CN112321385A - Preparation method of visible light catalyzed trifluoromethyl olefin derivative - Google Patents

Preparation method of visible light catalyzed trifluoromethyl olefin derivative Download PDF

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CN112321385A
CN112321385A CN202011171629.4A CN202011171629A CN112321385A CN 112321385 A CN112321385 A CN 112321385A CN 202011171629 A CN202011171629 A CN 202011171629A CN 112321385 A CN112321385 A CN 112321385A
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许孝良
任书剑
傅嘉辉
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Zhejiang University of Technology ZJUT
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Abstract

The invention discloses a preparation method of a trifluoromethyl olefin derivative by visible light catalysis, which takes alkyl boric acid and a Barbier-type trifluoromethyl derivative (BMBTD) modified by Boc as raw materials and inert gas N in a reaction solvent2Under the conditions of protection, visible light illumination, photocatalyst, Lewis base and inorganic base additive, and stirring at normal temperature and normal pressure, the tri-substituted trifluoromethyl olefin is prepared. The invention has no stoichiometric transition metal, and is at normal temperature and normal pressureThe reaction can be carried out, the usage amount of the catalyst is extremely low, and the reaction yield is high; and the method adopts visible light catalysis, has the characteristics of no pollution, environmental friendliness and the like, and has a wide prospect.

Description

Preparation method of visible light catalyzed trifluoromethyl olefin derivative
Technical Field
The invention belongs to the field of organic chemistry, and relates to a preparation method of a trifluoromethyl olefin derivative by visible light catalysis.
Background
The trifluoromethyl olefin derivative is an important organic synthesis intermediate, has important application value in synthesis, pharmaceutical chemistry and materials, and is widely used for synthesis of natural products and chiral and achiral drug molecules. The trifluoromethyl alkene is an important intermediate for preparing pharmacological active substances, such as cyhalothrin pesticide or antiestrogen agent such as famefen. In addition, because the C-F bond has large and stable energy, the introduction of trifluoromethyl in the dye can lead the dye to have particularly stable performance to light, not only has obvious improvement effect on the colorability and washability of the dye, but also has obvious improvement on the transparency, and the produced monoazo dye mainly adopts 3, 5-bis (trifluoromethyl) aniline and 2-chloro-5-trifluoromethyl aniline as aromatic fluoride of intermediates.
Because of the many possibilities of the double bond substituents, among them the polysubstituted trifluoromethylolefin derivatives shown below,
Figure BDA0002747476050000011
the synthesis method mainly comprises the following steps:
(1) the compound is synthesized by coupling reaction of transition metal catalysis and pre-functionalized olefin by common trifluoromethylating reagents such as Tognis reagent, Umemoto reagent, Langlois reagent, the Ruppert-Prakash reagent and the like, and can be specifically seen in the literature: (a) t.besset, d.cahard and x.pannecoucke, j.org.chem.,2014,79,413; (b) q.lin, x.xu and f.qing, j.org.chem.,2014,79,10434; (c) s.p.pitre, c.d.mcciernan, h.ismalli and j.c.scaiano, ACS cata., 2014,4,2530; (d) c.alonso, e.martinez de marigarta, g.rubiales and f.palacios, chem.rev.,2015,115,1847; (e) moon, y.k.moon, d.d.park, s.choi, y.you and e.j.cho, j.org.chem.,2019,84,12925, but this method has the disadvantage of requiring the use of expensive trifluoromethylating reagents and of being less atom economical and of synthesizing mostly disubstituted trifluoromethyl olefins;
(2) the alkynes are bifunctional by transition metal catalysts or in conjunction with other catalysts, see in particular the literature: (a) gao, X.Song, X.Liu and Y.LiangChem.eur.j.,2015,21,7648; (b) l.he, x.yang and g.c.tsui, j.org.chem.,2017,82,6192; (c) h.s.han, y.j.lee, y.s.jung and s.b.han, org.lett.,2017,19,1962; (d) y.yamamoto, j.org.chem.,2018,83,12775; (e) chen, l.wu, w.duan, t.wang, l.li, k.zhang, j.zhu, z.peng and f.xiong, j.org.chem.,2018,83,8607; (f) h.tang, y.kuang, j.zeng, x.li, w.zhou and y.lu, RSC adv.,2019,9,31474; (g) t.shang, j.zhang, y.zhang, f.zhang, x.li and g.zhu, org.lett.,2020,22,3667; (h) liu, x.zhang, g.kuang, n.lu, y.fu, y.peng, q.xiao and y.zhou, ACS omega, 2020,5,4158; (i) a series of c.tanaka, y.nakayama, y.konishi, t.koike and m.akita, org.lett.,2020,22,2801 can be constructedsp2-CF3Bonds, but highly depends on the transition metal catalyst which is complicated and expensive to prepare, and has harsh reaction conditions and poor substrate expansibility; (3) in recent years, there are continuously research reports on the photocatalytic implementation of Csp2-CF3The construction of the key, but still requires further exploration. From the viewpoint of green chemistry, development of a more convenient practical production method of a polysubstituted trifluoromethylolefin derivative is more urgently desired.
