CN111205185B - Preparation method of beta-trifluoromethyl alcohol catalyzed by visible light - Google Patents

Preparation method of beta-trifluoromethyl alcohol catalyzed by visible light Download PDF

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CN111205185B
CN111205185B CN202010148307.1A CN202010148307A CN111205185B CN 111205185 B CN111205185 B CN 111205185B CN 202010148307 A CN202010148307 A CN 202010148307A CN 111205185 B CN111205185 B CN 111205185B
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CN111205185A (en
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万小兵
龙文号
廉鹏程
李晶晶
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Suzhou University
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/293—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
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    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
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    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
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    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
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    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
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Abstract

The invention relates to a preparation method of beta-trifluoromethyl alcohol catalyzed by visible light, which comprises the following steps: the beta-trifluoromethyl alcohol is obtained by reacting in an organic solvent at room temperature by using visible light as an energy source, using aliphatic olefin and sodium trifluoromethyl sulfinate as reaction substrates, using organic manganese salt as a catalyst and using an oxygen-containing atmosphere as an oxidant. The method is more green and safe, is suitable for various substituted aliphatic olefins, and has mild and efficient reaction.

Description

Preparation method of beta-trifluoromethyl alcohol catalyzed by visible light
Technical Field
The invention relates to the technical field of synthesis of beta-trifluoromethyl alcohol, in particular to a preparation method of beta-trifluoromethyl alcohol catalyzed by visible light.
Background
The introduction of trifluoromethyl into organic compounds can significantly change the acidity, dipole moment, polarity, lipophilicity and chemical and metabolic stability of the compounds, and the compounds containing trifluoromethyl are widely applied in the fields of medicines, pesticides, materials and the like. The double functionalization reaction of olefin can construct two new functional groups through one-step conversion, and has important application in synthesis. At present, the trifluoromethyl hydroxylation reaction of olefin is mostly thermal reaction, and has the defects of expensive reagent, harsh reaction conditions, excessive oxidant consumption, limited substrate range, low yield and the like. For example:
(1) munetaka Akita et al reported the preparation of beta-trifluoromethylols using S- (trifluoromethyl) dibenzothiophene-phosphonium tetrafluoroborate and an olefin under the action of visible light over an iridium catalyst. The system needs expensive trifluoromethyl reagent and iridium catalyst, which greatly increases the reaction cost. In addition, the reaction can only realize the hydroxyl trifluoromethylation of aromatic olefin, and is not suitable for aliphatic olefin (see: Munetaka Akita; Angew. chem. int. Ed.2012,51, 9567-;
(2) XuzhongLuo et al prepared beta-trifluoromethylalcohols by reacting sodium trifluoromethylsulfinate with olefins. The process requires the use of dangerous and large excess of tert-butyl hydroperoxide and benzoquinone as oxidants, has low selectivity of reaction (obtaining a mixture of beta-trifluoromethyl alcohol and beta-trifluoromethyl ketone), and can only be applied to aromatic olefins (see: Luo Xuzhong; Synlett2014,25, 1307-1311);
(3) david a. vicic et al reported the preparation of β -trifluoromethylols using sodium trifluoromethylsulfinate reacted with olefins with manganese as the catalyst. However, it is only applicable to aromatic olefins, and the reaction has low yield and poor selectivity (a mixture of beta-trifluoromethyl alcohol and beta-trifluoromethyl ketone is obtained) (see: David A. Vicic; J. org. chem.2015,80, 6639-6648);
(4) FengLiu et al reported that beta-trifluoromethyl alcohol was synthesized using sodium trifluoromethylsulfinate and olefin in dimethyl sulfoxide as solvent and trifluoroacetic anhydride as additive. However, the yield of this reaction is low and the substrate range is narrow (the substrate is mainly an α, α -disubstituted olefin) (see: Liu Feng; Green chem.2019,21, 2983-2987).
(5) Recently, ZhigangZhao et al reported that beta-trifluoromethylols were synthesized using trifluoroiodomethane and olefins under visible light conditions. However, the reaction uses expensive, inconvenient and toxic trifluoroiodomethane gas (see: ZHao zhong; Chin. J. chem.2019,37, 597-604).
In view of the above, the currently reported methods for synthesizing β -trifluoromethyl alcohols generally have the following disadvantages: most of the raw materials are thermal reactions, so that the energy consumption is greatly accelerated, and the development trend of future organic chemistry is not met; the use of equivalent amounts of peroxide is dangerous and does not meet the requirements of green chemistry; reagents with higher price are needed, so that the reaction cost is increased; most are only used for aromatic olefins and the selectivity of the reaction itself is poor. Therefore, it is important to develop a method with green, low cost, safety, environmental protection and simple operation to effectively synthesize the beta-trifluoromethyl alcohol compound.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a preparation method of beta-trifluoromethyl alcohol by visible light catalysis.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention relates to a preparation method of visible light catalyzed beta-trifluoromethyl alcohol, which comprises the following steps:
visible light is used as energy, aliphatic olefin and sodium trifluoromethanesulfonate are used as reaction substrates, organic manganese salt is used as a catalyst, oxygen-containing atmosphere is used as an oxidant, and the reaction is carried out in an organic solvent at 23-25 ℃ to obtain beta-trifluoromethyl alcohol; the aliphatic olefin comprises a carbon-carbon double bond and a C9-C15 aliphatic chain covalently linked to the carbon-carbon double bond.
