CN1736599A - 交叉偶联反应 - Google Patents
交叉偶联反应 Download PDFInfo
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- CN1736599A CN1736599A CN200510088170.0A CN200510088170A CN1736599A CN 1736599 A CN1736599 A CN 1736599A CN 200510088170 A CN200510088170 A CN 200510088170A CN 1736599 A CN1736599 A CN 1736599A
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- 238000006880 cross-coupling reaction Methods 0.000 title description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 43
- 239000000084 colloidal system Substances 0.000 claims abstract description 26
- 239000010949 copper Substances 0.000 claims abstract description 20
- 229910052802 copper Inorganic materials 0.000 claims abstract description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 27
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 150000004675 formic acid derivatives Chemical class 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 239000003444 phase transfer catalyst Substances 0.000 claims description 13
- 150000002940 palladium Chemical class 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000004280 Sodium formate Substances 0.000 claims description 4
- ATZQZZAXOPPAAQ-UHFFFAOYSA-M caesium formate Chemical compound [Cs+].[O-]C=O ATZQZZAXOPPAAQ-UHFFFAOYSA-M 0.000 claims description 4
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 claims description 4
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 4
- 235000019254 sodium formate Nutrition 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 44
- 229910052763 palladium Inorganic materials 0.000 abstract description 19
- 238000006069 Suzuki reaction reaction Methods 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 50
- 238000006243 chemical reaction Methods 0.000 description 19
- -1 trifluoromethyl sulfonic acid (triflate) compound Chemical class 0.000 description 17
- 239000000243 solution Substances 0.000 description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 229910052707 ruthenium Inorganic materials 0.000 description 5
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 4