Disclosure of Invention
The invention aims to provide a method for synthesizing a tri-substituted trifluoromethyl olefin derivative shown in a formula (I) by using visible light to catalyze the reaction of alkyl boric acid and a Boc-modified Barbier-type trifluoromethyl derivative (BMBTD), wherein stoichiometric transition metal is not required to be used in the method, the use amount of a visible light catalyst is extremely low, the reaction yield is high, and the chemical synthesis way is expanded.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a trifluoromethyl olefin derivative catalyzed by visible light is disclosed, the trifluoromethyl olefin derivative is shown as a formula (I), in a reaction solvent, alkyl boric acid shown as a formula (III) and a Barbier-type trifluoromethyl derivative (BMBTD (Boc is tert-butyloxycarbonyl) shown as a formula (II) are used as raw materials, and N is inert gas2Under the conditions of protection, visible light illumination, visible light catalyst, Lewis base and inorganic base additive, stirring for 2-15h at normal temperature and normal pressure, and performing rotary evaporation and column chromatography on a reaction systemProcessing to obtain the tri-substituted trifluoromethyl olefin derivative shown in the formula (I); the photocatalyst is selected from the following compounds: eosin Y (Water soluble) eosin-Y, tris (2-phenylpyridine) iridium Ir (ppy)3Bis [2- (2, 4-difluorophenyl) -5-trifluoromethylpyridine][2-2' -bis (4-tert-butylpyridine)]Iridium bis (hexafluorophosphate) salt [ Ir (dFCF)3ppy)2(dtbbpy)]PF6Tris (2,2' -bipyrazinyl) ruthenium bis (hexafluoroborate) Ru (bpz)3(PF6)2Rhodamine B; the reaction solvent is selected from the following solvents: n-methylpyrrolidone, tetrahydrofuran, N-dimethylformamide, dichloromethane, 1, 2-dichloroethane, acetonitrile, dimethyl sulfoxide; the Lewis base is selected from the following: 1, 4-diazabicyclo [2.2.2]Octane, 4-dimethylaminopyridine, 1, 8-diazabicycloundec-7-ene, triphenylphosphine; the reaction additive is selected from the following components: sodium carbonate, potassium carbonate, cesium carbonate;
Figure BDA0002747476050000031
in the formula R1Is C1-C6 alkyl, aryl or substituted aryl; the aromatic ring of the substituted aryl is mono-substituted, R2Is C1-C6 alkyl; the substituted aryl is monosubstituted, and the substituent is selected from C1-C5 alkyl, fluorine, chlorine, bromine or methoxy.
Further, said R1Wherein, the aryl is phenyl or naphthyl; said R2Is an alkyl group.
Further, the photocatalyst is [ Ir (dFCF)3ppy)2(dtbbpy)]PF6The reaction solvent is 1, 2-dichloroethane, and the Lewis base is 1, 4-diazabicyclo [2.2.2]Octane and the additive is cesium carbonate.
Further, the volume amount of the organic solvent used was 12mL/mmol based on the amount of the raw material BMBTD substance represented by the formula (II).
Further, the ratio of the amount of the charged material of the raw material BMBTD represented by the formula (II) to the lewis base is 1:0.1 to 1.5, preferably 1: 0.25.
Further, the ratio of the amount of the BMBTD as the raw material represented by the formula (II) to the amount of the additive to be charged is 1:0.1 to 1.5, preferably 1: 0.25.
Further, the ratio of the BMBTD shown in the formula (II) to the alkyl boric acid shown in the formula (III) in the reaction material is 1: 1-2.5, preferably 1: 1.5.
Further, the ratio of the amount of the BMBTD represented by the formula (II) to the amount of the photocatalyst charging material is 1:0.0001 to 0.01, preferably 1: 0.001.
Further, the light source of the visible light is selected from the following: a 25-45W white light energy-saving lamp and a 7W blue light LED lamp.
Further, the light source of visible light is most preferably: 7W blue LED lamp.
The post-treatment method of the reaction system comprises the following steps: and (3) removing the solvent from the reaction solution by a rotary evaporator, and separating by silica gel or neutral alumina column chromatography, wherein the eluent is petroleum ether, thereby finally obtaining the trifluoromethyl olefin derivative shown in the formula (I).
Ir (dFCF) for use in the process3ppy)2(dtbbpy)]PF6Obtained by synthesis, the method is derived from the following documents:
1、D.M.Schultz,J.W.Sawicki and T.P.Yoon,Beilstein J.Org.Chem.,2015,11,61；2、J.D.Slinker,A.A.Gorodetsky,M.S.Lowry,J.Wang,S.Parker,R.Rohl,S.Bernhard and G.G.Malliaras,J.Am.Chem.Soc.,2004,126,2763；3、M.S.Lowry,J.I.Goldsmith,J.D.Slinker,R.Rohl,R.A.Pascal,G.G.Malliaras and S.Bernhard,Chem.Mater.,2005,17,5712.
compared with the prior art, the invention has the beneficial effects that:
the method has the advantages that stoichiometric transition metal is not involved, the reaction can be carried out at normal temperature and normal pressure, the usage amount of the catalyst is extremely low, and the reaction yield is high; and the method adopts visible light catalysis, has the characteristics of no pollution, environmental friendliness and the like, and has a wide prospect.