Further, the aliphatic olefin has the structural formula
Figure BDA0002401526650000021
The structural formula of the beta-trifluoromethyl alcohol is shown in the specification
Figure BDA0002401526650000022
Wherein n is 1-4;
R1selected from hydrogen or methyl;
R2selected from hydrogen, phthalimido, substituted or unsubstituted C9-C15 aromatic acyloxy or C9-C15 aromatic thioester.
Further, the aromatic acyloxy group is selected from acyloxy groups of phenyl, naphthyl, furyl or thienyl; the substituent on the substituted aromatic acyloxy is selected from C1-C6 alkyl, C1-C4 alkoxy, nitro, phenyl or halogen.
Further, the substituents on the substituted aryl groups are selected from methyl, t-butyl, methoxy, nitro, phenyl, fluoro, chloro or bromo.
Further, the aromatic thioester group is selected from phenyl-containing thioester groups.
Preferably, n is 1,2 or 4.
In the invention, the structural formula of the substrate sodium trifluoromethanesulfonate is as follows:
Figure BDA0002401526650000023
preferably, n is 1,2 or 4; r1Selected from hydrogen or methyl; r2Selected from phthalimide group,
Figure BDA0002401526650000031
Figure BDA0002401526650000032
Wherein R 'and R' are each independently selected from hydrogen, methyl, tert-butyl, methoxy, nitro, phenyl, fluoro, chloro or bromo.
Further, the organic manganese salt is manganese acetylacetonate (Mn (acac)3)。
Further, the organic manganese salt accounts for 10 percent of the molar weight of the aliphatic olefin.
Further, the oxygen-containing atmosphere is air or pure oxygen. Preferably, the oxygen-containing atmosphere is air. The air as the oxidant has the advantages of safety, greenness, low price and the like.
Further, sodium trifluoromethanesulfonate was 4 times the molar amount of the aliphatic olefin.
Further, the visible light is blue light, the blue light LED lamp is adopted to provide the visible light, the power of the blue light LED lamp is 18-40W, the reaction time is 12-24 hours, and preferably the reaction time is 24 hours under 40W.
Further, the organic solvent is one or more of ethyl acetate, 1, 2-dichloroethane, 1, 4-dioxane, nitromethane, acetonitrile, acetone and petroleum ether. Preferably, the organic solvent is 1, 4-dioxane and acetone.
Further, the reaction is completed, and the purification steps of diluting with ethyl acetate, removing the solvent and carrying out column chromatography are also included.
By the scheme, the invention at least has the following advantages:
1. the technology of the invention is carried out under the condition of visible light, compared with the traditional thermal reaction, the visible light catalytic reaction has the advantages of wide light energy source, low cost, greenness, cleanness, no toxicity, harmlessness, mild reaction condition and wide substrate application range, and is the future trend of organic chemistry development;
2. the technology is carried out under the condition of oxygen-containing atmosphere, and oxygen is taken as an oxidant, so that compared with other organic or inorganic oxidants, the oxygen-containing oxidant has the advantages of low price, wide source and higher safety;
3. the technology of the invention realizes the trifluoromethyl hydroxylation of aliphatic olefin compounds, while most of the prior art can only realize the trifluoromethyl hydroxylation of aromatic olefins or alpha, alpha-disubstituted aliphatic olefins, and the common trifluoromethyl hydroxylation of terminal unsubstituted aliphatic olefin compounds has relatively few reports;
4. the photocatalyst used by the technology of the invention is organic manganese salt, compared with the traditional expensive noble metal catalyst and the organic molecular catalyst with a complex structure, the organic manganese salt is commercialized and has low price, which is beneficial to the industrial amplification application;
5. the reaction is carried out at room temperature, heating is not needed, and compared with the traditional thermal reaction, the reaction is safer and more reliable.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a preferred embodiment of the present invention and is described in detail below.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The light source, the sodium trifluoromethanesulfonate, the catalyst and the organic solvent are all commercial products and can be directly purchased and obtained. The aliphatic olefin can be prepared by using carboxylic acid or amine substances as starting materials respectively according to different structures.
Example one
Figure BDA0002401526650000041
Add 1a (0.2mmol,46.5mg), 2a (0.8mmol,131.5mg), Mn (acac) in tube in one portion3(0.02mmol,7.3mg),1, 4-dioxane (3.0mL) and acetone (1.0 mL). Then the system is stirred for 24 hours under the conditions of 40W blue light LED irradiation and room temperature in the air, 2.0mL ethyl acetate is directly added for dilution, a rotary evaporator is used for removing the solvent, silica gel is used for adsorption, and the product 3a is obtained through simple column chromatography, wherein the yield is 80%. The main test data of the prepared product are as follows, and the actual synthesized product is consistent with the theoretical analysis through analysis.
1H NMR(400MHz,CDCl3)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).13C NMR(100MHz,CDCl3)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),36.31,35.05,31.02.19F NMR(376MHz,CDCl3)δ＝-63.44(s,3F).HRMS(ESI-TOF):Anal.Calcd.For C16H21F3O3+Na+:341.1335,Found:341.1346；IR(neat,cm-1):υ3446,2966,1701,1609,1458,1275,1190,1121,1018.
Example two
Figure BDA0002401526650000042
Add 1b (0.2mmol,35.3mg), 2a (0.8mmol,131.5mg), Mn (acac) in tube in one portion3(0.02mmol,7.3mg),14-dioxane (3.0mL) and acetone (1.0 mL). Then the system is stirred for 24 hours under the conditions of 40W blue light LED irradiation and room temperature in the air, 2.0mL of ethyl acetate is directly added for dilution, a rotary evaporator is used for removing the solvent, silica gel is used for adsorption, and the product 3b is obtained through simple column chromatography, wherein the yield is 75%. The main test data of the prepared product are as follows, and the actual synthesized product is consistent with the theoretical analysis through analysis.
