239000003446 ligand Substances 0.000 abstract description 5
- 239000003814 drug Substances 0.000 abstract description 4
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- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 230000003321 amplification Effects 0.000 abstract description 3
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 239000005740 Boscalid Substances 0.000 abstract description 2
- DIGGWMOTBUMCTG-UHFFFAOYSA-N P.[C] Chemical compound P.[C] DIGGWMOTBUMCTG-UHFFFAOYSA-N 0.000 abstract description 2
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 abstract description 2
- 229940118790 boscalid Drugs 0.000 abstract description 2
- WYEMLYFITZORAB-UHFFFAOYSA-N boscalid Chemical compound C1=CC(Cl)=CC=C1C1=CC=CC=C1NC(=O)C1=CC=CN=C1Cl WYEMLYFITZORAB-UHFFFAOYSA-N 0.000 abstract description 2
- 229920001940 conductive polymer Polymers 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 abstract description 2
- 229920000767 polyaniline Polymers 0.000 abstract description 2
- OMNWKPZIFZJANV-UHFFFAOYSA-N 1-(4-chlorophenyl)-2-nitrobenzene Chemical group [O-][N+](=O)C1=CC=CC=C1C1=CC=C(Cl)C=C1 OMNWKPZIFZJANV-UHFFFAOYSA-N 0.000 abstract 1
- 239000005555 hypertensive agent Substances 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 44
- 229910052786 argon Inorganic materials 0.000 description 22
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 21
- 239000007789 gas Substances 0.000 description 19
- 238000001291 vacuum drying Methods 0.000 description 12
- 238000010926 purge Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- QJPJQTDYNZXKQF-UHFFFAOYSA-N 4-bromoanisole Chemical compound COC1=CC=C(Br)C=C1 QJPJQTDYNZXKQF-UHFFFAOYSA-N 0.000 description 4
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 4
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 3