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The following detailed description is made with reference to the accompanying drawings and embodiments of the present invention
FIG. 1 shows the product (2- (cyclohexylmethyl) -3,3, 3-trifluoro-1Of (E) -en-1-yl) benzene1HNMR spectrogram;
FIG. 2 is a scheme of the production of (2- (cyclohexylmethyl) -3,3, 3-trifluoro-1-en-1-yl) benzene13CNMR spectrogram.
Detailed Description
The following specific examples are provided to illustrate the technical solutions of the present invention, but the scope of the present invention is not limited thereto.
The catalyst used in the embodiment of the invention has the following structural formula:
Figure BDA0002747476050000041
example 1
To a 25ml Schlenk tube, 0.75mmol of R was added in order2Boric acid as cyclohexyl, 0.0005mmol [ Ir (dFCF)3ppy)2(dtbbpy)]PF60.125mmol of 1, 4-diazabicyclo [2.2.2]Octane, double-row vacuum nitrogen exchange three times, 6ml of 1, 2-dichloroethane and 0.5mmol of R are added under nitrogen atmosphere1For phenyl BMBTD, 0.125mmol cesium carbonate was added with vigorous stirring and the reaction was irradiated with 7W blue LED light for 7 h. After the reaction is finished, the solvent 1, 2-dichloroethane is removed by a rotary evaporator, and the target product (2- (cyclohexylmethyl) -3,3, 3-trifluoro-1-en-1-yl) benzene is obtained by separation and purification through neutral alumina column chromatography (column chromatography developing agent: petroleum ether), colorless liquid and 94% yield. Product characterization data were as follows: cis-trans isomerism Z/E ═ 1: 2.16;
(Z formula):1H NMR(500MHz,Chloroform-d)δ7.34–7.28(m,5H),6.74(s,1H),2.23(d,J＝7.25Hz,2H),1.86–1.82(m,2H),1.75(td,J＝13.15,3.6Hz,2H),1.70–1.55(m,1H),1.31–1.26(m,2H),1.09–1.03(m,2H),0.93(qd,J＝12.15,3.4Hz,2H).
(formula E):1H NMR(500MHz,Chloroform-d)δ7.40–7.36(m,2H),7.34–7.28(m,3H),7.15(d,J＝2.0Hz,1H),2.34(d,J＝7.4Hz,2H),1.70–1.55(m,7H),1.19–1.14(m,2H),0.76(qd,J＝11.8,3.15Hz,2H).
13C NMR(126MHz,Chloroform-d)δ136.56(q,3JF-C＝4.07Hz),135.45,135.21,133.49(3JF-C＝6.56Hz),130.33(q,2JF-C＝27.49Hz),129.14(q,2JF-C＝28.30Hz),128.91,128.61(q,4JF-C＝2.46Hz),128.58,128.15,128.10,127.98,124.95(q,1JF-C＝275.02Hz),124.09(q,1JF-C＝276.47Hz),41.51,36.64,36.45,33.69,33.31,33.22,26.66,26.44,26.35.HRMS(EI)calcd for C16H19F3(M)+268.1439,found:268.1438.
example 2
To a 25ml Schlenk tube, 0.75mmol of R was added in order2Boric acid as cyclohexyl, 0.0005mmol [ Ir (dFCF)3ppy)2(dtbbpy)]PF60.125mmol of 1, 4-diazabicyclo [2.2.2]Octane, double-row vacuum nitrogen exchange three times, adding 6ml tetrahydrofuran and 0.5mmol R under nitrogen atmosphere1BMBTD as 4-fluorophenyl, 0.125mmol cesium carbonate was added with vigorous stirring and the reaction was irradiated with a 7W blue LED lamp for 7 h. After the reaction is finished, the solvent 1, 2-dichloroethane is removed by a rotary evaporator, and the target product 1- (2- (cyclohexylmethyl) -3,3, 3-trifluoropropane-1-en-1-yl) -4-fluorobenzene is obtained by separation and purification through neutral alumina column chromatography (column chromatography developing agent: petroleum ether), colorless liquid is obtained, and the yield is 87%. Product characterization data were as follows: cis-trans isomerism Z/E ═ 1: 2.44;
(Z formula):1H NMR(500MHz,Chloroform-d)δ7.30–7.26(m,2H),7.05–7.00(m,2H),6.68(s,1H),2.22(d,J＝7.2Hz,2H),1.85–1.81(m,2H),1.77–1.72(m,2H),1.70–1.52(m,1H),1.31–1.26(qt,J＝12.95,3.5Hz,2H),1.12–1.04(m,2H),0.93(qd,J＝12.1,3.4Hz,2H).
(formula E):1H NMR(500MHz,Chloroform-d)δ7.30–7.26(m,2H),7.12–7.06(m,3H),2.32(d,J＝7.4Hz,2H),1.70–1.52(m,7H),1.21–1.13(m,2H),0.76(qd,J＝12.5,2.85Hz,2H).
