CN1762595A - heterogeneous palladium catalyst, preparation method and application thereof - Google Patents
heterogeneous palladium catalyst, preparation method and application thereof Download PDFInfo
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- CN1762595A CN1762595A CN 200510029802 CN200510029802A CN1762595A CN 1762595 A CN1762595 A CN 1762595A CN 200510029802 CN200510029802 CN 200510029802 CN 200510029802 A CN200510029802 A CN 200510029802A CN 1762595 A CN1762595 A CN 1762595A
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Abstract
The present invention relates to a kind of heterogeneous palladium catalyst, preparation method and use.Catalyst structure is as scheming: wherein n is between 1～20; R is C
1～6Alkyl or phenyl; Z is triphenylphosphine, acetoxy group or dichloro two triphenylphosphines; The duct of mesoporous material is 2.0～50nm, and the mesoporous material crystallographic system is two dimension cube, two dimension six sides, three-dimensional cubic or three-dimensional six sides, preferably meets the earth silicon material of above-mentioned requirements.Preparation of Catalyst is simple, and catalyst has following characteristics: (1) catalytic activity height, promptly catalyst amount is few, can be used for suitability for industrialized production.(2) stable in the air, preserve safe and simple.When (3) participating in reaction, need not protective atmosphere, so consersion unit is simple, is easy to suitability for industrialized production.(4) reusable edible and water be as solvent, and be environmentally friendly, can realize the industrial production greenization.
Description
Technical field
The present invention relates to a class heterogeneous palladium catalyst, synthetic method and catalytic applications thereof.This method is a carrier with the mesoporous material with high-specific surface area and regular pore canal, by surface modified, the Metal Palladium complex compound is supported in the duct, generates the heterogeneous precious metal catalyst of high catalytic activity.Because the aperture of used mesoporous material is limit, and can generate the palladium catalyst of nano-scale.The preparation method of this nano Pd catalyst is different from traditional (the top down) from top to bottom or the method for (bottom up) from bottom to top, and this is a kind of preparation method of brand-new nanocatalyst.This catalysis material has very high catalytic activity for the chemical reaction that precious metal participates in, and stable in the air, and to ring or border close friend, reusable edible and water are as solvent.This class heterogeneous catalysis can be realized the industrial production greenization, for its application provides wide prospect.
Background technology
In recent years, be that the application of representative precious metal catalyst in organic synthesis obtained developing rapidly with the palladium." (a) E.Negishi, Handbook of Organoic and Catalysts; Wiley:Chichester, 2002. (b) J.Tsuji, Palladium Reagents and Catalyst; Wiley:Chichester, 1995. (c) R.F.Hech, Palladium Reagents in Organic Synthesis; Academic Press:New York, 1985. (d) Trost, B.M.Chem.Rev.1996,96,395. (e) I.P.Beletskaya, A.V.Cheprakov, Chem.Rev.2000,100,3009. (f) J.Tsuji, Palladium Reagents and Catalyst; Wiley:Chichester, 2003. " but the consumption of precious metal catalyst is the bottleneck that it is used for large-scale production always; because heterogeneous catalysis is easy to recycle the industrial production that can be widely used, therefore having highly active heterogeneous precious metal catalyst has caused numerous scientists' great interest." (a) Mori, K.; Yamaguchi, K.; Hara, T.; Mizugaki, T.; Ebitani, K.; Kaneda, K.J.Am.Chem.Soc.2002,124,11572. (b) Kim, S.