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Preparation method and application of asymmetric N,N'-bis(salicylaldehyde)o-phenylenediamine aluminum compound

A technology of o-phenylenediamine aluminum and o-phenylenediamine alkylaluminum, which is applied in the field of preparation of organic aluminum compounds, can solve problems such as cumbersome synthesis steps, and achieve the effects of convenient preparation, low cost and stable properties

Inactive Publication Date: 2017-06-13
QINGDAO UNIV OF SCI & TECH
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Problems solved by technology

People such as Nguyen and Gilheany have synthesized the asymmetric Salen class ligand by the method for stepwise synthesis and hydrochloric acid protection intermediate, but the synthetic steps are comparatively loaded down with trivial details (Tetrahedron Lett.2001,42,1221-1225; J.Mol.Catal.A: Chem.2005,231,205-220)

Method used

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  • Preparation method and application of asymmetric N,N'-bis(salicylaldehyde)o-phenylenediamine aluminum compound
  • Preparation method and application of asymmetric N,N'-bis(salicylaldehyde)o-phenylenediamine aluminum compound

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Embodiment 1

[0032] Embodiment 1, intermediate monosalicylaldimine (3,5- t Bu-2-(OH)C 6 h 2 CH=N-C 6 h 4 -NH 2 ) preparation.

[0033] Dissolve o-phenylenediamine (2.16g, 20mmol), 3,5-di-tert-butyl salicylaldehyde (2.34g, 10mmol) and catalytic amount of p-toluenesulfonic acid (20mg) in ethanol, at room temperature The reaction was stirred for 12 hours. The reaction liquid was concentrated under reduced pressure and filtered to obtain the monosalicylaldimine intermediate (2.85 g, 8.8 mmol, 88%). 1 H NMR (CDCl 3):δ13.40(s,1H,OH),8.64(s,1H,CH=N),7.45(s,1H),7.23(s,1H),7.09(t,1H,J=7.5Hz), 7.04(d,1H,J=7.5Hz),6.83-6.75(m,2H),4.41-3.39(br,2H,NH 2 ),1.50(s,9H,CMe 3 ),1.32(s,9H,CMe 3 ).Anal.Calcd for C 21 h 28 N 2 O: C, 77.74; H, 8.70; N, 8.63. Found: C, 77.75; H, 8.62; N, 8.55.

Embodiment 2

[0034] Example 2, unsymmetrical N, N'-bis(salicylaldehyde) phenylenediamine (3,5- t Bu-1-OH-C 6 h 2 )CH=N-C 6 h 4 -N=CH(3-Ph-1-OH-C 6 h 3 ) Preparation of Ligand L.

[0035] With the intermediate monosalicylaldimine (3,5- t Bu-2-(OH)C 6 h 2 CH=N-C 6 h 4 -NH 2 ) was dissolved in ethanol, 3-phenyl salicylaldehyde (1.74g, 8.8mmol) and p-toluenesulfonic acid (20mg) of catalyst amount were added, and reacted at room temperature for 12 hours. The reaction solution was concentrated under reduced pressure and filtered to obtain the unsymmetrical N,N'-bis(salicylaldehyde)o-phenylenediamine ligand (3.76 g, 7.5 mmol, 85%). 1 H NMR (CDCl 3 ):δ13.66(s,1H,OH),13.52(s,1H,OH),8.72(s,1H,CH=N),8.64(s,1H,CH=N),7.66(d,2H, J=7.5Hz),7.49-7.43(m,2H),7.41-7.38(m,3H),7.36-7.31(m,3H),7.26-7.18(m,3H),7.00(t,1H,J= 7.8Hz), 1.45(s, 9H, CMe 3 ),1.32(s,9H,CMe 3 ). 13 C NMR (CDCl 3 ):δ164.89,164.16,158.86,158.71,142.84,142.41,140.58,137.72,137.30,134.37,132.00,130.14,129.58,128.40,128.15,12...

Embodiment 3

[0036] Embodiment 3, the preparation of aluminum compound LAlMe.

[0037] Under a nitrogen atmosphere, dissolve ligand L (1.01 g, 2 mmol) in 50 mL of toluene, and slowly add 1.1 equivalents of AlMe 3 (1.1mmol, 1.1mL, 1M toluene solution), stirred at room temperature for 16 hours. The toluene solvent was removed under reduced pressure, and n-hexane (3×10 mL) was added to wash to obtain 1.03 g of a pale yellow solid, 1.90 mmol, 95%. 1 H NMR (C 6 D. 6 ):δ8.02(s,1H,CH=N),7.98(s,1H,CH=N),7.92(d,2H,J=7.2Hz),7.76(s,1H),7.50(d,1H ,J=7.0Hz),7.41(t,2H,J=7.4Hz),7.28(t,1H,J=7.4Hz),6.99(s,1H),6.93(d,1H,J=7.6Hz), 6.90-6.84(m,2H),6.75-6.68(m,3H),1.54(s,9H,CMe 3 ),1.38(s,9H,CMe 3 ),-0.39(s,3H,AlMe). 13 C NMR (C 6 D. 6 ):δ164.67,162.35,161.86,141.80,139.55,139.11,138.93,138.38,137.71,134.74,133.69,132.03,129.79,128.75,128.31,128.17,127.41,126.55,119.62,118.17,116.82,116.30,116.20,35.21, 34.17, 31.45, 29.10, -10.08. Anal. Calcd for C 35 h 37 AlN 2 o 2 : C, 77.18; H, 6.85; N, 5.14....

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Abstract

The invention discloses a preparation method of an asymmetric N,N'-bis(salicylaldehyde)o-phenylenediamine aluminum compound LAlX and application of the compound in ring opening polymerization of lactone and lactide. The asymmetric N,N'-bis(salicylaldehyde)o-phenylenediamine aluminum compound LAlX has very obvious advantages that the raw materials are easily available, the synthetic route is simple, the product yield is high, the property is stable, a prepared product has rich and changeable structures, the catalytic performance is easy to control, and the product can meet requirements of different ring opening polymerization of lactone and lactide; and a prepared aliphatic polyester high polymer material has controllable structure and performance and can meet the requirements of industrial departments.

Description

technical field [0001] The present invention relates to a preparation method and application of a class of organoaluminum compounds, in particular to a preparation method of an unsymmetrical N,N'-bis(salicylaldehyde) p-phenylenediamine aluminum compound and its development in caprolactone and lactide applications in ring polymerization. Background technique [0002] The study of tetradentate-coordinated Salen ligands (Salen) and its derivatives has a history of nearly a hundred years. In the past two decades, this class of compounds has become one of the most important metal compound ligands due to their wide applications in coordination chemistry and asymmetric catalysis. In the 1990s, Jacoben and Katsuki reported the Salen-Mn catalyst (J.Am.Chem.Soc.1990,112,2801-2803; Tetrahedron Lett.1990,31,7345-7348), which successfully realized the non- Symmetrical epoxidation reaction with extremely high efficiency and enantioselectivity. Inspired by this, Spassky, Baker, Coates a...

Claims

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Application Information

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IPC IPC(8): C07F5/06B01J31/22C08G63/84C08G63/08
CPCC07F5/066C07F5/069C08G63/08C08G63/84B01J31/2217B01J2531/0238B01J2531/31B01J2231/14
Inventor 刘绍峰罗文龙石同李志波
Owner QINGDAO UNIV OF SCI & TECH
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