Quinoline amino indolyl zinc, magnesium, calcium compound and its preparation method and application

A kind of aminoindolylzinc, aminoindole technology, applied in calcium compound, quinoline substituted aminoindolylzinc, magnesium field, can solve no isotactic selectivity, highly sensitive, electropositive Strong and other issues

Inactive Publication Date: 2017-01-04
EAST CHINA UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In 2013, Otero reported a chiral heteroscorpion-type zinc complex containing a cyanocene ligand, which obtained a moderately isotactic polymer (P m =0.77) (Organometallics, 2013, 32, 3437–3440)
However, there are few reports on ligand structures that can simultaneously stabilize metal zinc, magnesium, and calcium complexes, and the variability of substituents is not large (only a small amount of calcium complexes with large steric hindrance can exist stably), and magnesium and calcium complexes Does not exhibit significant isotactic selectivity
Among them, the synthesis and application of calcium complexes are restricted in many aspects: (i) highly sensitive to air and water; (ii) large atomic radius, Ca 2+ Strong electropositive; (iii) poor solubility, insoluble in common organic solvents; (iv) tends to occur Schlenk equilibrium to form inactive homogeneous complexes

Method used

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  • Quinoline amino indolyl zinc, magnesium, calcium compound and its preparation method and application
  • Quinoline amino indolyl zinc, magnesium, calcium compound and its preparation method and application
  • Quinoline amino indolyl zinc, magnesium, calcium compound and its preparation method and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0055] Synthesis of Ligand L1:

[0056] (1) Synthesis of (3-bromo-1H-indole-2-)methanamine

[0057] 1) Synthesis of N-Boc-3-bromo-2-bromomethylindole

[0058] (method one)

[0059]

[0060] Dissolve N-Boc-2-methylindole (7.51 g, 32.5 mmol), bromosuccinimide (11.56 g, 65.0 mmol) and benzoyl peroxide (0.079 g, 0.325 mmol) in 50 mL of carbon tetrachloride mmol), refluxed at 85°C for 12h, stopped heating, stood to cool, filtered to remove succinimide, concentrated the filtrate, and recrystallized to obtain light yellow needle crystals (9.80g, 77.5%). 1 H NMR (400MHz, CDCl 3 ):δ8.19(d,1H, 3 J=8.4Hz),7.53(d,1H, 3 J=7.8Hz),7.40(dd,1H, 3 J=11.6, 4 J=4.2Hz),7.32(t,1H, 3 J=7.6Hz), 5.07(s, 2H), 1.74(s, 9H).

[0061] (Method Two)

[0062] Carbon tetrachloride dissolved N-Boc-2-methyl-3-bromoindole (3.10g, 10.0mmol), bromosuccinimide (1.78g, 10mmol) and benzoyl peroxide (0.04g, 0.168mmol), after reflux at 85°C for 12h, stop heating, stand for cooling, remove succinimide by fi...

Embodiment 2

[0073] Synthesis of Ligand L2

[0074]

[0075] Except that 2-bromomethylquinoline (6.21g, 28.0mmol) and (3-bromo-1H-indolyl-2-)methanamine (3.15g, 14.0mmol) were used as raw materials, other operating steps were the same as in Example 1 . Recrystallization gave pale yellow crystals (2.00 g, yield 28.2%). 1 H NMR (400MHz, CDCl 3 ):δ11.75(s,1H),8.18(d,2H, 3 J=8.4Hz), 8.11(dd,2H, 3 J=8.4Hz, 4 J=1.6Hz),7.80(d,2H, 3 J=8.0Hz),7.77-7.73(m,2H),7.57-7.53(m,6H),7.24(td,1H, 3 J=8.0Hz, 4 J=1.2Hz),7.18(td,1H, 3 J=7.2Hz, 4 J=0.8Hz), 4.10(s,4H), 4.00(s,2H). 13 C NMR (100MHz, CDCl 3 ): δ159.5, 147.5, 136.9, 135.2, 133.0, 129.8, 128.9, 127.8, 127.6, 127.5, 126.60, 122.5, 121.9, 120.1, 118.9, 111.5, 91.2, 60.2, 48.8. Anal. Calcd. for C 29 h 23 BrN 4 : C, 68.64; H, 4.57; N, 11.04; Found: C, 68.38; H, 4.61; N, 11.07%.

Embodiment 3

[0077] Synthesis of Ligand L3

[0078] (1) Synthesis of 2-bromomethyl-8-isopropylquinoline

[0079]

[0080]Sodium borohydride (3.61g, 95.4mmol) was added batchwise to the ethanol solution of 8-isopropylquinoline-2-carbaldehyde (9.50g, 47.7mmol), stirred at 50°C for 5h, filtered, and the ethanol was spun off, 50mL of dichloro Methane was dissolved, washed with water, separated, dried, filtered, and the solvent was spun off to obtain an orange-yellow liquid (8-isopropylquinoline-2-methanol). In an ice-water bath, methanesulfonyl chloride (6.49g, 56.6mmol) was added dropwise to a dichloromethane solution of the crude product of the previous step, triethylamine (7.16g, 70.8mmol). Stir at room temperature for 2 hours, add 100 mL of water, separate the layers, wash with saturated brine, dry, filter, and spin off the solvent to obtain a brown liquid ([(8-isopropylquinoline-2-)methyl]methanesulfonate). Dissolve the crude product of the previous step and lithium bromide (20.0 g, ...

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Abstract

The invention discloses a quinoline substituted amido indolyl zinc, magnesium and calcium compound as well as a preparation method and application thereof in ring-opening polymerization of internal ester. The preparation method comprises the following steps: enabling a neutral ligand to directly react with a metal raw material compound in an organic medium, and then performing filtration, drying and recrystallization to obtain a target compound. The quinoline substituted amido indolyl zinc, magnesium and calcium compound is an efficient catalyst for ring-opening polymerization of internal ester, and can be used for catalyzing polymerization reactions of lactide, epsilon-caprolactone, beta-butyrrolactone, alpha-methyl (trimethylene carbonate) and the like; and particularly for racemic lactide, polylactic acid with medium miscellaneous isotacticity can be obtained. The substituted amido indolyl zinc, magnesium and calcium compound disclosed by the invention has very obvious advantages: the raw materials are easy to obtain, the synthetic route is simple, the target product is high in yield and has relatively high catalytic activity, polylactide with a high molecular weight and narrow molecular weight distribution can be obtained, and the requirements of industrial departments can be met. The structural formula of the compound is shown by a formula in the specification.

Description

technical field [0001] The present invention relates to a class of quinoline substituted amino indolyl zinc, magnesium and calcium compounds and the application of these compounds in lactone polymerization. Background technique [0002] As a class of polymers that can replace traditional polyolefin polymer materials, aliphatic polyesters have attracted extensive attention due to their good biocompatibility and degradability. Aliphatic polyesters that have been extensively studied include polylactic acid, polycaprolactone, and polybutyrolactone. Among them, polylactic acid can be degraded by microorganisms in nature and participate in the carbon cycle of nature, which is an environmentally friendly polymer. The biocompatibility and excellent processability of polylactic acid make it the most promising aliphatic polyester, which is mainly used in industrial and agricultural production and biomedicine (such as slow-release materials for drugs, medical suture materials, etc.). ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D401/14C07F3/06C07F7/10C07F3/02
CPCC07D401/14C07F3/02C07F3/06C07F7/10C08G63/823C08G63/83
Inventor 马海燕杨漾王号兵姚晨辉
Owner EAST CHINA UNIV OF SCI & TECH
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