-W.; Kim, M.; Le e, W.Y.; Hyeon, T.J.Am.Chem.Soc.2002,124,7642. (c) Choudary, B.M.; Madhi, S.; Chowdari, N.S.; Kantam, M.L.; Sreedhar, B.J.Am.Chem.Soc.2002,124,14127. (d) Trost, B.M.J.Am.Chem.Soc.1978,101,7779. (e) Uozumi, Y.; Danjo, H.; Hayashi, T.Tetrahedron Lett.1997,38,3557. (f) Zecca, M.; Fisera, R.; Palma, G.; Lora, S.; Hronec, M.; Kr á lik, M.Chem.-Eur.J.2000,6,1980. (g) Parrish, C.A.; Buchwald, S.L.J.Org.Chem.2001,66,3820. (h) Niu, Y.; Yeung, L K.; Crooks, R.M.J.Am.Chem.Soc.2001,123,6840. (i) Jansson, A.M.; Gr ti, M.; Halkes, K.M.; Meldal, M.Org.Lett.2002,4,27. " these precious metal catalysts that are supported on inorganic material or the macromolecular material run off easily, and also lower than corresponding homogeneous catalyst activity.Recently, Kobayashi has prepared the high-activity palladium catalyst of a series of polymer-bounds by the method for " incarcerated "." (a) R.Akiyama, S.Kobayashi, J.Am.Chem.Soc.2003; 125,3412. (b) K.Okamoto, S.Kobayashi; Org.Lett.2004,6,1987. (c) K.Okamoto; S.Kobayashi, J.Org.Chem.2004,69; 2871. (d) K.Okamoto, S.Kobayashi, J.Am.Chem.Soc.2005; 127,2125. " on the other hand, the MCM-41 mesoporous material that is taken the lead in reporting by the scientist of Mobil company has attracted numerous scientists' sight." (a) C.T.Kresge, M.E.Leonowicz, W.J.Roth, J.C.Vartuli; J.S.Beck, Nature, 1992,359; 710. (b) J.S.Beck, J.C.Vartuli, W.J.Roth, M.E.Leonowicz; C.T.Kresge, K.D.Schmitt, C.T-W.Chu, D.H.Olson; E.W.Sheppard, S.B.McCullen, J.B.Higgins, J.L.Schlenker; J.Am.Chem.Soc.1992,114,10834. " this material has very high specific area (500-1000m
2/ g), and the regular mesopore orbit of adjustable homogeneous, very high chemical stability and hydrothermal stability, and also its surface has abundant silicon hydroxyl, can carry out surface modification." (a) D.Zhao, J.Feng, Q.Huo, N.Melosh; G.H.Fredrickson, B.F.Chmelka, G.D.Stucky; Science1998,279,548. (b) Y.Liu; W.Zhang, T.J.Pinnavaia, J.Am.Chem.Soc.2000; 122,8791. (c) Y.Liu, W.Zhang; T.J.Pinnavaia, Angew.Chem.Int.Ed.2001,40,1255. (d) Y.Han, F.-S.Xiao, S.Wu, J.Phys.Chem.B 2001,105,7963. (e) Y.Han, D.Li, L.Zhao, F.-S.Xiao, Angew.Chem.Int.Ed.2003,42,3633. " mesoporous material with these superior functions provides a kind of desirable catalyst carrier for chemists.〖(a)P.T.Tanev，M.Chibwe，T.J.Pinnavaia，Nature，368，321(1994).(b)A.Corma，M.T.Navarra，J.P.Pariente，J.Chem.Soc.Chem.Comm.，1994，147.(c)D.E.De Vos，M.Dams，B.F.Sels，P.A.Jacobs，Chem.Rev.2002，102，3615.(d)R.Raja，J.M.Thomas，M.D.Jones，B.F.G Johnson，.D.E.W Vaughan，J.Am.Chem.Soc.，2003，125，14982.(e)S.Huh，H.-T.Chen，J.W.Wiench，M.Pruski，V.S.-Y.Lin，J.Am.Chem.Soc.2004，126，1010.(f) C.H.Christensen，K.Johannsen，I.Schmidt，C.H.Christensen，J.Am.Chem.Soc.2003，125，13370.(g)S.K.Mohapatra，S.U.Sonavane，R.V.Jayaram，P.Selvam，Org.Lett.2002；4，4297.(g)M.Jia，；A.Seifert，；W.R.Thiel，Chem.Mater.2003，15，2174.(i)M.Jia，A.Seifert，M.Berger，H.Giegengack，S.Schulze，W.R.Thiel，Chem.Mater.2004，16，877.(j)M.V.Vasylyev，R.Neumann，J.Am.Chem.Soc.2004，126，884.(k)K.Mukhopadhyay，A.B.Mandale，R.V.Chaudhari，Chem.Mater.2003，15，1766.(l)V.S.-Y.Lin，D.R.Radu，M.-K.Han，W.Deng，S.Kuroki，B.H.Shanks，M.Pruski，J.Am.Chem.Soc．2002，124，9040.(m)A.Vinu，T.Krithiga，V.Murugesan，M.Hartmann，Adv.Mater.2004，16，1817.(n)R.Becker，H.Parala，F.Hipler，O.P.Tkachenko，K.V.Klementiev，W.Grünert，H.Wilmer，O.Hinrichsen，M.Muhler，A.Birkner，C.Wll，S.Schfer，R.A.Fischer，Angew.Chem.Inter.Ed.2004，43，2839.(o)M.Chatterjee，F.Y.Zhao，Y.Ikushima，Adv.Syn.&Catal.2004，346，459.(p)D.S.Shephard，T.Maschmeyer，B.F.G.Johnson，J.M.Thomas，G.Sankar，D.Ozkaya，W.Zhou，R.D.Oldroyd，R.G.Bell，Angew.Chem.Inter.Ed.1997，36，2242.(q)P.Steekanth，S.-W.Kim，T.Hyeon，B.M.Kim，Adv.Syn.&Catal.2003.345，936.〗
Although document " (a) C.P.Mehnert, J.Y.Ying, Chem.Commum.1997,2215. (b) K.Mukhopadhyay; B.R.Sarkar, R.V.Chaudhari, J.Am.Chem.Soc.2002,124; 9692. (c) L.Li, J.-1.Shi, J.-N.Yan, Chem.Commum.2004; 1990. (d) L.Li, J.-1.Shi, L.-X.Zhang, L.-M.Xiong; J.-N.Yah, Adv.Mater.2004,16; 1079. (e) B.Blanco, A.Mehdi, M.Moreno-
