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Large steric hindrance ligand Pd complex catalyst as well as preparation method and application thereof

A technology of catalysts and complexes, applied in the chemical field, can solve the problems of difficult separation of palladium catalysts and difficult recovery and reuse of palladium black, and achieve good stability, catalysis, and high catalytic activity.

Inactive Publication Date: 2014-01-15
QILU UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the homogeneous catalytic system has its own shortcomings, such as the palladium catalyst is not easy to separate from the system after the reaction, and the generated palladium black is difficult to recycle and reuse, etc. People have developed many heterogeneous palladium catalytic systems

Method used

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  • Large steric hindrance ligand Pd complex catalyst as well as preparation method and application thereof
  • Large steric hindrance ligand Pd complex catalyst as well as preparation method and application thereof
  • Large steric hindrance ligand Pd complex catalyst as well as preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0050] Ligand 3 (R 1 Benzhydryl; R 2 Chlorine): Preparation of 2,6-bis(benzhydryl)-4-chloroaniline (1.06 g, 2.3 mmol) and 2-(2,6-bis(benzhydryl)-4-chlorophenylimine ) acenaphthylen-1-one (1.44g, 2.3mmol) was added with 150mg p-toluenesulfonic acid as a catalyst, stirred at reflux in 100mL toluene for 6h, filtered and removed the solvent, and the residue was dissolved in dichloromethane, passed through a silica gel column, and used petroleum After rinsing with ether / ethyl acetate (50:1), the second fraction was separated into the product, and the solvent was removed to obtain 0.25 g of a yellow solid with a yield of 10.2%. Melting point: 257–258°C. IR(KBr):3061,3029,2894,1655,1592,1493,1423,1180,1034,890,765,728,696cm -1 . 1 H NMR (400MHz, CDCl 3 ,TMS):δ=7.56(d,J=8.25Hz,2H),7.18-7.13(m,12H),7.09(s,4H),7.03(m,8H),6.92(t,J=7.55Hz, 2H),6.83(m,8H),6.67(t,J=8.64Hz,12H),6.16(d,J=7.15Hz,2H),5.65(s,4H)ppm. 13 C NMR (100MHz, CDCl 3 ,TMS): δ=163.8,147.5,142.9,141.8,134.0,129.8,12...

Embodiment 2

[0053] Pd complex catalyst 1 (R 1 is methyl; R 2 for the preparation of methyl): the N 2 Under protection, the PdCl 2 (CH 3 EN) 2 (0.04g, 0.14mmol) and ligand 4 (compound of formula II, R 1 is methyl; R 2 Methyl) (0.14mmol) was added to 10mL of dichloromethane, stirred at room temperature for 12h, passed through a silica gel column, and washed with petroleum ether / ethyl acetate (5:1). Rinse with methane, collect the second fraction, and the obtained is a Pd complex catalyst. After removing the solvent, 68 mg of a red solid is obtained, with a yield of 52.7%. IR(KBr):3056,2961,2871,1623,1600,1576,1490,1442,1299,1182,1076,768,742,698cm -1 . 1 H NMR (400MHz, CDCl 3 ,TMS):δ=7.89(d,J=8.31Hz,1H),7.68(d,J=8.30Hz,1H),7.35(m,5H),7.29–7.21(m,6H),7.14(d, J=7.48Hz,4H),7.03(s,2H),7.01(s,2H),6.99(d,J=7.73Hz,1H),6.45(t,J=9.88Hz,7H),6.16(t, J=7.40Hz,2H),5.69(d,J=7.22Hz,1H),2.55(s,6H),2.40(s,3H)ppm. 13 C NMR (100MHz, CDCl 3 ,TMS):δ=178.2,176.3,146.3,141.5,141.0,139.7,138.7,143.2,1...

Embodiment 3

[0055] Pd complex catalyst 2 (R 1 is ethyl; R 2 is methyl) is prepared with embodiment 2, and the difference is that ligand is ligand 2 (compound of formula II, R 1 is ethyl; R 2 For methyl), 82 mg of red solid was obtained, with a yield of 62.1%. IR (KBr):3060,2965,2933,2871,1625,1603,1581,1489,1442,1301,1182,1069,767,745,699cm -1 . 1 HNMR (400MHz, CDCl 3 ,TMS):δ=7.88(d,J=8.30Hz,1H),7.66(d,J=8.32Hz,1H),7.35(d,J=7.27Hz,4H),7.30-7.18(m,8H) ,7.13(d,J=5.57Hz,6H),7.03(s,2H),6.97(t,J=7.90Hz,1H),6.46(t,J=6.80Hz,6H),6.18(t,J= 7.34Hz, 2H), 5.69(d, J=7.10Hz, 1H), 3.15(m, 2H), 2.80(m, 2H), 2.44(s, 3H), 1.38(t, J=7.50Hz, 6H) ppm. 13 C NMR (100MHz, CDCl 3,TMS):δ=177.8,176.3,145.8,141.1,140.2,139.1,138.7,138.4,134.1,133.5,132.1,129.1,129.0,128.9,128.2,128.0,127.9,127.2,126.8,125.2 122.8, 122.1, 53.0, 24.3, 21.1, 13.7ppm. Elemental analysis C 55 h 45 Cl 3 N 2 Pd Theoretical value (%): C, 69.78, H, 4.79, N, 2.96; Experimental value (%): C, 69.39, H, 4.97, N, 2.75. Its NMR spec...

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Abstract

The invention provides a Pd complex catalyst as well as a preparation method and application thereof. The Pd metal complex catalyst provided by the invention has the structure shown by a formula (I), wherein R1 and R2 are alkyls or halogens; preferably, R1 is alkyl with 1-15 carbons, and R2 is alkyl with 1-5 carbons, or halogen; more preferably, R1 is methyl, ethyl, propyl or benzhydryl, and R2 is methyl or chlorine. DBCPh-NH2 is 2,6-bi (diphenylmethyl)-4-chloroaniline. According to the Pd metal complex catalyst, Heck reaction can be promoted when less Pd metal complex catalyst is used; and furthermore, the Pd metal complex catalyst has good catalytic performance and can be used for realizing the catalysis for the Heck reaction.

Description

technical field [0001] The invention belongs to the field of chemistry, and in particular relates to a Pd complex catalyst and its preparation method and application. Background technique [0002] The Heck reaction was proposed by Mizoroki [T.Mizoroki, K.Mori, A.Ozaki, Arylation of Olefin with Aryl Iodide Catalyzed by Palladium, Bull.Chem.Soc.Jap.1971, 44, 581.] and Heck [R.F.Heck, J.P.Nolley. Jr, Palladium-catalyzed vinylic hydrogen substitution reactions with aryl, benzyl, and styryl halides, J.Org.Chem.1972,37,2320.] found in the early 1970s, this type of reaction is halogenated aromatic alkenyl an important means of transformation. Heck himself also won the 2010 Nobel Prize in Chemistry for his outstanding contribution in this area. However, the homogeneous catalytic system has its own disadvantages, such as the palladium catalyst is not easy to separate from the system after the reaction, and the generated palladium black is difficult to recycle and reuse. People have...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C251/20C07C249/02B01J31/22C07F15/00C07B37/00C07C2/86C07C15/52C07D333/08C07C41/30C07C43/215C07C209/74C07C211/45
Inventor 班青张军
Owner QILU UNIV OF TECH
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