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Complexes of ruthenium with 2-(aminomethyl) pyridines and phosphines, their preparation and use as catalysts

A complex and aminomethyl technology, applied in the field of ruthenium complexes, can solve the problem of low activity

Active Publication Date: 2007-08-01
乌迪内大学
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

The activity of these above systems is all low, and the optical isomerism selectivity is medium (E.Mizushima, H.Ohi, M.Yamaguchi, T.Yamagishi, J.Mol.Catal.A 1999,149,43) or good (H .Brunner, M.Niemetz, Monatshefte für Chemie 2002, 133, 115; H.Brunner, F.Henning, M.Weber, Tetrahedron: Asymmetry 2002, 13, 37)

Method used

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  • Complexes of ruthenium with 2-(aminomethyl) pyridines and phosphines, their preparation and use as catalysts
  • Complexes of ruthenium with 2-(aminomethyl) pyridines and phosphines, their preparation and use as catalysts
  • Complexes of ruthenium with 2-(aminomethyl) pyridines and phosphines, their preparation and use as catalysts

Examples

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Effect test

example 1

[0083] Example 1: trans-RuCl 2 (PPh 3 ) 2 [2-(H 2 NCH 2 )C 5 h 4 Synthesis of N](3)

[0084] The complex RuCl 2 (PPh 3 ) 3 (1) (0.400g, 0.417mmol) was suspended in 5ml of distilled dichloromethane, and reacted with 2-(aminomethyl)pyridine (45L, 0.436mmol). After the reaction mixture was stirred at room temperature for 2 hours, the volume of the solution was reduced by half, and then 5 ml of pentane was added to precipitate the complex. The resulting solid was filtered off, washed twice with 10 ml of ether, and dried under reduced pressure.

[0085] Yield 250 mg (75%). C 42 h 38 Cl 2 N 2 P 2 Elemental analysis of Ru., calculated as (%): C, 62.69; H, 4.76; N, 3.48; found C, 62.85; H, 4.80; N, 3.54. 1 H nuclear magnetic resonance (NMR) analysis (200.1MHz, CDCl 3 , 20°C, TMS): δ8.53(d, J(HH)=4.2Hz, 1H; o-C 5 h 4 N), 7.60-6.50 (m, 33H; aromatic proton), 4.46 (broad s, 2H; CH 2 ), 3.29 (width s, 2H; NH 2 ). 13 C{ 1 H} NMR analysis (50.3MHz, CDCl 3 , 20°C, TMS...

example 2

[0086] Example 2: Complex trans-RuHCl (PPh 3 ) 2 [2-(H 2 NCH 2 )C 5 h 4 Synthesis of N](4)

[0087] The complex RuHCl (PPh 3 ) 3 (211mg, 0.228mmol) was suspended in 10ml of n-heptane, reacted with 2-(aminomethyl)pyridine (24L, 0.233mmol), and then heated under reflux for 1 hour. The yellow product was filtered off, washed with n-heptane (3 x 5 ml) and dried under reduced pressure.

[0088] Yield: 118mg (67%).C 42 h 39 ClN 2 P 2 Elemental analysis (%) of Ru, calculated as: C, 65.49; H, 5.10; N, 3.64; found: C, 65.23; H, 5.03; N, 3.41. 1 H NMR analysis (200.1MHz, CD 2 Cl 2 , 20°C, TMS): δ8.20(s, 1H; o-C 5 h 4 N), 7.70-6.40 (m, 33H; aromatic proton), 4.30 (false t, J(HH)=14.1Hz, 1H; CH 2 ), 4.07(d, J(HH)=14.3Hz, 1H; CH 2 ), 2.87 (false t, J(HH)=10Hz, 1H; NH 2 ), 2.20 (false d, J(HH)=10Hz, 1H; NH 2 ), -17.70 (dd, J(HP)=23.5, 29.7Hz). 13 C{ 1 H} NMR analysis (50.3MHz, CD 2 Cl 2 , 20°C, TMS): δ159.7(s; NCCH 2 ), 155.6(d, J(CP)=4.0Hz; NCH), 138.8-118.7(m; aro...

example 3

[0089] Example 3: Complex cis-RuCl 2 (PPh 3 ) 2 [2-(H 2 NCH 2 )C 5 h 4 Synthesis of N](5)

[0090] The complex RuCl 2(PPh 3 ) 3 (1) (1.34g, 1.40mmol) was suspended in 10ml of toluene, and reacted with 2-(aminomethyl)pyridine (0.160ml, 1.55mmol). The reaction mixture was heated under reflux for 2 hours, the volume of the solution was reduced by half, and the complex was precipitated after adding 5 ml of pentane. The filtered solid product was washed twice with 5 ml of ether and dried under reduced pressure.

[0091] Yield: 750 mg (66.4%).C 42 h 38 Cl 2 N 2 P 2 Elemental analysis (%) of Ru, calculated as: C, 62.69; H, 4.76; N, 3.48; found: C, 62.31; H, 4.87; N, 3.60. 1 H NMR analysis (200.1MHz, CD 2 Cl 2 , 20°C, TMS): δ9.16(d, J(HH)=5.7Hz, 1H; positive-C 5 h 4 N), 7.70-6.89 (m, 33H; aromatic proton), 3.65 (m, 2H; CHHNHH), 3.00 (m, 1H, CH 2 ), 1.42 (m, 1H, NH 2 ). 31 P{ 1 H} NMR analysis (81.0MHz, CD 2 Cl 2 , 20°C, H 3 PO 4 ): δ 50.5 (d, J(PP)=33.4Hz), ...

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Abstract

The patent describes a new class of ruthenium (II) complexes containing as ligands 2-(aminomethyl)pyridines and phosphines, proven to be extremely active catalysts in the reduction of ketones to alcohols via hydrogen transfer. By using 2-propanol as the hydrogen source with said ruthenium complexes, high yields of the corresponding alcohol can be rapidly obtained starting from linear and cyclic alkyl aryl, dialkyl and diaryl ketones. The conversion of ketones to alcohols can reach 100% if operating in a gaseous hydrogen atmosphere (2 - 3 standerd atmosphere). Where the phosphines used are optically active, starting from prochiral ketone compounds various types of optically active alcohols can be produced, being important intermediates in the pharmaceutical industry, in the agrochemical industry and for fine chemicals generally.

Description

technical field [0001] The present invention relates to a class of ruthenium(II) complexes with 2-(aminomethyl)pyridines and phosphines, which may in some cases be chiral, and their reduction of ketones to Use of Alcohols as Catalysts. Operating under low pressure (2-3 atmospheric pressure) hydrogen flow, the reduction rate and alcohol yield can be further improved. Background technique [0002] The reduction of carbonyl compounds to alcohols is a class of reactions with wide application value, and a series of catalytic methods have been developed in recent years, trying to replace the traditional stoichiometric reduction system. Reductions using transition metal (iridium, rhodium, palladium, nickel)-based catalytic systems under hydrogen flow have achieved promising results, but recent research has focused on more active ruthenium derivatives. In an alkaline environment [RuCl 2 (phosphine) 2 (1,2-diamine)] and [RuCl 2 Compounds of the (diphosphine)(1,2-diamine)] type ar...

Claims

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Application Information

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IPC IPC(8): C07F15/00C07B31/00C07C29/143
CPCC07F15/0053
Inventor 沃特·巴瑞塔凯特·西嘎密凯勒·汤纽特皮耶路基·瑞欧
Owner 乌迪内大学
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