- NHWQMJMIYICNBP-UHFFFAOYSA-N 2-chlorobenzonitrile Chemical compound ClC1=CC=CC=C1C#N NHWQMJMIYICNBP-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZOQCZTRFTARYGJ-UHFFFAOYSA-N chlorooxy(phenyl)borinic acid Chemical compound ClOB(O)C1=CC=CC=C1 ZOQCZTRFTARYGJ-UHFFFAOYSA-N 0.000 description 3
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 3
- LBBMOAOCCQOIAQ-UHFFFAOYSA-N methoxy(phenyl)borinic acid Chemical compound COB(O)C1=CC=CC=C1 LBBMOAOCCQOIAQ-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229940072033 potash Drugs 0.000 description 3
- 235000015320 potassium carbonate Nutrition 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- AASGLKDYFNBDAN-UHFFFAOYSA-N 1-(2-chlorophenyl)-2-nitrobenzene Chemical group [O-][N+](=O)C1=CC=CC=C1C1=CC=CC=C1Cl AASGLKDYFNBDAN-UHFFFAOYSA-N 0.000 description 1
- RHDYQUZYHZWTCI-UHFFFAOYSA-N 1-methoxy-4-phenylbenzene Chemical group C1=CC(OC)=CC=C1C1=CC=CC=C1 RHDYQUZYHZWTCI-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 206010020772 Hypertension Diseases 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- ZOUWOGOTHLRRLS-UHFFFAOYSA-N palladium;phosphane Chemical compound P.[Pd] ZOUWOGOTHLRRLS-UHFFFAOYSA-N 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
- B01J2231/4211—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group
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Abstract
本发明涉及一种金属钯催化剂及其制备方法和应用。该催化剂为含氮和膦的聚合物固载金属钯,其中金属钯占聚合物的质量负载量(通过ICP测得)为0.2~2%;由含氮和膦小分子在钯作用下,通过碳膦、碳氮偶联,生成包覆金属钯的大分子聚合物催化剂。由于固载的含膦配体以及聚苯胺共同作用提高了钯催化剂活性和稳定性。该催化剂在醇和水的混合溶液中可以超高效的催化Suzuki反应,可在极低的催化剂用量的条件下进行;该催化剂易于回收、便于应用,且该催化剂能够用于合成新型沙坦类高血压药的沙坦联苯(2-氰基-4′-甲基联苯)和4-氯-2′-硝基联苯(合成啶酰菌胺的药物中间体)药物中间体的放大实验,这在工业上有很大的应用价值。
Description
技术领域
本发明涉及一种金属钯催化剂及其制备方法和应用,具体涉及到聚合物固载的金属钯催化剂及制备方法和该催化剂在Suzuki反应中的应用。
背景技术
钯能够催化卤代芳烃与有机苯硼酸以及其衍生物的Suzuki反应,这在有机合成中的用途非常广泛,其反应条件比较温和,底物适用比较广泛、产物便于处理等特点,在碳-碳偶联反应中具有很重要的地位,是合成联苯类化合物的有效方法。近年来,钯催化剂具有很高的催化性能、反应条件温和、易于回收等优点,这就决定了负载型的钯催化剂具有潜在的应用价值。目前,已经有很多文献报道过各种各样的催化剂,在研究Suzuki反应的现有文献中,有很多含膦配体、含氮配体以及卡宾配体等,但是,在此反应中,常常存在一些的缺点,比如:大量的钯催化剂使用量、催化剂活性低、催化剂难回收使用等问题。膦配体对钯催化剂的催化效果影响很大,但是有些含膦钯催化剂在Suzuki反应中,活性不高甚至活性很低。另外,在Suzuki反应中常使用的有机溶剂(例如甲苯、DMF等)通常是有毒、昂贵的。因此,制备出催化活性很高的钯催化剂,在Suzuki反应中,使用毒性较低的有机溶剂在实际应用中非常重要。
