CN109096046B - Preparation method of halogenated alkane synthesized from styrene and derivatives thereof and trichloroalkane - Google Patents

Preparation method of halogenated alkane synthesized from styrene and derivatives thereof and trichloroalkane Download PDF

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CN109096046B
CN109096046B CN201810931855.4A CN201810931855A CN109096046B CN 109096046 B CN109096046 B CN 109096046B CN 201810931855 A CN201810931855 A CN 201810931855A CN 109096046 B CN109096046 B CN 109096046B
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CN109096046A (en
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张兴国
贺世瑜
张小红
叶寅璐
黄叶鑫
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Wenzhou University
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Abstract

The invention discloses halogenated alkane synthesized by styrene and derivatives thereof and trichloroalkane and a preparation method thereof, wherein the halogenated alkane is prepared by taking the styrene and the derivatives thereof and the trichloroalkane as substrates, carrying out chloroalkylation and dimerization reaction under the condition of illumination, and reacting for 10-14 h; wherein the reaction temperature is 10-45 ℃, and the reaction is carried out under normal pressure; during the reaction, the surface type tri (2-phenylpyridine) iridium is used as a catalyst to accelerate the reaction speed; simultaneously, adding alkali, an iodine source, triphenylphosphine and deionized water into the whole reaction system; the whole reaction is carried out in a solvent; meanwhile, the whole reaction is carried out under the nitrogen atmosphere. After the reaction is finished, halogenated alkane can be obtained after purification treatment, and the halogenated alkane is a tail-to-tail dimerization product prepared by taking styrene and derivatives thereof as reactants. Meanwhile, the invention has the advantages of simple and easily obtained raw materials, novel and simple preparation process, less pollution, low energy consumption and higher yield.

Description

Preparation method of halogenated alkane synthesized from styrene and derivatives thereof and trichloroalkane
Technical Field
The invention relates to the field of organic chemical synthesis, in particular to a preparation method of halogenated alkane synthesized by styrene and derivatives thereof and trichloroalkane.
Background
Introduction of halogen groups such as fluorine, chlorine, etc. into organic molecules has become a widely used drug discovery method, and among them, dimerization reaction of styrene and its derivatives has become one of important reactions for introduction of halogen groups, and many bronsted or Lewis acid catalysis and transition metal catalysis have been used for this conversion. It is known that two substances have different structural formulas even though they have the same chemical formula, and thus the two substances often have great differences in chemical, physical and pharmacological aspects. At present, in dimerization reaction of styrene and derivatives thereof, the generated dimerization product is mostly head-to-tail or head-to-head, even if the tail-to-tail dimerization product exists in a few reactions, the side reaction is generated, the content is very small, extraction and research are difficult, and the discovery of the medicament is not facilitated. However, no tail-to-tail dimerization product obtained by using styrene and derivatives thereof as reactants is available at present.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a preparation method of halogenated alkane synthesized by styrene and derivatives thereof and trichloroalkane, wherein the halogenated alkane is a tail-to-tail dimerization product formed by taking the styrene and the derivatives thereof and the trichloroalkane as reactants.
In order to achieve the purpose, the invention provides the following technical scheme: halogenated alkane synthesized by styrene and derivatives thereof and trichloroalkane, wherein the molecular structural formula of the halogenated alkane is shown in the specification
Figure GDA0002886671250000011
As a further improvement of the invention, the halogenated alkane is formed by reacting styrene and derivatives thereof with trichloroalkane; simultaneously adding triphenylphosphine, an iodine source, a catalyst, alkali and deionized water;
the styrene and the derivatives thereof have molecular structural formulas
Figure GDA0002886671250000021
Or a naphthylethylene or alpha-methylstyrene;
the molecular structural formula of the trichloroalkane is CCl3R2；
The reaction equation is as follows:
Figure GDA0002886671250000022
as a further improvement of the invention, R is1Is any one of hydrogen atom, 4-methyl, 3-methyl, 2, 4-dimethyl, 4-tertiary butyl, 4-methoxy, 4-acetoxyl, 4-fluorine, 4-chlorine, 3-chlorine, 2-bromine, 4-trifluoromethyl and 4-cyano; the R is2Is-chloro or trifluoromethyl.