- 101150003085 Pdcl gene Proteins 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-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
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000031709 bromination Effects 0.000 description 3
- 238000005893 bromination reaction Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052762 osmium Inorganic materials 0.000 description 3
- 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 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 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
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 108091008695 photoreceptors Proteins 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- QBVXKDJEZKEASM-UHFFFAOYSA-M tetraoctylammonium bromide Chemical compound [Br-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC QBVXKDJEZKEASM-UHFFFAOYSA-M 0.000 description 2
- 125000005259 triarylamine group Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 238000006443 Buchwald-Hartwig cross coupling reaction Methods 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- 150000005347 biaryls Chemical group 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
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- FHIVAFMUCKRCQO-UHFFFAOYSA-N diazinon Chemical compound CCOP(=S)(OCC)OC1=CC(C)=NC(C(C)C)=N1 FHIVAFMUCKRCQO-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/122—Halides of copper
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
- B01J27/13—Platinum group metals
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
一种制备用于铃木偶联反应的铜/钯胶体催化剂的方法。
Description
技术领域
本发明公开了一种制备胶体催化剂的方法。
背景技术
用于有机亲电试剂，如芳基卤、重氮盐或三氟甲基磺酸盐(triflate)化合物，与硼酸或硼酸酯交叉偶联的铃木(Suzuki)反应，是一种在合成有机化合物例如如下图所示的联芳基化合物中用于形成碳-碳键的反应。该反应也用于农用化学品、聚合物和药物中间体的合成。铃木反应也可以用于制备电荷传输分子，如三芳基胺。例如，该反应可以用于制备应用在感光器和有机发光二极管(“OLEDs”)中的空穴传输分子。
铃木反应范例
可供选择的铃木催化剂可以是在有磷配位体存在下的钯(0)络合物，例如Pd(dppf)2或Pd(PPh3)4。钯的高成本使得利用该反应制备有机化合物的过程十分昂贵。这项费用还包括从产品中除去催化剂过量造成的钯残留的清洁成本。这些催化剂同时具有如下缺点：它们对氧化反应非常敏感，而且由于它们的保存期限，尤其是溶液形式下的保存期限短暂，使其很难应用于工业生产。而且，这些化合物对热十分敏感，所以活性相对低的芳香化合物在高温下反应会导致催化剂迅速钝化沉淀出钯黑。据报道，氯化芳基镍也是一种有效的催化剂，但是会造成暴露危害。