发明内容
本发明的目的是为了改进现有技术的不足而提出了一种金属钯催化剂,本发明得另一目的是提供上述催化剂的制备方法,苯发明还有一目的是提供该催化剂在Suzuki反应中的应用。该催化剂在异丙醇和水的混合溶剂中可以很高效的催化Suzuki反应,可以在极低的催化剂用量的条件下进行,同时可以应用到某些药物中间体(例如沙坦联苯、4-氯-2硝基联苯)的放大实验。
本发明的技术方案为:由含氮和膦小分子在钯作用下,通过碳膦、碳氮偶联,生成包覆金属钯的大分子聚合物催化剂。钯盐先与DIPPF([1,1'-双(二异丙基膦)二茂铁)的配位,然后再催化胺化合物与含膦化合物的之间的反应,最后加入一定量的钯盐、胺化合物、哌嗪和碱,其中碱的作用是消除在反应过程中生成的HBr,在甲苯有机溶剂中,惰性气体保护下,一定温度下反应生成的包覆金属钯的聚合物。
本发明的具体技术方案为:一种金属钯催化剂,其特征在于含氮和膦的聚合物固载金属钯,其中金属钯占聚合物的质量负载量(通过ICP测得)为0.2~2%。
本发明还提供了上述金属钯催化剂的制备方法,其具体步骤入下:
①钯盐先与[1,1'-双(二异丙基膦)二茂铁(DIPPF)配位反应,再加入胺化合物与含膦化合物,最后加入碱,在80~120℃反应20~24小时;
②冷却后,加入一定量的钯盐(由金属钯占聚合物的理论负载量计算出所加钯盐的量)、胺化合物、哌嗪、碱(过量),在甲苯溶剂中,惰性气体保护下,在80~120℃反应20~24小时;
③冷却后,清洗,干燥得到包覆金属钯的聚合物,即金属钯催化剂。
优选上述的钯盐优选为二价钯盐或零价钯盐,更优选为醋酸钯、三(二亚苄基丙酮)二钯或氯化钯等。
优选上述的胺化合物为三(4-溴苯基)胺或者三(4-碘苯基)胺;所述的含膦化合物为二-1-金刚烷基膦、二苯基膦、二-叔丁基膦或二环己基膦;所述的碱为叔丁醇钠、叔丁醇钾。
优选步骤①中钯盐先与DIPPF([1,1'-双(二异丙基膦)二茂铁)的摩尔比为1:(1~2);步骤②中金属钯的加入量由最后生成催化剂中占聚合物的理论负载量计算得到。优选步骤①中钯盐占胺化合物的摩尔比为2~5%。
优选步骤①中胺化合物与膦化合物的摩尔比为1:1;步骤②中胺化合物与膦化合物的摩尔比为摩尔比为1~4:1。整个反应体系中胺化合物与膦化合物的摩尔比为摩尔比2~5:1。
优选步骤②中胺化合物与哌嗪之间的摩尔比为1:(1.75~2.5)。
本发明还提供了上述催化剂在催化的Suzuki反应中的应用;在合成新型沙坦类高血压药的沙坦联苯2-氰基-4′-甲基联苯、合成啶酰菌胺的药物中间体4-氯-2′-硝基联苯以及化工产品4-甲氧基联苯中的应用。
本发明所用溶剂优选为甲苯,溶剂的加入量为覆盖反应物即可。配位反应时间一般为2—5分钟左右;步骤①和②中碱的加入量优选过量;反应全部过程在惰性气体保护下,优选惰性气体为氩气或氮气;最后清洗优选分别用水、乙醇清洗数次;在真空干燥箱中真空干燥,干燥温度一般为30~50度。
有益效果:
本催化剂不但制备相对简单,而且由于固载的含膦配体以及聚苯胺共同作用提高了钯催化剂活性和稳定性。该催化剂在醇和水的混合溶液中可以超高效的催化Suzuki反应,这不但避免了水相反应的缺点,又可以在极低的催化剂用量的条件下进行(例如对溴苯甲醚与苯硼酸的反应,催化剂用量为百万分之五),该催化剂易于回收、合成路线简单、反应条件温和、后处理简单方便且产率很高、便于应用,稳定性好,不易失活,不仅具备纳米催化剂很高的催化性能,在反应条件下不易发生团聚,而且此催化剂可以应用到某些药物中间体以及化工产品的放大实验,这在工业上有很大的应用价值。
具体实施方式
实施案例1:
在氩气下,醋酸钯(1.2mg,0.005mmol)和DIPPF(3.2mg,0.0075mmol)加入到含有2mL甲苯的史林克管中,搅拌5分钟,继续加入三(4-溴苯基)胺(120.5mg,0.25mmol)、二-1-金刚烷基膦(75.6mg,0.25mmol)和叔丁醇钠(36mg,0.375mmol),110度反应24小时,;冷却以后,在氩气下,继续加入醋酸钯(9.2mg,0.041mmol)、三(4-溴苯基)胺(482.0mg,1mmol)、哌嗪(150.8mg,1.75mmol)和叔丁醇钠(672mg,7mmol),再加入30mL的甲苯溶液,120度,反应24小时;冷却以后,分别用水、乙醇清洗三次,50度真空干燥箱干燥24小时,获得催化剂C1(钯负载量为0.7%)。