As a further improvement of the invention, the preparation method of halogenated alkane synthesized by styrene and derivatives thereof and trichloroalkane comprises the steps of adding the styrene and the derivatives thereof, the trichloroalkane, a catalyst, deionized water, triphenylphosphine, an iodine source and alkali into a reaction vessel filled with a solvent under visible light, and reacting under nitrogen; then extracting, separating liquid, washing, drying an organic phase, evaporating in vacuum, and finally separating and purifying through a column layer to obtain the halogenated alkane.
As a further improvement of the invention, the molar parts of the materials added into the reaction vessel are as follows:
1 part of styrene and derivatives thereof;
5 parts of trichloroalkane;
0.03 part of catalyst;
5 parts of alkali;
5 parts of an iodine source;
10 parts of triphenylphosphine;
10 parts of deionized water.
As a further improvement of the invention, when styrene and derivatives thereof react with trichloroalkane, the reaction temperature is 10-45 ℃, and the reaction time is 10-14 h; before extraction and liquid separation, adding hydrogen peroxide into a reaction vessel, and then adding an extraction liquid to perform extraction and liquid separation; the extract is ethyl acetate.
As a further improvement of the invention, the catalyst is a facial tris (2-phenylpyridine) iridium complex.
As a further improvement of the present invention, the solvent is any one of dichloromethane and tetrahydrofuran.
As a further improvement of the invention, the iodine source is any one of sodium iodide, potassium iodide, TBAI and zinc iodide.
As a further improvement of the invention, the base is any one of cesium carbonate, potassium carbonate, triethylamine, DBU and potassium phosphate.
The invention has the beneficial effects that: styrene and derivatives thereof and trichloroalkane are taken as substrates, wherein the trichloroalkane is carbon tetrachloride or trifluorotrichloroethane, chloroalkylation/dimerization reaction is carried out under the illumination condition, and reaction lasts for 10-14h to prepare trifluorodichloroalkane; wherein the reaction temperature is 10-45 ℃, the reaction is carried out under normal pressure, and the reaction condition is very mild and is easy to achieve; during the reaction, the surface type tri (2-phenylpyridine) iridium is used as a catalyst, so that the reaction speed is accelerated, and the reaction time is shortened; simultaneously, adding alkali, an iodine source, triphenylphosphine and deionized water into the whole reaction system; the whole reaction is carried out in a solvent; meanwhile, the whole reaction is carried out in a nitrogen atmosphere, and the nitrogen plays a role in protection, so that the product is not easily oxidized by oxygen. After the reaction is finished, corresponding halogenated alkane can be obtained after a series of purification treatments of extraction and liquid separation, wherein the halogenated alkane is a tail-to-tail dimerization product prepared by taking styrene and derivatives thereof as reactants.
The invention can directly synthesize the target product without separating intermediate products, and can obtain the target product only by stirring and reacting under normal pressure, thereby greatly simplifying the process, reducing the energy consumption and having the advantage of higher yield. And in the reaction process, the waste solution is less, and other polluted gases and liquid are not discharged, so that the method reduces the discharge of the waste solution, and has the advantages of protecting the environment and ensuring the health of operators. In addition, a series of chloroalkylated and dimeric derivatives of styrene can be prepared, and the method has strong substrate universality. Therefore, the invention fills the blank of chloroalkylation and dimerization organic matters of styrene prepared at the present stage, promotes the development of polysubstituted derivatives, and can provide powerful guarantee for developing chlorinated alkane-containing biological medicines.