R.Pleixatsa, C.Rey é, Tetra.Lett.2004,45,8789. " in reported with the mesoporous material to be carrier, carrying metal precious metal palladium also is applied to catalytic reaction.But the activity of the palladium catalyst that these mesoporous materials support is compared with the activity of homogeneous catalyst and is not outstanding especially, and the reaction that participates in all is to use organic solvent.Reported first of the present invention the mesoporous material carrying metal palladium catalyst of modifying by organic silicon ether.This catalyst has shown high catalytic activity in reaction, and stable in the air, and is environmentally friendly, and reusable edible and water are as solvent.
Summary of the invention
The heterogeneous palladium catalyst that the purpose of this invention is to provide a series of novel high-activities.
The synthetic method that the purpose of this invention is to provide a kind of above-mentioned catalyst is utilized the complexing of modification mesoporous silicon material to palladium catalyst, supports and disperses synthetic this highly active heterogeneous palladium catalyst.
The purpose of this invention is to provide a kind of above-mentioned Application of Catalyst.
Highly active heterogeneous palladium catalyst of the present invention, its structural formula is:
Mesoporous silicon material,
Wherein n is between 1～20, preferred n=1～6, and R is C
1～6Alkyl, as C
1～6Alkyl or phenyl;
Being mesoporous material, can be that mesopore orbit is the silicon materials of 2.0～50nm, and the mesoporous material crystallographic system can be two dimension cube, two dimension six sides, three-dimensional cubic or three-dimensional six sides, preferably meets the earth silicon material of above-mentioned requirements.The part example represented as following table:
| Catalyst numbering n R | MAS-Pd-1 4 C 2H 5 | MAS-Pd-2 4 CH 3 | MAS-Pd-3 4 C 6H 5 | MAS-Pd-4 3 C 2H 5 | MAS-Pd-5 3 C 6H 5 |
| Organosilicon | 1 | 2 | 3 | 4 | 5 |
| Palladium content mol/g | 5.0×10 -5 | 5.4×10 -5 | 6.3×10 -5 | 4.6×10 -5 | 5.8×10 -5 |
Annotate: catalyst carrier is a mesoporous silicon oxide, and the organic palladium compound is a tetra-triphenylphosphine palladium.Palladium content is detected by ICP and obtains.
In the highly active heterogeneous palladium catalyst of the present invention, wherein the part of palladium can be triphenylphosphine, acetoxy group or dichloro two triphenylphosphines etc., and especially preferably from tetrakis triphenylphosphine palladium, its structural formula is as follows:
Mesoporous silicon material.
Highly active heterogeneous palladium catalyst synthetic method provided by the invention, typical reaction equation is as follows:
Wherein n is 1～20, and R is C
1～6Alkyl, as C
1～6Alkyl or phenyl; Mesoporous material can be that mesopore orbit is the silicon materials of 2.0～50nm, and the mesoporous material crystallographic system can be a two dimension cube, two dimension six sides, and three-dimensional cubic or three-dimensional six sides preferably meet the earth silicon material of above-mentioned requirements.
Synthetic method of the present invention is when the organic solvent neutral temperature is 20～200 ℃, and organic-silicon-modified above-mentioned mesoporous material and the reaction of organic palladium compound were obtained the heterogeneous metal palladium catalyst that mesoporous material supports in 4～48 hours.The recommendation response temperature is a room temperature, and the reaction time is 5～14 hours, and the mol ratio of organically-modified silicon mesoporous material and organic palladium compound is 100～100000: 1, and recommending mol ratio is 1000～10000: 1.Described organic palladium compound can be tetrakis triphenylphosphine palladium, palladium or dichloro two triphenylphosphine palladiums etc., recommends tetrakis triphenylphosphine palladium.