13C NMR(126MHz,Chloroform-d)δ162.52(d,1JF-C＝248.40Hz),162.46(d,1JF-C＝248.48Hz),135.42(q,3JF-C＝4.03Hz),132.41(q,3JF-C＝6.43Hz),131.38(d,3JF-C＝3.48Hz),131.17(d,3JF-C＝3.45Hz),130.69(d,3JF-C＝8.09Hz),130.49(d,4JF-C＝2.67Hz),130.42(q,3JF-C＝3.00Hz),124.84(q,1JF-C＝274.91Hz),124.02(q,1JF-C＝276.53Hz),115.67(d,2JF-C＝21.63Hz),115.17(d,2JF-C＝21.75Hz),115.26,115.08,41.50,36.62,36.44,33.64,33.33,33.21,26.63,26.41,26.33.HRMS(EI)calcd for C16H18F4(M)+286.1345,found:286.1342.
example 3
To a 25ml Schlenk tube, 0.75mmol of R was added in order2Boric acid as cyclohexyl, 0.0005mmol [ Ir (dFCF)3ppy)2(dtbbpy)]PF60.125mmol of 1, 4-diazabicyclo [2.2.2]Octane, exchanging nitrogen three times in vacuum in a double-row pipe, adding 6ml of dichloromethane and 0.5mmol of R in the nitrogen atmosphere1For 4-chlorophenyl BMBTD, 0.125mmol of cesium carbonate was added with vigorous stirring and the reaction was irradiated with 7W blue LED lamp for 7 h. After the reaction is finished, removing the solvent 1, 2-dichloroethane by a rotary evaporator, and separating and purifying by neutral alumina column chromatography (column chromatography developing agent: petroleum ether) to obtain the target product 1-chloro-4- (2- (cyclohexylmethyl) -3,3, 3-trifluoropropyl-1-en-1-yl) benzene as a colorless liquid with the yield of 91%. Product characterization data were as follows: cis-trans isomerism Z/E1: 3.73;
(Z formula):1H NMR(500MHz,Chloroform-d)δ7.31–7.29(m,2H),7.22(d,J＝10.0Hz,2H),6.66(s,1H),2.22(d,J＝7.2Hz,2H),1.85–1.78(m,2H),1.74(dt,J＝13.1,3.6Hz,2H),1.69–1.52(m,1H),1.30–1.25(m,2H),1.09–1.05(m,2H),0.92(qd,J＝11.7,3.1Hz,2H).
(formula E):1H NMR(500MHz,Chloroform-d)δ7.37–7.34(m,2H),7.22(d,J＝10.0Hz,2H),7.08(s,1H),2.30(d,J＝5.0Hz,2H),1.69–1.52(m,7H),1.19–1.12(m,2H),0.79–0.71(m,2H).
13C NMR(126MHz,Chloroform-d)δ135.20(q,3JF-C＝3.78Hz),134.09,134.00,133.83,133.62,132.28(q,3JF-C＝6.63Hz),131.10(q,2JF-C＝27.34Hz),130.24,130.03(q,2JF-C＝28.39Hz)129.98(q,4JF-C＝2.78Hz),128.87,124.75(q,1JF-C＝274.93Hz),123.94(q,1JF-C＝276.61Hz),41.47,36.59,36.46,33.72,33.33,33.21,26.62,26.39,26.32.HRMS(EI)calcd for C16H18F3Cl(M)+302.1049,found:302.1036.
example 4
To a 25ml Schlenk tube, 0.75mmol of R was added in order2Boric acid as cyclohexyl, 0.0005mmol [ Ir (dFCF)3ppy)2(dtbbpy)]PF60.125mmol of 1, 4-diazabicyclo [2.2.2]Octane, double-row vacuum nitrogen exchange three times, adding 6ml N, N-dimethyl formamide and 0.5mmol R under nitrogen atmosphere1For BMBTD with 4-bromophenyl, 0.125mmol of cesium carbonate was added with vigorous stirring and the reaction was irradiated with a 7W blue LED lamp for 7 h. After the reaction is finished, the solvent 1, 2-dichloroethane is removed by a rotary evaporator, and the target product 1-bromo-4- (2- (cyclohexylmethyl) -3,3, 3-trifluoro-1-en-1-yl) benzene is obtained by separation and purification through neutral alumina column chromatography (column chromatography developing agent: petroleum ether), with the yield of 90%. Product characterization data were as follows: cis-trans isomerism Z/E is 1: 2.57;
(Z formula):1H NMR(500MHz,Chloroform-d)δ7.45(dt,J＝8.5,2.6Hz,2H),7.15(d,J＝8.2Hz,2H),6.64(s,1H),2.21(d,J＝7.2Hz,2H),1.84–1.79(m,2H),1.77–1.72(m,2H),1.71–1.52(m,1H),1.29–1.24(m,2.0H),1.09–1.04(m,2H),0.92(qd,J＝12.1,3.4Hz,2H).
(formula E):1H NMR(500MHz,Chloroform-d)δ7.51(dt,J＝8.45,2.6Hz 2H),7.15(d,J＝8.2Hz,2H),7.06(s,1H),2.29(d,J＝7.4Hz,2H),1.71–1.52(m,7H),1.19–1.13(m,2H),0.78–0.70(m,2H).