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FIG. 1 is a reaction scheme of a first embodiment of the present invention;
FIG. 2 is a reaction scheme of twenty-eight examples of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
The first embodiment is as follows: under the irradiation of visible light, 0.2mmol of styrene, 1.0mmol of trifluorotrichloroethane, and 0.006mmol of photo-redox catalyst fac- [ Ir (ppy)3]2.0mmol of deionized water, 2.0mmol of triphenylphosphine, 1.0mmol of zinc iodide, and 1.0mmol of potassium phosphate were added to 2.0ml of tetrahydrofuran to carry out a reaction. The mixture was stirred under nitrogen at 25 ℃ for 12 hours. After the reaction was complete, hydrogen peroxide was added dropwise to the flask until the solution turned purple. Then, ethyl acetate was added to the mixture, and the mixture was washed with saturated sodium thiosulfate and brine. After extraction of the aqueous layer with ethyl acetate, the combined organic layers were dried over anhydrous sodium sulfate and evaporated in vacuo. The residue was purified by flash column chromatography to give 32.8mg of 2,2,7, 7-tetrachloro-1, 1,1,8,8, 8-hexafluoro-4, 5-diphenyloctane as a white solid in 64% yield. m.p.122-124 ℃.1H NMR(500MHz,CDCl3)δ7.31-7.28(m,2H),7.25-7.15(m,6H),6.87(d,J＝6.0Hz,2H),3.60(d,J＝5.5Hz,1H),3.36(d,J＝7.5Hz,1H),2.81(d,J＝15.0Hz,1H),2.63(dd,J＝5.5,15.0Hz,1H),2.54(dd,J＝7.5,15.0Hz,1H),2.39(d,J＝15.0Hz,1H)；13C NMR(125MHz,CDCl3)δ141.7,140.7,130.4,129.6,129.4,128.6,128.2,127.8,122.9(q,JC-F＝280.4Hz),122.7(q,JC-F＝280.3Hz),86.2(q,JC-F＝29.6Hz),85.7(q,JC-F＝34.3Hz),48.9,48.1,43.9,43.5；19F NMR(470MHz,CDCl3)δ-79.6(s,3F),-80.0(s,3F)；LRMS(EI,70eV)m/z(％):510(M+,4),275(71),273(100),201(19),143(73)；HRMS(EI+)Calcd for C20H16Cl4F6 +(M+):509.9910,Found:509.9919。
The second embodiment is as follows: under the irradiation of visible light, 0.2mmol of 4-methylstyrene, 1.0mmol of trifluorotrichloroethane, 0.006mmol of photo-redox catalyst fac- [ Ir (ppy)3]2.0mmol of deionized water, 2.0mmol of triphenylphosphine, 1.0mmol of zinc iodide, and 1.0mmol of potassium phosphate were added to 2.0ml of tetrahydrofuran to carry out a reaction. The mixture was stirred under nitrogen at 25 ℃ for 12 hours. After the reaction was complete, hydrogen peroxide was added dropwise to the flask until the solution turned purple. Then, ethyl acetate was added to the mixture, and the mixture was washed with saturated sodium thiosulfate and brine. After extraction of the aqueous layer with ethyl acetate, the combined organic layers were dried over anhydrous sodium sulfate and evaporated in vacuo. The residue was purified by flash column chromatography to give 29.7mg of 2,2,7, 7-tetrachloro-1, 1,1,8,8, 8-hexafluoro-4, 5-bis (4-methylphenyl) octane as a white solid in 55% yield. m.p.84-86 deg.C (uncoated);1H NMR(500MHz,CDCl3)δ7.16(d,J＝7.5Hz,2H),7.12(d,J＝7.5Hz,2H),7.06(d,J＝7.5Hz,2H),6.82(d,J＝7.5Hz,2H),3.65(s,1H),3.36(s,1H),2.82(d,J＝15.0Hz,1H),2.61-2.54(m,2H),2.45(d,J＝15.0Hz,1H),2.36(s,3H),2.34(s,3H)；13C NMR(125MHz,CDCl3)δ138.7,137.7,137.41,137.36,130.5,130.0,129.5,129.3,122.9(q,JC-F＝280.3Hz),122.8(q,JC-F＝280.3Hz),86.3(q,JC-F＝33.4Hz),85.8(q,JC-F＝34.5Hz),48.5,47.6,44.1,43.6,21.7,21.6；19F NMR(470MHz,CDCl3)δ-79.6(s,3F),-79.9(s,3F)；LRMS(EI,70eV)m/z(％):540(M+,3),271(63),269(100),141(18),139(53)；HRMS(EI+)Calcd for C22H20Cl4F6 +(M+):538.0223,Found:538.0219。