Used reaction dissolvent is conventional organic solvent, as n-hexane, cyclohexane, toluene, oxolane, carrene, dimethyl sulfoxide (DMSO), N, and dinethylformamide, 1,4-dioxane, acetone, ether or acetonitrile etc.
The heterogeneous metal palladium catalyst of novel high-activity of the present invention can be used for the various organic reactions of catalysis.
(1) the applied reaction of the catalyst of loaded palladium is an example with Suzuki coupled reaction and Heck reaction, but is not limited to this two classes reaction.
The Suzuki coupled reaction is as follows:
Wherein, X can be an iodine, bromine, perhaps chlorine, R
1And R
2Can be various electron riches or electron-withdrawing substituent; Described abundant electron substituents can be methyl, methoxyl group, hydroxyl or amino etc., and described electron-withdrawing substituent can be carbonyl, nitro, fat base or trifluoromethyl etc.
The above-mentioned heterogeneous palladium catalyst that provides is provided wherein used palladium catalyst.The mol ratio of palladium catalyst and substrate is 1: 100～1000000; Recommending mol ratio is 1: 1000～100000.
Wherein used alkali is potassium phosphate, sodium acid carbonate, potash or triethylamine etc.
Wherein used reaction dissolvent is conventional organic solvent or water, and organic solvent can be n-hexane, cyclohexane, toluene, oxolane, carrene, dimethyl sulfoxide (DMSO), N, dinethylformamide, 1,4-dioxane, acetone, ether or acetonitrile etc.; Reaction temperature is 20～200 ℃; Reaction time is 1～48 hour.
The Heck reaction is as follows:
Wherein, X can be an iodine, bromine, perhaps chlorine, R
1And R
2Can be various electron riches or electron-withdrawing substituent; Described abundant electron substituents can be methyl, methoxyl group, hydroxyl or amino etc., and described electron-withdrawing substituent can be carbonyl, nitro, fat base or trifluoromethyl etc.
The above-mentioned heterogeneous palladium catalyst that provides is provided wherein used palladium catalyst.The mol ratio of palladium catalyst and substrate is 1: 100～1000000; Recommending mol ratio is 1: 1000～100000.
Wherein used alkali is potassium phosphate, sodium acid carbonate, potash or triethylamine etc.
Wherein used reaction dissolvent is conventional organic solvent or water, and organic solvent can be n-hexane, cyclohexane, toluene, oxolane, carrene, dimethyl sulfoxide (DMSO), N, dinethylformamide, 1,4-dioxane, acetone, ether or acetonitrile etc.; Reaction temperature is 20～200 ℃; Reaction time is 1～48 hour.
The present invention is a carrier with the mesoporous material, supports precious metal catalyst by surface modification.Preparation is simple, is a kind of method easily and effectively.Prepared catalyst has following characteristics:
(1) catalytic activity height, promptly catalyst amount is few, can be used for suitability for industrialized production.
(2) stable in the air, preserve safe and simple.
When (3) participating in reaction, need not protective atmosphere, so consersion unit is simple, is easy to suitability for industrialized production.
(4) reusable edible and water be as solvent, and be environmentally friendly, can realize the industrial production greenization.
The specific embodiment
Following embodiment will help to understand the present invention, but be not limited to content of the present invention, and the Preparation of Catalyst example is an example with organosilicon 1 and mesoporous material SBA-15.
Embodiment 1
(1) preparation of organo-silicon compound 1:
Operate as follows: chloroplatinic acid (0.5mol%) adds ethyl-pi-allyl-tetraethylene glycol (0.1mol), triethoxysilicane hydrogen (0.3mol), stirring at room 1 day 180 ℃ of vacuum drying 2 hours.Steam and remove excessive triethoxysilicane hydrogen, the vavuum pump decompression, 178 ℃ steam colourless liquid, obtain product 27.5g.
1H NMR(300MHz，CDCl
3)：δ3.79(q，J＝7.2Hz，6H)，3.64-3.43(m，18H)，3.39(t，J＝6.9Hz，2H)，1.71-1.61(m，2H)，1.19-1.14(m，12H)，0.59(t，J＝8.4Hz，2H)。
13C NMR (75MHz, CDCl
3): δ 73.4,70.9, and 70.6,70.1,63.0,51.3,17.9,15.5,14.7,8.0; MS m/z (%) 337 (100), 427 (M
+, 35.45); The elementary analysis calculated value, C
19H
42O
8Si:C, 53.49; H, 9.92; Measured value: C, 53.65; H, 9.70.