1H NMR(400MHz,CDCl3)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).13C NMR(100MHz,CDCl3)δ167.00,133.23,129.76,129.60,128.46,126.14,(q,J＝276Hz),63.04(q,J＝3Hz),61.22,41.17,(q,J＝27Hz),36.28.19F NMR(376MHz,CDCl3)δ＝-63.45(s,3F).HRMS(ESI-TOF):Anal.Calcd.ForC12H13F3O3+Na+:285.0709,Found:285.0701；IR(neat,cm-1):υ3463,2963,1716,1602,1453,1387,1272,1146,1070.
EXAMPLE III
Figure BDA0002401526650000051
Add 1c (0.2mmol,38.9mg), 2a (0.8mmol,131.5mg), Mn (acac) in tube in one portion3(0.02mmol,7.3mg),1, 4-dioxane (3.0mL) and acetone (1.0 mL). Then the system is stirred for 24 hours under the conditions of 40W blue light LED irradiation and room temperature in the air, 2.0mL ethyl acetate is directly added for dilution, a rotary evaporator is used for removing the solvent, silica gel is used for adsorption, and the product 3c is obtained through simple column chromatography, wherein the yield is 76%. The main test data of the prepared product are as follows, and the actual synthesized product is consistent with the theoretical analysis through analysis.
1H NMR(400MHz,CDCl3)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).13C NMR(100MHz,CDCl3)δ167.18,165.34(d,J＝137Hz),132.19(d,J＝9Hz),126.13(q,J＝276Hz),126.02(d,J＝3Hz),115.64(d,J＝22Hz),63.01(q,J＝3Hz),61.34,41.19(q,J＝26Hz),36.24.19F NMR(376MHz,CDCl3)δ＝-63.47(s,3F),-105.10(s,1F).HRMS(ESI-TOF):Anal.Calcd.For C12H12F4O3+Na+:303.0615,Found:303.0619；IR(neat,cm-1):υ3481,2963,1715,1603,1508,1270,1115.
Example four
Figure BDA0002401526650000061
Add 1d (0.2mmol,42.2mg), 2a (0.8mmol,131.5mg), Mn (acac) all at once to the tube3(0.02mmol,7.3mg),1, 4-dioxane (3.0mL) and acetone (1.0 mL). Then the system is stirred for 24 hours under the conditions of 40W blue light LED irradiation and room temperature in the air, 2.0mL of ethyl acetate is directly added for dilution, a rotary evaporator is used for removing the solvent, silica gel is used for adsorption, and the product 3d is obtained through simple column chromatography, wherein the yield is 71%. The main test data of the prepared product are as follows, and the actual synthesized product is consistent with the theoretical analysis through analysis.
1H NMR(400MHz,CDCl3)δ7.96(d,J＝8.5Hz,2H),7.42(d,J＝8.7Hz,2H),4.66–4.60(m,1H),4.44–4.39(m,1H),4.20–4.15(m,1H),2.63(s,1H),2.47–2.23(m,2H),2.06-1.98(m,1H),1.95–1.87(m,1H).13C NMR(100MHz,CDCl3)δ166.10,139.73,130.93,128.82,128.81,126.12(q,J＝276Hz),63.00(q,J＝3Hz),61.45,41.20(q,J＝27Hz),36.19.19F NMR(376MHz,CDCl3)δ＝-63.46(s,3F).HRMS(ESI-TOF):Anal.Calcd.For C12H12ClF3O3+Na+:319.0319,Found:319.0325；IR(neat,cm-1):υ3463,2961,1716,1595,1489,1401,1270,1117,1091,1014.
EXAMPLE five
Figure BDA0002401526650000062
Add 1e (0.2mmol,44.3mg), 2a (0.8mmol,131.5mg), Mn (acac) all at once to the tube3(0.02mmol,7.3mg),1, 4-dioxane (3.0mL) and acetone (1.0 mL). Then the system is stirred for 24 hours under the conditions of 40W blue light LED irradiation and room temperature in the air, 2.0mL of ethyl acetate is directly added for dilution, a rotary evaporator is used for removing the solvent, silica gel is used for adsorption, and the product 3e is obtained through simple column chromatography, wherein the yield is 81%. The main test data of the prepared product are as follows, and the actual synthesized product is consistent with the theoretical analysis through analysis.
1H NMR(400MHz,CDCl3)δ8.85–8.84(m,1H),8.45–8.35(m,2H),7.68(t,J＝8.0Hz,1H),4.72–4.65(m,1H),4.54–4.49(m,1H),4.23–4.18(m,1H),2.56(s,1H),2.47–2.26(m,2H),2.12–2.04(m,1H),2.01–1.92(m,1H).13C NMR(100MHz,CDCl3)δ164.78,148.25,135.26,131.59,129.73,127.58,126.09(q,J＝275Hz),124.55,62.93(q,J＝3Hz),62.16,41.25(q,J＝27Hz),36.00.19F NMR(376MHz,CDCl3)δ＝-63.44(s,3F).HRMS(ESI-TOF):Anal.Calcd.For C12H12F3NO5+Na+:330.0560,Found:330.0558；IR(neat,cm-1):υ3343,2963,1720,1528,1345,1244,1129,1065.
