Asymmetric multi-hock type monophenoloxo magnesium complex as well as preparation method and application thereof

A single-phenoloxy, multi-tooth claw-type technology, applied in the direction of organic chemistry, can solve the problems of non-monomer coordination and insertion without selectivity, prone to chain transfer or chain exchange reaction, loose ligand structure, etc. , to achieve the effects of stable properties, convenient preparation and easy availability of raw materials

CN102153597AInactive Publication Date: 2011-08-17EAST CHINA UNIV OF SCI & TECH
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Authority / Receiving Office
CN · China
Current Assignee / Owner
Publication Date
2011-08-17
Estimated Expiration
Not applicable · inactive patent

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Abstract

The invention discloses an asymmetric multi-hock type monophenoloxo magnesium complex as well as a preparation method and application thereof. The preparation method comprises the following steps: reacting an asymmetric multi-hock type monophenol ligand L with a magnesium metal organic compound; and then collecting a target product from crude reaction products. The magnesium complex disclosed by the invention contains the asymmetric multi-hock type monophenol ligand, is an efficient lactone ring-opening polymerized catalyst, and can be used for ring-opening polymerization of lactide, caprolactone and the like. The magnesium complex of the asymmetric multi-hock type monophenoloxo ligand has the obvious advantages of no toxicity and no innocuity, available raw materials, simple synthesis routes, relatively stable property and high catalytic activity, and is easy to separate and purify; and the polylactone obtained by catalysis has high molecular weight and can meet the demand of industrial departments. The structure of the complex has the following general formula shown in the specification.
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Description

technical field

[0001] The invention relates to a class of metal magnesium complexes containing asymmetric multi-dentate claw-type monophenolic oxygen ligands and the application of such complexes in lactone ring-opening polymerization. Background technique

[0002] As the problem of "white pollution" caused by the non-degradability of polyolefin products is becoming more and more serious, biodegradable polymer materials are gradually regarded as environmentally friendly alternatives to polyolefin products. In the 1970s, researchers noticed that degradable polyester materials had many advantages comparable to polyolefin products, and gradually began to apply polyester materials to medical products such as sutures, various medical brackets and medical fibers (Angew .Chem.Int.Ed., 2004, 43, 1078). In the past three decades, rapid progress has been made in the synthesis, production and processing of degradable polyesters, which has played an important role in promoting the wid...

Examples

Embodiment 1

[0036] Synthesis of complex C1

[0037]

[0038] Under argon protection, add 4,6-di-tert-butyl-2-{N-(2-methoxybenzyl)-N-[(N',N'-diethylamino ) ethyl] aminomethyl} phenol (0.443g), toluene 20mL, add Mg[Si(NMe 3 ) 2 ] 2 (0.345g), stirred at room temperature for 24h, concentrated and placed in a -20°C refrigerator to obtain colorless crystals (0.387g, 60.7%).

[0039] 1 H NMR (C 6 D. 6 , 400MHz): δ7.60(d, 1H, J=2.4Hz, ArH), 7.14-7.12(m, 1H, ArH), 7.07-7.03(m, 1H, ArH), 6.92(d, 1H, J= 2.4Hz, ArH), 6.81(td, 1H, J 1 =7.2Hz,J 2 =0.8Hz, ArH), 6.44(d, 1H, J=8Hz, ArH), 4.36(d, 1H, J=13.6Hz, ArCH 2 N), 4.06(d, 1H, J=13.6Hz, ArCH 2 N), 3.88(d, 1H, J=12.8Hz, NCH 2 Ar), 3.60(d, 2H, J=12.8Hz, NCH 2 Ar), 3.18(s, 3H, OCH 3 ), 2.53-2.33 (m, 7H, NCH 2 CH 2 N, NCH 2 CH 2 N, NCH 2 CH 3 ), 2.15-2.10 (m, 1H, NCH 2 CH 3 ), 1.82(s, 9H, C(CH 3 ) 3 ), 1.37(s, 9H, C(CH 3 ) 3 ), 0.70(t, 6H, J=7.2Hz, NCH 2 CH 3 ), 1.72-1.70 (m, 6H, C (CH 3 ) 2 Ph), 0.57-0.60 (m, 6H, NCH 2 C...

