Novel green synthetic method for 1,2-benzothiazine derivative through transition metal catalyzed C-H activation/cyclization

A technology of transition metal catalysis and benzothiazine, applied in chemical recovery, organic chemistry, etc., can solve the problems of toxic organic solvents, low atom utilization rate, environmental pollution cost, etc., to avoid environmental pollution, improve atom utilization rate, Reduce the effect of producing finished products

Active Publication Date: 2019-08-09
SICHUAN UNIV
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  • Abstract
  • Description
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Problems solved by technology

[0004] The present invention realizes the use of sulfenimide as raw material, alkyne, diazo compound and sulfur ylide as coupling reagent, ionic liquid as solvent, and catalyzed by transition metal A new method for the synthesis of 1,2-benzothiazine by aryl C-H activated ring closure reaction, which solves the problems of high reaction temperature, low atom utilization rate, use of toxic organic solvents, environmental pollution and high cost in traditional synthesis methods, and provides A preparation method that is milder, simpler, more effective, environmentally friendly and the reaction system can be recycled than the existing reports has been developed, which reduces the production of finished products and avoids environmental pollution, and the by-product is only nitrogen, which greatly improves the utilization rate of atoms , has profound significance

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  • Novel green synthetic method for 1,2-benzothiazine derivative through transition metal catalyzed C-H activation/cyclization
  • Novel green synthetic method for 1,2-benzothiazine derivative through transition metal catalyzed C-H activation/cyclization
  • Novel green synthetic method for 1,2-benzothiazine derivative through transition metal catalyzed C-H activation/cyclization

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0019] Implementation Example 1: Synthesis of Compound 1

[0020]

[0021] (1) Add S-methyl-S-phenylsulfinimide (31.0 mg, 0.20 mmol), ethyl diazoacetoacetate (37.5 mg, 0.24 mmol), dichloro (Pentamethylcyclopentadienyl)rhodium(III) dimer (6.2 mg, 0.01 mmol), silver hexafluoroantimonate (13.7 mg, 0.04 mmol), 1-butyl-3-methylimidazolium hexa Fluorophosphate (0.6mL), stirred at 30°C for 24 hours;

[0022] (2) After the reaction was completed, diethyl ether was added for extraction, the diethyl ether layer was collected, and the solvent was removed under reduced pressure. The residue was separated and purified by silica gel column chromatography to obtain 50.4 mg of brown oil with a yield of 95%. 1 H NMR (400 MHz, DMSO- d 6 ) δ 8.16 (dd, J = 8.4,0.8 Hz 1H), 7.68 (t, J = 7.2 Hz, 1H), 7.60 (dd, J = 8.4, 0.8 Hz, 1H), 7.51(t, J = 7.2 Hz, 1H), 4.30 (q, J = 7.2 Hz, 2H), 3.84 (s, 3H), 2.25 (s, 3H), 1.30 (t, J = 7.2 Hz, 3H); 13 C NMR (150MHz, CDCl 3 ) δ 168.7, 152.1, 13...

Embodiment 2

[0023] Implementation Example 2: Synthesis of Compound 2

[0024]

[0025] (1) S-methyl-S-(4-methoxyphenyl)sulfinimide (37.0 mg, 0.20 mmol), ethyl diazoacetoacetate (37.5 mg , 0.24 mmol), dichloro(pentamethylcyclopentadienyl) rhodium (III) dimer (6.2 mg, 0.01 mmol), silver hexafluoroantimonate (13.7 mg, 0.04 mmol), 1-butyl -3-Methylimidazolium hexafluorophosphate (0.6 mL), stirred at 30°C for 24 hours;

[0026] (2) After the reaction was completed, ether was added for extraction, the ether layer was collected, and the solvent was removed under reduced pressure. The residue was separated and purified by silica gel column chromatography to obtain 54.9 mg of brown oil, with a yield of 93%. 1 H NMR (400 MHz, CDCl 3 ) δ 7.68 (d, J = 8.8 Hz,1H), 7.20 (s, 1H), 6.95 (d, J = 11.2 Hz, 1H), 4.37 (q, J = 7.2 Hz, 2H), 3.87(s, 3H), 3.41 (s, 3H), 2.36 (s, 3H), 1.39 (t, J = 7.2 Hz, 3H); 13 C NMR (100MHz, CDCl 3 ) δ 168.9, 163.2, 153.7, 137.0, 125.8, 115.3, 109.7, 106.4, 104.6, ...

Embodiment 3

[0027] Implementation Example 3: Synthesis of Compound 3

[0028]

[0029] (1) Add S-cyclohexyl-S-phenylsulfinimide (44.7 mg, 0.20 mmol), ethyl diazoacetoacetate (37.5 mg, 0.24 mmol), dichloro (Pentamethylcyclopentadienyl)rhodium(III) dimer (6.2 mg, 0.01 mmol), silver hexafluoroantimonate (13.7 mg, 0.04 mmol), 1-butyl-3-methylimidazolium hexa Fluorophosphate (0.6 mL), stirred at 30°C for 24 hours;

[0030] (2) After the reaction was completed, diethyl ether was added for extraction, the diethyl ether layer was collected, and the solvent was removed under reduced pressure. The residue was separated and purified by silica gel column chromatography to obtain 53.3 mg of brown oil with a yield of 80%. 1 H NMR (400 MHz, CDCl 3 ) δ 7.69 (d, J = 8.4 Hz,2H), 7.56 (t, J = 7.6 Hz, 1H), 7.35 (t, J = 7.6 Hz, 1H), 4.36 (q, J = 7.2 Hz,2H), 3.41 (t, J = 12.0 Hz, 1H), 2.37 (s, 3H), 2.24 (d, J = 12.8 Hz, 1H), 1.97(d, J = 12.8 Hz, 1H), 1.87 – 1.60 (m, 4H), 1.39 (t, J = 7.2 H...

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Abstract

The invention relates to a novel green synthetic method. According to the method, N1,N3-disubstituted imidazole type ionic liquid is taken as a solvent, NH-sulfoximine is taken as a raw material, a diazo compound, alkyne and sulfur ylide are taken as coupling reagents, and a 1,2-benzothiazine derivative is mildly and efficiently synthesized through a transition metal catalyzed C-H activation / cyclization reaction. Compared with other technologies, the condition is milder, the operation is simple, the method is safe, and the environmental friendliness is achieved; the catalytic activity is high,the reaction yield is high, and the application range of substrates is wide; the solvent and catalysts can be recycled, so that the reaction cost is reduced.

Description

technical field [0001] The present invention relates to a N-based 1 ,N 3 -Disubstituted imidazole-type ionic liquid as solvent, NH-sulfinimide as raw material, diazo compound, alkyne and sulfur ylide as coupling reagent, transition metal catalyzed C-H activation / cyclization reaction for mild and efficient synthesis of 1,2-benzene A new green method for the synthesis of thiazine derivatives. Background technique [0002] Sulfonylimides are stable compounds among many important bioactive molecules 1-3 . Its cyclization product 1,2-benzothiazine as an advantageous scaffold in the fields of medicinal chemistry and crop protection 4 , has also been studied to have antibacterial and antifungal properties 5 ,Antiviral 6,7 ,Antitumor 8,9 and antioxidant 10,11 and other biological activity. The application and development of 1,2-benzothiazine in physiological and pathological sciences has promoted the production of many preparation methods, among which transition metal-catal...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D279/02
CPCC07D279/02Y02P20/584
Inventor 海俐吴勇管玫刘艳昭彭瑶聂瑞芳胡瑶
Owner SICHUAN UNIV
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