the third concrete embodiment: under the irradiation of visible light, 0.2mmol of 3-methylstyrene, 1.0mmol of trifluorotrichloroethane, 0.006mmol of photo-redox catalyst fac- [ Ir (ppy)3]2.0mmol of deionized water, 2.0mmol of triphenylphosphine, 1.0mmol of zinc iodidePotassium phosphate (K) was added to 2.0ml of tetrahydrofuran to conduct a reaction. The mixture was stirred under nitrogen at 25 ℃ for 12 hours. After the reaction was complete, hydrogen peroxide was added dropwise to the flask until the solution turned purple. Then, ethyl acetate was added to the mixture, and the mixture was washed with saturated sodium thiosulfate and brine. After extraction of the aqueous layer with ethyl acetate, the combined organic layers were dried over anhydrous sodium sulfate and evaporated in vacuo. The residue was purified by flash column chromatography to give 36.2mg of 2,2,7, 7-tetrachloro-1, 1,1,8,8,8 hexafluoro-4, 5-bis (3-methylphenyl) octane as a white solid in 67% yield. m.p.75-77 deg.C (undercorrected);1H NMR(500MHz,CDCl3)δ7.25-7.22(m,1H),7.15-7.12(m,1H),7.09(d,J＝7.5Hz,1H),7.06-7.02(m,3H),6.75(d,J＝7.5Hz,1H),6.65(s,1H),3.65-3.64(m,1H),3.34(d,J＝8.5Hz,1H),2.84-2.80(m,1H),2.62-2.54(m,2H),2.42(d,J＝15.0Hz,1H),2.36(s,3H),2.28(s,3H)；13C NMR(125MHz,CDCl3)δ141.7,140.3,138.8,137.9,131.3,130.3,129.1,128.8,128.5,128.3,127.6,126.7,122.8(q,JC-F＝280.1Hz),122.7(q,JC-F＝280.4Hz),86.2(q,JC-F＝34.4Hz),85.7(q,JC-F＝34.1Hz),48.7,47.7,43.8,43.4,22.1,22.0；19F NMR(470MHz,CDCl3)δ-79.6(s,3F),-80.0(s,3F)；LRMS(EI,70eV)m/z(％):540(M+,1),271(64),269(100),139(35)；HRMS(EI+)Calcd for C22H20Cl4F6 +(M+):538.0223,Found:538.0225。
the fourth concrete embodiment: under the irradiation of visible light, 0.2mmol of 2-methylstyrene, 1.0mmol of trifluorotrichloroethane, 0.006mmol of photo-redox catalyst fac- [ Ir (ppy)3]2.0mmol of deionized water, 2.0mmol of triphenylphosphine, 1.0mmol of zinc iodide, and 1.0mmol of potassium phosphate were added to 2.0ml of tetrahydrofuran to carry out a reaction. The mixture was stirred under nitrogen at 25 ℃ for 12 hours. After the reaction was complete, hydrogen peroxide was added dropwise to the flask until the solution turned purple. Then, ethyl acetate was added to the mixture, and the mixture was washed with saturated sodium thiosulfate and brine. After extraction of the aqueous layer with ethyl acetate, the combined organic layers were dried over anhydrous sodium sulfate and evaporated in vacuo. Removing residuesThe residue was purified by flash column chromatography to give 20.0mg of 2,2,7, 7-tetrachloro-1, 1,1,8,8,8 hexafluoro-4, 5-bis (2-methylphenyl) octane as a white solid in 37% yield. (2d-1) m.p.146-149 deg.C (uncoated);1H