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Difluoropropargyl-containing compound, preparation method and application

A technology for difluoropropargyl compounds, applied in the preparation of organic compounds, steroids, organic silicon compounds, etc., can solve the problems of low reaction yield, lengthy reaction steps, poor regioselectivity, etc.

Active Publication Date: 2019-06-28
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0005] The technical problem to be solved by the present invention is to overcome the tedious reaction steps, low reaction yield, limited substrate, and the need to use some highly toxic fluorine in the preparation method of the compound containing difluoropropargyl in the prior art. A kind of difluoropropargyl compound, preparation method and application are provided because of disadvantages such as oxidizing agent and poor regioselectivity

Method used

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  • Difluoropropargyl-containing compound, preparation method and application
  • Difluoropropargyl-containing compound, preparation method and application
  • Difluoropropargyl-containing compound, preparation method and application

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Experimental program
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Effect test

Embodiment 1

[0072]

[0073] To a 25 mL reaction tube, add 0.72 mmol phenylboronic acid, 2.8 mg (0.5 mol%) tris(dibenzylideneacetone) dipalladium, 5.6 mg (3 mol%) tris(o-methylphenyl)phosphine, potassium carbonate ( 1.8 mmol), inject 136 mg (0.6 mmol) of 1-triisopropylsilyl-3-bromo-3,3-difluoropropyne, 1,4-dioxane (3.0 mL). After stirring at 80°C for 24 hours, the yield was 91%, and the purity was greater than 98% as identified by hydrogen spectrum. 1 H NMR (400MHz, CDCl 3 )7.72-7.70(m,2H),7.45-7.41(m,3H),1.15-1.10(m,21H). 19 F NMR (376MHz, CDCl 3 )-74.3(s,2F). 13 C NMR (126MHz, CDCl 3 )136.2(t, J=27.9Hz), 130.6(t, J=1.9Hz), 128.4, 125.4(t, J=4.5Hz), 111.6(t, J=231.0Hz), 98.9(t, J=39.9 Hz), 92.5(t, J=4.9Hz), 18.5, 11.0.IR (thin film method) ν max 3440,2945,2868,2186,1742cm -1 .MS(EI):m / z(%)308(M+),265,115(100).HRMSCalculated for(theoretical value):308.1772; Found(measured value):308.1771.

Embodiment 2

[0075]

[0076] To a 25 mL reaction tube, add 0.72 mmol 2-methylphenylboronic acid, 2.8 mg (0.5 mol%) tris(dibenzylideneacetone) dipalladium, 5.6 mg (3 mol%) tris(o-methylphenyl)phosphine, Potassium carbonate (1.8 mmol), injection of 136 mg (0.6 mmol) 1-triisopropylsilyl-3-bromo-3,3-difluoropropyne, 1,4-dioxane (3.0 mL). After stirring at 80°C for 24 hours, the yield was 77%, and the purity was greater than 98% as identified by hydrogen spectrum. 1 H NMR (400MHz, CDCl 3 )δ7.68(d, J=7.9Hz, 1H), 7.34(t, J=7.5Hz, 1H), 7.28-7.20(m, 2H), 2.56(s, 3H), 1.16–1.05(m, 21H ). 19 FNMR (376MHz, CDCl 3 )δ-77.0(s,2F). 13 C NMR (126MHz, CDCl 3 )δ136.5(t, J=2.1Hz), 134.1(t, J=26.2Hz), 131.8, 130.4(t, J=1.5Hz), 125.63(t, J=7.4Hz), 125.57, 111.8(t , J=232.9Hz), 99.2(t, J=40.3Hz), 91.9(t, J=5.0Hz), 19.8, 18.5, 11.0.IR (thin film method) ν max 3416,2946,2868,2184,1463cm -1 .MS(EI):m / z(%)323(M + +H + ),322(M + ), 279.129(100).HRMS: Calculated (theoretical value): 322.1928; Found (meas...

