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Supported arsine catalyst as well as synthesizing method and application thereof in Wittig reaction

一种合成方法、催化剂的技术，应用在有机化学方法、化学仪器和方法、有机化合物的制备等方向，能够解决低反应活性、低反应程度、长反应时间等问题

Active Publication Date: 2013-06-19
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0024]1) Requires a large amount of loaded reagents;
[0025]2) Low reactivity, long reaction time, and lower degree of reaction;
[0034] Coordination polymerization of ethylene and polar monomers can effectively realize the loading of organic catalysts, but there is no exploration in this area, so it is necessary to use this method Development of Highly Loaded Organocatalysts

Method used

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  • Supported arsine catalyst as well as synthesizing method and application thereof in Wittig reaction
  • Supported arsine catalyst as well as synthesizing method and application thereof in Wittig reaction
  • Supported arsine catalyst as well as synthesizing method and application thereof in Wittig reaction

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0067] Embodiment 1: the preparation of isooctyl acetoacetate:

[0068] Sodium acetate (0.369g, 4.5mmol) was added to a three-neck flask equipped with a pumping head and a constant pressure dropping funnel, and diketene (7.56g, 90mmol) and acetonitrile (50.0mL), ice salt The temperature of the bath was cooled to -5°C, and then iso-octanol (11.7 g, 90 mmol) was added through a constant pressure dropping funnel, stirred for 3 hours, warmed to room temperature, and stirred overnight. After traced by TLC that the starting material disappeared, the reaction was stopped. Water and diethyl ether were added for separation and extraction, the diethyl ether solution was collected, washed twice with water and once with saturated brine, dried overnight with anhydrous magnesium sulfate, concentrated and used directly for the next reaction.

[0069] Add isooctyl acetoacetate and acetonitrile (250mL) obtained in the previous step into a 500mL egg-shaped flask, stir in an ice bath for 15 min...

Embodiment 2

[0073] Embodiment 2: the synthesis of arsine monomer

[0074]

[0075] Under ice-bath conditions, 10-undecen-1-ol (11.6mL, 60mmol) and anhydrous pyridine (30mL) were added into a 100ml egg-shaped flask, and after stirring and mixing to dissolve each other, p-toluenesulfonyl chloride (13.75g , 72 mmol), after stirring in an ice bath for 6 hours, TLC plate tracking showed that the reaction was basically complete (PE: EA = 6: 1, potassium permanganate color). Filter, add 100ml ether to the filtrate, and wash the ether solution with 2N hydrochloric acid (100mL*4). anhydrous sodium sulfate, and dry the organic layer. Most of the ether was spun off, separated by column chromatography, the developer was PE:EA=10:1, and 15.26 g of the product was obtained with a yield of 79%.

[0076] 1 H NMR (300MHz, CDCl 3 / TMS): δ7.79(d, J=7.8Hz, 2H), 7.34(d, J=8.4Hz, 2H), 5.87-5.73(m, 1H), 5.02-4.91(m, 2H), 4.02( t, J = 6.3 Hz, 2H), 2.45 (s, 3H), 2.06-2.00 (m, 2H), 1.65-1.57 (m, 2H), 1.39-...

Embodiment 3

[0082] Embodiment 3: the polyethylene support of arsine

[0083] Pretreatment of arsine monomer:

[0084] Add monomer (5.01g, 13.2mmol) to the stopcock bottle, replace nitrogen, add toluene (18ml), cool in a dry ice-acetone bath, add triisobutylaluminum (4mL, 16mmol) dropwise to form a 0.5M solution, Stir overnight and warm to room temperature naturally.

[0085] Preparation of supported catalyst PE-1:

[0086]

[0087] The dry Schlenk bottle was replaced with ethylene gas three times. Under ethylene flow, toluene (70 mL) was added, and the temperature of the oil bath was controlled to 30° C. and stirred for 10 minutes, so that the solution reached the specified temperature and was saturated with ethylene. Triisobutylaluminum-protected arsine monomer (0.5M, 24mL), stirred for 2 minutes, added cocatalyst (MMAO) (1.9M, 15.0mL), stirred for 2 minutes. A toluene solution (3.5 μmol / ml, 8.0 mL) of the metal catalyst was added and the timer was started simultaneously. After 3...

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Abstract

The invention relates to a polyethylene-supported arsine catalyst with a structural formula shown in the specification as well as a synthesizing method and application thereof. The catalyst is simple and convenient to synthesize, can be conveniently used for catalyzing an aldehyde or ketone Wittig reaction to synthesize olefin compounds, and can be recycled conveniently.

Description

technical field [0001] The present invention relates to polyethylene supported arsine catalyst, synthesis method and application in Wittig reaction. The catalyst is obtained by copolymerization of arsenic-containing olefin and ethylene under the action of polyolefin catalyst, can be used for Wittig reaction and realize the recycling of the catalyst. Background technique [0002] It has long been recognized that if the phosphine catalyst is immobilized on a polymer, the separation of the phosphine oxide compound and the reaction system can be conveniently realized. In 1972, Mckinley et al loaded ylides on cross-linked polystyrene to realize the supported phosphine ylides Wittig reaction [McKinley, S.V.; Rakshys, J.W.J.Chem.Soc., Chem.Commun., 1972, 134]. After the reaction, the by-product phosphine oxide compound only needs to be filtered. However, there is the problem of low conversion rate in the reaction, and the conversion rate of the reaction is basically below 70% (r...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J31/12C08F210/02C07B37/00C07C67/343C07C69/65C07C69/618C07C69/734C07C201/12C07C205/56C07C253/30C07C255/57C07D307/54C07C69/608C07C69/533C07D317/30C07D263/04C07D309/20C07C69/587C07C45/72C07C49/807C07C49/794C07D309/22C07C49/80
CPCY02P20/52
Inventor 唐勇刘春荣孙秀丽
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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