NMR(500MHz,CDCl3)δ7.17(d,J＝8.0Hz,2H),7.10-7.07(m,2H),6.99-6.96(m,2H),6.87(d,J＝7.5Hz,2H),3.82(d,J＝6.5Hz,2H),2.95(d,J＝15.0Hz,2H),2.89(dd,J＝6.5,15.0Hz,2H),2.21(s,6H)；13C NMR(125MHz,CDCl3)δ141.2,137.0,130.9,128.4,127.1,126.2,122.8(q,JC-F＝280.4Hz),86.3(q,JC-F＝34.0Hz),45.3,42.6,20.7；19F NMR(470MHz,CDCl3)δ-79.9(s,6F)；(2d-2):White solid(13.0mg,24％yield,dr＝1.54:1),m.p.143-145℃(uncorrected)；1H NMR(500MHz,CDCl3)δ7.21-7.19(m,2H),7.16-7.15(m,4H),7.11(d,J＝7.0Hz,2H),3.77-3.75(m,2H),2.73-2.68(m,2H),2.41(d,J＝14.5Hz,2H),2.26(s,6H)；13C NMR(125MHz,CDCl3)δ140.6,137.9,131.2,127.6,127.2,127.0,122.6(q,JC-F＝280.5Hz),85.9(q,JC-F＝34.1Hz),43.0,42.8,20.8；19F NMR(470MHz,CDCl3)δ-80.1(s,6F)；LRMS(EI,70eV)m/z(％):540(M+,1),271(63),269(100),139(33),118(9)；HRMS(EI+)Calcd for C22H20Cl4F6 +(M+):538.0223,Found:538.0216。
the fifth concrete embodiment: under the irradiation of visible light, 0.2mmol of 2, 4-dimethylstyrene, 1.0mmol of trifluorotrichloroethane, 0.006mmol of photo-redox catalyst fac- [ Ir (ppy)3]2.0mmol of deionized water, 2.0mmol of triphenylphosphine, 1.0mmol of zinc iodide, and 1.0mmol of potassium phosphate were added to 2.0ml of tetrahydrofuran to carry out a reaction. The mixture was stirred under nitrogen at 25 ℃ for 12 hours. After the reaction was complete, hydrogen peroxide was added dropwise to the flask until the solution turned purple. Then, ethyl acetate was added to the mixture, and the mixture was washed with saturated sodium thiosulfate and brine. After extraction of the aqueous layer with ethyl acetate, the combined organic layers were dried over anhydrous sodium sulfate and evaporated in vacuo. The residue was purified by flash column chromatography to give 39.2mg of 2,2,7, 7-tetrachloro 1,1,1,8,8,8 hexafluoro-4 as a white solid,5-bis (2, 4-dimethylphenyl) octane in 69% yield. m.p.105-107 deg.C (undercorrected);1H NMR(500MHz,CDCl3)δ6.99-6.96(m,4H),6.90(d,J＝8.0Hz,1H),6.76(s,1H),3.80(d,J＝5.5Hz,1H),3.69(d,J＝8.0Hz,1H),2.90(d,J＝15.0Hz,1H),2.79(dd,J＝5.5,15.0Hz,1H),2.66(dd,J＝8.0,14.5Hz,1H),2.42(d,J＝14.5Hz,1H),2.30(s,6H),2.22(s,6H)；13C NMR(125MHz,CDCl3)δ138.0,137.63,137.60,137.0,136.8,136.5,131.9,131.7,128.9,127.9,126.98,126.92,122.7(q,JC-F＝281.0Hz),122.3(q,JC-F＝280.4Hz),86.4(q,JC-F＝33.7Hz),86.1(q,JC-F＝33.9Hz),45.2,43.0,42.9,42.3,21.6,21.5,20.67,20.66；19F NMR(470MHz,CDCl3)δ-79.8(s,3F),-80.1(s,3F)；LRMS(EI,70eV)m/z(％):568(M+,1),285(63),283(100),153(17),132(9)；HRMS(EI+)Calcd for C24H24Cl4F6 +(M+):566.0536,Found:566.0524。
the sixth specific embodiment: under the irradiation of visible light, 0.2mmol of 4-tert-butylstyrene, 1.0mmol of trifluorotrichloroethane, 0.006mmol of photo-redox catalyst fac- [ Ir (ppy)3]2.0mmol of deionized water, 2.0mmol of triphenylphosphine, 1.0mmol of zinc iodide, and 1.0mmol of potassium phosphate were added to 2.0ml of tetrahydrofuran to carry out a reaction. The mixture was stirred under nitrogen at 25 ℃ for 12 hours. After the reaction was complete, hydrogen peroxide was added dropwise to the flask until the solution turned purple. Then, ethyl acetate was added to the mixture, and the mixture was washed with saturated sodium thiosulfate and brine. After