在J.Am.Chem.Soc.2002，124，11858-11959中描述了将包含钯-Pt和/或Ru和/或Cu混合物的改进型胶体催化剂用于铃木反应。该文献记载这种胶体催化剂可以用作铃木催化剂。据报道，在该文献中引用的双金属胶体催化剂组合中，Cu/Pd在苯基硼酸和碘苯交叉偶联形成联苯的过程中最具活性(与纯钯水平相当)。虽然该文献中指出在(磷)配位体存在下钯(0)络合物是一种铃木反应中可选择的催化剂，但是文中并没有对该催化剂作直接的比较。
日本公开03160876JP中也对Cu∶Pd催化剂进行了描述。据描述，这种催化剂可用于无电电镀过程，以简化形成无电金属电镀膜的金属电镀图案的过程。无电电镀的催化剂包括一种含有合金的胶体，该合金由选自第一组金属元素中的一种和选自第二组金属元素中的至少一种组成，其中第一组金属由钯和铂组成，第二组金属由括银和铜组成。
在该文献中描述了J.Am.Chem.Soc.2002，124，11858-11959中的纳米胶体的制备方法(在已发表的“参考文献”中作为文章的参考)，该方法需要混合金属氯化物前体的均匀储备溶液，随后在二甲基甲酰胺(“DMF”)中用四辛基甲酸铵(“TOAF”)进行还原。据报道纳米簇催化剂可以通过将二甲基甲酰胺(“DMF”)中的金属氯化物放入装备有橡胶隔膜和磁力搅拌、已经被抽真空并且重新充入N2的Schlenk型容器中而形成。然后向溶液中加入溶于二甲基甲酰胺(“DMF”)的四辛基甲酸铵(“TOAF”)，并且加热至65℃，混合物在N2轻微超压下连续搅拌24小时。据载当胶态悬浮体形成时，混合物的颜色发生变化。之后，该悬浮体保存于氮气中。
据载四辛基甲酸铵(“TOAF”)是通过Masse，Ph.D.Thesis，VerlagMainz，Aachen，1999，ISBN 3089653-463方法的改进方法制得的。四辛基甲酸铵(“TOAF”)的制备过程涉及四正辛基溴化铵(“TOAB”)与甲酸通过使用离子交换树脂进行的交换反应，是相当复杂的。所述离子交换树脂悬浮于氢氧化钠溶液中并且填充入离子交换柱，随后用NaOH冲洗该离子交换柱。然后用蒸馏水冲洗该离子交换柱，随后用甲酸溶液、蒸馏水和甲醇冲洗。树脂放置膨胀1小时，然后用四正辛基溴化铵(“TOAB”)的甲醇溶液冲洗，直至用AgNO3检测流出物中的氯化物呈阳性。用旋转蒸发仪蒸出适量的甲醇，四辛基甲酸铵(“TOAF”)的粗产品(轻油)在真空下干燥24小时。四辛基甲酸铵(“TOAF”)溶于二甲基甲酰胺(DMF)的储备溶液将用于合成胶体。
由于催化剂的制备时间是冗长的，所以这个方法是相当费时的。制备该树脂可能需要一天或者更长的时间，并且在每次使用之前，树脂必须进行更新。树脂的价格可为每公斤树脂$100-$500，并且每交换一克物质至少必须使用20倍于其数量的树脂。
发明内容
本发明公开了以下方面的内容：
甲酸盐、铜金属盐和铜以外的金属盐形成反应混合物，用来形成铜：金属盐胶体催化剂，以及
一种方法，包括在惰性气氛下、在包括至少一种铜盐和至少一种钯盐的溶液中，形成还原试剂，其数量能够还原所述铜盐和钯盐。
具体实施方式
在实施方案中阐明了一种制备在J.Am.Chem.Soc.2002，124，11858-11959中描述的胶体催化剂的方法，该方法无需通过离子交换树脂单独形成四辛基甲酸铵(“TOAF”)。进一步的实施方案可以将J.Am.Chem.Soc.2002，124，11858-11959中提出的用于形成胶体催化剂的辛苦的多步过程，简化为一个简单反应。如J.Am.Chem.Soc.2002，124，11858-11959中所述的金属盐胶体催化剂可以不必通过首先生成四辛基甲酸铵(“TOAF”)的辛苦方法来制备，而是以原位制备代替。
通过这种方法制备的胶体催化剂可以用于众多交叉偶联反应，包括但不限于铃木反应、Stille、Heck、Sonagashira、Negishi、Ullmann、Grignard交叉偶合反应、Buchwald-Hartwig胺化反应和催化成醚反应。
在一个实施方案中，提供了一种方法，该方法包括将以下化合物混合成为一种溶液，所述化合物包括：有机溶剂、相转移催化剂、与相转移催化剂的摩尔比为约0.25到约5.0或约0.5到约2.5的甲酸盐、和至少一种铜盐、其他金属盐或它们的混合物，盐的浓度为混合物的约0.0001到约8当量或者约0.0001到约2当量，或者约0.001到约0.8当量。该方法还可包括将这种溶液加热至约40℃到约100℃的温度，以形成铜：金属盐胶体催化剂。反应温度也可以为约55℃到约70℃。甲酸盐可选自下述化合物中的至少一种：甲酸锂、甲酸钠、甲酸钾、甲酸铯、NR1R2R3R4甲酸盐，其中R1、R2、R3和R4独立地是H或C2-C18烃基，或PR1R2R3R4甲酸盐，其中R1、R2、R3和R4独立地中H或C2-C18烃基。所述相转移催化剂为NR1R2R3R4卤化物，其中R1、R2、R3和R4独立地是H或C2-C18烃基。所述相转移催化剂可以是四辛基卤化铵。至少一种盐可以是CuCl2。所述金属盐中的至少一种金属可以选自下列金属中的至少一种：镍、钌、铑、钯、银、锇、铱、铂和金，或者所述金属盐中的至少一种金属选自下列金属中的至少一种：铂、钯和钌。金属盐中的金属可以是钯。金属盐可包括PdCl2。有机溶剂可包括二甲基甲酰胺。甲酸盐可为甲酸铵。
