Heteroaryl-containing chelating nitrogen heterocyclic carbene palladium compound and preparation method thereof

A technology for nitrogen-heterocyclic carbene and palladium compounds, which is applied in the field of organic compound synthesis, can solve problems such as hindering the further application of nitrogen-heterocyclic carbene palladium compounds, difficult separation and recovery of homogeneous catalysts, and no active groups, etc., and achieves a simple and easy synthesis method Line, easy to separate, simple operation effect

Active Publication Date: 2017-08-25
HENAN UNIVERSITY OF TECHNOLOGY
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  • Abstract
  • Description
  • Claims
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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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  • Heteroaryl-containing chelating nitrogen heterocyclic carbene palladium compound and preparation method thereof
  • Heteroaryl-containing chelating nitrogen heterocyclic carbene palladium compound and preparation method thereof
  • Heteroaryl-containing chelating nitrogen heterocyclic carbene palladium compound and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] (1) In a 250mL three-neck flask, dissolve L-leucinol (60mmol, 7.03g) and ammonium chloride (60mmol, 3.21g) in 120mL of methanol, and then add the mass percentage dropwise with a constant pressure funnel under ice-water bath cooling. 36% formaldehyde solution (60mmol, 4.6mL) and 40% mass percent glyoxal solution (60mmol, 7.6mL). After the dropwise addition, the temperature was raised to 60° C. 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 washed with anhydrous NaOH 2 SO 4 Dry, filter, remove the solvent under reduced pressure, separate and purify by column chromatography to obtain pure (S)-2-(1-imidazolyl)-4-methylpentanol (7.57 g, yield 75%).

[0029] (2) Add (S)-2-(1-imidazolyl)-4-methylpentanol (5.0mmol, 0.84g), 2-bromopyridine (3mL) and 2mL toluene into a 50mL r...

Embodiment 2

[0033] Step (1) is the same as embodiment 1

[0034] (2) Add (S)-2-(1-imidazolyl)-4-methylpentanol (5.0mmol, 0.84g), 2-chloropyrimidine (6mmol, 0.69g) and 15mL toluene into a 50mL round bottom flask , heated to 110°C for 72h, cooled to room temperature, collected viscous yellow solid in the system, 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, yield 79%). 1 H NMR(400MHz,DMSO):δ10.34(s,1H,CH in imidazole),9.08(d,J=4.9Hz,2H,CH in pyrimidine),8.55(t,J=1.8Hz,1H,CH in imidazole), 8.22(t, J=1.7Hz, 1H, CH in imidazole), 7.79(t, J=4.9Hz, 1H, CH in pyrimidine), 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 C NMR (100MHz, DMSO): δ160.5, 152.7, 136.3, 12...

Embodiment 3

[0038] (1) In a 250mL three-necked flask, dissolve L-phenylalaninol (60mmol, 9.07g) and ammonium chloride (60mmol, 3.21g) in 120mL of methanol, and drop the mass of A 36% formaldehyde solution (60mmol, 4.6mL) and a 40% mass percent glyoxal solution (60mmol, 7.6mL). After the dropwise addition, the temperature was raised to 60° C. 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 150mL NaOH solution (2M), extracted with dichloromethane (20mL×3), the organic phases were combined, and washed with anhydrous NaOH 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%).

[0039] (2) Add (S)-2-(1-imidazolyl)-3-phenylalaninol (5.0mmol, 1.01g), 2-bromopyridine (3mL) and 2mL toluene into a 50mL round bottom flask and heat to After reacting at 110°C for 72 hour...

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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 heteroaryl-containing chelating nitrogen heterocyclic carbene palladium compound and a synthesis and immobilization method thereof. [0002] technical background [0003] 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 Ligands have become one of the very important ligands in the field of organometallic chemistry and homogeneous catalysis [references 1-4Hopkinson, 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 organometallic catalysis, carbon-carbon and carbon-heterobond coupling reactions catalyzed by nitrogen hetero...

Claims

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Application Information

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Patent Type & Authority Patents(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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