EXAMPLE six
Figure BDA0002401526650000071
Add 1f (0.2mmol,44.3mg), 2a (0.8mmol,131.5mg), Mn (acac) in tube in one portion3(0.02mmol,7.3mg),1, 4-dioxane (3.0mL) and acetone (1.0 mL). Then the system is stirred for 24 hours under the conditions of 40W blue light LED irradiation and room temperature in the air, 2.0mL of ethyl acetate is directly added for dilution, a rotary evaporator is used for removing the solvent, silica gel is used for adsorption, and the product 3f can be obtained through simple column chromatography, wherein the yield is 82%. The main test data of the prepared product are as follows, and the actual synthesized product is consistent with the theoretical analysis through analysis.
1H NMR(400MHz,CDCl3)δ7.98(d,J＝8.9Hz,2H),6.92(d,J＝8.9Hz,2H),4.65–4.59(m,1H),4.16(m,1H),3.86(s,3H),2.88(s,1H),2.40–2.22(m,2H),2.01-1.97(m,1H),1.92–1.84(m,1H).13C NMR(100MHz,CDCl3)δ166.78,163.58,131.65,126.15(q,J＝275Hz),120.77,113.69,63.00(q,J＝3Hz),60.90,55.41,41.11(q,J＝26Hz),36.39.19F NMR(376MHz,CDCl3)δ＝-63.45(s,3F).HRMS(ESI-TOF):Anal.Calcd.For C13H15F3O4+Na+:315.0815,Found:315.0809；IR(neat,cm-1):υ3467,2922,1708,1605,1512,1250,1102,1025.
EXAMPLE seven
Figure BDA0002401526650000072
Into a test tube were added 1g (0.2mmol,38.1mg), 2a (0.8mmol,131.5mg), Mn (acac) in one portion3(0.02mmol,7.3mg),1, 4-dioxane (3.0mL) and acetone (1.0 mL). Then the system is stirred for 24 hours under the conditions of 40W blue light LED irradiation and room temperature in the air, 2.0mL of ethyl acetate is directly added for dilution, a rotary evaporator is used for removing the solvent, silica gel is used for adsorption, and the product 3g can be obtained through simple column chromatography, wherein the yield is 81%. The main test data of the prepared product are as follows, and the actual synthesized product is consistent with the theoretical analysis through analysis.
1H NMR(400MHz,CDCl3)δ7.90–7.88(m,1H),7.41(t,J＝7.1Hz,1H),7.25(dd,J＝8.9,4.9Hz,2H),4.65–4.59(m,1H),4.41-4.36(m,1H),4.20-4.15(m,1H),2.68(s,1H),2.59(s,3H),2.47–2.22(m,2H),2.06-1.97(m,1H),1.94–1.86(m,1H).13C NMR(100MHz,CDCl3)δ167.95,140.32,132.24,131.80,130.49,129.17,126.15(q,J＝275Hz),125.79,63.11(q,J＝3Hz),60.95,41.17(q,J＝27Hz),36.31,21.72.19F NMR(376MHz,CDCl3)δ＝-63.47(s,3F).HRMS(ESI-TOF):Anal.Calcd.For C13H15F3O3+Na+:299.0866,Found:299.0874；IR(neat,cm-1):υ3511,2960,1700,1451,1245,1131,1065.
Example eight
Figure BDA0002401526650000081
Add 1h (0.2mmol,50.5mg), 2a (0.8mmol,131.5mg), Mn (acac) all at once to the tube3(0.02mmol,7.3mg),1, 4-dioxane (3.0mL) and acetone (1.0 mL). Then the system is stirred for 24 hours under the conditions of 40W blue light LED irradiation and room temperature in the air, 2.0mL of ethyl acetate is directly added for dilution, a rotary evaporator is used for removing the solvent and silica gel adsorption, and the product can be obtained by simple column chromatography for 3 hours, wherein the yield is 80%. The main test data of the prepared product are as follows, and the actual synthesized product is consistent with the theoretical analysis through analysis.
1H NMR(400MHz,CDCl3)δ7.82(dd,J＝7.7,1.2Hz,1H),7.54(td,J＝7.5,1.4Hz,1H),7.42-7.32(m,7H),4.23–4.11(m,2H),3.59–3.51(m,1H),2.19–1.95(m,3H),1.50-1.46(m,2H).13C NMR(100MHz,CDCl3)δ169.27,142.06,141.72,131.40,130.88,130.64,129.86,128.37,128.23,127.33,127.12,126.08(q,J＝276Hz),62.47(q,J＝3Hz),61.00,41.00(q,J＝27Hz),35.41.19F NMR(376MHz,CDCl3)δ＝-63.33(s,3F).HRMS(ESI-TOF):Anal.Calcd.ForC18H17F3O3+Na+:361.1022,Found:361.1023；IR(neat,cm-1):υ3482,2962,1714,1385,1249,1123.
Example nine
Figure BDA0002401526650000082
Add 1i (0.2mmol,40.3mg), 2a (0.8mmol,131.5mg), Mn (acac) in tube in one portion3(0.02mmol,7.3mg),1, 4-dioxane (3.0mL) and acetone (1.0 mL). Then the system is stirred for 24 hours under the conditions of 40W blue light LED irradiation and room temperature in the air, 2.0mL of ethyl acetate is directly added for dilution, a rotary evaporator is used for removing the solvent, silica gel is used for adsorption, and the product 3i can be obtained through simple column chromatography, wherein the yield is 80%. Main test data of the products obtainedAs shown below, the analysis revealed that the actual synthesized product was consistent with the theoretical analysis.
