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Method for preparing 2,2-difluoro-3-hydroxy-1,4-dione compound

A technology for compounds and diketones, applied in the field of synthesizing 2,2-difluoro-3-hydroxy-1,4-dione compounds

Active Publication Date: 2022-01-11
TAIZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the use of ketoaldehydes to obtain 2,2-difluoro-3-hydroxy-1,4-diones is still rarely reported, and to the best of our knowledge, only one example of substituted ketoaldehydes using phenyl groups has been reported, with H 2 O was synthesized as a solvent to give 2,2-difluoro-3-hydroxy-1,4-dione in only 40% yield (Angew.Chem., Int.Ed.2014, 53, 9512-9516)

Method used

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  • Method for preparing 2,2-difluoro-3-hydroxy-1,4-dione compound

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Experimental program
Comparison scheme
Effect test

Embodiment 3a

[0014] The crude products were purified by column chromatography with petroleum ether / ethyl acetate(15 / 1,v / v) as eluent to give compound 3a(whitesolid,81.9mg,94%yield).M.p.:61–63℃; 1 H NMR (400MHz, CDCl 3 )δ8.07–8.03(m,4H),7.69–7.62(m,2H),7.56–7.47(m,4H),5.73(ddd,J=17.8,7.5,4.0Hz,1H),4.26(d, J=7.6Hz,1H); 19 F NMR (376MHz, CDCl 3 )δ-100.63(d,J=279.8Hz,1F),-113.10(dd,J=278.2,17.9Hz,1F); 13 C{ 1 H}NMR (100MHz, CDCl 3 )δ195.1,189.3(C-F,dd, 2 J C-F =30.0,27.0Hz),134.7,134.4,132.6(C-F,d, 4 J C-F =1.6Hz), 130.1(C-F,dd, 3 J C-F =4.1,2.7Hz),129.5(C-F,d, 4 J C-F =1.5Hz), 128.7, 128.6, 115.9 (C-F, dd, 1 J C-F =266.1,261.7Hz),72.3(C-F,t, 2 J C-F =27.0Hz).HRMS(ESI)m / z:[M+Na] + Calcd for C 16 h 12 f 2 o 3 Na 313.0652; Found 313.0655.

Embodiment 3b

[0016] The crude products were purified by column chromatography with petroleum ether / ethyl acetate(15 / 1,v / v) as eluent to give compound 3b(whitesolid,79.4mg,87%yield).M.p.:69–71℃; 1 H NMR (400MHz, CDCl 3 )δ8.06(d,J=7.6Hz,2H),7.95(d,J=7.6Hz,2H),7.65–7.61(m,1H),7.48(dd,J=10.8,4.8Hz,2H), 7.33(d, J=8.0Hz, 2H), 5.71(ddd, J=18.3, 7.4, 3.7Hz, 1H), 4.30(d, J=7.6Hz, 1H), 2.45(s, 3H); 19 FNMR (376MHz, CDCl 3 )δ-100.57(d,J=276.4Hz,1F),-113.71(dd,J=276.7,18.8Hz,1F); 13 C{ 1 H}NMR (100MHz, CDCl 3 )δ194.4,189.4(C-F,dd, 2 J C-F=29.9,26.7Hz),146.1,134.4,132.7,131.9,130.1(C-F,dd, 3 J C-F =4.1,2.5Hz),129.6,129.5,128.6,115.9(C-F,dd, 1 J C-F =266.1,261.2Hz),72.1(C-F,t, 2 J C-F =27.1Hz), 21.8; HRMS (ESI) m / z: [M+Na] + Calcd for C 17 h 14 f 2 o 3 Na 327.0809; Found 327.0813.

Embodiment 3c

[0018] The crude products were purified by column chromatography with petroleum ether / ethyl acetate(15 / 1,v / v) as eluent to give compound 3c(whitesolid,75.7mg,83%yield).M.p.:72–74℃; 1 H NMR (400MHz, CDCl 3 )δ8.06(d,J=7.6Hz,2H),7.84–7.82(m,2H),7.63(dd,J=10.6,4.3Hz,1H),7.51–7.47(m,3H),7.42(t ,J=7.6Hz,1H),5.71(ddd,J=17.8,7.6,4.1Hz,1H),4.25(d,J=7.6Hz,1H),2.44(s,3H); 19 F NMR (376MHz, CDCl 3 )δ-100.65(d,J=277.6Hz,1F),-113.17(dd,J=277.5,17.5Hz,1F); 13 C{ 1 H}NMR (100MHz, CDCl 3 )δ195.2,189.3(C-F,dd, 2 J C-F =30.0,26.9Hz),138.7,135.6,134.5,134.4,132.7(C-F,d, 4 J C-F =1.9Hz), 130.1(C-F,dd, 3 J C-F =4.1,2.7Hz),129.8(C-F,d, 4 J C-F =1.0Hz), 128.6, 128.6, 126.8 (C-F, d, 4 J C-F =1.6Hz), 115.9(C-F,dd, 1 J C-F =266.1,261.7Hz),72.3(C-F,t, 2 J C-F =26.9Hz), 21.3; HRMS (ESI) m / z: [M+Na] + Calcd for C 17 h 14 f 2 o 3 Na 327.0809; Found 327.0815.

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Abstract

The invention discloses a method for preparing a 2,2-difluoro-3-hydroxyl-1,4-dione compound. According to the method, a difluoroenoxysilane compound and a substituted glyoxal hydrate are used as raw materials, toluene is used as a solvent, and a reaction is carried out at room temperature under the catalytic action of hexafluoroisopropanol to synthesize a target compound. The synthesis method is simple, high in yield and mild in condition, does not need a metal catalyst, and has a good application prospect.

Description

technical field [0001] The invention relates to a method for synthesizing 2,2-difluoro-3-hydroxyl-1,4-diketone compounds in a relatively mild reaction system under high-efficiency, green, metal-free catalytic conditions. Background technique [0002] Fluorochemicals are playing an increasingly important role in drug synthesis. The introduction of fluorine atoms or fluoroalkyl groups into the molecule can significantly change its physicochemical properties and biological activities, and has a wide range of applications in the fields of agrochemicals and materials science (Chem.Soc.Rev.2008,37,320-330; J. Med.Chem.2015,58,8315-8359; ), about 40% of agricultural chemicals and 25% of pharmaceuticals in the global market contain fluorine atoms (J.Med.Chem.2018,61,5822-5880; J.Med Chem. 2020, 63, 6315-6386; Org. Process Res. Dev. 2020, 24, 470-480). Therefore, chemists are working hard to develop new and effective synthetic methods to synthesize new fluorinated compounds (Chem.R...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B41/06C07C45/45C07C49/83C07C49/84C07D317/54
CPCC07B41/06C07C45/45C07D317/54C07C49/83C07C49/84
Inventor 杨健国刘赛梅洪鹏李金山任君王治明
Owner TAIZHOU UNIV