在另外一个实施方案中，提供了一种方法，该方法包括在置于惰性气氛中的、包含至少一种铜盐和至少一种钯盐的溶液中，形成用于还原所述至少一种铜盐和至少一种钯盐的还原剂。该方法也可包括将所述溶液加热至约40℃到约100℃，或约55℃到约70℃，以形成一种铜：钯胶体催化剂。所述还原剂可以通过甲酸盐与相转移催化剂反应制得。
在一个可替换的实施方案中，提供了一种方法，包括在置于惰性气氛中的、包含有机溶剂、金属盐和铜盐的溶液中，形成用于还原该溶液中所述金属盐和所述铜盐的还原剂。该方法可进一步包括加热该溶液至约40℃到约100℃，或约55℃到约70℃，以形成纳米胶体催化剂。所述还原剂可以通过甲酸盐和相转移催化剂反应制得。所述甲酸盐可选自下述化合物中的至少一种：甲酸锂、甲酸钠、甲酸钾、甲酸铯或NR1R2R3R4甲酸盐，其中R1、R2、R3和R4独立地是H或C2-C18烃基，或PR1R2R3R4甲酸盐，其中R1、R2、R3和R4独立地是H或C2-C18烃基。相转移催化剂为NR1R2R3R4卤化物，其中R1、R2、R3和R4独立地是H或C2-C18烃基，并可以为四辛基卤化铵。有机溶剂可以包括二甲基甲酰胺。甲酸盐可以是甲酸铵。所述金属盐中的金属可以选自以下金属中的至少一种：镍、钌、铑、钯、银、锇、铱、铂和金，或选自铂、钯和钌中的至少一种。金属盐可以为CuCl2或PdCl2。
胶体催化剂可以通过同时混合甲酸盐、相转移催化剂和金属盐来制备，其中，所述甲酸盐包括锂、钠、钾、铯、NR1R2R3R4的甲酸盐，其中R1、R2、R3和R4可独立地选自H或含有约2至约18个碳的烃基，PR1R2R3R4甲酸盐，其中R1、R2、R3和R4可独立地选自H或含有约2至约18个碳的烃基；所述相转移催化剂包括NR1R2R3R4卤化物，其中R1、R2、R3和R4可独立地选自H或含有约2至约18个碳的烃基(如四辛基溴化铵)；所述金属盐包括铜盐和含Ni、Pd、Pt、Rh、Ir、Ru、Os等金属的非铜金属盐。催化剂的制备数量可以足够完成铃木反应的催化循环，即依次进行的氧化加成反应-金属转移反应-还原消除反应。
甲酸盐可以选自以下甲酸盐中的至少一种：甲酸锂、甲酸钠、甲酸钾、甲酸铯、或NR1R2R3R4甲酸盐，其中R1、R2、R3和R4独立地是H或C2-C18烃基，如甲酸铵，或PR1R2R3R4甲酸盐，其中R1、R2、R3和R4独立地是H或C2-C18烃基。相转移催化剂为NR1R2R3R4卤化物，其中R1、R2、R3和R4独立地是H或C2-C18烃基。相转移催化剂可以是四辛基卤化铵。至少一种铜盐可以为CuCl2。至少一种钯盐可以为PdCl2。溶液可以包含二甲基甲酰胺。反应混合物中甲酸盐与相转移催化剂的摩尔比可以为约0.25到约5.0，或约0.5到约2.5。至少一种铜盐、其他金属盐、或它们的混合物的加入量可以为约0.0001当量到约0.8当量，或约0.001当量到约0.08当量。反应混合物的温度可以为约40℃到约100℃，或约50℃到约70℃。
可以通过本文所述方法制得的可以用于进行铃木反应的特别有用的胶体催化剂是50％∶50％Cu/Pd催化剂，该催化剂可提供与在磷配位体存在下的钯(0)络合物(如四(三苯基膦)钯)相同的收率。
实施例I
催化剂的制备
将二甲基甲酰胺(“DMF”)放入氩气气氛下的烧瓶中。向烧瓶中加入1.0当量的甲酸铵、1.0当量的四辛基溴化铵和总共0.4当量的CuCl2和PdCl2。然后将混合物加热至65℃，保持约8至约24小时，然后冷却。该胶体催化剂可以直接用于铃木反应。
典型反应
将以上制备的催化剂用于典型的铃木反应，即溴化苯和苯基硼酸在含有K2CO3的二甲基甲酰胺(“DMF”)中，于100℃进行约8到约24小时的偶联反应。与四(三苯基膦)钯(2mol％)相比，50％Cu/50％Pd催化剂具有相似的产率，即联苯的产率接近100％。
实施例II
N，N-(3，4-二甲基苯基)-4-氨基联苯，一种众所周知的用于感光器的空穴传输材料(“HTM”，(Bender等，Chem.Mater.2001，13，4105-4111)的合成可以利用铃木反应，使适当的溴代三芳基胺与苯基硼酸发生偶联反应随后产生联芳基体系来实现。
在0.412g碳酸钾和10mL二甲基甲酰胺(DMF)存在下，在6mL胶体催化剂溶液(2mol％)的作用下(三种不同的催化剂，其中钯含量逐渐增加)，浓度为160mM的N，N-(3，4-二甲基苯基)-4-溴苯胺(0.38g)与浓度为240mM的苯基硼酸(0.183g)在100℃下反应8-24小时，制得N，N-(3，4-二甲基苯基)-4-氨基联苯。在产品收率方面与市售的四(三苯基膦)钯催化剂进行比较。在每个反应中，每种催化剂的使用浓度为2mol％。结果在表I中列出。从中看见，对于50％Pd∶50％Cu胶体，产品与原料的百分比几乎与Pd(PPh3)4的相同(74％对76％)。