1H NMR(400MHz,CDCl3)δ7.82(dd,J＝5.4,3.1Hz,2H),7.54(dd,J＝5.5,3.0Hz,2H),4.02–3.85(m,3H),3.29(d,J＝4.5Hz,1H),2.46–2.32(m,1H),2.21-2.14(m,1H),1.92-1.74(m,2H).13C NMR(100MHz,CDCl3)δ168.91,134.23,131.84,126.01(q,J＝275Hz),123.48,62.94(q,J＝3Hz),40.83(q,J＝27Hz),36.04,34.01.19F NMR(376MHz,CDCl3)δ＝-63.48(s,3F).HRMS(ESI-TOF):Anal.Calcd.For C13H12F3NO3+Na+:310.0661,Found:310.0667；IR(neat,cm-1):υ3462,2943,1681,1375,1261,1140,1008.
Example ten
Figure BDA0002401526650000091
Add 1j (0.2mmol,33.3mg), 2a (0.8mmol,131.5mg), Mn (acac) in tube in one portion3(0.02mmol,7.3mg),1, 4-dioxane (3.0mL) and acetone (1.0 mL). Then the system is stirred for 24 hours under the conditions of 40W blue light LED irradiation and room temperature in the air, 2.0mL of ethyl acetate is directly added for dilution, a rotary evaporator is used for removing the solvent, silica gel is used for adsorption, and the product 3j can be obtained through simple column chromatography, wherein the yield is 63%. The main test data of the prepared product are as follows, and the actual synthesized product is consistent with the theoretical analysis through analysis.
1H NMR(400MHz,CDCl3)δ7.59(d,J＝0.8Hz,1H),7.20(d,J＝3.5Hz,1H),6.53(dd,J＝3.5,1.7Hz,1H),4.65–4.59(m,1H),4.43–4.37(m,1H),4.20–4.15(m,1H),2.69(d,J＝4.5Hz,1H),2.44–2.25(m,2H),2.07-1.97(m,1H),1.95-1.1.85(m,1H).13C NMR(100MHz,CDCl3)δ158.90,146.59,144.24,126.12(q,J＝277Hz),118.43,111.97,63.10(q,J＝3Hz),61.30,41.14(q,J＝27Hz),36.09.19F NMR(376MHz,CDCl3)δ＝-63.48(s,3F).HRMS(ESI-TOF):Anal.Calcd.For C10H11F3O4+Na+:275.0502,Found:275.0499；IR(neat,cm-1):υ3446,2928,1717,1474,1298,1148.
EXAMPLE eleven
Figure BDA0002401526650000101
Add 1k (0.2mmol,36.5mg), 2a (0.8mmol,131.5mg), Mn (acac) in tube in one portion3(0.02mmol,7.3mg),1, 4-dioxane (3.0mL) and acetone (1.0 mL). Then the system is stirred for 24 hours under the conditions of 40W blue light LED irradiation and room temperature in the air, 2.0mL ethyl acetate is directly added for dilution, a rotary evaporator is used for removing the solvent, silica gel is used for adsorption, and a product 3k is obtained through simple column chromatography, wherein the yield is 79%. The main test data of the prepared product are as follows, and the actual synthesized product is consistent with the theoretical analysis through analysis.
1H NMR(400MHz,CDCl3)δ7.81(dd,J＝3.8,1.2Hz,1H),7.58(dd,J＝5.0,1.2Hz,1H),7.11(dd,J＝5.0,3.8Hz,1H),4.63–4.56(m,1H),4.42–4.36(m,1H),4.20–4.16(m,1H),2.79(s,1H),2.44–2.26(m,2H),2.04-1.97(m,1H),1.93-1.1.85(m,1H).13C NMR(100MHz,CDCl3)δ162.59,133.82,133.21,132.81,127.92,126.18(q,J＝275Hz),63.04(q,J＝3Hz),61.43,41.17(q,J＝27Hz),36.20.19F NMR(376MHz,CDCl3)δ＝-63.46(s,3F).HRMS(ESI-TOF):Anal.Calcd.For C10H11F3O3S+Na+:291.0273,Found:291.0269；IR(neat,cm-1):υ3446,1707,1419,1264,1150,1098.
Example twelve
Figure BDA0002401526650000102
1l (0.2mmol,45.3mg), 2a (0.8mmol,131.5mg), Mn (acac)3(0.02mmol,7.3mg),1, 4-dioxane (3.0mL) and acetone (1.0 mL). Then the system is stirred for 24 hours under the conditions of 40W blue light LED irradiation and room temperature in the air, 2.0mL of ethyl acetate is directly added for dilution, a rotary evaporator is used for removing the solvent,Silica gel adsorption and simple column chromatography to obtain 3l of product with yield of 52%. The main test data of the prepared product are as follows, and the actual synthesized product is consistent with the theoretical analysis through analysis.
1H NMR(400MHz,CDCl3)δ8.58(s,1H),7.96(ddd,J＝36.4,18.5,5.1Hz,4H),7.57(dtd,J＝16.2,6.9,1.3Hz,2H),4.73–4.67(m,1H),4.50–4.44(m,1H),4.25–4.20(m,1H),2.80(d,J＝4.3Hz,1H),2.47–2.28(m,2H),2.11-2.03(m,1H),1.99-1.1.90(m,1H).13C NMR(100MHz,CDCl3)δ167.17,135.61,132.42,131.21,129.35,128.42,128.27,127.76,126.95,126.75,126.17(q,J＝275Hz),125.06,63.07(q,J＝3Hz),61.36,41.18(q,J＝26Hz),36.34.19F NMR(376MHz,CDCl3)δ＝-63.40(s,3F).HRMS(ESI-TOF):Anal.Calcd.For C16H15F3O3+Na+:335.0866,Found:335.0862；IR(neat,cm-1):υ3463,2925,1713,1468,1278,1128,1098.
