Nickel catalyst for denitrification cyclization synthesis of sulfonamide and its preparation method

Abstract

This invention provides a nickel catalyst for the denitrification and cyclization synthesis of sulfonamides, having the structures described in formulas (I), (II), (III), and (IV) and their preparation methods. It develops an alternative catalytic system with good economic efficiency and operational stability to overcome the problems of existing nickel-based catalytic systems, such as high sensitivity to air and water, inconvenient operation, and high cost. This improves the overall efficiency and industrial applicability of sulfonamide compound synthesis reactions and enables catalytic processes suitable for large-scale production. Ni2+[L1][L2]...Formula (I); Ni0[L1][L3]...Formula (II);

Claims

1. A nickel catalyst for the denitrification and cyclization synthesis of sulfonylureas, having the structure described in formula (I): Ni²⁺[L1][L2]……Formula (I) wherein, L1 is a bidentate diaryl phosphino ligand or a bidentate alkyl phosphino ligand; L2 is one of thiatriazinine N₂ released diradical, tetramethylpiperidine oxide (TEMPO), or a free radical.

2. The nickel catalyst for the denitrification cyclization synthesis of sulfonamide as described in claim 1, wherein, The L1 series includes 1,2-bis(diphenylphosphino)ethane (dppe); 1,3-bis(diphenylphosphino)propane (dppp); 1,4-bis(diphenylphosphino)butane (dppb); 1,2-bis(diphenylphosphino)benzene (dppbz); or 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (Xantphos).

3. The nickel catalyst for the denitrification cyclization synthesis of sulfonamides as described in claim 1, wherein, The L1 series consists of 1,2-bis(diethylphosphino)ethane (depe); 1,2-bis(dicyclohexylphosphino)ethane (dcpe); 1,3-bis(dicyclohexylphosphino)propane (dcpp); or 1,4-bis(dicyclohexylphosphino)butane (dcpb).

4. A method for preparing a nickel catalyst for the denitrogenation cyclization synthesis of sulfonylureas, comprising preparing the nickel catalyst for the denitrogenation cyclization synthesis of sulfonylureas as described in claim 1, including: 20 mg of 1,2,3,4-benzothiatriazine-1,1(2H)-dioxide, 28 mg of bis(1,5-cyclooctadiene)nickel(0), Ni(cod)₂, and 40 mg of 1,2-bis(diphenylphosphino)ethane (dppe) were placed in a 10 mL sealed tube, purged with nitrogen, and 2.0 mL of tetrahydrofuran (THF) was added to form a reaction solution. The reaction solution was stirred in an 80°C oil bath for 3 hours to carry out the reaction; after concentration under reduced pressure, a residue was obtained; it was then washed with diethyl ether and pentane, and concentrated under reduced pressure again to obtain 48 mg of a brown solid system as a nickel catalyst, with a yield of 76%.

5. A nickel catalyst for the denitrification and cyclization synthesis of sulfonylurea, having the structure described in formula (II): Ni0[L1][L3]……Formula (II) wherein, L1 is a bidentate diaryl phosphino ligand or a bidentate alkyl phosphino ligand; L3 is one of cyclooctadiene, phosphine or a neutral ligand.

6. The nickel catalyst for the denitrification cyclization synthesis of sulfonamides as described in claim 5, wherein, The L1 series includes 1,2-bis(diphenylphosphino)ethane (dppe); 1,3-bis(diphenylphosphino)propane (dppp); 1,4-bis(diphenylphosphino)butane (dppb); 1,2-bis(diphenylphosphino)benzene (dppbz); or 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (Xantphos).

7. The nickel catalyst for the denitrification cyclization synthesis of sulfonamides as described in claim 5, wherein, The L1 series consists of 1,2-bis(diethylphosphino)ethane (depe); 1,2-bis(dicyclohexylphosphino)ethane (dcpe); 1,3-bis(dicyclohexylphosphino)propane (dcpp); or 1,4-bis(dicyclohexylphosphino)butane (dcpb).

8. A method for preparing a nickel catalyst for the denitrogenation cyclization synthesis of sulfonylureas, comprising preparing the nickel catalyst for the denitrogenation cyclization synthesis of sulfonylureas as described in claim 5, comprising: 200 mg of bis(1,5-cyclooctadiene)nickel and 578 mg of 1,2-bis(diphenylphosphine)ethane were placed in a 25 mL round-bottom flask, purged with nitrogen, and then 10 mL of tetrahydrofuran was added to form a reaction solution. The reaction solution was stirred at room temperature for 3 hours to carry out the reaction. After concentration under reduced pressure, a residue was obtained. After washing with diethyl ether, the residue was dissolved in chloroform and filtered, and then concentrated under reduced pressure again to obtain 541 mg of a white solid system, which was the nickel catalyst, with a yield of 87%.

9. A nickel catalyst for the denitrification and cyclization synthesis of sulfonamides, having a structure as described in formula (III): ... formula (III); wherein, L4 and R are one of the coordination-controlled groups containing phosphorus, sulfur, nitrogen, oxygen, or carbon.

10. The nickel catalyst for the denitrification cyclization synthesis of sulfonamides as described in claim 9, wherein, Formula (III) is synthesized by the following route: ; where L5 is one of the coordination-dominant groups containing phosphorus, sulfur, nitrogen, oxygen, and carbon.

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