Method for synthesizing aryl trifluoromethyl sulphydryl compound

A synthesis method, trifluoromethyl technology, applied in the field of synthesis of trifluoromethyl mercapto compounds, can solve the problems of high application cost and the like

Active Publication Date: 2012-06-27
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Recently, Professor Buchwald of the Massachusetts Institute of Technology reported a palladium metal-catalyzed method for preparing aryl trifluoromethyl mercapto compounds (Teverovskiy, G.; Surry, D.S.; Buchwald, S.L.Angew.Chem.Int.Ed.2011, 50, 7312), can efficiently prepare such compounds, but they use expensive palladium metal catalysts, and the synthetic raw materials also include silver trifluoromethylmercapto, an expensive and rare metal compound

Method used

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  • Method for synthesizing aryl trifluoromethyl sulphydryl compound
  • Method for synthesizing aryl trifluoromethyl sulphydryl compound
  • Method for synthesizing aryl trifluoromethyl sulphydryl compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] Example 1: Coupling reaction of phenylboronic acid, elemental sulfur and trifluoromethyltrimethylsilane under the catalysis of monovalent copper.

[0031]

[0032] Using N,N-dimethylformamide (5ml) as solvent, add phenylboronic acid (0.2), elemental sulfur (0.6mmol), and trifluoromethyltrimethylsilane (1.0-mmol) at any monovalent Stir at room temperature for 24 hours under the catalysis of a copper catalyst such as cuprous iodide (0.02 mmol). pass 19F NMR followed the reaction until completion. After removal of the solvent, column chromatography or distillation gave the corresponding aryl trifluoromethyl sulfide. Yield 45%. The relevant data are as follows: 1 H NMR (300MHz, CDCl3, 293K, TMS): δppm 7.35-7.39 (m, 4H), 7.23 (t, J=8.4Hz, 1H). 19 F NMR (282MHz, CDCl3): δppm-42.81(s, 3F). 13 C NMR (100.7MHz, CDCl3, 293K, TMS): δppm 166.04, 129.53 (d, J=0.8Hz), 128.93, 125.40, 36.46. IR (ATR): vmax 2955.49, 1436.91, 1284.86, 1160.71, 1017.51, 764.68 , 693.19cm -1 .M...

Embodiment 2

[0033] Example 2: Coupling reaction of phenylboronic acid, elemental sulfur and trifluoromethyltrimethylsilane under the catalysis of monovalent copper and organic ligands.

[0034]

[0035] Using N,N-dimethylformamide (5ml) as solvent, add phenylboronic acid (0.2mmol), elemental sulfur (0.6mmol), additive potassium phosphate (0.4mmol) and silver carbonate (0.4mmol) (without the additive) lead to a decrease in yield, and the use of other oxidants and bases also led to a certain decrease in yield), and trifluoromethyltrimethylsilane (1.0-mmol) in 1,10-phenanthroline (phen, 0.04mmol) Under the catalysis of the catalyst composed of CuSCN (0.02 mmol), stir at 25 ° C (parallel experiments show that the yield changes little between the reaction temperature of 0-50 ° C, and the reaction temperature exceeds this range, resulting in a decrease in yield) for 24 Hour( 19 F NMR tracking revealed comparable product formation after 1 hour). pass 19 F NMR followed the reaction until co...

Embodiment 3

[0036] Example 3: Coupling reaction of phenylboron tetrafluoride, elemental sulfur and trifluoromethyltriethylsilane under the catalysis of monovalent copper and organic ligands.

[0037]

[0038] Using N,N-dimethylformamide (5ml) as solvent, add phenylboron tetrafluoride (0.2mmol), elemental sulfur (0.6mmol), potassium phosphate (0.4mmol) and silver carbonate (0.4mmol), and Trifluoromethyltriethylsilane (1.0-mmol) was stirred at room temperature for 24 hours under the catalysis of a catalyst consisting of 1,10-phenanthroline (phen, 0.04 mmol) and CuSCN (0.02 mmol). After removal of the solvent, column chromatography or distillation gave the corresponding aryl trifluoromethyl sulfide. The yield was 89%, and it was found through experiments that phenylboronic esters also had similar reactivity in this reaction.

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Abstract

The invention relates to a method for synthesizing an aryl trifluoromethyl sulphydryl compound. According to the invention, cheap industrial raw materials organic boric acid, elemental sulfur and fluorine-containing building block are used as raw materials to react under the catalysis of monovalent copper salt at room temperature by one kettle way so as to prepare the fluoro-substituted alkyl sulfhydryl ether compound with good yield being about 90%.

Description

technical field [0001] The invention relates to a new method for synthesizing trifluoromethyl mercapto compounds, in particular to a new method for synthesizing trifluoromethyl mercapto aryl compounds. Background technique [0002] Trifluoromethyl mercapto is not only a strong electron withdrawing group, the introduction of this group can significantly improve the lipid solubility of aromatic compounds, so this group is widely used as a tool for structural modification to reduce toxic side effects and improve biological active purpose. Compounds with such structural units also appear widely in drug molecules, pesticide molecules (eg, Toltrazuril by Bayer, DE3516630, 1986), biologically active molecules, and intermediates in organic synthesis. Trifluoromethyl mercapto compounds are also important intermediates for the synthesis of fluorine-containing methyl sulfoxide and sulfone compounds - fluorine-containing methyl sulfoxide and sulfone compounds are also important groups ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B45/06C07C319/14C07C323/03C07C323/09C07C323/36C07C323/22C07C323/65C07C323/62C07C323/21C07C323/20C07C323/32C07D213/70C07D239/38C07D471/04C07D333/42C07D277/74C07D307/64C07D263/58C07D307/68
Inventor 卿凤翎王若文陈超谢岩
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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