Chelate-type N-heterocyclic carbene palladium compound containing heteroaromatic group and preparation method of same

A nitrogen heterocyclic carbene and palladium compound technology, applied in the field of organic compound synthesis, can solve the problems of polluted products, difficult immobilization, no active groups, etc., and achieve the effects of high-efficiency catalytic performance, high catalytic yield and simple operation

Active Publication Date: 2015-12-09
HENAN UNIVERSITY OF TECHNOLOGY
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Problems solved by technology

However, there is no active group on the imidazole ring in this type of catalyst that can be further reacted, so it is difficult to immobilize and can only be used as a homogeneous catalyst [References 8-11Krishnan, D.; Wu, M.; Chiang, M.; Li, Y.; Leung, P.-H.; Pullarkat, S.A. Organometallics 2013, 32, 2389. Hahn, F.E.; Jahnke, M.C.; J. Y. Inorg. Chim. Acta. 2004, 357, 4313. Tsoureas, N.; Danopoulos, A.A.; Tulloch, A.A.; Light, M. E. Organometallics 2003, 22, 4750.]
Homogeneous catalysts are not easy to separate and recover, use high cost and pollute products, which largely hinder the further application of nitrogen heterocyclic carbene palladium compounds in the field of catalysis

Method used

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  • Chelate-type N-heterocyclic carbene palladium compound containing heteroaromatic group and preparation method of same
  • Chelate-type N-heterocyclic carbene palladium compound containing heteroaromatic group and preparation method of same
  • Chelate-type N-heterocyclic carbene palladium compound containing heteroaromatic group and preparation method of same

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] (1) In a 250mL three-necked flask, L-leucinol (60mmol, 7.03g) and ammonium chloride (60mmol, 3.21g) were dissolved in 120mL methanol, and under cooling in an ice-water bath, the mass percentage was added dropwise with a constant pressure funnel successively 36% formaldehyde solution (60 mmol, 4.6 mL) and 40% mass percent glyoxal solution (60 mmol, 7.6 mL). After the dropwise addition was completed, the temperature was raised to 60° C. to react for 5 h, and the reaction solution was spin-dried to obtain a reddish-brown viscous liquid. The above reddish-brown viscous liquid was dissolved in 150mL NaOH solution (2M), extracted with dichloromethane (20mL×3), the organic phases were combined, and anhydrous Na 2 SO 4 Dry, filter, remove the solvent under reduced pressure, and separate and purify by column chromatography to obtain pure (S)-2-(1-imidazolyl)-4-methylpentanol (7.57 g, yield 75%).

[0028] (2) Add (S)-2-(1-imidazolyl)-4-methylpentanol (5.0mmol, 0.84g), 2-bromopy...

Embodiment 2

[0032] Step (1) is the same as Example 1

[0033] (2) Add (S)-2-(1-imidazolyl)-4-methylpentanol (5.0 mmol, 0.84 g), 2-chloropyrimidine (6 mmol, 0.69 g) and 15 mL of toluene into a 50 mL round bottom flask , heated to 110 °C for 72 h, cooled to room temperature, and the viscous yellow solid formed in the system was collected, separated and purified by column chromatography to obtain N-(1-hydroxy-4-methyl-2-pentyl)-N'- Pure (2-pyrimidinyl)-imidazolium chloride salt (1.12 g, 79% yield). 1 HNMR (400MHz, DMSO): δ10.34(s, 1H, CHinimidazole), 9.08(d, J=4.9Hz, 2H, CHinpyrimidine), 8.55(t, J=1.8Hz, 1H, CHinimidazole), 8.22(t, J=1.7Hz, 1H, CHinimidazole), 7.79 (t, J=4.9Hz, 1H, CHinpyrimidine), 5.47 (t, J=5.4Hz, 1H, CH 2 OH), 4.75-4.71 (m, 1H, NCH), 3.68-3.77 (m, 2H, CH) 2 OH),1.99-1.92(m,1H,CH 2 CH(CH 3 ) 2 ),1.67-1.60(m,1H,CH 2 CH(CH 3 ) 2 ),1.43-1.36(m,1H,CH 2 CH(CH 3 ) 2 ),0.93(d,J=6.5Hz,3H,CH 2 CH(CH 3 ) 2 ),0.88(d,J=6.6Hz,3H,CH 2 CH(CH 3 ) 2 ))ppm. 13 CNMR (100MH...