表I
| 催化剂类型 | ％原料 | ％产物 |
| 5％Pd∶95％Cu胶体 | 80.5 | 19.5 |
| 25％Pd∶75％Cu胶体 | 71 | 29 |
| 50％Pd∶50％Cu胶体 | 26 | 74 |
| Pd(PPh3)4 | 24 | 76 |
反应条件，如反应温度、溶剂、催化剂可在任何一个具体的铃木反应中优化，并且Cu/Pd胶体催化剂中钯的最适宜量可以在反应方案之间稍做改变。
Claims (3)
1.一种方法，包括混合有机溶剂、相转移催化剂、甲酸盐、铜金属盐和非铜金属盐形成反应混合物，以形成铜：金属盐胶体催化剂。
2.根据权利要求1的方法，其中所述甲酸盐是一种或多种下列甲酸盐：甲酸锂，甲酸钠，甲酸钾，甲酸铯，或NR1R2R3R4甲酸盐，其中R1、R2、R3和R4独立地为H或C2-C18烃基，或PR1R2R3R4甲酸盐，其中R1、R2、R3和R4独立地为H或C2-C18烃基。
3.一种方法，包括在惰性气氛下、在含有至少一种铜盐和至少一种钯盐的溶液中，形成其数量能够还原所述铜盐和所述钯盐的还原试剂。
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| CN105504305A (zh) * | 2015-12-31 | 2016-04-20 | 郑州大学 | 一种含3-（4-吡啶）吡唑-丙酸的配位聚合物及其制备方法、用途 |
| CN106824278A (zh) * | 2017-01-13 | 2017-06-13 | 华南理工大学 | 一种多孔温控型凝胶负载钯铜双金属催化剂及制备与应用 |
| CN109529879A (zh) * | 2018-12-26 | 2019-03-29 | 盐城锦明药业有限公司 | 一种PdNi/RGO纳米催化剂及其制备方法 |
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| JP5700624B2 (ja) * | 2010-06-18 | 2015-04-15 | 学校法人 関西大学 | 遷移金属超微粒子からなるクロスカップリング用触媒およびそれを用いたクロスカップリング法 |
| EP3103786A1 (en) * | 2015-06-08 | 2016-12-14 | Hexion Research Belgium SA | Process for the production of higher carboxylic acid vinyl esters |
| KR101760469B1 (ko) | 2015-09-09 | 2017-07-21 | 고려대학교 산학협력단 | 층상자기조립법을 이용한 다중촉매 콜로이드의 제조방법 및 이로부터 제조된 다중촉매 콜로이드 |
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| CN105504305A (zh) * | 2015-12-31 | 2016-04-20 | 郑州大学 | 一种含3-（4-吡啶）吡唑-丙酸的配位聚合物及其制备方法、用途 |
| CN105504305B (zh) * | 2015-12-31 | 2018-03-20 | 郑州大学 | 一种含3‑（4‑吡啶）吡唑‑丙酸的配位聚合物及其制备方法、用途 |
| CN106824278A (zh) * | 2017-01-13 | 2017-06-13 | 华南理工大学 | 一种多孔温控型凝胶负载钯铜双金属催化剂及制备与应用 |
| CN109529879A (zh) * | 2018-12-26 | 2019-03-29 | 盐城锦明药业有限公司 | 一种PdNi/RGO纳米催化剂及其制备方法 |
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| CA2513979A1 (en) | 2006-01-30 |
| US20060025303A1 (en) | 2006-02-02 |
| US7214644B2 (en) | 2007-05-08 |
| CA2513979C (en) | 2010-11-30 |
| JP5026680B2 (ja) | 2012-09-12 |
| CN100537033C (zh) | 2009-09-09 |
| JP2006043697A (ja) | 2006-02-16 |
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