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Method for preparing fluoroalkane substituted compound by reducing halogenated fluoroalkane and olefin through metal elementary substance

A technology for halogenated fluoroalkanes and fluoroalkanes, which is applied in the field of compound preparation, can solve the problems of high cost, limited substrates, complicated operations and the like, and achieves the effects of good yield, mild reaction process conditions and low cost

Active Publication Date: 2021-07-16
SUN YAT SEN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] At present, there have been a small number of reports on the method of simultaneously introducing a trifluoromethyl or polyfluoroalkyl group and a hydrogen atom into an olefin compound through an addition reaction, but the cost of the reagent used in the existing technology is relatively high, the operation is relatively complicated, or the base relatively limited

Method used

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  • Method for preparing fluoroalkane substituted compound by reducing halogenated fluoroalkane and olefin through metal elementary substance
  • Method for preparing fluoroalkane substituted compound by reducing halogenated fluoroalkane and olefin through metal elementary substance
  • Method for preparing fluoroalkane substituted compound by reducing halogenated fluoroalkane and olefin through metal elementary substance

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0062] Preparation of compound 2-1:

[0063]

[0064] Add elemental metal Zn (327.5mg, 5mmol) and benzoic acid (305.3mg, 2.5mmol) into the reaction device, then seal the system, vacuumize, feed bromotrifluoromethane, then add CH to the reaction system 3 CN (3mL) and styrene 1-1 (115μL, 1.00mmol) were reacted at room temperature for 2 hours, then 3mL of saturated aqueous sodium carbonate was added, stirred at room temperature for 15min, filtered, concentrated, and column chromatography gave 2-1 (146.0mg, 84 %yield), pale yellow oil.

[0065] TLC:R f =0.79in petroleum ether.

[0066] 1 H NMR (400MHz, CDCl 3 )δ7.36–7.27(m,2H),7.25–7.17(m,2H),2.91–2.85(m,2H),2.47–2.32(m,2H).

[0067] 13 C NMR (101MHz, CDCl 3 )δ139.16, 128.86, 128.36, 126.87(q, J=276.7Hz), 126.79, 35.80(q, J=28.4Hz), 28.35(q, J=3.3Hz).

[0068] 19 F NMR (375MHz, CDCl 3 ):δ–67.21.

[0069] MS(EI):m / z(%)174(M + ,25.60),91(100).

Embodiment 2

[0071] Preparation of compound 2-2:

[0072]

[0073] Preparation method reference example 1, Zn (328.0mg, 5.0mmol), PhCOOH (305.8mg, 2.5mmol), olefin 1-2 (132μL, 1.0mmol), CF 3 Br,CH 3 CN (3 mL), 2-2 (158.0 mg, 84% yield) was obtained as pale yellow oil.

[0074] TLC:R f =0.78in petroleum ether.

[0075] 1 H NMR (400MHz, CDCl 3 )δ7.12(d, J=8.0Hz, 2H), 7.08(d, J=8.1Hz, 2H), 2.87–2.78(m, 2H), 2.46–2.28(m, 5H).

[0076] 13 C NMR (101MHz, CDCl 3 )δ136.35, 136.13, 129.54, 131.16–122.71(m), 128.24, 35.91(q, J=28.1Hz), 27.94(q, J=3.6Hz), 21.09.

[0077] 19 F NMR (375MHz, CDCl 3 ):δ–67.21.

[0078] MS(EI):m / z(%)188(M + ,30.96),105(100).

Embodiment 3

[0080] Preparation of compound 2-3:

[0081]

[0082] Preparation method reference example 1, Zn (328.0mg, 5.0mmol), PhCOOH (305.8mg, 2.5mmol), olefin 1-3 (133μL, 1.0mmol), CF 3 Br,CH 3 CN (3 mL), 2-3 (190.0 mg, 93% yield) was obtained as pale yellow oil.

[0083] TLC:R f =0.34in petroleum ether.