实施案例2:
在氩气下,醋酸钯(1.2mg,0.005mmol)和DIPPF(3.2mg,0.0075mmol)加入到含有2mL甲苯的史林克管中,搅拌5分钟,继续加入三(4-溴苯基)胺(120.5mg,0.25mmol)、二-1-金刚烷基膦(75.6mg,0.25mmol)和叔丁醇钠(36mg,0.375mmol),110度反应20小时,;冷却以后,在氩气下,继续加入醋酸钯(18.4mg,0.082mmol)、三(4-溴苯基)胺(482.0mg,1mmol)、哌嗪(150.8mg,1.75mmol)和叔丁醇钠(672mg,7mmol),再加入30mL的甲苯溶液,120度,反应24小时;冷却以后,分别用水、乙醇清洗三次,30度真空干燥箱干燥20小时,获得催化剂C2(钯负载量为2%)。
实施案例3:
在氩气下,醋酸钯(1.2mg,0.005mmol)和DIPPF(3.2mg,0.0075mmol)加入到含有2mL甲苯的史林克管中,搅拌5分钟,继续加入三(4-溴苯基)胺(120.5mg,0.25mmol)、二-1-金刚烷基膦(75.6mg,0.25mmol)和叔丁醇钠(36mg,0.375mmol),110度反应22小时,;冷却以后,在氩气下,继续加入醋酸钯(4.6mg,0.021mmol)、三(4-溴苯基)胺(482.0mg,1mmol)、哌嗪(150.8mg,1.75mmol)和叔丁醇钠(672mg,7mmol),再加入30mL的甲苯溶液,120度,反应24小时;冷却以后,分别用水、乙醇清洗三次,40度真空干燥箱干燥22小时,获得催化剂C3(钯负载量为0.2%)。
实施案例4:
在氩气下,三(二亚苄基丙酮)二钯(2.3mg,0.0025mmol)和DIPPF(3.2mg,0.0075mmol)加入到含有2mL甲苯的史林克管中,搅拌5分钟,继续加入三(4-溴苯基)胺(120.5mg,0.25mmol)、二-1-金刚烷基膦(75.6mg,0.25mmol)和叔丁醇钠(36mg,0.375mmol),80度反应24小时,;冷却以后,在氩气下,继续加入三(二亚苄基丙酮)二钯(18.3mg,0.02mmol)、三(4-溴苯基)胺(482.0mg,1mmol)、哌嗪(150.8mg,1.75mmol)和叔丁醇钠(672mg,7mmol),再加入30mL的甲苯溶液,80度,反应24小时;冷却以后,分别用水、乙醇清洗三次,50度真空干燥箱干燥24小时,获得催化剂C4(钯负载量为0.8%)。
实施案例5:
在氮气下,三(二亚苄基丙酮)二钯(2.3mg,0.0025mmol)和DIPPF(3.2mg,0.0075mmol)加入到含有4mL甲苯的史林克管中,搅拌2分钟,继续加入三(4-溴苯基)胺(120.5mg,0.25mmol)、二-1-金刚烷基膦(75.6mg,0.25mmol)和叔丁醇钾(42.1mg,0.375mmol),120度反应20小时,;冷却以后,在氮气下,继续加入三(二亚苄基丙酮)二钯(18.3mg,0.02mmol)、三(4-溴苯基)胺(482.0mg,1mmol)、哌嗪(150.8mg,1.75mmol)和叔丁醇钾(785.5mg,7mmol),再加入20mL的甲苯溶液,120度,反应20小时;冷却以后,分别用水、乙醇清洗三次,50度真空干燥箱干燥24小时,获得催化剂C5(钯负载量为0.7%)。
实施案例6:
在氩气下,氯化钯(1.8mg,0.01mmol)和DIPPF(4.2mg,0.01mmol)加入到含有2mL甲苯的史林克管中,搅拌5分钟,继续加入三(4-溴苯基)胺(120.5mg,0.25mmol)、二-1-金刚烷基膦(75.6mg,0.25mmol)和叔丁醇钠(36mg,0.375mmol),100度反应24小时,;冷却以后,在氩气下,继续加入氯化钯(7.3mg,0.041mmol)、三(4-溴苯基)胺(482.0mg,1mmol)、哌嗪(150.8mg,1.75mmol)和叔丁醇钠(672mg,7mmol),再加入30mL的甲苯溶液,100度,反应24小时;冷却以后,分别用水、乙醇清洗三次,50度真空干燥箱干燥24小时,获得催化剂C6(钯负载量为0.9%)。
实施案例7:
在氩气下,醋酸钯(3mg,0.0125mmol)和DIPPF(10.8mg,0.025mmol)加入到含有2mL甲苯的史林克管中,搅拌5分钟,继续加入三(4-碘苯基)胺(155.8mg,0.25mmol)、二环己基膦(49.6mg,0.25mmol)和叔丁醇钠(36mg,0.375mmol),110度,避光条件下,反应24小时,;冷却以后,在氩气下,继续加入醋酸钯(9.2mg,0.041mmol)、三(4-碘苯基)胺(623.0mg,1mmol)、哌嗪(150.8mg,1.75mmol)和叔丁醇钠(672mg,7mmol),再加入30mL的甲苯溶液,120度,避光条件下,反应24小时;冷却以后,分别用水、乙醇清洗三次,50度真空干燥箱干燥24小时,获得催化剂C7(钯负载量为0.8%)。
实施案例8:
在氩气下,醋酸钯(1.2mg,0.005mmol)和DIPPF(3.2mg,0.0075mmol)加入到含有2mL甲苯的史林克管中,搅拌5分钟,继续加入三(4-碘苯基)胺(155.8mg,0.25mmol)、二苯基膦(46.5mg,0.25mmol)和叔丁醇钠(36mg,0.375mmol),110度,避光条件下,反应20小时,;冷却以后,在氩气下,继续加入醋酸钯(4.6mg,0.021mmol)、三(4-碘苯基)胺(623.0mg,1mmol)、哌嗪(150.8mg,1.75mmol)和叔丁醇钠(672mg,7mmol),再加入30mL的甲苯溶液,120度,避光条件下,反应24小时;冷却以后,分别用水、乙醇清洗三次,40度真空干燥箱干燥24小时,获得催化剂C8(钯负载量为0.4%)。
实施案例9:
在氩气下,醋酸钯(1.2mg,0.005mmol)和DIPPF(3.2mg,0.0075mmol)加入到含有2mL甲苯的史林克管中,搅拌5分钟,继续加入三(4-溴苯基)胺(120.5mg,0.25mmol)、二-叔丁基膦(36.6mg,0.25mmol)和叔丁醇钠(36mg,0.375mmol),110度反应23小时,;冷却以后,在氩气下,继续加入醋酸钯(9.2mg,0.041mmol)、三(4-溴苯基)胺(120.5mg,0.25mmol)、哌嗪(53.8mg,0.625mmol)和叔丁醇钠(240.3mg,2.5mmol),再加入30mL的甲苯溶液,110度,反应24小时;冷却以后,分别用水、乙醇清洗三次,50度真空干燥箱干燥24小时,获得催化剂C9(钯负载量为1.9%)。
实施案例10:
在氩气下,醋酸钯(1.2mg,0.005mmol)和DIPPF(3.2mg,0.0075mmol)加入到含有2mL甲苯的史林克管中,搅拌5分钟,继续加入三(4-碘苯基)胺(155.8mg,0.25mmol)、二-1-金刚烷基膦(75.6mg,0.25mmol)和叔丁醇钠(36mg,0.375mmol),110度,避光条件下,反应24小时,;冷却以后,在氩气下,继续加入醋酸钯(9.2mg,0.041mmol)、三(4-碘苯基)胺(311.6mg,0.5mmol)、哌嗪(86.1mg,1mmol)和叔丁醇钠(384.4mg,4mmol),再加入30mL的甲苯溶液,120度,避光条件下,反应24小时;冷却以后,分别用水、乙醇清洗三次,50度真空干燥箱干燥24小时,获得催化剂C10(钯负载量为1.3%)。
实施案例11:
聚合物负载的钯催化剂催化对溴苯甲醚与苯硼酸的反应。
在250mL的反应器中,加入100mmol对溴苯甲醚和120mmol苯硼酸,加入200mmol的碳酸钾,加入100mL的异丙醇和水的混合液(异丙醇与水体积比为1:1),分别加入催化剂C0(商业钯碳催化剂),C1,C2,C3,C4,C5,C6,C7,C8,C9,C10(体系中钯含0.0005mol%),充入氩气置换空气,100度,反应6小时。其反应式如下所示,反应结果列于表1中。
表1金属钯催化剂催化对溴苯甲醚与苯硼酸的反应:
催化剂 | 转化率 | 收率 |
C0 | 30% | 30% |
C1 | 100% | 100% |
C2 | 100% | 100% |
C3 | 99% | 99% |
C4 | 100% | 100% |
C5 | 99% | 99% |
C6 | 100% | 100% |
C7 | 96% | 95% |
C8 | 95% | 95% |
C9 | 95% | 94% |
C10 | 99% | 99% |
实施案例12:
聚合物负载的钯催化剂催化邻氯硝基苯与对氯苯硼酸的反应。
在250mL的反应器中,加入100mmol邻氯硝基苯和120mmol对氯苯硼酸,加入200mmol的碳酸钾,加入100mL的异丙醇和水的混合液(异丙醇与水体积比为1:1),分别加入催化剂C0(商业钯碳催化剂),C1,C2,C3,C4,C5,C6,C7,C8,C9,C10(体系中钯含0.02mol%),充入氩气置换空气,100度,反应6小时。其反应式如下所示,反应结果列于表2中,催化剂C1的回收使用结果列于表3中。
