Difluoroalkyl-substituted aryl or hetetoaryl compounds, and preparation method and application thereof

A difluoroalkyl and compound technology, applied in the preparation of carbon-based compounds, the preparation of hydroxyl compounds, the preparation of organic compounds, etc., can solve the problems of poor functional group compatibility, harsh reaction conditions, and poor broad spectrum.

Active Publication Date: 2016-06-15
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] The technical problem to be solved by the present invention is to overcome the harsh reaction conditions, expensive catalysts, poor functional group compatibility, and the scope of application of substrates in the existing preparation methods of aryl or heteroaryl compounds containing difluoroalkyl substitutions. Narrow, poor broad-spectrum and other defects, and provide a difluoroalkyl-substituted aryl or heteroaryl compound, preparation method and application

Method used

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  • Difluoroalkyl-substituted aryl or hetetoaryl compounds, and preparation method and application thereof
  • Difluoroalkyl-substituted aryl or hetetoaryl compounds, and preparation method and application thereof
  • Difluoroalkyl-substituted aryl or hetetoaryl compounds, and preparation method and application thereof

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0108]

[0109] Into a 25mL reaction tube, add 110mg (0.9mmol) phenylboronic acid, 6.6mg (5mol%, refers to the percentage of 5-bromo-5,5'-difluoropentylbenzene molar weight) NiCl 2 DME, 8mg (5mol%) 4,4'-d t Bubpy (4,4'-di-tert-butylbipyridine), 14.6mg (20mol%) DMAP, 166mg (1.2mmol) K 2 CO 3 , 4 mL of triglyme, injected with 157 mg (0.6 mmol) of 5-bromo-5,5'-difluoropentylbenzene, and stirred at 80°C for 24 hours, the isolated yield was 92%. The purity is greater than 95% identified by hydrogen spectrum. 1 HNMR (400MHz, CDCl 3 )δ7.48–7.38(m,5H),7.27(t,J=7.3Hz,2H),7.20–7.11(m,3H),2.58(t,J=7.6Hz,2H),2.21–2.07(m ,2H),1.68–1.59(m,2H),1.54–1.45(m,2H). 19 FNMR (376MHz, CDCl 3 )δ-95.5(t, J=16.2Hz, 2F). 13 CNMR (125.7MHz, CDCl 3 )δ142.1, 137.5(t, J=26.6Hz), 129.5(t, J=1.5Hz), 128.34, 128.32, 128.30, 125.8, 124.9(t, J=6.2Hz), 123.0(t, J=242.1Hz) ,38.9(t,J=27.5Hz),35.7,31.1,22.2(t,J=4.0Hz).IR(thinfilm)ν max 3027,2934,1496,1452,1327cm -1 .MS(EI):m / z(%)260(M + ),240,127,91(1...

Embodiment 2

[0111]

[0112] Into a 25mL reaction tube, add 178.2mg (0.9mmol) 4-phenylphenylboronic acid, 6.6mg (5mol%, refers to the percentage of moles of 5-bromo-5,5'-difluoropentylbenzene) NiCl 2 DME, 8mg (5mol%) 4,4'-d t Bubpy (4,4'-di-tert-butylbipyridine), 14.6mg (20mol%) DMAP, 166mg (1.2mmol) K 2 CO 3 , 4 mL of triglyme, injected with 157 mg (0.6 mmol) of 5-bromo-5,5'-difluoropentylbenzene, and stirred at 80°C for 24 hours, the isolated yield was 95%. The purity is greater than 95% identified by hydrogen spectrum. 1 HNMR (400MHz, CDCl 3 )δ7.64(d, J=8.2Hz, 2H), 7.61(d, J=7.4Hz, 2H), 7.53(d, J=8.2Hz, 2H), 7.47(t, J=7.5Hz, 2H) ,7.38(t,J=7.4Hz,1H),7.27(t,J=7.4Hz,2H),7.21–7.11(m,3H),2.61(t,J=7.8Hz,2H),2.26–2.12( m,2H),1.73–1.61(m,2H),1.56–1.50(m,2H). 19 FNMR (376MHz, CDCl 3)δ-95.1(t, J=16.2Hz, 2F). 13 CNMR (125.7MHz, CDCl 3 )δ142.4(t, J=1.4Hz), 142.1, 140.2, 136.3(t, J=26.9Hz), 128.8, 128.30, 128.27, 127.7, 127.12, 127.05, 125.7, 125.4(t, J=6.1Hz) ,123.1(t,J=242.1Hz),38.8(t...

