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Bidentate phosphite ester ligand, synthetic method and use thereof in alkene unsymmetrical catalysis hydroformylation reaction

A bidentate phosphite and ligand technology, applied in organic compound/hydride/coordination complex catalysts, carbon monoxide reaction preparation, chemical instruments and methods, etc., can solve unsatisfactory product regioselectivity and harsh reaction conditions , low activity and other issues

Inactive Publication Date: 2008-11-05
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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Problems solved by technology

There are three breakthroughs in the development of asymmetric hydroformylation reactions, namely: the catalyst composed of chiral bidentate phosphite ligand (R, R)-Chiraphite and Rh developed by United Carbon Corporation in 1993, It has been greatly improved in the activity and selectivity of the reaction; the phosphine-phosphite ligand (R, S)-BINAPHOS / Rh(I) catalyst developed by Takaya et al. in the same year in 1993, it A breakthrough has been achieved in the enantioselectivity of the reaction, but the activity of this catalytic system is relatively low, the regioselectivity of the product is not ideal, and the reaction conditions are harsh; the Diazaphospholane / Rh(I) asymmetric hydrogen form developed by Klosin et al. in 2005 Acylation catalyst, which has a breakthrough in catalytic activity under the premise of ensuring product selectivity

Method used

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  • Bidentate phosphite ester ligand, synthetic method and use thereof in alkene unsymmetrical catalysis hydroformylation reaction
  • Bidentate phosphite ester ligand, synthetic method and use thereof in alkene unsymmetrical catalysis hydroformylation reaction
  • Bidentate phosphite ester ligand, synthetic method and use thereof in alkene unsymmetrical catalysis hydroformylation reaction

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0057] Example 1: Compound 4a of (2R, 3R, 5S, 6S) configuration (wherein R 3 , R 3 '=H)

[0058] A 500ml there-necked flask, add (S, S) configuration 1,2-cyclohexanediamine (5.0g) and absolute ethanol (50ml) in the bottle, drop salicylaldehyde 2a (11.2 g) in ethanol (20mL), reflux for 12h after the dropwise addition. The reaction was stopped, cooled to room temperature, the solvent was evaporated under reduced pressure, and the oil was pumped dry to obtain an orange oil. The oil was dissolved in a mixed solvent of acetonitrile (180mL) and toluene (20mL), Mn powder (5.3g) was added to the solution under an argon atmosphere, the system was cooled to 0°C, and trifluoroacetic acid (15.7g) was added dropwise. mL), then stirred at room temperature for 24 hours. Stop the reaction, cool to 0°C, then add trifluoroacetic acid (7.9mL), precipitate a large amount of solid, filter, wash with petroleum ether (20mL×2) to obtain a white solid, dissolve the solid in 100mL water, saturated ...

Embodiment 2

[0060] Example 2: Preparation of (2S, 3S, 5R, 6R) configuration compound 4b (wherein R 3 = 3-Me,R 3 '=H)

[0061] Using the method of Example 1, the first step is to react cyclohexanediamine in (R, R) configuration with 3-methylsalicylaldehyde, and the yield is 78%.

[0062] Colorless needle-like solid; melting point 188-189°C; [α] 20 D -59(c 0.3, CHCl 3 ); 1 H NMR (300MHz, CDCl 3 )δ=1.39-1.42(m, 4H), 1.75-1.82(m, 4H), 2.23(s, 6H), 2.37(broad s, 2H), 2.68(broad, 2H), 4.13(s, 2H), 5.97(d, 2H, J=8.1Hz), 6.32(t, 2H, J=7.7Hz), 6.93(d, 2H, J=7.2Hz), 11.06(broad, 2H); 13 C NMR (75MHz, CDCl 3)δ=155.0, 130.0, 127.8, 125.1, 122.6, 118.0, 63.3, 59.7, 31.6, 24.3, 15.8; 925,745cm -1 ; EI-MS: m / z=352 (M + , 5.8), 254 (1.8), 217 (44), 136 (100); elemental analysis (%): theoretical value C 22 h 28 N 2 o 2 : C 74.97, H 8.01, N 7.95; Experimental value: C 74.73, H 8.13, N 7.82.

Embodiment 3

[0063] Example 3: Compound 4c of (2S, 3S, 5R, 6R) configuration (where R 3 = 4-Me, R 3 '=H)

[0064] Using the method of Example 1, the first step is to react cyclohexanediamine in (R, R) configuration with 4-methylsalicylaldehyde, yield: 78%.

[0065] Colorless needle-like solid; melting point 216-217°C; [α] 20 D -67(c 0.3, CHCl 3 ); 1 H NMR (300MHz, CDCl 3 )δ=1.38-1.41(m, 4H), 1.65-1.81(m, 4H), 2.21(s, 6H), 2.61(broad, 2H), 4.04(d, 2H, J=2.1Hz), 6.00(d , 2H, J=7.5Hz), 6.25(d, 2H, J=7.5Hz), 6.63(s, 2H), 10.79(broad, 2H); 13 C NMR (75MHz, CDCl 3 )δ=156.6, 138.8, 130.0, 120.3, 119.4, 117.1, 63.1, 59.7, 31.5, 24.3, 21.1; 1120,808cm -1 ; EI-MS: m / z=352 (M + , 8.8), 217 (51.9), 136 (100); elemental analysis (%) theoretical value C 22 h 28 N 2 o 2 : C 74.97, H 8.01, N 7.95; Experimental values: C 74.79, H 8.03, N 7.74.

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Abstract

The invention relates to a novel bidentate phosphite ester ligand and a synthetic method thereof as well as applications in an unsymmetrical hydrogen formylation of alkene. The synthetic method of the invention is simple, convenient and direct; an obtained chiral ligand is comparatively stable; under the atmosphere of inert gases, the ligand is reacted with Rh salt in an organic medium to obtain a ligand / Rh catalyst; under the atmosphere of inert gases, olefin substrates are added into the liquor of the ligand / Rh catalyst and then CO and H[2] are respectively injected to react and obtain the product of chiral aldehyde of the unsymmetrical hydrogen formylation; the ligand / Rh catalyst of the invention obtains excellent area and enantio-selectivity in the unsymmetrical hydrogen formylation of alkene.

Description

technical field [0001] The invention relates to a novel bidentate phosphite ligand, a synthesis method and application of the ligand. Such ligands can be used to prepare catalysts for asymmetric hydroformylation reactions. The catalyst can be used to catalyze the asymmetric hydroformylation reaction of olefin compounds, and directly synthesize optically active chiral aldehyde compounds. Background technique [0002] Olefin hydroformylation can conveniently and effectively convert the cheap and easy-to-obtain basic chemical raw material olefins into a variety of important fine chemicals. It is the largest homogeneous catalytic process so far. [Qian Yanlong, Liao Shijian, "Progress in Homogeneous Catalysis", Chemical Industry Press, Beijing, 1989], [Yin Yuanqi, "Oxylation Chemistry", Chemical Industry Press, Beijing, 1995], [Bhaduri, S.; Mukesh , D. Homogeneous Catalysis: Mechanisms and Industrial Applications, John Wiley & Sons, 2000, pp85-103.], [Frohning, C.D.; Kohlpaintn...

Claims

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Application Information

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IPC IPC(8): C07F9/6509C07F17/02C07F19/00B01J31/24B01J31/28C07C45/49C07B41/06
Inventor 丁奎岭赵宝国彭新高王正
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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