表2金属钯催化剂催化邻氯硝基苯与对氯苯硼酸的反应:
催化剂 | 转化率 | 收率 |
C0 | 40% | 30% |
C1 | 99% | 99% |
C2 | 99% | 98% |
C3 | 98% | 98% |
C4 | 98% | 97% |
C5 | 99% | 99% |
C6 | 97% | 97% |
C7 | 98% | 98% |
C8 | 99% | 96% |
C9 | 99% | 98% |
C10 | 99% | 99% |
表3催化剂C1的回收使用结果:
回收次数 | 转化率 | 收率 |
1 | 99% | 99% |
2 | 96% | 96% |
3 | 90% | 90% |
实施案例13:
聚合物负载的钯催化剂催化邻氯苯甲腈与对甲基苯硼酸的反应。
在250mL的反应器中,加入100mmol邻氯苯甲腈和120mmol对甲基苯硼酸,加入200mmol的碳酸钾,加入100mL的异丙醇和水的混合液(异丙醇与水体积比为1:1),分别加入催化剂C0(商业钯碳催化剂),C1,C2,C3,C4,C5,C6,C7,C8,C9,C10(体系中钯含0.02mol%),充入氩气置换空气,100度,反应6小时。其反应式如下所示,反应结果列于表4中,催化剂C1的回收使用结果列于表5中。
表4金属钯催化剂催化邻氯苯甲腈与对甲基苯硼酸的反应:
催化剂 | 转化率 | 收率 |
C0 | 20% | 18% |
C1 | 99% | 99% |
C2 | 99% | 99% |
C3 | 99% | 98% |
C4 | 98% | 97% |
C5 | 98% | 98% |
C6 | 97% | 97% |
C7 | 99% | 99% |
C8 | 99% | 96% |
C9 | 97% | 97% |
C10 | 99% | 99% |
表5催化剂C1的回收使用结果:
回收次数 | 转化率 | 收率 |
1 | 98% | 98% |
2 | 96% | 96% |
3 | 90% | 90% |
Claims (8)
1.一种金属钯催化剂,其特征在于含氮和膦的聚合物固载金属钯,其中金属钯占聚合物的质量负载量为0.2~2%。
2.一种制备如权利要求1所述的金属钯催化剂的方法,其具体步骤入下:
①钯盐先与[1,1'-双(二异丙基膦)二茂铁进行配位反应,再加入胺化合物与含膦化合物,最后加入碱,在80~120℃反应20~24小时;
②冷却后,根据金属钯占聚合物的理论负载量加入一定量的钯盐、胺化合物、哌嗪和碱,在甲苯溶剂中,惰性气体保护下,在80~120℃反应20~24小时;
③冷却后,清洗,干燥得到包覆金属钯的聚合物,即金属钯催化剂。
3.根据权利2所述的方法,其特征在于所述的钯盐为醋酸钯、三(二亚苄基丙酮)二钯或氯化钯。
4.根据权利要求2所述的方法,其特征在于所述的胺化合物为三(4-溴苯基)胺或者三(4-碘苯基)胺;所述的含膦化合物为二-1-金刚烷基膦、二苯基膦、二-叔丁基膦或二环己基膦;所述的碱为叔丁醇钠、叔丁醇钾。
5.根据权利要求2所述的方法,其特征在于步骤①中胺化合物与膦化合物的摩尔比为1:1;步骤②中胺化合物与膦化合物的摩尔比为摩尔比为1~4:1。
6.根据权利要求2所述的方法,其特征在于步骤①中钯盐与DIPPF([1,1'-双(二异丙基膦)二茂铁)的摩尔比为1:(1~3);步骤①中钯盐占胺化合物的摩尔比为1~5%。
7.根据权利要求2所述的方法,其特征在于步骤②中胺化合物与哌嗪之间的摩尔比为1:(1.75~2.5)。
8.一种如权利要求1所述的催化剂在催化的Suzuki反应中的应用。
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CN110078921B (zh) * | 2019-05-20 | 2021-04-30 | 南京工业大学 | 一种钯催化的非均相的烯丙基聚合反应合成聚砜的方法 |
CN113956231A (zh) * | 2021-09-27 | 2022-01-21 | 哈尔滨工业大学(深圳) | 一种基于连续流反应器的联芳基化合物的制备方法 |
CN114181048A (zh) * | 2021-12-20 | 2022-03-15 | 宁夏清研高分子新材料有限公司 | 一种高产率的4-氟联苯酚的制备方法 |
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