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Alpha-quaternary carbon trifluoromethyl ketone compound and preparation method thereof

A technology of quaternary carbon trifluoromethyl ketone and trifluoromethyl ketone is applied in the field of α-quaternary carbon trifluoromethyl ketone compound and its preparation, and can solve problems such as high price and excess

Inactive Publication Date: 2019-08-27
SOUTHWEST UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

First of all, most of the existing methods are based on the direct introduction of trifluoromethyl groups into molecules, however, trifluoromethyl reagents such as Umemoto reagents (T. Umemoto, S. Ishihara, J. Am. Chem. Soc. 1993, 115 , 2156), Togni reagent (I.Kieltsch, P. Eisenberger, A. Togni, Angew. Chem. Int. Ed. 2007, 46 , 754), Ruppert-Prakash reagent (Me 3 SiCF 3 ) (G. K. S. Prakash, R. Krishnamurti, G. A. Olah, J. Am. Chem. Soc. 1989, 111 , 393) are very expensive, and in these schemes, excessive trifluoromethylation reagents need to be added; secondly, most of the compounds obtained by the existing methods are some compounds with simple structures, and some compounds with novel structures will be synthesized. Potential to discover compounds with new functions

Method used

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  • Alpha-quaternary carbon trifluoromethyl ketone compound and preparation method thereof
  • Alpha-quaternary carbon trifluoromethyl ketone compound and preparation method thereof
  • Alpha-quaternary carbon trifluoromethyl ketone compound and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

example 1

[0024] Example 1 Preparation of 2-(p-methylcinnamyl)-2-trifluoroacetyl-3,4-dihydro-1-naphthalenone (A)

[0025]

[0026] Under argon protection, add Pd (PPh 3 ) 4 (0.005 mmol), dried solvent (1 mL), then add 2-trifluoroacetyl-3,4-dihydro-1-naphthone (0.11 mmol,), p-methylcinnamyl carbonate (1 mmol), TLC monitoring, column chromatography purification after the reaction to obtain the target product, yield 98%. 1 H NMR (600 MHz, CDCl 3 ) δ 8.07 (dd, J = 7.8, 0.7 Hz, 1H), 7.55 (td, J = 7.5, 1.3 Hz, 1H), 7.36(t, J = 7.6 Hz, 1H), 7.27 (d, J = 7.7 Hz, 1H), 7.22 (d, J = 8.0 Hz, 2H), 7.10(d, J= 7.9 Hz, 2H), 6.48 (d, J = 15.8 Hz, 1H), 6.20 – 6.02 (m, 1H), 3.22 –3.08 (m, 1H), 2.98 (ddd, J = 14.8, 11.5, 6.0 Hz, 2H), 2.74 (dd, J = 14.3, 8.6Hz, 2H), 2.32 (s, 3H), 2.24 (dt, J = 13.6, 4.8 Hz, 1H). 13 C NMR (151 MHz, CDCl 3 ) δ 194.24, 190.48 (q, J = 33.8 Hz), 142.78, 137.85, 135.02, 134.73,134.16, 130.70, 129.52, 129.16, 128.52, 127.58, 126.47, 122.59, 115.78 (q, ...

example 2

[0027] Example 2 Preparation of (S)-2-(p-methylcinnamyl)-2-trifluoroacetyl-3,4-dihydro-1-naphthalenone (B)

[0028]

[0029] Under argon protection, add Pd in ​​a 10 mL catalytic test tube 2 (dba) 3 (0.005 mmol), chiral ligand (0.012 mmol) dried solvent (1 mL), at 30 o C stirred for half an hour, then added 2-trifluoroacetyl-3,4-dihydro-1-naphthone (0.11 mmol), p-methylcinnamyl carbonate (1 mmol), monitored by TLC, after the reaction, the column Purification by chromatography gave the target product in a yield of 96% and an enantiomeric excess of 94%. 1 H NMR (600 MHz, CDCl 3 ) δ 8.07 (dd, J = 7.8,0.7 Hz, 1H), 7.55 (td, J = 7.5, 1.3 Hz, 1H), 7.36 (t, J = 7.6 Hz, 1H), 7.27(d, J = 7.7 Hz, 1H), 7.22 (d, J = 8.0 Hz, 2H), 7.10 (d, J = 7.9 Hz, 2H), 6.48(d, J = 15.8 Hz, 1H), 6.20 – 6.02 (m, 1H), 3.22 – 3.08 (m, 1H), 2.98 (ddd, J = 14.8, 11.5, 6.0 Hz, 2H), 2.74 (dd, J = 14.3, 8.6 Hz, 2H), 2.32 (s, 3H), 2.24 (dt, J = 13.6, 4.8 Hz, 1H). 13 C NMR (151 MHz, CDCl ...

