Method for preparing beta-lactone through carbonylation of epoxy compound under catalysis of gallium porphyrin-cobalt carbonyl

An epoxy compound and carbonylation technology, which is applied in the field of β-lactone preparation, can solve the problems of few types of catalysts, sensitivity, and difficulty in catalyst preparation.

Pending Publication Date: 2022-06-28
SHANGHAI ZHONGHUA TECH CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] Although some of the above-mentioned catalysts have shown good catalytic ability in the carbonylation reaction of epoxy compounds, there are still some problems, such as: (1) There are few types of catalysts, and Lewis acid metal anions are mainly limited to chromium and aluminum, while Aluminum-based catalysts need to use more dangerous alkylaluminum reagents, and chromium-based catalysts need to use highly toxic metal chromium, which does not meet the purpose of green chemistry; (2) [Lewis acid] + [Co(CO) 4 ] - Form catalysts are difficult to prepare and are highly sensitive to water and oxygen. Synthesis, purification, storage and use require strict anhydrous and oxygen-free conditions, which are not conducive to l

Method used

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  • Method for preparing beta-lactone through carbonylation of epoxy compound under catalysis of gallium porphyrin-cobalt carbonyl
  • Method for preparing beta-lactone through carbonylation of epoxy compound under catalysis of gallium porphyrin-cobalt carbonyl
  • Method for preparing beta-lactone through carbonylation of epoxy compound under catalysis of gallium porphyrin-cobalt carbonyl

Examples

Experimental program
Comparison scheme
Effect test

preparation example

[0078] Preparation Example: Preparation of Porphyrin Gallium Complex IIIa-IIIe

[0079]

[0080] Porphyrin gallium complexes IIIa-IIIe were synthesized according to the method reported in the literature (Angew.Chem.Int.Ed.2019,58,494).

[0081] Taking compound IIIa as an example, under nitrogen atmosphere, the GaCl 3 (528 mg) was added to a solution of tetraphenylporphyrin IVa (615 mg) in benzonitrile (PhCN). The reaction solution was heated to 150°C and reacted for 20 hours. During the reaction, the solution gradually changed from green to dark purple. The reaction was cooled to room temperature and the solvent was removed under reduced pressure. The residue was purified by neutral alumina column chromatography (CH 2 Cl 2 / MeOH). The eluate was washed with 1M HCl, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure to obtain the porphyrin gallium complex IIIa. Yield 82%, purple solid.

[0082] Tetraphenylporphyrin IVa is replaced ...

Embodiment 1

[0083] Example 1: Solvent p-tetraphenylporphyrin gallium / Co 2 (CO) 8 The effect of synergistically catalyzed propylene oxide carbonylation

[0084]

[0085] Into a 125mL autoclave, add tetraphenylporphyrin gallium complex IIIa (0.050mmol), Co 2 (CO) 8 (25.6 mg, 0.075 mmol), solvent (10 mL), propylene oxide (5.81 g, 100.0 mmol). After sealing the autoclave, replace N 2 Three times, 20 atm of carbon monoxide was charged into the autoclave, and the temperature was raised to 80° C. and stirred for 16 hours. After cooling the autoclave in an ice-water bath for 1.5 hours, the excess carbon monoxide was slowly released. 1.5 mL of internal standard n-tridecane was added to the autoclave, and the mixture was stirred uniformly. Use gas chromatography method (using the standard curve method, that is, take n-tridecane as the internal standard, make a standard curve for β-butyrolactone on the gas chromatography with the peak area ratio of n-tridecane, by measuring the reaction sys...

Embodiment 2

[0089] Example 2: Reaction temperature and pressure p-tetraphenylporphyrin gallium / Co 2 (CO) 8 The effect of synergistically catalyzed propylene oxide carbonylation

[0090]

[0091] Into a 125mL autoclave, add tetraphenylporphyrin gallium complex IIIa (0.050mmol), Co 2 (CO) 8 (25.6 mg, 0.075 mmol), tetrahydrofuran (10 mL), propylene oxide (5.81 g, 100.0 mmol). After the autoclave was sealed, nitrogen was replaced three times, carbon monoxide was charged into the autoclave to the required pressure, and the reaction was stirred at a predetermined temperature for 16 hours. After cooling the autoclave in an ice-water bath for 1.5 hours, the excess carbon monoxide was slowly released. 1.5 mL of internal standard n-tridecane was added to the autoclave, and the mixture was stirred uniformly. Use gas chromatography method (using the standard curve method, that is, take n-tridecane as the internal standard, make a standard curve for β-butyrolactone on the gas chromatography wi...

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Abstract

The invention provides a method for preparing beta-lactone through carbonylation of an epoxy compound, which comprises the following step: in the presence of a porphyrin gallium complex and cobalt octacarbonyl, by taking CO as a carbonyl source, converting the epoxy compound into a beta-lactone compound through a carbonyl insertion ring expansion reaction. The method provided by the invention has efficient catalytic activity and excellent chemical selection, does not need a tedious catalyst preparation process, avoids the use of high-toxicity chromium metal and sensitive carbonyl cobalt salt, is high in catalyst stability, can be fed in air, is simple to operate, and is easy for large-scale production.

Description

technical field [0001] The invention belongs to the field of β-lactone preparation, in particular to a method for preparing β-lactone by carbonylation of epoxy compounds catalyzed by porphyrin gallium-cobalt carbonyl. Background technique [0002] For a long time, the synthesis of β-lactone compounds has been a research hotspot. Such compounds can undergo ring-opening polymerization to obtain biodegradable poly-β-hydroxycarboxylates, thereby solving the increasingly serious problem of environmental pollution. In addition, β-lactone can be used to synthesize other compounds including acrylic acid and acrylate, and is also widely used in the synthesis of natural products. The carbonylation ring expansion reaction of epoxy compounds provides a simple and atom-economical route for the synthesis of such important organic compounds. Therefore, the reaction of epoxide carbonylation and ring expansion to obtain the corresponding β-lactone has become a hotspot in related research f...

Claims

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Application Information

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IPC IPC(8): C07D305/12C07D305/14B01J31/22
CPCC07D305/12C07D305/14B01J31/183B01J2531/32Y02P20/584
Inventor 汤易天董开武李永刚李会敏李志坚徐玉贵王涛
Owner SHANGHAI ZHONGHUA TECH CO LTD
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