EXAMPLE thirteen
Figure BDA0002401526650000111
Add 1m (0.2mmol,38.5mg), 2a (0.8mmol,131.5mg), Mn (acac) in tube in one portion3(0.02mmol,7.3mg),1, 4-dioxane (3.0mL) and acetone (1.0 mL). Then the system is stirred for 24 hours under the conditions of 40W blue light LED irradiation and room temperature in the air, 2.0mL of ethyl acetate is directly added for dilution, a rotary evaporator is used for removing the solvent, silica gel is used for adsorption, and the product of 3m can be obtained through simple column chromatography, wherein the yield is 63%. The main test data of the prepared product are as follows, and the actual synthesized product is consistent with the theoretical analysis through analysis.
1H NMR(400MHz,CDCl3)δ7.98(dd,J＝8.4,1.2Hz,2H),7.61-7.57(m,1H),7.48-7.44(m,1H),4.11–4.06(m,1H),3.36–3.29(m,1H),3.19–3.12(m,1H),3.03(d,J＝4.3Hz,1H),2.42–2.21(m,2H),1.97-1.78(m,2H).13C NMR(100MHz,CDCl3)δ193.20,136.64,133.69,128.66,127.30,126.15(q,J＝276Hz),64.04(q,J＝3Hz),40.92(q,J＝27Hz),37.24,24.75.19F NMR(376MHz,CDCl3)δ＝-63.41(s,3F).HRMS(ESI-TOF):Anal.Calcd.ForC12H13F3O2S+Na+:301.0481,Found:301.0479；IR(neat,cm-1):υ3446,2926,1660,1448,1206,1109.
Example fourteen
Figure BDA0002401526650000112
1n (0.2mmol,58.0mg), 2a (0.8mmol,131.5mg), Mn (acac)3(0.02mmol,7.3mg),1, 4-dioxane (3.0mL) and acetone (1.0 mL). Then the system is stirred for 24 hours under the conditions of 40W blue light LED irradiation and room temperature in the air, 2.0mL of ethyl acetate is directly added for dilution, a rotary evaporator is used for removing the solvent, silica gel is used for adsorption, and the product 3n can be obtained through simple column chromatography, wherein the yield is 81%. The main test data of the prepared product are as follows, and the actual synthesized product is consistent with the theoretical analysis through analysis.
1H NMR(400MHz,CDCl3)δ7.93(d,J＝2.4Hz,1H),7.54(dd,J＝8.6,2.4Hz,1H),7.32(d,J＝8.6Hz,1H),4.64–4.58(m,1H),4.49–4.44(m,1H),4.25–4.20(m,1H),2.59(s,1H),2.38–2.23(m,2H),2.04-1.99(m,1H),1.96-1.88(m,1H).13C NMR(100MHz,CDCl3)δ164.71,135.60,134.11,132.55,132.49,131.35,126.10(q,J＝275Hz),120.23,64.04(q,J＝3Hz),62.27,41.22(q,J＝27Hz),35.87.19F NMR(376MHz,CDCl3)δ＝-63.44(s,3F).HRMS(ESI-TOF):Anal.Calcd.For C12H11BrClF3O3+Na+:396.9424,Found:396.9432；IR(neat,cm-1):υ3446,2926,1660,1448,1206,1109.
Example fifteen
Figure BDA0002401526650000121
Add 1o (0.2mmol,46.5mg), 2a (0.8mmol,131.5mg), Mn (acac) in tube in one portion3(0.02mmol,7.3mg),1, 4-dioxane (3.0mL) and acetone (1.0 mL). Then the system is stirred for 24 hours under the conditions of 40W blue light LED irradiation and room temperature in the air, 2.0mL of ethyl acetate is directly added for dilution, a rotary evaporator is used for removing the solvent, silica gel is used for adsorption, and the product 3o can be obtained through simple column chromatography, wherein the yield is 79%. The main test data of the prepared product are as follows, and the actual synthesized product is consistent with the theoretical analysis through analysis.
1H NMR(400MHz,CDCl3)δ7.99–7.97(m,2H),7.48(d,J＝8.5Hz,2H),4.33–4.26(m,2H),2.57–2.46(m,2H),1.46(s,3H),1.34(s,9H).13C NMR(100MHz,CDCl3)δ166.40,157.25,129.56,126.58,125.80,(q,J＝276Hz),125.53,70.58,69.77(q,J＝2Hz),41.94(q,J＝27Hz),35.11,31.04,24.34.19F NMR(376MHz,CDCl3)δ＝-60.40(s,3F).HRMS(ESI-TOF):Anal.Calcd.For C16H21F3O3+Na+:341.1335,Found:341.1330；IR(neat,cm-1):υ3446,2944,1701,1620,1458,1275,1190,1127.
Example sixteen
Figure BDA0002401526650000122
Add 1p (0.2mmol,51.1mg), 2a (0.8mmol,131.5mg), Mn (acac) in tube in one portion3(0.02mmol,7.3mg),1, 4-dioxane (3.0mL) and acetone (1.0 mL). Then the system is stirred for 24 hours under the conditions of 40W blue light LED irradiation and room temperature in the air, 2.0mL of ethyl acetate is directly added for dilution, a rotary evaporator is used for removing the solvent, silica gel is used for adsorption, and the product 3p can be obtained through simple column chromatography, wherein the yield is 80%. The main test data of the prepared product are as follows, and the actual synthesized product is consistent with the theoretical analysis through analysis.