Embodiment 2

[0041] Synthesis of complex C2

[0042]

[0043] Under argon protection, add 4,6-dicumyl-2-{N-(2-methoxybenzyl)-N-[(N',N'-diethylamino) into a 100mL Schlenk bottle Ethyl]aminomethyl}phenol (0.579g), toluene 20mL, add Mg[Si(NMe 3 ) 2 ] 2 (0.345g), stirred at room temperature for 24h, concentrated and placed in a -20°C refrigerator to obtain colorless crystals (0.444g, 58.4%).

[0044] 1 H NMR (C 6 D. 6 , 400MHz): δ7.62(s, 1H, ArH), 7.57(d, 2H, J=6.8Hz, ArH), 7.37(d, 2H, J=7.2Hz, ArH), 7.16(s, 3H, ArH ), 7.09-7.00 (m, 4H, ArH), 6.92 (d, 1H, J = 6.8Hz, ArH), 6.84 (s, 1H, ArH), 6.72 (t, 1H, J = 7.2Hz, ArH), 6.42(d, 1H, J=8Hz, ArH), 4.47(d, 1H, J=13.6Hz, ArCH 2 N), 3.87-3.84 (m, 1H, ArCH 2 N), 3.72-3.57 (m, 2H, ArCH 2 N), 3.08(s, 3H, OCH 3 ), 2.42-2.38 (m, 1H, NCH 2 CH 2 N), 2.31-2.28 (m, 1H, NCH 2 CH 2 N), 2.25-2.12 (m, 6H, NCH 2 CH 2 N, NCH 2 CH 3 , C(CH 3 ) 2 Ph), 2.08-2.03 (m, 1H, NCH 2 CH 3 ), 1.95-1.93 (m, 2H, NCH 2 CH 3 ), 1.80(s, 3H, C(CH 3 ) 2...

Embodiment 3

[0046] Synthesis of complex C3

[0047]

[0048] Under argon protection, add 4,6-di-tert-butyl-2-{N-(2-fluoro)-N-[(N',N'-diethylamino)ethyl to a 100mL Schlenk bottle ]aminomethyl}phenol (0.411g), toluene 20mL, add Mg[Si(NMe 3 ) 2 ] 2 (0.345g), stirred at room temperature for 24h, concentrated and placed in a -20°C refrigerator to obtain colorless crystals (0.415g, 66.5%).

[0049] 1 H NMR (C 6 D. 6 , 400MHz): δ7.61(s, 1H, ArH), 7.20-7.17(m, 1H, ArH), 6.89-6.84(m, 2H, ArH), 6.70-6.78(m, 2H, ArH), 6.82- 6.71(m, 2H, ArH), 4.35(d, 1H, J=14.0Hz, ArCH 2 N), 4.05(d, 1H, J=14Hz, ArCH 2 N), 3.56(q, 2H, J=12.8Hz, CH 2 -CH 3 ), 2.72-2.59 (m, 1H, NCH 2 Ar), 2.49-2.45(m, 1H, J=12.4Hz, NCH 2 Ar), 2.38-2.30 (m, 4H, NCH 2 CH 2 , N), 2.16-2.11 (m, 1H, NCH 2 CH 3 ), 2.09-2.00 (m, 1H, NCH 2 CH 3 ), 1.81(s, 9H, C(CH 3 ) 3 ), 1.39(s, 9H, C(CH 3 ) 3 ), 0.82-0.80 (m, 3H, NCH2 CH 3 ), 0.50(s, 18H, Si(N(CH 3 ) 2 ) 3 ), 0.46-0.39 (m, 3H, NCH 2 -CH 3 );Anal.Calc.forC 34 h...