CN101792458B - Cyano-bridged mixed-valence copper polynuclear complex, and preparation method and application thereof - Google Patents
Cyano-bridged mixed-valence copper polynuclear complex, and preparation method and application thereof Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 38
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 4
- 238000010668 complexation reaction Methods 0.000 title 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 66
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims abstract description 27
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 24
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 18
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims abstract description 14
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 6
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 5
- 150000002500 ions Chemical class 0.000 claims abstract description 4
- -1 phenyl aldehyde Chemical class 0.000 claims description 31
- 150000001875 compounds Chemical class 0.000 claims description 30
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 12
- 150000004699 copper complex Chemical class 0.000 claims description 9
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical group N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 7
- 229940125904 compound 1 Drugs 0.000 claims description 4
- 229940125782 compound 2 Drugs 0.000 claims description 4
- 229940126214 compound 3 Drugs 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 17
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 239000003054 catalyst Substances 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 abstract description 6
- 150000001879 copper Chemical class 0.000 abstract description 3
- 238000004128 high performance liquid chromatography Methods 0.000 abstract description 3
- 239000007800 oxidant agent Substances 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract 3
- 238000012512 characterization method Methods 0.000 abstract 1
- 239000003446 ligand Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 21
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 14
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 14
- 229910020366 ClO 4 Inorganic materials 0.000 description 10
- 229910017489 Cu I Inorganic materials 0.000 description 10
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 0 CC(CC1)=CC(c2*3ccc(C)c2)=*1*3(*)*(ccc(C)c1)c1-c1*(C)ccc(C)c1 Chemical compound CC(CC1)=CC(c2*3ccc(C)c2)=*1*3(*)*(ccc(C)c1)c1-c1*(C)ccc(C)c1 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- 239000005749 Copper compound Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 150000001880 copper compounds Chemical class 0.000 description 4
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000010504 bond cleavage reaction Methods 0.000 description 3
- COVZYZSDYWQREU-UHFFFAOYSA-N Busulfan Chemical compound CS(=O)(=O)OCCCCOS(C)(=O)=O COVZYZSDYWQREU-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000005452 food preservative Substances 0.000 description 2
- 235000019249 food preservative Nutrition 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- NUKYPUAOHBNCPY-UHFFFAOYSA-N 4-aminopyridine Chemical compound NC1=CC=NC=C1 NUKYPUAOHBNCPY-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000404144 Pieris melete Species 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001559 benzoic acids Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- YXGZTNUNHBXFAX-UHFFFAOYSA-N copper;1,10-phenanthroline Chemical compound [Cu+2].C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1 YXGZTNUNHBXFAX-UHFFFAOYSA-N 0.000 description 1
- NKRNGKIEDAVMHL-UHFFFAOYSA-L dihydroxy(dioxo)chromium;pyridine Chemical compound O[Cr](O)(=O)=O.C1=CC=NC=C1 NKRNGKIEDAVMHL-UHFFFAOYSA-L 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229960004979 fampridine Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 150000002503 iridium Chemical class 0.000 description 1
- 150000004698 iron complex Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000003408 phase transfer catalysis Methods 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
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Abstract
The invention discloses a cyano-bridged mixed-valence copper polynuclear complex, which is a cyano-ion bridged cuprous and cupric polynuclear complex taking 2,2'-bipyridyl or 1,10-phenanthroline as ligand. Positive ions of the polynuclear complex have the following structural general formula: the cyano-bridged mixed-valence copper polynuclear complex is a catalyst (dissolving in a little amount of acetonitrile), and hydrogen peroxide (w is 30 percent) is an oxidant for catalytically oxidizing benzaldehyde to form benzoic acid. The molar ratio of the benzaldehyde to a copper salt catalyst to the hydrogen peroxide is 200 to 1 to 400. After the mixture is stirred for 0.5 hour at the normal temperature and normal pressure, the HPLC characterization shows that the yield of the benzoic acid reaches 80.4 percent, while the yield is only 11.4 percent in the absence of a catalyst. Therefore, the cyano-bridged mixed-valence copper polynuclear complex prepared in the invention has good catalytic activity in the process of oxidizing the benzaldehyde into the benzoic acid. The invention discloses a preparation method for the complex.