example 3

[0030] Example 3 Preparation of 2-p-chlorocinnamyl-2-trifluoroacetyl-3,4-dihydro-1-naphthalenone (C)

[0031]

[0032] Under argon protection, add Pd (PPh 3 ) 4 (0.005 mmol), dried solvent (1 mL), then added 2-trifluoroacetyl-3,4-dihydro-1-naphthone (0.11 mmol,), p-chlorocinnamyl carbonate (1 mmol), TLC After monitoring, after the reaction was completed, the target product was obtained by column chromatography purification with a yield of 95%. 1 H NMR (600 MHz, CDCl 3 ) δ 8.08 (d, J = 7.3 Hz, 1H), 7.56 (td, J = 7.6, 1.2 Hz, 1H), 7.46 (s,1H), 7.39 (d, J = 7.6 Hz, 1H), 7.37 – 7.34 (m, 1H), 7.29 (s, 1H), 7.26 (s,2H), 7.24 (d, J = 7.8 Hz, 1H), 7.16 (t, J = 7.8 Hz, 1H), 6.44 (d, J = 15.8Hz, 1H), 6.25 – 6.11 (m, 1H), 3.22 – 3.09 (m, 1H), 3.01 (ddd, J = 15.1, 10.8,5.7 Hz, 3H), 2.85 – 2.70 (m, 2H), 2.22 (dt, J = 13.6, 4.9 Hz, 2H). 13 C NMR (151MHz, CDCl 3 ) δ 194.01, 190.42 (q,J=33.8 Hz), 142.64, 139.07, 134.85, 133.76,130.86, 130.71, 130.34, 129.5, 129.19, 128....

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Abstract

The invention discloses a method for preparing an alpha-quaternary carbon trifluoromethyl ketone compound and the alpha-quaternary carbon trifluoromethyl ketone compound. A trifluoromethyl ketone compound is subjected to alkylation under the action of a catalyst to rapidly and efficiently synthesize the alpha-quaternary carbon trifluoromethyl ketone compound shown in a formula (I). The method forpreparing the alpha-quaternary carbon trifluoromethyl ketone compound has the advantages that the raw materials are cheap and easy to obtain, the reaction condition is mild, the compatibility of substrate functional groups is high, and the structure of the product can be rapidly expanded. The invention also provides a method for preparing a polyfunctional-group trifluoromethyl synthon.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis chemistry, and relates to an alpha-quaternary carbon trifluoromethyl ketone compound and a preparation method thereof. Background technique [0002] Fluorine and hydrogen atoms have similar radii, but have a large difference in electronegativity. The fluorine-containing compounds obtained after replacing the hydrogen in the molecule with fluorine have special physical and chemical properties. For example, materials with perfluoroalkyl groups often have high chemical and thermal stability, ultra-low interfacial tension, and hydrophobic properties; the introduction of fluorine-containing groups into the molecule can significantly improve the stability and pharmacological activity of drugs , to increase the lipophilicity, metabolic stability and bioavailability of the drug. Therefore, fluorine-containing compounds play an important role in the national economy, national defense science an...

Claims

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Application Information

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IPC IPC(8): C07C45/68C07C49/697
CPCC07C45/68C07B2200/07C07C2602/10C07C2601/14C07C49/697
Inventor 陈贵华彭云贵蒋顶
Owner SOUTHWEST UNIVERSITY
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