Embodiment 3

[0037] (1) In a 250mL three-necked flask, dissolve L-phenylalaninol (60mmol, 9.07g) and ammonium chloride (60mmol, 3.21g) with 120mL methanol, under ice-bath cooling, use a constant pressure funnel to drop the mass successively 36% formaldehyde solution (60 mmol, 4.6 mL) and 40 mass percent glyoxal solution (60 mmol, 7.6 mL). After the dropwise addition was completed, the temperature was raised to 60° C. to react for 5 h, and the reaction solution was spin-dried to obtain a reddish-brown viscous liquid. The above yellow oily viscous substance was dissolved in 150 mL NaOH solution (2M), extracted with dichloromethane (20 mL×3), the organic phases were combined, and anhydrous Na 2 SO 4 Dry, filter, remove the solvent under reduced pressure, and separate and purify by column chromatography to obtain pure (S)-2-(1-imidazolyl)-3-phenylalaninol (9.71 g, yield 80%).

[0038] (2) Add (S)-2-(1-imidazolyl)-3-phenylalaninol (5.0 mmol, 1.01 g), 2-bromopyridine (3 mL) and 2 mL of toluene...

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Abstract

The invention belongs to the field of organic compound synthesis and discloses a chelate-type N-heterocyclic carbene palladium compound containing heteroaromatic groups, and a synthetic and immobilization method thereof. The general formula of the compound is represented as follows. In the invention, with a polyfunctional compound amino alcohol as an initial raw material, a cyclization reaction and a condensation reaction are carried out to prepare an imidazole derivative of which an N-substituent group contains hydroxyl groups. The derivative then is subjected to an ionization reaction with a hetero-aromatic hydrocarbon halogenate to obtain a hetero-aromatic and hydroxyl groups di-substituted imidazolium salt. The imidazolium salt is further subjected to a metallization reaction to obtain an NHC-N chelate-type palladium compound. The compound has the activity of a homogeneous-phase N-heterocyclic carbene palladium catalyst, is simple in synthetic method, is high in yield, is easy to separate and is recyclable in catalysis of a C-H activating reaction, is greatly reduced in use cost and has a good application prospect in the field of catalysis.

Description

technical field [0001] The invention belongs to the field of organic compound synthesis, and relates to a chelated nitrogen heterocyclic carbene palladium compound containing a heteroaryl group and a method for synthesizing and immobilizing the same. technical background [0002] Nitrogen heterocyclic carbene (NHC) has strong σ-coordination ability, and the compound formed with transition metal contains stable metal-carbene bond, which is usually stable to air, moisture and heat. Therefore, nitrogen heterocyclic carbene is The ligand has become one of the very important ligands in the field of organometallic chemistry and homogeneous catalysis [References 1-4 Hopkinson, M.N.; Richter, C.; Schedler, M.; Glorius, F.Nature.2014,510,485.Crabtree, R.H.Coord.Chem.Rev.2013,257,755.Nelson,D.J.;Nolan,S.P.Chem.Soc.Rev.2013,42,6723.Scott,N.M.;Nolan,S.P.Eur.J.Inorg.Chem.2005,1815.] . In metal-organic catalysis, carbon-carbon and carbon-heterobond coupling reactions catalyzed by nitrog...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F15/00B01J31/22
CPCY02P20/50
Inventor 杨亮茹买文鹏肖咏梅毛璞屈凌波张文军郭旗
Owner HENAN UNIVERSITY OF TECHNOLOGY
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