13C NMR(126MHz,Chloroform-d)δ135.20(q,3JF-C＝4.11Hz),134.30,134.08,132.31(q,3JF-C＝6.43Hz),131.83,131.36,131.16(q,2JF-C＝27.56Hz),130.51,130.25(q,4JF-C＝2.43Hz),130.09(q,2JF-C＝28.27Hz),124.73(q,1JF-C＝275.34Hz),123.92(q,1JF-C＝276.47Hz),122.26,122.19,41.47,36.57,36.45,33.74,33.32,33.20,26.61,26.38,26.32.HRMS(EI)calcd for C16H18F3Br(M)+346.0544,found:346.0538.
example 5
To a 25ml Schlenk tube, 0.75mmol of R was added in order2Boric acid as cyclohexyl, 0.0005mmol [ Ir (dFCF)3ppy)2(dtbbpy)]PF60.125mmol of 1, 4-diazabicyclo [2.2.2]Octane, changing nitrogen three times in vacuum with double-row pipe, adding 6ml acetonitrile and 0.5mmol R under nitrogen atmosphere1BMBTD as 4-methylphenyl, 0.125mmol cesium carbonate was added with vigorous stirring and the reaction was irradiated with 7W blue LED lamp for 7 h. After the reaction is finished, removing the solvent 1, 2-dichloroethane by a rotary evaporator, and separating and purifying by neutral alumina column chromatography (column chromatography developing agent: petroleum ether) to obtain the target product 1- (2- (cyclohexylmethyl) -3,3, 3-trifluoropropane-1-en-1-yl) -4-toluene as a colorless liquid with the yield of 91%. Product characterization data were as follows: cis-trans isomerism Z/E is 1: 1.6;
(Z formula):1H NMR(500MHz,Chloroform-d)δ7.21–7.17(m,2H),7.14(d,J＝8.0Hz,2H),6.69(s,1H),2.37–2.33(m,3H),2.21(d,J＝7.2Hz,2H),1.84–1.80(m,2H),1.73(dt,J＝13.1,3.55Hz,2H),1.71–1.56(m,1H),1.29–1.26(m,2H),1.11–1.02(m 2H),0.91(qd,J＝12.05,3.4Hz，2H).
(formula E):1H NMR(500MHz,Chloroform-d)δ7.21–7.17(m,4H),7.09(s,1H),2.37–2.33(m,5H),1.71–1.56(m,7H),1.18–1.14(m,2H),0.78(qd,J＝11.9,3.2Hz,2H).
13C NMR(126MHz,Chloroform-d)δ138.07,137.94,136.63(q,3JF-C＝3.82Hz),133.39(q,3JF-C＝6.59Hz),132.46,132.22,129.51(q,2JF-C＝27.18Hz),129.29,128.95,128.88,128.65(q,4JF-C＝2.80Hz),128.35(q,2JF-C＝28.43Hz),125.06(q,1JF-C＝275.21Hz),124.19(q,1JF-C＝276.19Hz),41.64,36.69,36.47,33.72,33.33,33.20,26.66,26.46,26.38,26.35,21.40,21.38.HRMS(EI)calcd for C17H21F3(M)+282.1595,found:282.1589.
example 6
To a 25ml Schlenk tube, 0.75mmol of R was added in order2Boric acid as cyclohexyl, 0.0005mmol [ Ir (dFCF)3ppy)2(dtbbpy)]PF60.125mmol of 1, 4-diazabicyclo [2.2.2]Octane, changing nitrogen three times in vacuum with double-row pipe, adding 6ml dimethyl sulfoxide and 0.5mmol R under nitrogen atmosphere1BMBTD as 4-methoxyphenyl, 0.125mmol cesium carbonate was added with vigorous stirring and the reaction was irradiated with 7W blue LED lamp for 7 h. After the reaction is finished, the solvent 1, 2-dichloroethane is removed by a rotary evaporator, and the target product 1- (2- (cyclohexylmethyl) -3,3, 3-trifluoropropane-1-en-1-yl) -4-methoxybenzene is obtained by separation and purification through silica gel column chromatography (column chromatography developing agent: petroleum ether/ethyl acetate ═ 20:1) and is colorless liquid with the yield of 94%. Product characterization data were as follows: cis-trans isomerism Z/E1: 1.54;
(Z formula):1H NMR(500MHz,Chloroform-d)δ7.29–7.26(m,2H),6.87(td,J＝8.75,3.1Hz,2H),6.66(s,1H),3.82(s,3H),2.21(d,J＝7.2Hz,2H),1.85–1.80(m,2H),1.76–1.59(m,3H),1.30–1.26(m,2H),1.14–1.06(m,2H),0.96–0.89(m,2H).
(formula E):1H NMR(500MHz,Chloroform-d)δ7.29–7.26(m,2H),7.07(s,1H),6.92(dt,J＝8.75,2.15Hz,2H),3.85(s,3H),2.36(d,J＝7.4Hz,2H),1.76–1.59(m,7H),1.20–1.15(m,2H),0.85–0.78(m,2H).
