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A kind of method of synthesizing n-methylsulfonamide in water

A technology of methylsulfonamide and sulfonamide, which is applied in the field of synthesizing N-methylsulfonamide, can solve the problems of pollution, solvent waste and the environment, and achieve the effect of broad development prospects

Active Publication Date: 2022-04-15
NANJING UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0006] However, the previously reported reactions were carried out in a large amount of methanol as a solvent, which easily caused waste of solvent and environmental pollution.

Method used

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  • A kind of method of synthesizing n-methylsulfonamide in water
  • A kind of method of synthesizing n-methylsulfonamide in water
  • A kind of method of synthesizing n-methylsulfonamide in water

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Example 1: N-methylbenzenesulfonamide

[0026] N-Methylbenzenesulfonamide

[0027]

[0028] Benzenesulfonamide (78.6 mg, 0.5 mmol), iridium catalyst (5.1 mg, 0.005 mmol, 1 mol%), potassium hydroxide (28 mg, 0.5 mmol, 1 Equiv), methanol (0.3 ml), water (0.9ml) Add to the reaction vessel. The reaction mixture was reacted at 130 ° C in the reaction vessel for 12 hours, cooled to room temperature. The solvent was removed by rotary evaporation, and then pure target compound was obtained by column chromatography (unfolder: petroleum ether / ethyl acetate), yield: 88%.

[0029] 1 H NMR (500MHz, CDCL 3 Δ7.88 (D, J = 7.4 Hz, 2H, ARH), 7.59 (T, J = 7.3Hz, 1H, ARH), 7.52 (T, J = 7.9 Hz, 2H, ARH), 2.64 (s, 3h CH 3 ); 13 C {1H} NMR (125MHz, CDCL 3 Δ138.6, 132.7, 129.2, 127.2, 29.3.

Embodiment 2

[0030] Example 2: N, 4-dimethylbenzenesulfonamide

[0031] N, 4-Dimethylbenzenesulfonamide

[0032]

[0033] Methylbenzenesulfonamide (85.6 mg, 0.5 mmol), rhodium catalyst (5.1 mg, 0.005 mmol, 1 mol%), potassium hydroxide (28 mg, 0.5 mmol, 1 Equiv), and methanol (0.3 ml), water (0.9 ML) sequentially add to the reaction vessel. The reaction mixture was reacted at 130 ° C in the reaction vessel for 12 hours, cooled to room temperature. The solvent was removed by rotary evaporation, and then pure target compound was obtained by column chromatography (ethyl ester / ethyl acetate), yield: 94%.

[0034] 1 H NMR (500MHz, CDCL 3 Δ7.75 (D, J = 8.3Hz, 2H, ARH), 7.31 (D, J = 8.0 Hz, 2H, ARH), 2.60 (S, 3H, CH 3 ), 2.41 (s, 3h, ch 3 ); 13 C {1H} NMR (125MHz, CDCL 3 Δ143.6, 135.7, 129.8, 127.4, 29.3, 21.6.

Embodiment 3

[0035] Example 3: 4-methoxy-N-methylbenzenesulfonamide

[0036] 4-Methoxy-N-Methylbenzenesulfonamide

[0037]

[0038] Methoxybenzenesulfonamide (93.6 mg, 0.5 mmol), iridium hydroxide (5.1 mg, 0.005 mmol, 1 mol%), potassium hydroxide (28 mg, 0.5 mmol, 1 Equiv), and methanol (0.3 mL), water ( 0.9ml) Sequentially added to the reaction vessel. The reaction mixture was reacted at 130 ° C in the reaction vessel for 12 hours, cooled to room temperature. The solvent was removed by rotary evaporation, then pure target compounds were obtained by column chromatography (unfolder: petroleum ether / ethyl acetate), yield: 93%.

[0039] 1 H NMR (500MHz, CDCL 3 ) Δ7.79 (D, J = 8.9 Hz, 2H, ARH), 6.97 (D, J = 8.9 Hz, 2H, ARH), 3.85 (S, 3H, CH 3 ), 2.59 (s, 3h, ch 3 ); 13 C {1H} NMR (125MHz, CDCL 3 Δ163.0, 130.3, 129.5, 114.4, 55.7, 29.3.

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Abstract

The invention discloses a method for synthesizing N-methylsulfonamide in water, using sulfonamide and methanol as raw materials, and adopting a transition metal iridium catalyst to catalyze N-methylation reaction. The invention uses non-toxic and harmless water as a solvent, avoiding the use of organic reagents; the reaction only generates water as a by-product, without environmental hazards; the reaction temperature is milder than the previous one; the reaction only generates monomethylated products, which has good The selectivity; the reaction atom economy is high, and has broad application prospects.

Description

Technical field [0001] The present invention is an organic synthetic chemical technology, which relates to a method of synthesizing N-methylsulfonamide in water. Background technique [0002] N-methylsulfamide is widely used in synthetic natural products, fine chemicals, pharmaceuticals and key intermediates. The traditional N-methylated primary amine method is by reacting with the use of highly toxic and dangerous sulfonyl chloride and methylamine. [0003] Because of the environmentally friendly advantages, it has been widely valued in recent years, which has also caused extensive attention to the use of alcohol replacement, which is currently considered to be a relatively reasonable speculation reaction mechanism: First, the alcohol is generated by a ferrous catalyst oxidative dehydrogenation The aldehyde and transition metal hydrogen complex; subsequently formed aldehyde and nucleophilic reactant amine compounds generate condensation products and water; Complete dehydrogenati...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C303/40C07C311/16C07C311/29C07C311/03C07C311/14
CPCC07C303/40C07C2601/02C07C311/16C07C311/29C07C311/03C07C311/14
Inventor 李峰孟冲汤亚文
Owner NANJING UNIV OF SCI & TECH