1H NMR(400MHz,CDCl3)δ7.90(d,J＝8.6Hz,2H),7.60(d,J＝8.6Hz,2H),4.44–4.18(m,2H),2.64–2.34(m,3H),1.46(s,3H).13C NMR(100MHz,CDCl3)δ165.65,131.91,131.12,128.65,128.28,125.72(q,J＝276Hz),70.84,69.70(q,J＝2Hz),41.97(q,J＝27Hz),24.43.19FNMR(376MHz,CDCl3)δ＝-60.38(s,3F).HRMS(ESI-TOF):Anal.Calcd.ForC12H12BrF3O3+Na+:362.9814,Found:362.9818；IR(neat,cm-1):υ3463,2957,1713,1477,1267,1115,1016.
Example seventeen
Figure BDA0002401526650000131
Add 1q (0.2mmol,40.3mg), 2a (0.8mmol,131.5mg), Mn (acac) in tube in one portion3(0.02mmol,7.3mg),1, 4-dioxane (3.0mL) and acetone (1.0 mL). Then the system is stirred for 24 hours under the conditions of 40W blue light LED irradiation and room temperature in the air, 2.0mL of ethyl acetate is directly added for dilution, a rotary evaporator is used for removing the solvent, silica gel is used for adsorption, and the product 3q can be obtained through simple column chromatography, wherein the yield is 73%. The main test data of the prepared product are as follows, and the actual synthesized product is consistent with the theoretical analysis through analysis.
1H NMR(400MHz,CDCl3)δ7.89(dd,J＝5.5,3.0Hz,2H),7.77(dd,J＝5.5,3.1Hz,2H),3.87(s,2H),3.16(s,1H),2.43(q,J＝11.2Hz,2H),1.37(s,3H).13C NMR(100MHz,CDCl3)δ169.15,134.46,131.66,125.79(q,J＝276Hz),123.73,70.99(q,J＝2Hz),48.12,43.25(q,J＝27Hz),25.07.19F NMR(376MHz,CDCl3)δ＝-59.91(s,3F).HRMS(ESI-TOF):Anal.Calcd.ForC13H12F3NO3+Na+:310.0661,Found:310.0669；IR(neat,cm-1):υ3523,2976,1709,1383,1265,1192,1079.
EXAMPLE eighteen
Figure BDA0002401526650000132
Add 1r (0.2mmol,36.5mg), 2a (0.8mmol,131.5mg), Mn (acac) in tube in one portion3(0.02mmol,7.3mg),1, 4-dioxane (3.0mL) and acetone (1.0 mL). The system was then exposed to 40W blue LED radiation and airStirring for 24 hours at room temperature, directly adding 2.0mL ethyl acetate for dilution, removing the solvent by using a rotary evaporator, adsorbing by using silica gel, and carrying out simple column chromatography to obtain a product 3r with the yield of 80%. The main test data of the prepared product are as follows, and the actual synthesized product is consistent with the theoretical analysis through analysis.
1H NMR(400MHz,CDCl3)δ7.85(dd,J＝3.8,1.2Hz,1H),7.61(dd,J＝5.0,1.2Hz,1H),7.13(dd,J＝5.0,3.8Hz,1H),4.31–4.24(m,2H),2.49(q,J＝11.3Hz,3H),1.45(s,3H).13C NMR(100MHz,CDCl3)δ161.86,134.05,133.04,132.67,127.98,125.73(q,J＝276Hz),70.73,69.68(q,J＝2Hz),41.88(q,J＝27Hz),24.28.19F NMR(376MHz,CDCl3)δ＝-60.39(s,3F).HRMS(ESI-TOF):Anal.Calcd.For C10H11F3O3S+Na+:291.0273,Found:291.0279；IR(neat,cm-1):υ3482,2983,1699,1417,1254,1180,1093.
Example nineteen
Figure BDA0002401526650000141
Add 1s (0.2mmol,45.3mg), 2a (0.8mmol,131.5mg), Mn (acac) in tube in one portion3(0.02mmol,7.3mg),1, 4-dioxane (3.0mL) and acetone (1.0 mL). Then the system is stirred for 24 hours under the conditions of 40W blue light LED irradiation and room temperature in the air, 2.0mL ethyl acetate is directly added for dilution, a rotary evaporator is used for removing the solvent, silica gel is used for adsorption, and the product can be obtained by simple column chromatography for 3s, wherein the yield is 64%. The main test data of the prepared product are as follows, and the actual synthesized product is consistent with the theoretical analysis through analysis.
1H NMR(400MHz,CDCl3)δ8.59(s,1H),8.03(dd,J＝8.6,1.6Hz,1H),7.93(d,J＝8.1Hz,1H),7.86(d,J＝8.7Hz,2H),7.61–7.52(m,2H),4.40–4.33(m,2H),2.68(s,1H),2.55(q,J＝11.3Hz,2H),1.49(s,3H).13C NMR(100MHz,CDCl3)δ166.55,135.65,132.36,131.29,129.34,128.52,128.34,127.75,126.80,126.56,126.06(q,J＝276Hz),124.96,70.87,69.76(q,J＝2Hz),41.98(q,J＝27Hz),24.38.19F NMR(376MHz,CDCl3)δ＝-60.28(s,3F).HRMS(ESI-TOF):Anal.Calcd.For C16H15F3O3+Na+:335.0866,Found:335.0876；IR(neat,cm-1):υ3466,2984,1704,1631,1370,1260,1094.