Embodiment 3

[0078]

[0079] Into a 25 mL reaction tube, add 0.72 mmol 3-methylphenylboronic acid, 2.8 mg (0.5 mol%) tris(dibenzylideneacetone) dipalladium, 5.6 mg (3 mol%) tris(o-methylphenyl)phosphine, Potassium carbonate (1.8 mmol), injection of 136 mg (0.6 mmol) 1-triisopropylsilyl-3-bromo-3,3-difluoropropyne, 1,4-dioxane (3.0 mL). After stirring at 80°C for 24 hours, the yield was 85%, and the purity was greater than 98% as identified by hydrogen spectrum. 1 H NMR (400MHz, CDCl 3 )δ7.56–7.48(m,2H),7.32(t,J=7.6Hz,1H),7.28–7.26(m,1H),2.39(s,3H),1.14–1.08(m,21H). 19 F NMR (376MHz, CDCl 3 )δ-74.3(s,2F). 13 C NMR (126MHz, CDCl3) δ138.3, 136.1(t, J=27.6Hz), 131.4(t, J=1.8Hz), 128.3, 126.1(t, J=4.4Hz), 122.5(t, J=4.5Hz) ,111.7(t,J=230.9Hz),99.0(t,J=39.9Hz),92.3(t,J=5.0Hz),21.4,18.5,11.0.IR(thin film method)ν max 3387,2946,2868,2359,2182,1277cm -1 .MS(EI):m / z(%)322(M + ),279,129(100).HRMS: Calculated (theoretical value): 322.1928; Found (measured value): 322.1925.

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Abstract

The present invention discloses a difluoropropargyl-containing compound, a preparation method and applications. The preparation method comprises that in the presence of an organic solvent, a catalyst, a ligand and an alkali, a compound A and a compound B are subjected to a coupling reaction to obtain a compound C, wherein the catalyst is one or a plurality of materials selected from palladium acetate, palladium trifluoroacetate, tetrakis(triphenylphosphine)palladium, tris(dibenzylideneacetone)dipalladium chloroform adduct, and tris(dibenzylideneacetone)dipalladium, and the ligand is one or a plurality of materials selected from triphenylphosphine, tris(o-methoxyphenyl)phosphine, tris(o-methylphenyl)phosphine, tri-tert-butylphosphine fluoroborate, 2-(dicyclohexylphosphino)-2'-methylbiphenyl, 2-(di-tert-butylphosphino)biphenyl, and 4,5-bisdiphenylphosphino-9,9-dimethyl xanthene. According to the present invention, the method has characteristics of low catalyst consumption, mild reaction condition, high region selectivity, wide application range, and high reaction yield, and is suitable for industrial production. The compounds A, B and C are defined in the specification.

Description

technical field [0001] The invention relates to a compound containing difluoropropargyl, a preparation method and an application. Background technique [0002] α-aryl or alkenyl-α,α-difluoropropargyl compounds and their derivative building blocks have been widely used in biomedicine, pesticides and materials science. However, traditional methods for the synthesis of α-aryl or alkenyl-α,α-difluoropropargyl building blocks involve direct difluoropropargylations (such as those reported in the following literature, a) S.T. Laughlin, J.M. Baskin, S.L.Amacher, C.R.Bertozzi, Science 2008, 320, 664; b) J.A.Codelli, J.M.Baskin, N.J.Agard, C.R.Bertozzi, J.Am.Chem.Soc.2008, 130, 11486; c) H. A.A.Neves, S.Stairs, H.Ireland-Zecchini, K.M.Brindle, F.J.Leeper, Chem.Sci. 2011, 2, 932; d) C.A.DeForest, K.S.Anseth, Nature Chem. 2011, 3, 925; e) G.de Almeida, E.M. Sletten, H. Nakamura, K.K. Palaniappan, C.R. Bertozzi, Angew. Chem. 2007, 124, 2493; f) P. Shieh, M.J. Hangauer, C.R. Bertozzi, ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F7/08C07C22/08C07C17/263C07C69/76C07C67/343C07C255/50C07C253/30C07D249/04C07J51/00
Inventor 张新刚喻艳波
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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