N-aryl t-butyl sulfonamide, synthetic method and application thereof

A synthetic method and technology of sulfonamides, applied in chemical instruments and methods, preparation of hydroxyl compounds, preparation of organic compounds, etc., can solve problems such as inability to successfully remove methyl groups

Inactive Publication Date: 2012-06-27
CHENGDU UNIVERSITY OF TECHNOLOGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Qin Yong and co-workers adopted a similar approach, namely, the reaction of o-methoxyaniline with tert-butylsulfinic acid thio-tert-butyl ester in an in situ generated lithium amide / liquid ammonia system to obtain 80% ee o-methoxyaniline phenyl tert-butyl sulfinamide, but the compound is iodotrimethylsilane (CH 3 SiI), BF 3 , AlCl 3 demethylation

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0015] Weigh (R)-tert-butylsulfinamide (0.121g, 1.0 mmol), p-bromonitrobenzene (0.262g, 1.3 mmol), Pd 2 (dba) 3 (0.018g, 0.02 mmol), t Bu-XPhos (0.0212 g, 0.05 mmol), NaOH (0.080 g, 2 mmol), and sequentially added to the ground test tube, covered with a reverse rubber stopper, in the Schlenk vacuum line (also known as double-row tube vacuum gas distribution The ground-mouth test tube was replaced with argon for 3 times. Then add 6 ml of anhydrous toluene and 0.3 ml of deoxygenated water with a syringe, and then replace the ground test tube with argon for 3 times. Next, put the ground test tube replaced with inert gas into a 90°C oil bath, and stir at this temperature for 20 hours. After cooling, it was quenched with water, and the reaction mixture was extracted with ethyl acetate (10 ml × 3). The organic phases were combined and washed with 10 ml of saturated brine. The organic layer was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated und...

Embodiment 2

[0017] p-Chloronitrobenzene (0.204g, 1.3 mmol) was used instead of p-bromonitrobenzene (0.262g, 1.3 mmol), and other experimental conditions and operating methods were the same as in Example 1. (R)-N-(p-nitrophenyl)tert-butylsulfinamide (0.223 g, 92%) was obtained as a yellow solid. Various characterization data of the reaction product are also the same as the product (R)-N-(p-nitrophenyl) tert-butylsulfinamide of Example 1.

Embodiment 3

[0019] Use p-bromoacetophenone (0.258g, 1.3mmol) instead of p-bromonitrobenzene (0.262g, 1.3mmol), and other experimental conditions and operating methods are the same as in Example 1. (R)-N-(p-acetylphenyl)tert-butylsulfinamide (0.220 g, 92%) was obtained as a yellow solid. MP: 110.5-111.4 o c. 1 H NMR (300 MHz, CDCl 3 ), δ (ppm): 7.67 (d, J = 8.6 Hz, 2H), 6.94 (d, J = 8.7 Hz, 2H), 2.43 (s, 3H), 1.30(s, 9H). 13 C NMR (75 MHz, CDCl 3), δ (ppm): 196.6, 147.2, 130.7, 129.9, 115.9, 56.8, 26.1, 22.3. IR (KBr), n (cm -1 ) 3456, 3276, 2961, 1693, 1611, 1509, 1475, 1356, 1182, 1119, 1056, 861, 840, 712. [α] D 21 = -69.6 (c = 0.05, ethyl acetate).

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Abstract

The invention relates to N-aryl t-butyl sulfonamide, a synthetic method and an application thereof. N-aryl t-butyl sulfonamide has the general molecular formula as shown in the invention, wherein the structure of sulfur atom is R structure, S structure or an arbitrary mixture of the two structures; R1 and R5 are H, C1-C6 alkyl, and R1 and R5 can be the same or different; R2, R3 and R4 are H, C1-C6 alkyl, aryl, nitro, hydrocarbon acyl, formyl, carboxyl, alkoxy and halogen, and R2, R3 and R4 can be the same or different; and R1 and R2 or R2 and R3 form naphthalene ring with A ring. The compound is obtained by a coupling reaction between t butyl sulfenamides and aryl halide C-N under the catalysis of palladium. Under the condition of the catalytic reaction, the chiral structure of the raw material t butyl sulfonamide sulfur atom is maintained in the product. Obvious racemization phenomenon is not generated during the reaction process. The compound provided by the invention can be used as a ligand to promote the addition reaction of zinc ethyl and aromatic aldehyde.

Description

technical field [0001] The present invention belongs to organic chemistry, organic synthesis, and synthesis of chiral compounds, and more specifically relates to N-aryl tert-butylsulfinamide and its synthesis method and application. Background technique [0002] Enantiomerically pure R-configuration and S-configuration tert-butylsulfinamides are widely used as chiral auxiliary agents for the synthesis of chiral amines, and can also be converted into chiral ligands for asymmetric catalytic reactions, which have extensive and important the use of. Chiral N-o-hydroxy tert-butyl sulfinamide and chiral N-o-methoxyphenyl tert-butyl sulfinamide have been reported as chiral ligands for the asymmetric catalysis of ethyl zinc on aromatic aldehydes Addition reaction ( J. Org. Chem. 2007, 72 , 1373-1378) and the nucleophilic addition reaction of trichlorosilane to imines (but no specific data, patent document CN 1927830A). In addition, tert-butylsulfinyl is also a good amino protect...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C313/06B01J31/22C07C33/20C07C29/40
Inventor 曾庆乐孙晓菲涂兴钊张斌彬郭培江
Owner CHENGDU UNIVERSITY OF TECHNOLOGY
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