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Difluoromethyl silver compound, single crystal, synthetic method and application

A technology of difluoromethyl silver and dimethyl silver, applied in silver organic compounds, organic chemical methods, chemical instruments and methods, etc., can solve the problem of low yield, difficulty in synthesizing difluoromethyl compounds, long routes, etc. question

Active Publication Date: 2015-05-27
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] The technical problem to be solved by the present invention is to provide a difluoromethyl silver compound, single crystal, synthetic Method and application, the difluoromethylsilver compound of the present invention has good stability, and can undergo difluoromethylation reactions with substrates such as diaryl iodides, acyl chloride substrates, and active halogenated hydrocarbons, and this type The reaction conditions are mild, the group compatibility is good, and it has good market development prospects

Method used

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  • Difluoromethyl silver compound, single crystal, synthetic method and application
  • Difluoromethyl silver compound, single crystal, synthetic method and application
  • Difluoromethyl silver compound, single crystal, synthetic method and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0109] Example 1 [(SIPr)AgCF 2 Preparation of H]1a-1

[0110]

[0111] [(SIPr)AgCl] (831mg, 1.50mmol) and NaO under argon atmosphere t Bu (285mg, 3.00mmol) was dissolved in THF (30mL), TMSCF was added at room temperature 2 H (375uL, 3.00mmol). Stirred at room temperature in the dark for 1 hour under the protection of Ar, filtered with diatomaceous earth, and the filtrate was dried under reduced pressure. The obtained yellow solid was recrystallized under the condition of dichloromethane / n-pentane to obtain a white solid [(SIPr )AgCF 2 H] 1a-1 (698mg, 82%). Purity identified by hydrogen spectrum greater than 95%.

[0112] 1 H NMR (400MHz,THF-d 8 )δ7.36(t,J=8.0Hz,2H),7.26(d,J=8.0Hz,2H),5.90(td,J=52,14Hz,1H),4.04(s,4H),3.15(hept ,J=6.8Hz,4H),1.34(d,J=7.2Hz,12H),1.32(d,J=7.2Hz,12H);

[0113] 19 F NMR (376MHz,THF-d 8 )δ-113.66(dd,J 109 Ag-F =64.0Hz,J 107 Ag-F =56.4Hz,J H-F =45.1Hz); 13 C NMR (101MHz, CDCl 3 )δ24.11, 25.76, 28.96, 124.55, 129.78, 134.80, 146.76, 1...

Embodiment 2

[0115] Example 2 [(IPr)AgCF 2 Preparation of H]1b-1

[0116]

[0117] [(IPr)AgCl] (552mg, 1.00mmol) and KO under argon atmosphere t Bu (225mg, 2.00mmol) was dissolved in THF (90mL) and TMSCF was added 2 H (250 μL 3.00 mmol) in THF (10 mL). Under the protection of argon, stir at room temperature in the dark for 4 hours, then filter with diatomaceous earth, and vacuum the filtrate to dryness. The obtained yellow solid is recrystallized under the condition of dichloromethane / n-pentane to a white solid [(IPr)AgCF 2 H] 1b-1 (189mg, 35%). The purity is greater than 95% identified by hydrogen spectrum.

[0118] 1 H NMR (400MHz, CDCl 3 )δ7.48(t,J=7.6Hz,2H),7.28(d,J=7.6Hz,2H),7.14(s,2H),6.25(td,J=64.0,16.0Hz),2.53(hept, J=7.2Hz,4H),1.26(d,J=6.8Hz,12H),1.20(d,J=6.8Hz,12H);

[0119] 19 F NMR (376MHz, CDCl 3 )-112.76(dd,J 109 Ag-F =63.9Hz,J 107 Ag-F =56.2,J H-F =41.4Hz). 13 C NMR (126MHz, CDCl 3 ) 23.94, 24.54, 28.68, 123.23, 124.10, 125.03, 130.39, 134.67, 145.61, 155....

Embodiment 3

[0125] Example 3 Difluoromethyl metal silver compound 1a-1 (SIPrAgCF 2 Study on the reactivity of H[SIPr=1,3-bis(2,6-diisopropylphenyl)imidazole])

[0126] First, we used the difluoromethylation reaction of difluoromethyl metal silver compound and diaryl iodide, and through the screening of conditions (see Table 2 for details), we determined that the difluoromethyl metal silver compound with two equivalents , two equivalents of cuprous iodide, and acetonitrile as a solvent, the difluoromethylation reaction of diaryl iodides was realized at room temperature.

[0127]

[0128] Table 2 Screening of reaction conditions for diaryl iodides

[0129] Numbering

[0130] Reaction conditions: a) the diaryl iodide of 0.05mmol, the difluoromethyl silver of 0.05mmol, the cuprous iodide of 0.05mmol are dissolved in the acetonitrile of 0.5ml; b) take trifluoromethoxybenzene as internal standard Fluorine spectrum yield; c) 5 equivalents of cuprous iodide added; d) 2 equivalents...

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Abstract

The invention discloses a difluoromethyl silver compound, a single crystal, a synthetic method and an application. The invention provides a difluoromethyl silver compound (1a) or a difluoromethyl silver compound (1b), wherein R and R' are independently a phenyl group or a naphthyl group having substituent groups at any position of the phenyl group or the naphthyl group. The substituent group is one or more in number and is an alkyl group with the carbon number of 1-6, an alkoxy group with carbon number of 1-6 or an alkyl-substituted amino group with the carbon number of 1-6, wherein the substituent groups on the phenyl group or the naphthyl group are same or different and the R and R' are same or different. The invention also provides the synthetic method of the difluoromethyl silver compound (1a) or the difluoromethyl silver compound (1b), which includes following steps: carrying out a reaction with aza-carbene complexed silver chloride and trimethyl silyl difluoromethane. The difluoromethyl silver compound is good in stability, can be subjected to an electrophilic substrate through a difluromethylated reaction, is mild in reaction condition, is good in group compatibility and is excellent in market development prospect.

Description

technical field [0001] The invention relates to a difluoromethyl silver compound, single crystal, synthesis method and application. Background technique [0002] Since the introduction of fluorine atoms and fluoroalkyl groups into drug molecules can enhance their lipid solubility and metabolic stability, the introduction of fluorine atoms and fluoroalkyl groups into molecules has become an important goal in the design of drug molecules in recent years. . (a) Kirsch, P. Modern Fluoroorganic Chemistry: Synthesis, Reactivity, Applications; Wiley–VCH: Weinheim, 2004. b) Hiyama, T. Organofluorine Compounds: Chemistry and Properties; Springer-Verlag: Berlin, 2000. c) Uneyama, K.Organofluorine\Chemistry;Blackwell:Oxford,U.K.,2006.(d)O'Hagan,D.Chem.Soc.Rev.2008,37,308.d)Leroux,F.;Jeschke,P.;Schlosser,M.Chem .Rev.2005,105,827.e)Ma,J.-A.;Cahard,D.Chem.Rev.2004,104,6119;f)Ma,J.-A.;Cahard,D.Chem.Rev.2008 ,108,PR1;g)Nie,J.;Guo,H.-C.;Cahard,D.;Ma,J.-A.Chem.Rev.2011,111,455.) where difl...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F1/10C07C25/13C07C69/78C07C22/08C07C43/225C07C17/263C07C41/22C07C67/307C30B29/54C30B7/00
CPCC07B2200/13C07C17/263C07C41/22C07C67/307C07F1/00C07C22/08C07C25/02C07C43/174C07C69/76
Inventor 沈其龙古阳
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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