Description
Technical field
The present invention relates to cyano-bridged mixed-valence copper polynuclear complex, their method for making and prepare the application in the phenylformic acid in oxidation of Benzaldehyde as catalyzer.
Background technology
Carbon-carbon single bond cleavage reaction in the organic cpds is one type of extremely important and challenging reaction.Still organic synthesis field, field of medicaments all have extensively and important use on petroleum industry.Yet the Average bond energy of the carbon-carbon single bond in the common alkane compound has reached 83 kilocalories every mole, and the fracture that carbon-carbon single bond takes place in the organifying compound becomes very difficult.Discover through people, can come the carbon-carbon single bond cleavage reaction process in the catalysis organic cpds through adding some transistion metal compounds, and this catalyzed reaction has been applied in the industrial production.One of them typical industrial application example is exactly that the method for synthesizing adiponitrile by divinyl and prussic acid three steps under the katalysis of transition metal nickel compound of DuPont invention is [referring to R.J.McKinney in Homogeneous Catalysis; (Ed.:G.W.Parshall); Wiley; New York, 1992; Pp 42-50.].This reaction has proved that the carbon-carbon single bond of organic nitrile compound (C-CN) can rupture under nickel compound catalysis.According to the document of having reported at present; Relevant organic nitrile compound (particularly acetonitrile molecule, its carbon-carbon single bond bond energy reaches 133 kilocalories every mole) is under the reaction conditions of harshnesses such as anhydrous and oxygen-free, control illumination, to carry out in the reaction overwhelming majority that the carbon-carbon single bond fracture takes place under the transistion metal compound catalysis.For example the iron complex of the siliceous part of Nakazawa group study series [referring to a) H.Nakazawa, T.Kawasaki, K.Miyoshi, C.H.Suresh, N.Koga, Organometallics 2004,23,117-126; B) H.Nakazawa, K.Kamata, M.Itazaki, Chem.Commun.2005,4004-4006; C) H.Nakazawa, M.Itazaki, K.Kamata, K.Ueda; Chem.Asian J.2007,2,882-888.], the rhodium of the siliceous part of Bergman, Brookhart group study, complex of iridium series are [referring to a) F.L.Taw; P.S.White, R.G.Bergman, M.Brookhart; J.Am.Chem.Soc.2002,124,4192-4193; B) F.L.Taw, A.H.Mueller, R.G.Bergman, M.Brookhart, J.Am.Chem.Soc.2003,125,9808-9813; C) S.R.Klei, T.D.Tilley, R.G.Bergman, Organometallics 2002,21,4648-4661.3] or the like.The transition metal compound catalyst that this metalloid organic reaction is used is difficult in air usually or illumination condition is preserved down, and many reactions also are in conceptual phase at present, and the industrial applications cost is higher.Can under the reaction conditions of gentleness, utilize the report of transistion metal compound catalysis organic nitrile compound (especially acetonitrile molecule) generation carbon-carbon single bond fracture few.In the document, have only the compound of two routine copper can under mild conditions, make the acetonitrile molecule generation carbon-carbon single bond fracture in the solution now.But other transistion metal compound that their used copper compound and front relate to all be comparatively complicated, structure is special [referring to D.S.Marlin, M.M.Olmstead, P.K.Mascharak, Angew.Chem.2001,113,4888-4890; Angew.Chem.Int.Ed.2001,40,4752-4754; T.Lu, X.Zhuang, Y.Li, S.Chen, J.Am.Chem.Soc.2004,126,4760-4761.4,5].
Under mild conditions, using the simple transition metallic compound just can make in nitrile compounds (like acetonitrile) carbon-carbon single bond that fracture takes place does not also have to report at present.