Embodiment 2
(2) preparation of organo-silicon compound 2:
Operate as follows: operate as follows: chloroplatinic acid (0.5mol%) adds methyl-pi-allyl-tetraethylene glycol (0.1mol), triethoxysilicane hydrogen (0.3mol), stirring at room 1 day 180 ℃ of vacuum drying 2 hours.Steam and remove excessive triethoxysilicane hydrogen, the vavuum pump decompression, 178 ℃ steam colourless liquid, obtain product 27.3g.
1H NMR(300MHz，CDCl
3)：δ3.78(q，J＝7.2Hz，6H)，3.64-3.43(m，18H)，3.39(t，J＝6.9Hz，2H)，3.25(t，J＝8.4Hz，3H)，1.71-1.61(m，2H)，1.23(t，J＝8.2Hz，9H)，0.59(t，J＝8.4Hz，2H)。
13C NMR (75MHz, CDCl
3): δ 70.9,70.6, and 70.1,63.0,53.9,51.3,17.9,15.5,8.0; MS m/z (%) 323 (100), 413 (M
+, 22.23); The elementary analysis calculated value, C
18H
40O
8Si:C, 52.40; H, 9.77; Measured value: C, 52.62; H, 9.65.
Embodiment 3
(3) preparation of organo-silicon compound 3:
Operate as follows: chloroplatinic acid (0.5mol%) adds phenyl-pi-allyl-tetraethylene glycol (0.1mol), triethoxysilicane hydrogen (0.3mol), stirring at room 1 day 180 ℃ of vacuum drying 2 hours.Steam and remove excessive triethoxysilicane hydrogen, the vavuum pump decompression, 178 ℃ steam colourless liquid, obtain product 32.8g.
1H NMR(300MHz，CDCl
3)：δ6.90-6.76(m，5H)，4.20(t，J＝6.9Hz，2H)，3.79(q，J＝7.2Hz，6H)，3.64-3.43(m，16H)，1.70-1.64(m，2H)，1.19-1.14((t，J＝7.2Hz，9H)，0.69(t，J＝8.4Hz，2H)。
13C NMR (75MHz, CDCl
3): δ 158.8,129.1, and 120.1,114.2,73.4,70.9,70.6,70.5,51.3,17.9,15.5,14.7,8.0; MS m/z (%) 385 (100), 475 (M
+, 22.54); The elementary analysis calculated value, C
23H
42O
8Si:C, 58.20; H, 8.92; Measured value: C, 58.45; H, 8.70.
Embodiment 4
(4) preparation of organo-silicon compound 4:
Operate as follows: chloroplatinic acid (0.5mol%) adds ethyl-pi-allyl-triethylene glycol ether (0.1mol), trimethoxy silicon hydrogen (0.3mol), stirring at room 1 day 180 ℃ of vacuum drying 2 hours.Steam and remove excessive trimethoxy silicon hydrogen, the vavuum pump decompression, 169 ℃ steam colourless liquid, obtain product 28.6g.
1H NMR(300MHz，CDCl
3)：δ3.74(q，J＝7.2Hz，6H)，3.64-3.43(m，14H)，3.38(t，J＝6.9Hz，2H)，1.70-1.56(m，2H)，1.17-1.10(m，12H)，0.58(t，J＝8.4Hz，2H)。
13C NMR (75MHz, CDCl
3): δ 73.4,70.9, and 70.6,70.1,63.0,51.3,17.9,15.5,14.7,8.0; MS m/z (%) 293 (100), 383 (M
+, 53.21); The elementary analysis calculated value, C
19H
42O
8Si:C, 53.37; H, 10.01; Measured value: C, 53.55; H, 9.73.
Embodiment 5
(5) preparation of organo-silicon compound 5:
Operate as follows: chloroplatinic acid (0.5mol%) adds phenyl-pi-allyl-triethylene glycol ether (0.1mol), triethoxysilicane hydrogen (0.3mol), stirring at room 1 day 180 ℃ of vacuum drying 2 hours.Steam and remove excessive triethoxysilicane hydrogen, the vavuum pump decompression, 178 ℃ steam colourless liquid, obtain product 32.8g.