Example twenty
Figure BDA0002401526650000151
Add 1t (0.2mmol,52.1mg), 2a (0.8mmol,131.5mg), Mn (acac) in tube in one portion3(0.02mmol,7.3mg),1, 4-dioxane (3.0mL) and acetone (1.0 mL). Then the system is stirred for 24 hours under the conditions of 40W blue light LED irradiation and room temperature in the air, 2.0mL of ethyl acetate is directly added for dilution, a rotary evaporator is used for removing the solvent, silica gel is used for adsorption, and the product 3t can be obtained through simple column chromatography, wherein the yield is 66%. The main test data of the prepared product are as follows, and the actual synthesized product is consistent with the theoretical analysis through analysis.
1H NMR(400MHz,CDCl3)δ7.96(d,J＝8.6Hz,2H),7.45(d,J＝8.6Hz,2H),4.33(t,J＝6.5Hz,2H),4.08–3.99(m,1H),2.35-2.20(m,2H),2.08(s,1H),1.86–1.73(m,2H),1.69–1.48(m,4H),1.34(s,9H).13C NMR(100MHz,CDCl3)δ166.72,156.59,129.39,126.40,(q,J＝216Hz),125.32,62.94(q,J＝3Hz),64.41,41.18(q,J＝26Hz),36.65,35.04,31.07,28.51,21.79.19F NMR(376MHz,CDCl3)δ＝-63.47(s,3F).HRMS(ESI-TOF):Anal.Calcd.For C18H25F3O3+Na+:369.1648,Found:369.1655；IR(neat,cm-1):υ3447,2958,1716,1271,1118,1016.
Example twenty one
Figure BDA0002401526650000152
1u (0.2mmol,56.7mg), 2a (0.8mmol,131.5mg), Mn (acac)3(0.02mmol,7.3mg),1, 4-dioxane (3.0mL) and acetone (1.0 mL). Then the system is stirred for 24 hours under the conditions of 40W blue light LED irradiation and room temperature in the air, 2.0mL of ethyl acetate is directly added for dilution, a rotary evaporator is used for removing the solvent, silica gel is used for adsorption, and the product 3u is obtained through simple column chromatography, wherein the yield is 65%. The main test data of the prepared product are as follows, and the actual synthesized product is consistent with the theoretical analysis through analysis.
1H NMR(400MHz,CDCl3)δ7.89(d,J＝8.6Hz,2H),7.58(d,J＝8.6Hz,2H),4.33(t,J＝6.5Hz,2H),4.07–4.02(m,1H),2.35–2.21(m,2H),2.00(d,J＝4.2Hz,1H),1.84–1.77(m,2H),1.69–1.49(m,4H).13C NMR(100MHz,CDCl3)δ165.93,131.70,131.05,129.16,128.03,126.37(q,J＝276Hz),65.91(q,J＝3Hz),64.93,41.22(q,J＝26Hz),36.60,28.44,21.77.19F NMR(376MHz,CDCl3)δ＝-60.48(s,3F).HRMS(ESI-TOF):Anal.Calcd.For C14H16BrF3O3+Na+:391.0127,Found:391.0128；IR(neat,cm-1):υ3460,2943,1700,1473,1245,1113.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A preparation method of visible light catalyzed beta-trifluoromethyl alcohol is characterized by comprising the following steps:
visible light is used as energy, aliphatic olefin and sodium trifluoromethanesulfonate are used as reaction substrates, organic manganese salt is used as a catalyst, oxygen-containing atmosphere is used as an oxidant, and the reaction is carried out in an organic solvent at 23-25 ℃ to obtain beta-trifluoromethyl alcohol; the aliphatic olefin comprises a carbon-carbon double bond and a C9-C15 aliphatic chain covalently linked to the carbon-carbon double bond.
2. The process according to claim 1, whereinCharacterized in that the structural formula of the aliphatic olefin is shown as
Figure DEST_PATH_IMAGE001
(ii) a The structural formula of the beta-trifluoromethyl alcohol is shown in the specification
Figure DEST_PATH_IMAGE002
；
Wherein n is 1-4;
R1selected from hydrogen or methyl;
R2selected from hydrogen, phthalimido, substituted or unsubstituted C9-C15 aromatic acyloxy or C9-C15 aromatic thioester; the substituent on the substituted aromatic acyloxy is selected from C1-C6 alkyl, C1-C4 alkoxy, nitro, phenyl or halogen.
3. The method according to claim 2, wherein the aromatic acyloxy group is selected from an acyloxy group of a phenyl group, a naphthyl group, a furyl group, or a thienyl group.
4. The method according to claim 2, wherein the aromatic thioester group is selected from phenyl-containing thioester groups.
5. The method of claim 2, wherein n is 1,2 or 4.
6. The method according to any one of claims 1 to 5, wherein the organic manganese salt is manganese acetylacetonate; the organic manganese salt accounts for 10 percent of the molar weight of the aliphatic olefin.
7. The method according to any one of claims 1 to 5, wherein the oxygen-containing atmosphere is air or pure oxygen.
8. The method according to any one of claims 1 to 5, wherein the molar amount of sodium trifluoromethanesulfonate is 4 times that of the aliphatic olefin.
9. The preparation method of any one of claims 1 to 5, wherein the visible light is blue light, a blue LED lamp is used for providing the visible light, and the power of the blue LED lamp is 18-40W.
10. The method according to any one of claims 1 to 5, wherein the organic solvent is one or more selected from the group consisting of ethyl acetate, 1, 2-dichloroethane, 1, 4-dioxane, nitromethane, acetonitrile, acetone, and petroleum ether.
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