[0084] 1 H NMR (400MHz, CDCl 3 )δ7.14–7.08(m,2H),6.88–6.82(m,2H),3.79(s,3H),2.85–2.78(m,2H),2.42–2.27(m,2H).

[0085] 13 C NMR (101MHz, CDCl 3 )δ158.50, 131.18, 129.30, 126.89(q, J=276.7Hz), 114.24, 55.35, 36.02(q, J=28.0Hz), 27.46(q, J=3.1Hz).

[0086] 19 F NMR (375MHz, CDCl 3 ):δ 19 F NMR (377MHz) δ–67.16.

[0087] MS(EI):m / z(%)204(M + ,27.94),121(100).

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Abstract

The invention discloses a method for preparing a fluoroalkane substituted compound, which comprises the steps of taking a compound containing carbon-carbon double bonds and halogenated fluoroalkane as raw materials, taking a metal elementary substance as a reducing agent, taking a substance containing active protons as a hydrogen source, and carrying out an addition reaction to prepare a compound which is simultaneously substituted by hydrogen and fluoroalkyl, thereby obtaining the fluoroalkane substituted compound. According to the method, the metal elementary substance is used as the reducing agent for the first time, the compound containing active hydrogen is used as the hydrogen source, one hydrogen atom and one fluoroalkyl group are introduced to the two ends of olefin respectively, only one-step reaction is needed, the reaction process conditions are mild, the reaction raw materials are cheap and easy to obtain, the cost is low, and all reaction reagents are green and environmentally friendly; and the reaction substrate has strong applicability, can participate in the reaction as long as carbon-carbon double bonds exist in the structure, and is not influenced by the types of substituent groups on carbon atoms of the double bonds, and the yield of the product is good.

Description

technical field [0001] The invention relates to a preparation method of a compound, in particular to a method for preparing a fluoroalkane-substituted compound by reducing a halogenated fluoroalkane and an alkene with a metal element. Background technique [0002] Compounds containing trifluoromethyl or polyfluoroalkyl structures are ubiquitous in small molecule drugs and pesticides. The introduction of trifluoromethyl or other polyfluoroalkyl groups can improve the chemical and metabolic stability of compounds and enhance lipophilicity, which are important elements in the design of biologically active molecular structures. After decades of development, a variety of trifluoromethylation reagents and polyfluoroalkylation reagents have been developed. However, the preparation of these trifluoromethylation reagents or polyfluoroalkylation reagents is relatively complicated, expensive, or unstable, such as TMSCF 3 , Togni reagent, Umemoto reagent, Langlois reagent, etc. The c...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B39/00C07C17/32C07C22/00C07C25/13C07C22/08C07C41/30C07C43/225C07C45/69C07C49/80C07C49/477C07C67/293C07C69/76C07C69/157C07C67/343C07C69/65C07C69/74C07C67/347C07C69/63C07C231/12C07C233/05C07C233/18C07C233/15C07C303/30C07C309/73C07C319/20C07C323/20C07D207/27C07D209/08C07D211/18C07D213/26C07D295/185C07D307/33C07D311/46C07D493/04C07F7/08C07J1/00C07J3/00C07J5/00C08F8/24C08F236/06
CPCC07B39/00C07C17/32C07C67/347C07C67/343C07C41/30C07C67/293C07C231/12C07C45/69C07D307/33C07D207/27C07D295/185C07D211/18C07D213/26C07F7/081C07F7/083C07D311/46C07C303/30C07J1/0059C07J3/00C07J5/0053C07D493/04C07D209/08C07C319/20C08F8/24C07C2602/28C07C2601/08C07C2601/14C07C2602/24C07C22/08C07C69/74C07C43/225C07C25/13C07C69/157C07C233/15C07C69/63C07C69/76C07C22/00C07C233/05C07C233/18C07C69/65C07C49/477C07C49/80C07C309/73C07C323/20C08F236/06
Inventor 李苏华彭德乾赵雪棋
Owner SUN YAT SEN UNIV