Phenylformic acid is a kind of important chemical material; It is as a kind of important food preservatives; Be mainly used in and produce the Sodium Benzoate food preservatives, dyestuff intermediate, agricultural chemicals, softening agent, mordant, medicine, spices also can be used as the properties-correcting agent of Synolac and polyamide resin etc.Have 3 kinds of methods to produce phenylformic acid in the industry: toluene liquid phase oxidation, the disproportionation reaction of phenyl aldehyde prepare and prepare through phase transfer catalysis process.Wherein the liquid phase oxidation of toluene is to produce phenylformic acid at present to get main method, but there are shortcomings such as energy consumption is high, environmental pollution is big in it.The reaction that formoxy-turns to carboxylic acid is to realize as oxygenant with heavy metallic salt (like SRM 935a, Pyridine chromate salt etc.) and peracid etc.Because of its oxygenant costs an arm and a leg, and harmful to human body and environment, seek the attention that eco-friendly catalytic oxidation more and more receives people.
Hydrogen peroxide is a kind of common good oxygenant that can satisfy this requirement, and enrich in inexpensive and source, and the title of " Mr. cleaning " is arranged in fine chemistry industry.Its principal feature as oxygenant is that reaction conditions is gentle, environmentally friendly.Therefore, prepare phenylformic acid with hydrogen peroxide as oxygen source and have very tempting prospect.
Present mainly containing of report about preparing benzoic literature method with the catalytic oxidation of hydrogen peroxide phenyl aldehyde: Liu Chunsheng etc. and Li Dongsheng etc. report respectively under acid additive and influence of surfactant, with Na
2WO
42H
2O be catalyst Oxybenzene formaldehyde be benzoic method (referring to [1] Liu Chunsheng, Yan Hongyan, Zhang Shaohuas etc.: the clean catalytic oxidization phenyl aldehyde prepares phenylformic acid Liaoming Petrochemical Univ journal, 2004,24 (2): 16-18; [2] Li Dongsheng, Yan Hongyan, Liu Chunsheng etc.: Na
2WO
42H
2O-H
2O
2The catalyzed oxidation phenyl aldehyde prepares phenylformic acid synthetic chemistry, 2004,12:595-597; [3] Yan Hongyan, Cheng Yun, Liu Chunsheng, etc.Methanesulfonic copper catalyzed oxidation phenyl aldehyde system phenylformic acid Fusun PetroleumCollege journal, 2003,23 (3): 10-12; [4] discipline is intelligent, Li Huaming, and Shu Huoming, etc.Catalysis of phosphotungstic acid synthesizing benzoic acids Guangdong chemical industry, 2006,33 (161): 14-15.), their yield is higher, but the reaction times is longer, more than 5 hours.Yan Hongyan etc. are catalyzer with methanesulfonic copper, and it is 70% that oxidation of Benzaldehyde synthesizes benzoic yield, and long reaction time needs 16 hours.Again relevant for the research of using phospho-wolframic acid as catalyzer, productive rate reaches more than 80% recently, and reaction needs was accomplished in 4 hours under the heating condition.
Summary of the invention
The invention provides through the cyanide ion bridging and form a series of one, divalence mixed state multinuclear copper complex; The method of carbon-carbon single bond cleavage reaction in the catalytic nitrile compounds of mantoquita under a kind of mild conditions also provides the easy compound method of above-mentioned mixed-valence copper coordination compound and this mixed-valence copper coordination compound purposes as the aldehydes oxide catalyst.
Technical scheme of the present invention is following:
A kind of cyano-bridged mixed-valence copper polynuclear complex, they with dipyridyl or phenanthroline be part, with monovalence copper and cupric polynuclear coordination compound of cyanide ion bridging, their positive ion has following general structure:
A kind of method for preparing above-mentioned polynuclear coordination compound 1, its reaction is following:
It is with two (2; 2 '-dipyridyl) methanol solution of the acetonitrile solution of copper complex and 4-aldehyde benzoic acid ester mixes backflow, and solution gradually becomes deep yellow by blueness, cooling; Filter; With filtrating slowly volatilization remove desolvate to be about original volume 1/5 after, separate out the mixed-valence copper three caryogamy compound crystallizations of the cyanogen root bridging of a large amount of deep yellows in the solution, filtering separation can obtain compound 1 with the small amount of ethanol washing.