1H NMR(300MHz，CDCl
3)：δ6.90-6.76(m，5H)，4.20(t，J＝6.9Hz，2H)，3.79(q，J＝7.2Hz，6H)，3.64-3.43(m，12H)，1.70-1.64(m，2H)，1.19-1.14((t，J＝7.2Hz，9H)，0.69(t，J＝8.4Hz，2H)。
13C NMR (75MHz, CDCl
3): δ 158.8,129.1, and 120.1,114.2,73.4,70.9,70.6,70.5,51.3,17.9,15.5,14.7,8.0; MS m/z (%) 341 (100), 431 (M
+, 32.22); The elementary analysis calculated value, C
23H
42O
8Si:C, 58.58; H, 8.89; Measured value: C, 58.29; H, 8.92.
Embodiment 6
(6) organosilicon 1 carries out mesoporous material synthetic of surface modification:
Operate as follows: mesoporous material (SBA-15) 13.0g that handled with alcohol reflux places the 100ml three-necked bottle, 120 ℃ of vacuum drying 3 hours.After the cooling, add toluene (60ml) and organosilicon 1 (9.3g), 110 ℃ were refluxed 6 hours.Be spin-dried for solvent, 150 ℃ of vacuum drying 12 hours, obtain white powder then.The mesoporous material that obtains surface modification is dried in ethanol washing 3 times in the air.Elementary analysis, C content are 15.42%, and organosilicon content is 1.0mmol/g.
Embodiment 7
(7) preparation of novel high-activity heterogeneous palladium catalyst (MAS-Pd-1):
Operate as follows: under nitrogen protection, the mesoporous material and the 20ml oxolane mixed solution and dripping 0.11g Pd (PPh of the 1.0g surface modification that past embodiment 6 obtains
3)
4Mixed solution with the 10ml oxolane.After dropwising, stirring at room 6 hours.In air, filter oxolane washing (20ml * 3), vacuum drying.Elementary analysis palladium content is: 5 * 10
-5Mol/g.
Embodiment 8
(8) the Suzuki coupled reaction of heterogeneous palladium catalyst (MAS-Pd-1) participation:
Example 1:
Operate as follows: in reaction tube, add MAS-Pd-1 (50mg, 0.15mol%), to methoxyphenylboronic acid (55mg, 0.36mmol), o-iodobenzoic acid formicester (78mg, 0.3mmol), three hypophosphite monohydrate potassium (160mg, 0.6mmol) and distilled water (3ml), add stirring 8 hours at 50 ℃, TLC follows the tracks of reaction to finishing, and adds extracted with diethyl ether product (5ml * 4), anhydrous magnesium sulfate drying.Filter, add silica gel, be spin-dried for solvent, directly (benzinum: purifying ether=10: 1) obtains 2-(4-methoxyphenyl)-benzoic acid formicester, productive rate 98% to column chromatography.IR (neat) 2950,1731,1611,1288cm
-1 1H NMR (300MHz, CDCl
3): δ 7.69 (d, J=7.8Hz, 1H), 7.42-7.35 (m, 1H), 7.30-7.22 (m, 2H), 7.15 (d, J=8.7Hz, 2H), 6.84 (d, J=8.7Hz, 2H), 3.73 (s, 3H), 3.56 (s, 3H);
13C NMR (75MHz, CDCl
3): δ 169.3,158.8, and 141.9,133.5,131.1,130.7,130.6,129.6,129.3,126.7,113.4,55.1,51.9; MS m/z (%) 242 (M
+, 100); The elementary analysis calculated value, C
15H
14O
3: C, 74.36; H, 5.82; Measured value: C, 74.08; H, 5.74.
Example 2:
Operate as follows: in reaction tube, add MAS-Pd-1 (50mg, 0.15mol%), phenyl boric acid (44mg, 0.36mmol), the o-iodobenzoic acid formicester (78mg, 0.3mmol), three hypophosphite monohydrate potassium (160mg, 0.6mmol) and distilled water (3ml), adding stirring 8 hours at 50 ℃, TLC follows the tracks of reaction to finishing, add extracted with diethyl ether product (5ml * 4), anhydrous magnesium sulfate drying filters, and adds silica gel, be spin-dried for solvent, directly (benzinum: purifying ether=10: 1) obtains 2-phenyl-benzoic acid formicester, productive rate 97% to column chromatography.IR (neat) 2952,1736,1622cm
-1 1H NMR (300MHz, CDCl
3): δ 7.85 (d, J=7.5Hz, 1H), 7.58-7.52 (m, 1H), 7.46-7.35 (m, 7H), 3.66 (s, 3H);
13C NMR (75MHz, CDCl
3): δ 169.1,142.4, and 141.2,131.2,130.7,130.6,129.7,128.2,128.0,127.2,51.9; MS m/z (%) 181 (100), 212 (M
+, 50.77); The elementary analysis calculated value, C
14H
12O
2: C, 79.23; H, 5.70; Measured value: C, 79.09; H, 5.72.