extraction of the aqueous layer with ethyl acetate, the combined organic layers were dried over anhydrous sodium sulfate and evaporated in vacuo. The residue was purified by flash column chromatography to give 46.8mg of 2,2,7, 7-tetrachloro-1, 1,1,8,8,8 hexafluoro-4, 5-bis (4-tert-butylphenyl) octane as a white solid in 77% yield. m.p.98-100 deg.c (undercorrected);1H NMR(500MHz,CDCl3)δ7.34(d,J＝8.0Hz,2H),7.20(d,J＝7.5Hz,2H),7.14(d,J＝7.5Hz,2H),6.81(d,J＝8.0Hz,2H),3.61(d,J＝5.0Hz,1H),3.33(d,J＝8.0Hz,1H),2.82(d,J＝15.0Hz,1H),2.63(dd,J＝5.0,15.0Hz,1H),2.53(dd,J＝8.0,14.5Hz,1H),2.40(d,J＝14.5Hz,1H),1.32(s,9H),1.30(s,9H)；13C NMR(125MHz,CDCl3)δ151.2,150.6,138.6,137.6,130.0,129.2,126.1,125.3,122.9(q,JC-F＝280.4Hz),122.7(q,JC-F＝280.1Hz),86.4(q,JC-F＝34.1Hz),85.8(q,JC-F＝33.9Hz),48.4,47.6,43.8,43.4,35.1,35.0,31.95,31.94；19F NMR(470MHz,CDCl3)δ-79.6(s,3F),-80.1(s,3F)。
the seventh specific embodiment: under the irradiation of visible light, 0.2mmol of 4-methoxystyrene, 1.0mmol of trifluorotrichloroethane, 0.006mmol of photo-redox catalyst fac- [ Ir (ppy)3]2.0mmol of deionized water, 2.0mmol of triphenylphosphine, 1.0mmol of zinc iodide, and 1.0mmol of potassium phosphate were added to 2.0ml of tetrahydrofuran to carry out a reaction. The mixture was stirred under nitrogen at 25 ℃ for 12 hours. After the reaction was complete, hydrogen peroxide was added dropwise to the flask until the solution turned purple. Then, ethyl acetate was added to the mixture, and the mixture was washed with saturated sodium thiosulfate and brine. After extraction of the aqueous layer with ethyl acetate, the combined organic layers were dried over anhydrous sodium sulfate and evaporated in vacuo. The residue was purified by flash column chromatography to give 33.1mg of 2,2,7, 7-tetrachloro-1, 1,1,8,8,8 hexafluoro-4, 5-bis (4-methoxyphenyl) octane as a pale yellow solid in 58% yield. m.p.109-111 deg.C (undercorrected);1H NMR(500MHz,CDCl3)δ7.13(d,J＝8.5Hz,2H),6.88(d,J＝8.5Hz,2H),6.82(d,J＝9.0Hz,2H),6.77(d,J＝9.0Hz,2H),3.82(s,3H),3.79(s,3H),3.60-3.59(m,1H),3.32-3.30(m,1H),2.79-2.76(m,1H),2.54(dd,J＝6.5,15.0Hz,1H),2.52-2.46(m,1H),2.43(d,J＝15.0Hz,2H)；13C NMR(125MHz,CDCl3)δ159.5,159.3,133.6,132.3,131.5,130.5,122.9(q,JC-F＝280.5Hz),122.7(q,JC-F＝280.3Hz),114.7,113.9,86.2(q,JC-F＝34.1Hz),85.7(q,JC-F＝34.3Hz),55.81,55.77,48.1,47.2,44.3,43.5；19F NMR(470MHz,CDCl3)δ-79.6(s,3F),-79.9(s,3F)；LRMS(EI,70eV)m/z(％):572(M+,1),287(63),285(100),134(25),119(4)；HRMS(EI+)Calcd for C22H20O2Cl4F6 +(M+):570.0122,Found:570.0111。
the eighth embodiment: under the irradiation of visible light, 0.2mmol of 4-acetoxystyrene, 1.0mmol of trifluorotrichloroethane, 0.006mmol of photo-redox catalyst fac- [ Ir (ppy)3]2.0mmol of deionized water, 2.0mmol of triphenylphosphine, 1.0mmol of zinc iodide, and 1.0mmol of potassium phosphate were added to 2.0ml of tetrahydrofuran to carry out a reaction. The mixture was stirred under nitrogen at 25 ℃ for 12 hours. After the reaction was complete, hydrogen peroxide was added dropwise to the flask until the solution turned purple. Then, ethyl acetate