A kind of method for preparing above-mentioned polynuclear coordination compound 2, its reaction is following:
It is with two (1; The 10-phenanthroline) ethanolic soln of the acetonitrile solution of copper complex and 2-EL-970 mixes backflow, and solution gradually becomes deep green by blueness, cooling; Filter; With filtrating slowly volatilization remove desolvate to be about original volume 1/5 after, separate out the mixed-valence copper three caryogamy compound crystallizations of a large amount of bottle-green cyanogen root bridgings in the solution, filtering separation can obtain compound 2 with the small amount of ethanol washing.
A kind of method for preparing above-mentioned polynuclear coordination compound 3, its reaction is following:
It is that two (4,4 '-dimethyl--2, the 2 '-dipyridyl) acetonitrile solutions of copper complex and the methanol solution of phenyl aldehyde are mixed backflow; Solution gradually becomes deep yellow by blueness; Cooling is filtered, and filtrating is slowly volatilized to remove desolvate to being about 1/5 of original volume; Separate out the mixed-valence copper three caryogamy compound crystallizations of the cyanogen root bridging of a large amount of deep yellows in the solution, filtering separation can obtain compound 3 with the small amount of ethanol washing.
A kind of method for preparing above-mentioned polynuclear coordination compound 4, its reaction is following:
It is with two (1; The 10-phenanthroline) methanol solution of the acetonitrile solution of copper complex and phenyl aldehyde mixes backflow, and solution gradually becomes dark chlorine look by blueness, cooling; Filter; Filtrating is slowly volatilized except that desolvating to being about 1/5 of original volume, separated out the mixed-valence copper four caryogamy compound crystallizations of the cyanogen root bridging of a large amount of brown in the solution, filtering separation can obtain compound 4 with the small amount of ethanol washing.
The present invention has used [Cu (bpy)]
2+, [Cu (bpy)
2]
2+[Cu (phen)
2]
2+(bpy=2; 2 '-dipyridyl; Phen=1; The 10-phenanthroline) and the substituting group verivate of bpy, phen series title complex as catalyst for reaction, have under the compound existence condition of certain reductibility at some organic aldehyde compounds (like phenyl aldehyde, terephthalaldehyde, terephthalaldehydic acid methyl esters etc.) and pyridine amine compound (like 2-EL-970,3-EL-970,4-aminopyridine) etc., with organic nitrile solvent or the solution that contains the organic nitrile compounds through popular response condition (not needing the anaerobic anhydrous condition); Long period refluxes, and just can obtain the various title complexs of cyanide ion bridging.And the fracture that cyanide ion is exactly the organic nitrile compounds through carbon-carbon single bond produces.This reaction cost through carbon-carbon single bond generation fracture in the simple mantoquita catalysis nitrile compounds (acetonitrile) is low, and raw material obtains easily, and reaction conditions is gentle, and is simple to operate, has certain application prospect.
A typical reaction is with [Cu (bpy)
2] (ClO
4)
2Be dissolved in respectively in isopyknic acetonitrile and the ethanolic soln according to certain molar ratio with terephthalaldehydic acid methyl esters or different substituted-amino pyridine; Mix 80 ℃ of backflows behind two kinds of solution; Obtain deep yellow solution; Solution is through slowly promptly obtaining a kind of deep yellow crystal after the volatilization; This crystal through conventional infrared, ultraviolet, mass spectral characteristi and x-ray crystal structure characterize resolve after, prove three nuclear copper compounds by two cyanide ion bridgings, cyanide ion acetonitrile molecular carbon carbon single bond fracture back just forms.This reactor product purity is high, and impurity is few, can reach more than 80% when productive rate is the highest.
The present invention is catalyzer (being dissolved in minor amounts of acetonitrile) with above-mentioned synthetic cyano-bridged mixed-valence copper polynuclear complex, is that oxidizer catalytic Oxybenzene formaldehyde is phenylformic acid with hydrogen peroxide (w=30%).Phenyl aldehyde, copper salt catalyst and hydrogen peroxide mol ratio are 200: 1: 400.After stirring 0.5h at normal temperatures and pressures, show that the phenylformic acid productive rate has reached 80.4% through HPLC; And do not have under the condition of catalyzer, productive rate is merely 11.4%.Explanation thus, the cyano-bridged mixed-valence copper polynuclear complex for preparing among the present invention is to have good catalytic activity in the benzoic process in oxidation of Benzaldehyde.So compare with catalyzer and method in the document; The mild condition of this reaction, if stirring at normal temperature, and also reactive behavior is high; The reaction times just can make productive rate reach 70%～80% than long in the document, and this reaction is then as long as just can reach the productive rate more than 80% half a hour.Easy preparation of this mixed-valence copper catalyst series and cost are lower, and consumption is few, is one type of novel catalyzer, has certain research and application prospect.In addition, in the middle of other catalytic perfomance of such mixed-valence copper compound is being studied.