Example 3:
Operate as follows: in reaction tube, add MAS-Pd-1 (50mg, 0.15mol%), O-methoxy phenyl boric acid (55mg, 0.36mmol), adjacent bromobenzene first cyanogen (55mg, 0.3mmol), three hypophosphite monohydrate potassium (160mg, 0.6mmol) and distilled water (3ml), adding stirring 8 hours at 50 ℃, TLC follows the tracks of reaction to finishing, add extracted with diethyl ether product (5ml * 4), anhydrous magnesium sulfate drying filters, and adds silica gel, be spin-dried for solvent, directly (benzinum: purifying ether=10: 1) obtains 1-cyano group-1 '-methoxyl biphenyl, productive rate 95% to column chromatography.IR (neat) 3066,2226,1602,1500cm
-1 1H NMR (300MHz, CDCl
3): δ 7.77-7.72 (m, 1H), 7.67-7.60 (m, 1H), 7.50-7.39 (m, 3H), 7.29-7.26 (m, 1H), 7.11-7.02 (m, 1H), 3.85 (s, 3H);
13CNMR (75MHz, CDCl
3): δ 156.3,142.4, and 132.6,132.3,130.8,130.7,130.2,127.2,127.1,120.6,118.6,113.2,111.1,55.3; MS m/z (%) 209 (M
+, 100); The elementary analysis calculated value, C
14H
12O
2: C, 80.36; H, 5.30; Measured value: C, 80.09; H, 5.62.
Embodiment 15
(15) heterogeneous palladium catalyst (MAS-Pd-1) is recycling:
Operate as follows: add in the reaction tube MAS-Pd-1 (100mg, 0.3mol%), to methoxyphenylboronic acid (55mg, 0.36mmol), iodobenzene (61mg, 0.3mmol), (160mg 0.6mmol) and distilled water (3ml), adds at 50 ℃ and to stir 8 hours three hypophosphite monohydrate potassium, TLC follows the tracks of reaction to finishing, and adds extracted with diethyl ether product (5ml * 4), anhydrous magnesium sulfate drying, filter, add silica gel, be spin-dried for solvent, directly column chromatography (benzinum: purifying ether=10: 1).Reaction mother liquor add once more to methoxyphenylboronic acid (55mg, 0.36mmol), iodobenzene (61mg, 0.3mmol), three hypophosphite monohydrate potassium (160mg, 0.6mmol), add stirring 8 hours at 50 ℃, TLC follows the tracks of reaction to finishing, and adds extracted with diethyl ether product (5ml * 4), anhydrous magnesium sulfate drying, filter, add silica gel, be spin-dried for solvent, directly column chromatography (benzinum: purifying ether=10: 1).So circulation is 10 times, and it is as follows successively to obtain product yield: 92%, 92%, 91%, 89%, 85%, 83%, 87%, 83%, 85%, 80%.
Embodiment 9
(9) the Heck reaction of heterogeneous palladium catalyst (MAS-Pd-1) participation:
Operate as follows: add in the reaction tube MAS-Pd-1 (10mg, 0.001mol%), ETHYL CYANOACRYLATE (7.5g, 75mmol), iodobenzene 10.2g, 50mmol), triethylamine (10.6mg, 75mmol) and N, dinethylformamide (50ml) adds stirring 20 hours at 120 ℃, and TLC follows the tracks of reaction to finishing, add extracted with diethyl ether product (50ml * 4), saturated aqueous common salt flush away N, dinethylformamide, anhydrous magnesium sulfate drying, filter, add silica gel, be spin-dried for solvent, directly column chromatography (benzinum: purifying ether=10: 1), obtain (E)-beta-phenyl-ETHYL CYANOACRYLATE (8.3g), productive rate 94%.IR (neat) 1713,1683,1624,1170cm
-1 1H NMR (300MHz, CDCl
3): δ 7.69 (d, J=16.0Hz, 1H), 7.53-7.48 (m, 2H), 7.40-7.32 (m, 3H), 6.44 (d, J=16.0Hz, 1H), 4.26 (q, J=7.1Hz, 2H), 1.34 (t, J=7.1Hz, 3H);
13C NMR (75MHz, CDCl
3): δ 166.9,144.5, and 134.4,130.2,128.8,128.0,118.2,60.4,14.3; MS m/z (%) 176 (M
+, 100); The elementary analysis calculated value, C
11H
12O
2: C, 74.98; H, 6.86; Measured value: C, 74.66; H, 6.63.