13C NMR(126MHz,Chloroform-d)δ159.53,136.32(q,3JF-C＝4.06Hz),132.93(q,3JF-C＝6.78Hz),130.54,130.29(q,4JF-C＝2.53Hz),128.57(q,2JF-C＝27.24Hz),127.71,127.53,127.40(q,2JF-C＝27.54Hz),125.17(q,1JF-C＝274.50Hz),124.30(q,1JF-C＝276.13Hz),114.05,113.64,55.40,55.37,41.78,36.79,36.51,33.69,33.37,33.21,26.67,26.48,26.40,26.36.HRMS(EI)calcd for C17H21F3O(M)+298.1545,found:298.1539.
example 7
To a 25ml Schlenk tube, 0.75mmol of R was added in order2Boric acid as cyclohexyl, 0.0005mmol [ Ir (dFCF)3ppy)2(dtbbpy)]PF60.125mmol of 1, 4-diazabicyclo [2.2.2]Octane, double-row vacuum nitrogen exchange three times, 6ml of 1, 2-dichloroethane and 0.5mmol of R are added under nitrogen atmosphere1For phenylethyl BMBTD, 0.125mmol cesium carbonate was added with vigorous stirring and the reaction was irradiated with 7W blue LED lamp for 7 h. After the reaction is finished, the solvent 1, 2-dichloroethane is removed by a rotary evaporator, and the target product (4- (cyclohexylmethyl) -5,5, 5-trifluoro-3-en-1-yl) benzene is obtained by separation and purification through neutral alumina column chromatography (column chromatography developing agent: petroleum ether), colorless liquid and 94% yield. Product characterization data were as follows: cis-trans isomerism Z/E ═ 1: 2.62;
(Z formula):1H NMR(500MHz,Chloroform-d)δ7.32(q,J＝7.6Hz,2H),77.26–7.19(m,3H),5.68(t,J＝7.7Hz,1H),2.77–2.72(m,2H),δ2.64–2.59(m,2H),2.03(d,J＝7.25Hz,2H),1.75–1.65(m,4H),1.43–1.37(m,1H),1.25–1.14(m,4H),0.91–0.79(m,2H).
(formula E):1H NMR(500MHz,Chloroform-d)δ7.32(q,J＝7.6Hz,2H),7.26–7.19(m,3H),6.23(t,J＝7.45Hz,1H),2.77–2.72(m,2H),2.46(dd,J＝7.75,7.1Hz,2H),2.08(d,J＝7.5Hz,2H),1.75–1.65(m,6H),1.54–1.46(m,1H),1.25–1.14(m,2H),0.91–0.79(m,2H).
13C NMR(126MHz,Chloroform-d)δ141.12,137.82(q,3JF-C＝3.91Hz),134.40(q,3JF-C＝6.14Hz),128.83(q,2JF-C＝27.51Hz),128.69(q,2JF-C＝27.73Hz),128.65,128.57,128.54,128.51,126.35,126.21,124.75(q,1JF-C＝274.39Hz),124.69(q,1JF-C＝276.85Hz),40.80,37.10,36.48,35.73,35.17,33.60,33.40,33.04,30.14,29.99,26.66,26.55,26.45,26.33.HRMS(EI)calcd for C18H23F3(M)+296.1752,found:296.1744.
example 8
In 25ml SchleTo the nk tube, 0.75mmol of 2-boronic acid butane and 0.0005mmol of [ Ir (dFCF) were added3ppy)2(dtbbpy)]PF60.125mmol of 1, 4-diazabicyclo [2.2.2]Octane, double-row vacuum nitrogen exchange three times, 6ml of 1, 2-dichloroethane and 0.5mmol of R are added under nitrogen atmosphere1For phenyl BMBTD, 0.125mmol cesium carbonate was added with vigorous stirring and the reaction was irradiated with 7W blue LED light for 7 h. After the reaction, the solvent 1, 2-dichloroethane was removed by a rotary evaporator, and the target product 4-methyl-2- (trifluoromethyl) hex-1-en-1-yl) benzene was obtained by separation and purification through silica gel column chromatography (column chromatography developing solvent: ethyl acetate/petroleum ether: 1:100) in a colorless liquid with a yield of 93%. Product characterization data were as follows: cis-trans isomerism Z/E1: 1.66;
(Z formula):1H NMR(500MHz,Chloroform-d)δ7.40–7.29(m,5H),6.76(s,1H),2.47–2.41(m,1H),2.07(dd,J＝13.95,8.5Hz,1H),1.72–1.63(m,1H),1.52–1.46(m,1H),1.26–1.20(m,1H),0.97–0.94(m,6H).
(formula E):1H NMR(500MHz,Chloroform-d)δ7.40–7.29(m,5H),7.17(s,1H),2.47–2.41(m,1H),2.29(dd,J＝14.3,8.7Hz,1H),1.72–1.63(m,1H),1.37–1.30(m,1H),1.10–1.03(m,1H),0.83–0.79(m,6H).