Description of drawings
The structure iron of this three caryogamy compound that the mixed-valence copper three caryogamy compound crystalline X-ray diffraction analyses of the cyanogen root bridging that Fig. 1 makes for embodiment 1 obtain (for clear, wherein two not the coordination perchlorate do not draw, down with).
The structure iron of this three caryogamy compound that the mixed-valence copper three caryogamy compound crystalline X-ray diffraction analyses of the cyanogen root bridging that Fig. 2 makes for embodiment 2 obtain.
The structure iron of this three caryogamy compound that the mixed-valence copper three caryogamy compound crystalline X-ray diffraction analyses of the cyanogen root bridging that Fig. 3 makes for embodiment 3 obtain.
The structure iron of this four caryogamy compound that the mixed-valence copper four caryogamy compound crystalline X-ray diffraction analyses of the cyanogen root bridging that Fig. 4 makes for embodiment 4 obtain.
Embodiment
Embodiment 1
10 milliliters of [Cu
II(bpy)
2(ClO
4)
22H
2O] acetonitrile solution of (0.0611 gram, 0.1 mmole) joins 10 ml methanol 4-fbame (0.0164 gram, 0.1 mmole) solution. and mixture refluxed 50 hours; Solution colour slowly becomes deep yellow by blueness; Cooling is then filtered, and lets solution in air, slowly volatilize and obtains deep yellow crystal 1; Collection obtains 0.0310g, productive rate 70%.1:FT-IR(KBr):v＝3116(w)，2966(w)，2926(w)，2872(w)，2126(m)，2109(s)，1604(m)，1510(m)，1444(m)，1085(vs)，766(s)，and?622(s).UV/Vis(CH
3OH)：λ
max＝244and
298nm.ESI-MS(m/z)：278([Cu
II(bpy)(CN)(CH
3OH)]
+)，375([Cu
I(bpy)
2]
+)，434([Cu
II(bpy)
2(CN)(CH
3OH)]
+)，483([Cu
I 2(bpy)
2(CN)(H
2O)]
+)，563([Cu
II 2Cu
I(bpy)
5(CN)
2(ClO
4)]
2+/2).2:FT-IR(KBr):v＝3422(m)，3115(w)，3083(w)，3034(w)，2924(w)，2175(w)，2109(w)，1602(m)，1445(s)，1091(vs)，770(s)，and?623(s)。Its X-ray diffraction analysis is seen Fig. 1.
Embodiment 2
10 milliliters of [Cu
II(phen)
2(ClO
4)
2H
2O] acetonitrile solution of (0.0641 gram, 0.1 mmole) joins 10 milliliters of ethanol 3-EL-970s (0.0094 gram, 0.1 mmole) solution; Mixture refluxed 20 hours, and solution colour slowly becomes deep green by blueness, then cooling; Filter; Let solution in air, slowly volatilize and obtain green crystals 1, collect and obtain 0.0471g, productive rate 70%.FT-IR(KBr)：3113(s)，3082(m)，2126(s)，2108(s)，1690(s)，1600(s)，1567(s)，1492(m)，1443(m)，1384(s)，1316(m)，1086(vs)，1013(s)，765(m)，731(s)，and?623(m).ESI-MS(m/z)：278([Cu
II(bpy)(CN)(CH
3OH)]
+)，375([Cu
I(bpy)
2]
+)，401([Cu
II(bpy)
2(CN)]
+)，474([Cu
II(bpy)
2(CN)(CH
3CN)]
+)，488([Cu
II(bpy)
2(CN)(CH
3CN)(C
2H
5OH)]
+)。Its X-ray diffraction analysis is seen Fig. 2.
