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Preparation method of visible-light-catalyzed [beta]-trifluoromethyl alcohol

A technology of trifluoromethyl alcohol and visible light, applied in the preparation of organic compounds, chemical instruments and methods, preparation of carboxylate esters, etc., can solve the problems that do not conform to the development trend of organic chemistry, do not conform to green chemistry, and accelerate energy consumption. , to achieve the effect of wide substrate application, low price and low cost

Active Publication Date: 2020-05-29
SUZHOU UNIV
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AI Technical Summary

Problems solved by technology

[0008] In summary, these methods for the synthesis of β-trifluoromethyl alcohol reported at present usually have the following disadvantages: mostly thermal reactions, which greatly accelerate the consumption of energy, do not conform to the development trend of organic chemistry in the future; Peroxides are more dangerous and do not meet the requirements of green chemistry; more expensive reagents need to be used, which increases the cost of the reaction; most of them can only be used for aromatic olefins, and the selectivity of the reaction itself is poor

Method used

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  • Preparation method of visible-light-catalyzed [beta]-trifluoromethyl alcohol
  • Preparation method of visible-light-catalyzed [beta]-trifluoromethyl alcohol
  • Preparation method of visible-light-catalyzed [beta]-trifluoromethyl alcohol

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Experimental program
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Effect test

Embodiment 1

[0040]

[0041] Add 1a (0.2mmol, 46.5mg), 2a (0.8mmol, 131.5mg), Mn(acac) once in the test tube 3 (0.02mmol, 7.3mg), 1,4-dioxane (3.0mL) and acetone (1.0mL). Then the system was stirred for 24 hours under 40W blue light LED irradiation and room temperature in the air, then directly added 2.0mL ethyl acetate to dilute, removed the solvent with a rotary evaporator, adsorbed on silica gel, and obtained the product 3a through simple column chromatography. The yield is 80%. The main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.

[0042] 1 H NMR (400MHz, CDCl 3 )δ7.97–7.94(m,2H),7.45–7.47(m,2H),4.65–4.59(m,1H),4.42–4.37(m,1H),4.20–4.14(m,1H),2.99( s,1H),2.52–2.19(m,2H),2.08-1.97(m,1H),1.93–1.85(m,1H). 13 C NMR (100MHz, CDCl 3)δ167.06, 156.96, 129.47, 126.93, 126.14, (q, J=276Hz), 124.76, 62.96 (q, J=3Hz), 61.01, 41.11, (q, J=27Hz), 36.31, 35.05, 31.02. 19 F...

Embodiment 2

[0044]

[0045] Add 1b (0.2mmol, 35.3mg), 2a (0.8mmol, 131.5mg), Mn(acac) once in the test tube 3 (0.02mmol, 7.3mg), 1,4-dioxane (3.0mL) and acetone (1.0mL). Then the system was stirred for 24 hours under 40W blue light LED irradiation and room temperature in the air, then directly added 2.0mL ethyl acetate to dilute, removed the solvent with a rotary evaporator, adsorbed on silica gel, and obtained the product 3b through simple column chromatography. The yield is 75%. The main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.

[0046] 1 H NMR (400MHz, CDCl 3 )δ8.03(d, J=8.0Hz, 2H), 7.58(t, J=16.0Hz, 1H), 7.45(t, J=16.0Hz, 2H), 4.68–4.62(m, 1H), 4.44– 4.39(m,1H),4.21–4.16(m,1H),2.70(s,1H),2.47–2.23(m,2H),2.07-1.99(m,1H),1.95–1.87(m,1H). 13 C NMR (100MHz, CDCl 3 )δ167.00, 133.23, 129.76, 129.60, 128.46, 126.14, (q, J = 276Hz), 63.04 (q, J = 3Hz), 61.22, 41....

Embodiment 3

[0048]

[0049] Add 1c (0.2mmol, 38.9mg), 2a (0.8mmol, 131.5mg), Mn(acac) once in the test tube 3 (0.02mmol, 7.3mg), 1,4-dioxane (3.0mL) and acetone (1.0mL). Then the system was stirred for 24 hours under 40W blue light LED irradiation and room temperature in the air, then directly added 2.0mL ethyl acetate to dilute, removed the solvent with a rotary evaporator, adsorbed on silica gel, and obtained the product 3c through simple column chromatography. The yield was 76%. The main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.

[0050] 1 H NMR (400MHz, CDCl 3 )δ8.06–8.03(m,2H),7.12(t,J=16.0Hz,2H),4.66–4.60(m,1H),4.44–4.38(m,1H),4.20–4.15(m,1H) ,2.65(s,1H),2.49–2.23(m,2H),2.06-1.98(m,1H),1.95–1.86(m,1H). 13 C NMR (100MHz, CDCl 3 ( q, J=3Hz), 61.34, 41.19 (q, J=26Hz), 36.24. 19 F NMR (376MHz, CDCl 3 )δ=-63.47(s,3F),-105.10(s,1F).HRMS(ESI-TOF):Anal.Calcd....

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Abstract

The invention relates to a preparation method of visible-light-catalyzed [beta]-trifluoromethyl alcohol. The method comprises the following steps: by using visible light as an energy source, aliphaticolefin and sodium trifluoromethanesulfinate as reaction substrates, organic manganese salt as a catalyst and oxygen-containing atmosphere as an oxidant, performing reacting in an organic solvent at room temperature to obtain [beta]-trifluoromethyl alcohol. The method is greener and safer, is suitable for various substituted aliphatic olefins, and is mild and efficient in reaction.

Description

technical field [0001] The invention relates to the technical field of synthesis of β-trifluoromethyl alcohol, in particular to a preparation method of β-trifluoromethyl alcohol catalyzed by visible light. Background technique [0002] The introduction of trifluoromethyl into organic compounds can significantly change the acidity, dipole moment, polarity, lipophilicity, and chemical and metabolic stability of the compound. Compounds containing trifluoromethyl have been used in the fields of medicine, pesticides and materials. be widely used. The difunctionalization reaction of alkenes can construct two new functional groups through one-step transformation, which has important applications in synthesis. At present, the trifluoromethyl hydroxylation reaction of olefins is mostly a thermal reaction, which has disadvantages such as expensive reagents, harsh reaction conditions, excessive use of oxidants, limited range of substrates, and low yields. For example: [0003] (1) M...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C67/293C07C69/76C07C69/78C07C69/92C07C201/12C07C205/57C07D209/48C07D307/68C07D333/38C07B41/02
CPCC07C67/293C07C201/12C07D209/48C07D307/68C07D333/38C07B41/02C07C69/76C07C69/78C07C69/92C07C205/57
Inventor 万小兵龙文号廉鹏程李晶晶
Owner SUZHOU UNIV
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