13C NMR(126MHz,Chloroform-d)δ136.62(q,3JF-C＝4.11Hz),135.47,135.19,133.54(q,3JF-C＝6.4Hz),130.80(q,2JF-C＝27.58Hz),129.75(q,2JF-C＝28.14Hz),128.90,128.59(q,4JF-C＝2.36Hz),128.58,128.16,128.12,128.00,124.95(q,1JF-C＝274.62Hz),124.11(q,1JF-C＝276.75Hz),123.86,123.01,41.05,33.60,33.21,33.19,29.87,29.62,29.44,18.98,18.81,11.48,11.45.HRMS(EI)calcd for C14H17F3(M)+242.1282,found:242.1290.
example 9
To a 25ml Schlenk tube, 0.75mmol of R was added in order2Boric acid as cyclohexyl, 0.0005mmol [ Ir (dFCF)3ppy)2(dtbbpy)]PF60.125mmol of 1, 4-diazabicyclo [2.2.2]The octane is a mixture of the octane and the octane,the nitrogen is exchanged for three times in a vacuum way by a double-row pipe, and 6ml of 1, 2-dichloroethane and 0.5mmol of R are added under the nitrogen atmosphere1BMBTD as 3-phenoxyphenyl, 0.125mmol cesium carbonate was added with vigorous stirring and the reaction was irradiated with 7W blue LED lamp for 7 h. After the reaction is finished, the solvent 1, 2-dichloroethane is removed by a rotary evaporator, and the target product (2- (cyclopentylmethyl) -3,3, 3-trifluoropropane-1-en-1-yl) benzene is obtained by separation and purification through silica gel column chromatography (column chromatography developing agent: ethyl acetate petroleum ether ═ 1:100) and is colorless liquid with the yield of 85%. Product characterization data were as follows: cis-trans isomerism Z/E is 1: 1.5;
(Z formula):1H NMR(500MHz,Chloroform-d)δ7.39–7.33(m,2H),7.30(t,J＝7.85Hz,1H),7.12–7.10(m,2H),7.05–7.00(m,2H),6.97–6.94(m,2H),6.70(s,1H),2.21(d,J＝7.5Hz,2H),1.83–1.80(m,2H),1.76–1.71(m,2H),1.72–1.67(m,1H),1.32–1.23(m,2H),1.21–1.02(m,2H),0.96–0.88(m,2H).
(formula E):1H NMR(500MHz,Chloroform-d)δ7.39–7.33(m,3H),7.15(tt,J＝7.45,1.3Hz 1H),7.05–7.00(m,5H),6.97–6.94(m,1H),2.28(d,J＝7.5Hz,2H),1.64–1.62(m,6H),1.55–1.50(m,1H),1.21–1.02(m,2H),0.75–0.67(m,2H).
13C NMR(126MHz,Chloroform-d)δ157.72,157.28,157.08,157.02,137.17,136.84,135.76(q,3JF-C＝4Hz),132.84(q,3JF-C＝6.45Hz),130.86(q,2JF-C＝27.27Hz),130.02,129.99,129.88,129.47,124.81(q,1JF-C＝274.96Hz),123.96(q,1JF-C＝276.67Hz),123.88,123.79,123.57(q,4JF-C＝2.43Hz),123.43,119.32,119.17(q,4JF-C＝2.37Hz),118.96,118.74,118.66,118.52,41.41(d,3JF-C＝2.19Hz),36.58,36.45,33.70,33.26,33.20,26.63,26.39,26.35,26.32.HRMS(EI)calcd for C22H23OF3(M)+360.1701,found:360.1686.
example 10 (comparative example illumination)
To a 25ml Schlenk tube, 0.75mmol of R was added in order2Boric acid as cyclohexyl, 0.0005mmol [ Ir (dFCF)3ppy)2(dtbbpy)]PF60.125mmol of 1, 4-diazabicyclo [2.2.2]Octane, double-row vacuum nitrogen exchange three times, 6ml of 1, 2-dichloroethane and 0.5mmol of R are added under nitrogen atmosphere1BMBTD as a phenyl group, 0.125mmol cesium carbonate was added with vigorous stirring and reacted for 7h in the dark. After the reaction is finished, the target product can not be detected by TLC.
Example 11 (comparative example photocatalyst)
To a 25ml Schlenk tube, 0.75mmol of R was added in order2Boric acid as cyclohexyl, 0.125mmol1, 4-diazabicyclo [2.2.2 ]]Octane, double-row vacuum nitrogen exchange three times, 6ml of 1, 2-dichloroethane and 0.5mmol of R are added under nitrogen atmosphere1For phenyl BMBTD, 0.125mmol cesium carbonate was added with vigorous stirring and the reaction was irradiated with 7W blue LED light for 7 h. After the reaction is finished, the target product can not be detected by TLC.
Example 12 (Lewis base of comparative example)
To a 25ml Schlenk tube, 0.75mmol of R was added in order2Boric acid as cyclohexyl, 0.0005mmol [ Ir (dFCF)3ppy)2(dtbbpy)]PF6The nitrogen is exchanged three times in a double-row vacuum, and 6ml of 1, 2-dichloroethane and 0.5mmol of R are added in the nitrogen atmosphere1For phenyl BMBTD, 0.125mmol cesium carbonate was added with vigorous stirring and the reaction was irradiated with 7W blue LED light for 7 h. After the reaction is finished, the target product can not be detected by TLC.