Embodiment 3

[0114]

[0115] Into a 25mL reaction tube, add 178.2mg (0.9mmol) of 3-phenylphenylboronic acid, 6.6mg (5mol%, refers to the percentage of moles of 5-bromo-5,5'-difluoropentylbenzene) NiCl 2 DME, 8mg (5mol%) 4,4'-d t Bubpy (4,4'-di-tert-butylbipyridine), 14.6mg (20mol%) DMAP, 166mg (1.2mmol) K 2 CO 3 , 4 mL of triglyme, injected with 157 mg (0.6 mmol) of 5-bromo-5,5'-difluoropentylbenzene, and stirred at 80°C for 24 hours, the isolated yield was 90%. The purity is greater than 95% identified by hydrogen spectrum. 1 HNMR (400MHz, CDCl 3 )δ7.71(s,1H),7.67(d,J=7.8Hz,1H),7.63(d,J=7.8Hz,2H),7.54–7.44(m,4H),7.41(t,J=7.3 Hz,1H),7.28(t,J=7.0Hz,2H),7.22–7.14(m,3H),2.63(t,J=7.6Hz,2H),2.30–2.14(m,2H),1.74–1.64 (m,2H),1.61–1.51(m,2H). 19 FNMR (376MHz, CDCl 3 )δ-95.4(t, J=16.3Hz, 2F). 13 CNMR (125.7MHz, CDCl 3 )δ142.1, 141.5, 140.5, 138.0 (t, J = 26.8Hz), 128.9, 128.32, 128.29, 127.7, 127.2, 125.8, 123.78 (t, J = 6.2Hz), 123.72 (t, J = 6.3Hz), 123.0 (t, J=242.4Hz), 39.0(t, J=27...

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Abstract

The invention discloses difluoroalkyl-substituted aryl or hetetoaryl compounds, and a preparation method and application thereof. The preparation method comprises the following step: in a solvent, carrying out Suzuki coupling reaction disclosed in the specification on compounds disclosed as Formula A and compounds disclosed as Formula B in the presence of an alkali, a ligand, a catalyst and additives, thereby obtaining the compounds disclosed as Formula C. The preparation method has the advantages of simple and accessible raw materials, fewer reaction steps, high conversion rate, high reaction yield, cheap and accessible catalyst, low cost, favorable compatibility of functional groups, wide applicability of the substrate, broad spectrum and high safety, is simple to operate, can avoid using virulent reagent, and has favorable industrialized application prospects.

Description

technical field [0001] The invention relates to an aryl or heteroaryl compound substituted with a difluoroalkyl group, a preparation method and an application. Background technique [0002] Difluoroalkyl substituted arenes / heteroarenes have important applications in the fields of medicine, pesticides and materials science. The traditional introduction of difluoromethylene is mainly through the deoxyfluorination of carbonyl and aldehyde groups by deoxyfluorination reagents such as DAST (ie, diethylaminosulfur trifluoride), or the use of nucleophilic fluorination in the presence of oxidizing agents. Reagents HF-Py, TBABF, etc. can fluorinate thioketal or hydrazone. However, due to the high activity of fluorinated reagents, complex reactions, and incompatibility of many important functional groups, this method is not suitable for the synthesis of complex difluoromethylene-containing compounds, thus limiting the application of this method. Although the methods of introducing d...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C25/18C07C25/13C07F7/18C07C47/55C07C69/76C07C255/50C07C255/57C07C43/225C07C49/813C07C49/80C07C211/56C07C317/14C07D209/86C07C33/46C07C69/157C07C317/22C07D211/46C07F17/00C07D277/56C07D209/48C07J51/00C07C271/22C07C69/675C07C17/263C07C45/68C07C67/343C07C253/30C07C41/30C07C209/68C07C29/32C07C315/04C07C269/06
CPCC07C17/263C07C25/13C07C25/18C07C29/32C07C33/46C07C41/30C07C43/225C07C45/68C07C47/55C07C49/80C07C49/813C07C67/343C07C69/157C07C69/675C07C69/76C07C209/68C07C211/56C07C253/30C07C255/50C07C255/57C07C269/06C07C271/22C07C315/04C07C317/14C07C317/22C07D209/48C07D209/86C07D211/46C07D277/56C07F7/1804C07F17/00C07J51/00
Inventor 张新刚肖玉兰闵巧桥
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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