Nickel-based metal-organic framework as catalyst for chemical fixation of CO2 in oxazolidinone synthesis

Patent metadata

Field	Value
Publication number	US-11529621-B1
Application number	US-202217831961-A
Country	US
Kind code	B1
Filing date	Jun 3, 2022
Priority date	Jun 3, 2022
Publication date	Dec 20, 2022
Grant date	Dec 20, 2022

Abstract

A method of fixating CO2 to form a substituted oxazolidinone is described. The method includes mixing a nickel-based metal-organic framework (Ni-MOF) catalyst of formula [Ni3(BTC)2(H2O)3]·(DMF)3(H2O)3, a cocatalyst, an aromatic amine, and at least one epoxide to form a reaction mixture, and further contacting the reaction mixture with a gas stream containing carbon dioxide to react the carbon dioxide in the gas stream with the epoxide and the aromatic amine to form a substituted oxazolidinone mixture. The method further includes adding a polar protic solvent to the substituted oxazolidinone mixture, centrifuging, and filtering to produce a recovered Ni-MOF; and further washing the recovered Ni-MOF with an organochloride solvent and drying for at least 5 hours to produce a recycled Ni-MOF.

First claim

The invention claimed is:

1. A method of fixating carbon dioxide to form a substituted oxazolidinone, comprising:
mixing a nickel-based metal organic framework catalyst of formula [Ni 3 (BTC) 2 (H 2 O) 3 ]·(DMF) 3 (H 2 O) 3 , a cocatalyst, an aromatic amine, and at least one epoxide to form a reaction mixture; and
contacting the reaction mixture with a gas stream containing carbon dioxide to react the carbon dioxide in the gas stream with the epoxide and the aromatic amine to form the substituted oxazolidinone.

2. The method of claim 1 , wherein the nickel-based metal organic framework catalyst is recyclable for 9 to 20 consecutive cycles.

3. The method of claim 1 , wherein the nickel-based metal organic framework catalyst has an average carbon dioxide uptake of 37 to 60 cc/g at 800 Torr.

4. The method of claim 1 , wherein the nickel-based metal organic framework catalyst has an average isosteric heat of adsorption of 18 to 40 KJ. mol −1 .

5. The method of claim 1 , wherein the epoxide is selected from a group comprising of epoxycyclohexane, 1,2-epoxypropane, 1,2-epoxybutane, 1,2-epoxyhexane, styrene oxide, allyl glycidyl ether, and phenyl glycidyl ether.

6. The method of claim 1 , wherein the cocatalyst is selected from a group comprising of tetrabutylammonium iodide, tetrabutylammonium bromide, tetrabutylammonium chloride, and tetrabutylammonium fluoride.

7. The method of claim 1 , wherein the aromatic amine is at least one selected from a group consisting of aniline, 4-chloroaniline, 4-nitroaniline, toluidine, para-anisidine, and 4-aminothiophenol.

8. The method of claim 1 , wherein the reaction mixture has a 1 to 100-500 molar ratio of the cocatalyst to the nickel-based metal organic framework.

9. The method of claim 1 , wherein the reaction mixture has a 1 to 1-5 molar ratio of the nickel-based metal organic framework to the aromatic amine.

10. The method of claim 1 , wherein the contacting occurs at a temperature of 30 to 160° C.

11. The method of claim 1 , wherein the contacting occurs at a pressure of 1 to 15 bar of carbon dioxide.

12. The method of claim 1 , wherein the contacting occurs for 5 to 20 hours.

13. The method of claim 1 , wherein 20 to 99% of the aromatic amine is converted into the substituted oxazolidinone.

14. The method of claim 13 , wherein 60 to 99% of the aromatic amine is converted into the substituted oxazolidinone with tetrabutylammonium iodide cocatalyst.

15. The method of claim 1 , wherein the substituted oxazolidinone has a formula (I); wherein

X is selected from a group consisting of an alkyl chain, an allyoxy group, an aromatic group, a methoxybenzene, and a cyclohexane; and
Y is selected from a group consisting of a hydrogen, a halogen, a nitro group, an alkyl chain, a methoxy group, and a thiol.

16. The method of claim 1 , further comprising:
adding a polar protic solvent to the substituted oxazolidinone mixture, centrifuging, and filtering to produce a recovered nickel-based metal organic framework; and
washing the recovered nickel-based metal organic framework with an organochloride solvent and drying for at least 5 hours to produce a recycled nickel-based metal organic framework.

17. The method of claim 15 , wherein the contacting forms only a 5-substituted oxazolidinone.

Assignees

• Univ King Fahd Pet & Minerals

Inventors

• Helal Aasif
• Fettouhi Mohammed
• Arafat Md Eyasin
• Khan Mohd Yusuf
• Sanhoob Mohammed Ahmed

Classifications

• C07D263/52 Primary

  condensed with carbocyclic rings or ring systems · CPC title

• C07D263/22

  with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to other ring carbon atoms · CPC title

• B01J38/54

  halogen-containing · CPC title

• B01J31/1691 Primary

  Coordination polymers, e.g. metal-organic frameworks [MOF] (preparation of metal complexes containing carboxylic acid moieties C07C51/418; MOF's per se C07F) · CPC title

• B01J2531/847

  Nickel · CPC title