Embodiment 3
10 milliliters of [Cu
II(dmbpy)
2(ClO
4)
22H
2O] acetonitrile solution of (0.0639 gram, 0.1 mmole) joins the phenyl aldehyde of 10 ml methanol (0.0106 gram, 0.1 mmole) solution; Mixture refluxed 16 hours, and solution colour slowly becomes deep yellow by blueness, then cooling; Filter; Let solution in air, slowly volatilize and obtain deep yellow crystal 1, collect and obtain 0.0345g, productive rate 62%.FT-IR(KBr)：3072(w)，2960(w)，2924(w)，2123(m)，2108(s)，1663(s)，1614(s)，1559(m)，1489(m)，1380(m)，1090(vs)，833(s)，623(s).ESI-MS(m/z)：216([Cu
II(dmbpy)
2]
2+)，353([Cu
2 I，II(bpy)
3(CN)]
2+)，432([Cu
I(dmbpy)
2]
+)，458([Cu
II(dmbpy)
2(CN)]
+)。Its X-ray diffraction analysis is seen Fig. 3.
Embodiment 4
10 milliliters of [Cu
II(phen)
2(ClO
4)
2H
2O] acetonitrile solution of (0.0641 gram, 0.1 mmole) joins 10 milliliters of alcoholic acid phenyl aldehydes (0.0106 gram, 0.1 mmole) solution; Mixture refluxed 20 hours, and solution colour slowly becomes deep green by blueness, then cooling; Filter; Let solution in air, slowly volatilize and obtain green crystals 1, collect and obtain 0.0471g, productive rate 70%.FT-IR(KBr)：3072(s)，2129(s)，2110(s)，1637(s)，1619(s)，1518(s)，1494(m)，1384(m)，1146(s)，1083(vs)，868(s)，848(s)，722(s)，623(m).ESI-MS(m/z)：212([Cu
II(phen)
2]
2+/2)，232([Cu
II(phen)
2(CH
3CN)]
2+/2)，302([Cu
II(phen)(CN)(CH
3OH)]
+)，423([Cu
I(phen)
2]
+)，449([Cu
II(phen)
2(CN)]
+)，512([Cu
I 2(phen)
2(CN)]
+)，538([Cu
IICu
I(phen)
2(CN)
2]
+)。Its X-ray diffraction analysis is seen Fig. 4.
Embodiment 5. oxidation of Benzaldehyde prepare phenylformic acid
Mixed-valence copper three karyogamy compounds 1 with above-mentioned synthetic cyanogen root bridging: [Cu
II(bpy)
2(NC) Cu
I(bpy) (CN) Cu
II(bpy)
2(ClO
4)] (ClO
4)
2Being catalyzer (being dissolved in minor amounts of acetonitrile), is that oxidizer catalytic Oxybenzene formaldehyde is phenylformic acid with hydrogen peroxide (w=30%).Phenyl aldehyde, copper salt catalyst and hydrogen peroxide mol ratio are 200: 1: 400.After stirring 0.5h at normal temperatures and pressures, show that the phenylformic acid productive rate has reached 80.4% through HPLC; And do not have under the condition of catalyzer, productive rate is merely 11.4%.Explanation thus, the mixed valency three nuclear mantoquita [Cu that prepare in this patent
II(bpy)
2(NC) Cu
I(bpy) (CN) Cu
II(bpy)
2(ClO
4)] (ClO
4)
2In oxidation of Benzaldehyde is to have good catalytic activity in the benzoic process.So compare with catalyzer and method in the document; The mild condition of this reaction, if stirring at normal temperature, and also reactive behavior is high; The reaction times just can make productive rate reach 70%～80% than long in the document, and this reaction is then as long as just can reach the productive rate more than 80% half a hour.
Carry out identical experiment with compound 2,3 and 4, obtain similar result.
Easy preparation of the mixed-valence copper three karyogamy system row catalyzer of cyanogen root bridging of the present invention and cost are lower, and consumption is few, is one type of novel catalyzer, has certain research and application prospect.In addition, in the middle of other catalytic perfomance of such mixed-valence copper compound is being studied.
