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Synthesis method of beta-hydroxyl substituted sulfonyl compound

A synthesis method and compound technology, applied in the field of synthesis of sulfonyl compounds, achieving the effects of low cost, simple raw materials, and good application prospects

Active Publication Date: 2019-01-04
JIAXING UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] The above works are all based on substrates containing sulfonyl structures, such as sulfonyl chloride, sulfonic acid or sodium sulfonate; however, the direct use of sulfur dioxide insertion strategy to efficiently construct β-hydroxyl-substituted sulfonyl compounds through a one-step reaction has not been reported yet.

Method used

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  • Synthesis method of beta-hydroxyl substituted sulfonyl compound
  • Synthesis method of beta-hydroxyl substituted sulfonyl compound
  • Synthesis method of beta-hydroxyl substituted sulfonyl compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Add CuBr in turn to the reaction tube 2 (0.04mmol, 0.2 equivalent), 1,10-phenanthroline (0.04mmol, 0.2 equivalent), DABCO.(SO 2 ) 2 (0.4mmol, 2.0 equivalents), alkenes (0.2mmol, 1.0 equivalents), p-nitrophenylhydrazine (0.04mmol, 0.2 equivalents) and solvent acetonitrile (2mL), in air, stirred at room temperature for 24 hours, until TLC detected complete reaction , the reaction solution was concentrated under reduced pressure and separated by column chromatography to obtain the corresponding β-hydroxyl-substituted sulfonyl compound 3a in a yield of 47%.

[0026] The prepared β-hydroxyl-substituted sulfonyl compound 3a has the following structural formula:

[0027]

[0028] Detected by proton nuclear magnetic resonance spectrum and carbon spectrum, the results are as follows:

[0029] 1 H NMR (400MHz, CDCl 3 ): δ (ppm) 8.11 (d, J = 8.7Hz, 2H), 7.69 (d, J = 8.7Hz, 2H), 7.44 (d, J = 4.2Hz, 4H), 7.40-7.32 (m, 3H) , 7.30-7.22 (m, 2H), 4.37 (s, 1H), 3.90 (d, J = 15.0...

Embodiment 2

[0032] Add CuBr in turn to the reaction tube 2 (0.04mmol, 0.2 equivalent), 1,10-phenanthroline (0.04mmol, 0.2 equivalent), DABCO . (SO 2 ) 2 (0.4mmol, 2.0 equivalents), alkene (0.2mmol, 1.0 equivalents), p-fluorophenylhydrazine (0.04mmol, 0.2 equivalents) and solvent acetonitrile (2mL), in air, stirred at room temperature for 24 hours, until TLC detected complete reaction, The reaction solution was concentrated under reduced pressure and separated by column chromatography to obtain the corresponding β-hydroxyl-substituted sulfonyl compound 3b in a yield of 61%.

[0033] The prepared β-hydroxyl-substituted sulfonyl compound 3b is as follows:

[0034]

[0035] Detected by proton nuclear magnetic resonance spectrum and fluorine spectrum, the results are as follows:

[0036] 1 H NMR (400MHz, CDCl 3): δ (ppm) 7.57-7.50 (m, 4H), 7.46 (t, J = 7.3Hz, 2H), 7.37 (t, J = 7.3Hz, 3H), 7.33-7.24 (m, 2H), 6.98 ( t,J=8.1Hz, 2H), 4.64(s,1H), 3.84(d,J=14.8Hz,1H), 3.69(d,J=14.9Hz,1H), ...

Embodiment 3

[0039] Add CuBr in turn to the reaction tube 2 (0.04mmol, 0.2 equivalent), 1,10-phenanthroline (0.04mmol, 0.2 equivalent), DABCO.(SO 2 ) 2 (0.4mmol, 2.0 equivalent), solvent acetonitrile (2mL), and then inject olefin (0.2mmol, 1.0 equivalent) and phenylhydrazine (0.04mmol, 0.2 equivalent) with a micro-syringe, stir at room temperature for 24 hours in air, until TLC detection After complete reaction, the reaction solution was concentrated under reduced pressure and separated by column chromatography to obtain the corresponding β-hydroxyl-substituted sulfonyl compound 3c in a yield of 46%.

[0040] The prepared β-hydroxyl-substituted sulfonyl compound 3c is as follows:

[0041]

[0042] Detected by proton nuclear magnetic resonance spectrum and carbon spectrum, the results are as follows:

[0043] 1 H NMR (400MHz, CDCl 3 ): δ (ppm) 7.63 (d, J = 7.4Hz, 2H), 7.56 (t, J = 7.4Hz, 1H), 7.42 (t, J = 7.5Hz, 2H), 6.77 (t, J = 10.9Hz ,1H),6.68(s,1H),6.61(d,J=8.1Hz,1H),5.88(d,J=1...

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Abstract

The invention discloses a synthesis method of a beta-hydroxyl substituted sulfonyl compound. The synthesis method of the beta-hydroxyl substituted sulfonyl compound comprises the following steps: catalyzing reaction of phenylhydrazine and DABCO.(SO2)2 in the air by copper salt in an organic solvent and at room temperature to generate sulfonylfree radical so as to perform free radical addition on olefin; and then combining with oxygen molecules in the air to form a peroxide intermediate and performing catalytic reduction to prepare the beta-hydroxyl substituted sulfonyl compound. According to the method, the beta-hydroxyl substituted sulfonyl compound is constructed at one step by utilizing an olefin bifunctionalization strategy under very mild condition, and the functional group diversityof the sulfonyl compound is enriched; the reaction raw materials are simple and easily available; and the method is low in cost, simple to operate and suitable for large-scale preparation, and has good application prospect.

Description

technical field [0001] The invention belongs to the technical field of organic chemistry, in particular to a method for synthesizing sulfonyl compounds substituted with β-hydroxyl groups. Background technique [0002] The sulfonyl group is a very important structural fragment, which widely exists in many natural products and drug molecules with biological activity [(a) M.Bartholow, Top 200 Drug of 2011.Pharmacy Times.http: / / www.pharmacytimes. com / publications / is sue / 2012 / July2012 / Top-200-Drugs-of-2011, accessed on Jan 9, 2013; (b) P.S. Santos, M.T.S. Mello, J.Mol.Struc.1988, 178, 121]. At present, the introduction of sulfonyl moieties into molecules mainly uses existing substrates containing sulfonyl structures, such as sulfonyl chloride, sulfinic acid, sulfinate, sulfonic acid, etc., and the synthesis of these compounds is generally cumbersome. , and the substrate has great limitations. Therefore, in recent years, chemists have been working hard to develop new methods tha...

Claims

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Application Information

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IPC IPC(8): C07C317/18C07C315/00C07D317/56C07B60/00
CPCC07B61/02C07C317/18C07D317/56
Inventor 邱观音生张俊吴劼
Owner JIAXING UNIV
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