Claims (10)
1, a kind of heterogeneous metal palladium catalyst, its structural formula is as follows:
Mesoporous silicon material,
Wherein, n=1～20, R is C
1～6Alkyl or phenyl; Z is triphenylphosphine, acetoxy group or dichloro two triphenylphosphines,
Be mesoporous material, its mesopore orbit is 2.0～50nm, and the mesoporous material crystallographic system is two dimension cube, two dimension six sides, three-dimensional cubic or three-dimensional six sides.
2, heterogeneous metal palladium catalyst as claimed in claim 1 is characterized in that described its structural formula of heterogeneous metal palladium catalyst is as follows:
Mesoporous silicon material, wherein n and R are according to claim 1.
3, heterogeneous metal palladium catalyst as claimed in claim 1 or 2 is characterized in that described mesoporous material is a silica.
4, heterogeneous metal palladium catalyst as claimed in claim 1 or 2 is characterized in that described n=1～6.
5, a kind of synthetic method of heterogeneous metal palladium catalyst as claimed in claim 1, it is characterized in that in organic solvent, organic-silicon-modified mesoporous material and organic palladium compound react down at 20～200 ℃ and obtained the heterogeneous metallic catalyst that mesoporous material supports in 4～48 hours, wherein, modification silicon materials and palladium compound mol ratio are 100～100000: 1, and organic-silicon-modified mesoporous material structural formula is:
6, the synthetic method of heterogeneous precious metal catalyst as claimed in claim 5 is characterized in that described modification silicon materials and metallic compound mol ratio are 1000～10000: 1.
7, the synthetic method of heterogeneous metal palladium catalyst as claimed in claim 5, it is characterized in that described organic solvent is n-hexane, cyclohexane, toluene, oxolane, carrene, dimethyl sulfoxide (DMSO), N, dinethylformamide, 1,4-dioxane, acetone, ether or acetonitrile.
8, a kind of application of heterogeneous metal palladium catalyst as claimed in claim 1 is characterized in that being used for Suzuk coupled reaction and Heck catalyst for reaction.
9, the application of heterogeneous metal palladium catalyst as claimed in claim 8 is characterized in that described Suzuki coupled reaction adopts the high activity heterogeneous palladium catalyst, and in organic solvent or water, palladium catalyst and molecular formula are
Or/and
The mol ratio of substrate be 1: 100～1000000 o'clock, reaction temperature is 20～200 ℃; Reaction time is 1～48 hour, obtains molecular formula to be
Product, wherein, X is an iodine, bromine, perhaps chlorine, R
1And R
2Be electron rich or electron-withdrawing substituent.
10, the application of the heterogeneous metal palladium catalyst of high activity as claimed in claim 8 is characterized in that described Heck reaction employing high activity heterogeneous palladium catalyst, and in organic solvent or water, palladium catalyst and molecular formula are
Or/and
The mol ratio of substrate be 1: 100～1000000 o'clock, reaction temperature is 20～200 ℃; Reaction time is 1～48 hour, obtains molecular formula to be
Product, wherein, X is an iodine, bromine, perhaps chlorine, R
1And R
2Be electron rich or electron-withdrawing substituent.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103447086A (en) * | 2012-05-28 | 2013-12-18 | 国家纳米科学中心 | Loaded palladium catalyst, its preparation method and application |
| CN105800703A (en) * | 2016-03-31 | 2016-07-27 | 任晓明 | Silicon dioxide modified nitrite removal material and preparation and regeneration method thereof |
-
2005
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103447086A (en) * | 2012-05-28 | 2013-12-18 | 国家纳米科学中心 | Loaded palladium catalyst, its preparation method and application |
| CN103447086B (en) * | 2012-05-28 | 2015-05-06 | 国家纳米科学中心 | Loaded palladium catalyst, its preparation method and application |
| CN105800703A (en) * | 2016-03-31 | 2016-07-27 | 任晓明 | Silicon dioxide modified nitrite removal material and preparation and regeneration method thereof |
| CN105800703B (en) * | 2016-03-31 | 2018-12-21 | 任晓明 | A kind of silica modified nitrite removal material and its preparation regeneration method |
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