Claims (6)
1. cyano-bridged mixed-valence copper polynuclear complex, it is characterized in that: they are with 2,2 '-dipyridyl or 1,10-o-phenanthroline be part, with monovalence copper and cupric polynuclear coordination compound of cyanide ion bridging, their positive ion has following general structure:
Wherein negative ion is a perchlorate.
2. method for preparing the said polynuclear coordination compound 1 of claim 1 is characterized in that: it is that methanol solution with acetonitrile solution of two (2,2 '-dipyridyl) copper complex and 4-aldehyde benzoic acid ester mixes and refluxes; Solution gradually becomes deep yellow by blueness; Cooling is filtered, with filtrating slowly volatilization remove desolvate to original volume 1/5 after; Separate out the mixed-valence copper three caryogamy compound crystallizations of the cyanogen root bridging of a large amount of deep yellows in the solution, filtering separation can obtain compound 1 with the small amount of ethanol washing.
3. method for preparing the said polynuclear coordination compound 2 of claim 1 is characterized in that: it is two (1, the 10-o-phenanthroline) acetonitrile solutions of copper complex and the ethanolic soln of 3-EL-970 to be mixed reflux; Solution gradually becomes deep green by blueness; Cooling is filtered, with filtrating slowly volatilization remove desolvate to original volume 1/5 after; Separate out the mixed-valence copper three caryogamy compound crystallizations of a large amount of bottle-green cyanogen root bridgings in the solution, filtering separation can obtain compound 2 with the small amount of ethanol washing.
4. method for preparing the said polynuclear coordination compound 3 of claim 1 is characterized in that: it be with two (4,4 '-dimethyl--2; 2 '-dipyridyl) methanol solution of the acetonitrile solution of copper complex and phenyl aldehyde mixes backflow, and solution gradually becomes deep yellow by blueness, cooling; Filter; Filtrating is slowly volatilized except that desolvating to 1/5 of original volume, separated out the mixed-valence copper three caryogamy compound crystallizations of the cyanogen root bridging of a large amount of deep yellows in the solution, filtering separation can obtain compound 3 with the small amount of ethanol washing.
5. method for preparing the said polynuclear coordination compound 4 of claim 1 is characterized in that: it is two (1, the 10-o-phenanthroline) acetonitrile solutions of copper complex and the methanol solution of phenyl aldehyde to be mixed reflux; Solution gradually becomes deep green by blueness; Cooling is filtered, and filtrating is slowly volatilized to remove desolvate to 1/5 of original volume; Separate out the mixed-valence copper four caryogamy compound crystallizations of the cyanogen root bridging of a large amount of brown in the solution, filtering separation can obtain compound 4 with the small amount of ethanol washing.
6. cyano-bridged mixed-valence copper polynuclear complex according to claim 1 prepares the application in the phenylformic acid as catalyzer in oxidation of Benzaldehyde.
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Non-Patent Citations (5)
| Title |
|---|
| Jia-Cheng Liu et al.Different Oxidation States of Copper(I, I/II, II) Thiocyanate Complexes Containing 1,2,4-Triazole as a Bridging Ligand: Syntheses, Crystal Structures, and Magnetic Properties of 2-D Polymer CuI(admtrz)SCN,Linear Trinuclear [CuI2CuII(admtrz)6(SCN)2](ClO4)2.《Inorganic Chemistry》.2002,第42卷(第1期),235-243. * |
| Ling-Chen Kang et al.Synthesis, structure and magnetic property of a cyanamido bridged trinuclear copper complex.《Inorganic Chemistry Communications》.2009,第13卷109-111. * |
| Ling-ChenKangetal.Synthesis structure and magnetic property of a cyanamido bridged trinuclear copper complex.《Inorganic Chemistry Communications》.2009 |
| Tongbu Lu et al.C-C Bond Cleavage of Acetonitrile by a Dinuclear Copper(II) Cryptate.《Journal of the American Chemical Society》.2004,第126卷4760-4761. * |
| 严红燕等.甲烷磺酸铜催化氧化苯甲醛制苯甲酸.《抚顺石油学院学报》.2003,第23卷(第3期),10-12. * |
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