Example 13 (comparative example inorganic base)
To a 25ml Schlenk tube, 0.75mmol of R was added in order2Boric acid as cyclohexyl, 0.0005mmol [ Ir (dFCF)3ppy)2(dtbbpy)]PF60.125mmol of 1, 4-diazabicyclo [2.2.2]Octane, double-row vacuum nitrogen exchange three times, 6ml of 1, 2-dichloroethane and 0.5mmol of R are added under nitrogen atmosphere1BMBTD as phenyl, the reaction was irradiated with 7W blue LED lamp for 7h with strong stirring. After the reaction is finished, the reaction solution is extracted for three times by saturated ammonium chloride solution and dichloromethane, organic phases are combined, dried by anhydrous sodium sulfate, separated and purified by neutral alumina column chromatography (column chromatography developing agent: petroleum ether) to obtain the target product (2- (cyclohexylmethyl) -3,3, 3-trifluoro-1-en-1-yl) benzene with the yield of 61 percent.

Claims (10)

1. A preparation method of a trifluoromethyl olefin derivative catalyzed by visible light is characterized by comprising the following steps: the trifluoromethyl olefin derivative is shown as a formula (I), in a reaction solvent, alkyl boric acid shown as a formula (III) and a Boc modified Barbier-type trifluoromethyl derivative shown as a formula (II), namely BMBTD are used as raw materials, and inert gas N is used2Under the conditions of protection and visible light illumination, a visible light catalyst, a Lewis base and an inorganic base additive, stirring for 2-15h at normal temperature and normal pressure, and carrying out rotary evaporation and post-column chromatography treatment on a reaction system to prepare the tri-substituted trifluoromethyl olefin derivative shown in the formula (I); the photocatalyst is selected from the following compounds: eosin Y (Water soluble) eosin-Y, tris (2-phenylpyridine) iridium Ir (ppy)3Bis [2- (2, 4-difluorophenyl) -5-trifluoromethylpyridine][2-2' -bis (4-tert-butylpyridine)]Iridium bis (hexafluorophosphate) salt [ Ir (dFCF)3ppy)2(dtbbpy)]PF6Tris (2,2' -bipyrazinyl) ruthenium bis (hexafluoroborate) Ru (bpz)3(PF6)2Rhodamine B; the reaction solvent is selected from the following solvents: n-methylpyrrolidone, tetrahydrofuran, N-dimethylformamide, dichloromethane, 1, 2-dichloroethane, acetonitrile, dimethyl sulfoxide; the Lewis base is selected from the following: 1, 4-diazabicyclo [2.2.2]Octane, 4-dimethylaminopyridine, 1, 8-diazabicycloundec-7-ene, triphenylphosphine; the reaction additive is selected from the following components: sodium carbonate, potassium carbonate, cesium carbonate;
Figure FDA0002747476040000011
in the formula R1Is C1-C6 alkyl, aryl or substituted aryl; the aromatic ring of the substituted aryl is mono-substituted, R2Is C1-C6 alkyl; the substituted aryl is monosubstituted, and the substituent is selected from C1-C5 alkyl, fluorine, chlorine, bromine or methoxy.
2. The method of claim 1, wherein: said R1Wherein, the aryl is phenyl or naphthyl; said R2Is an alkyl group.
3. The method of claim 1, wherein: the photocatalyst is [ Ir (dFCF)3ppy)2(dtbbpy)]PF6The reaction solvent is 1, 2-dichloroethane, and the Lewis base is 1, 4-diazabicyclo [2.2.2]Octane and the additive is cesium carbonate.
4. The method of claim 1, wherein: the volume amount of the organic solvent used was 12mL/mmol based on the amount of the raw material BMBTD substance represented by the formula (II).
5. The method of claim 1, wherein: the ratio of the amount of the raw material BMBTD represented by the formula (II) to the amount of the Lewis base is 1:0.1 to 1.5, preferably 1: 0.25.
6. The method of claim 1, wherein: the ratio of the amount of the BMBTD as the raw material to the amount of the additive as the additive shown in the formula (II) is 1: 0.1-1.5, preferably 1: 0.25.
7. The method of claim 1, wherein: the ratio of the BMBTD shown in the formula (II) to the alkyl boric acid shown in the formula (III) in the reaction material feeding matter is 1: 1-2.5, preferably 1: 1.5.
8. The method of claim 1, wherein: the ratio of the amount of BMBTD represented by the formula (II) to the amount of the photocatalyst charging material is 1:0.0001 to 0.01, preferably 1: 0.001.
9. The method of claim 1, wherein: the light source of visible light is selected from the following: a 25-45W white light energy-saving lamp and a 7W blue light LED lamp.
10. The method of claim 9, wherein: the light source of visible light is a 7W blue LED lamp.
CN202011171629.4A 2020-10-28 2020-10-28 Preparation method of visible light catalyzed trifluoromethyl olefin derivative Pending CN112321385A (en)

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