was added to the mixture, and the mixture was washed with saturated sodium thiosulfate and brine. After extraction of the aqueous layer with ethyl acetate, the combined organic layers were dried over anhydrous sodium sulfate and evaporated in vacuo. The residue was purified by flash column chromatography to give 11.9mg of 2,2,7, 7-tetrachloro-1, 1,1,8,8,8 hexafluoro-4, 5-bis (4-acetoxyphenyl) octane as a white solid in 19% yield. m.p.210-213 deg.C (undercorrected);1H NMR(500MHz,CDCl3)δ7.19(d,J＝8.0Hz,4H),7.10(d,J＝8.0Hz,4H),3.43(d,J＝8.0Hz,2H),2.57(dd,J＝8.0,15.0Hz,2H),2.46(d,J＝15.0Hz,2H),2.29(s,6H)；13C NMR(125MHz,CDCl3)δ169.6,150.7,138.8,130.4,122.6(q,JC-F＝280.6Hz),122.4,85.5(q,JC-F＝34.4Hz),48.3,43.4,21.7；19F NMR(470MHz,CDCl3)δ-79.9(s,6F)；(2h-2):Colorless oil(27.0mg,43％yield,dr＝2.23:1)；1H NMR(500MHz,CDCl3)δ6.98(d,J＝8.5Hz,4H),6.89(d,J＝8.5Hz,4H),3.68-3.66(m,2H),2.82(d,J＝15.0Hz,2H),2.62(dd,J＝5.5,15.0Hz,2H),2.28(s,6H)；13C NMR(125MHz,CDCl3)δ169.7,150.5,137.8,131.2,122.8(q,JC-F＝280.4Hz),121.8,86.0(q,JC-F＝34.4Hz),47.4,44.2,21.7；19F NMR(470MHz,CDCl3)δ-79.6(s,6F)；LRMS(EI,70eV)m/z(％):628(M+,1),315(8),313(14),273(61),271(100),141(10)；HRMS(EI+)Calcd for C24H20O4Cl4F6 +(M+):626.0020,Found:626.0020。
the specific embodiment is nine: under the irradiation of visible light, 0.2mmol of 4-fluorostyrene, 1.0mmol of trifluorotrichloroethane and 0.006mmol of photoredox catalyst are addedOxidant fac- [ Ir (ppy)3]2.0mmol of deionized water, 2.0mmol of triphenylphosphine, 1.0mmol of zinc iodide, and 1.0mmol of potassium phosphate were added to 2.0ml of tetrahydrofuran to carry out a reaction. The mixture was stirred under nitrogen at 25 ℃ for 12 hours. After the reaction was complete, hydrogen peroxide was added dropwise to the flask until the solution turned purple. Then, ethyl acetate was added to the mixture, and the mixture was washed with saturated sodium thiosulfate and brine. After extraction of the aqueous layer with ethyl acetate, the combined organic layers were dried over anhydrous sodium sulfate and evaporated in vacuo. The residue was purified by flash column chromatography to give 28.0mg of 2,2,7, 7-tetrachloro-1, 1,1,8,8,8 hexafluoro-4, 5-bis (4-fluorophenyl) octane as a yellow oily liquid in 51% yield.1H NMR(500MHz,CDCl3)δ7.21-7.18(m,2H),7.08-7.05(m,2H),6.93-6.90(m,2H),6.88-6.86(m,2H),3.58(d,J＝6.0Hz,1H),3.38(d,J＝8.5Hz,1H),2.82(d,J＝15.0Hz,1H),2.64(dd,J＝6.0,15.0Hz,1H),2.52(dd,J＝8.5,15.0Hz,1H),2.41(d,J＝15.0Hz,1H)；13C NMR(125MHz,CDCl3)δ162.8(d,JC-F＝245.4Hz),162.5(d,JC-F＝245.4Hz),137.1(d,JC-F＝3.8Hz),136.3(d,JC-F＝3.3Hz),131.6(d,JC-F＝7.9Hz),131.0(d,JC-F＝7.9Hz),122.8(q,JC-F＝280.4Hz),122.6(q,JC-F＝280.5Hz),116.4(d,JC-F＝21.4Hz),115.7(d,JC-F＝21.3Hz),85.9(q,JC-F＝34.5Hz),85.4(q,JC-F＝34.1Hz),48.1,47.5,44.3,43.6；19F NMR(470MHz,CDCl3)δ-79.7(s,3F),-80.0(s,3F),-114.3(s,1F),-114.9(s,1F)；LRMS(EI,70eV)m/z(％):548(M+,1),277(10),275(62),273(100),143(53)；HRMS(EI+)Calcd for C20H14Cl4F8 +(M+):545.9722,Found:545.9720。
The specific embodiment ten: under the irradiation of visible light, 0.2mmol of 4-chlorostyrene, 1.0mmol of trifluorotrichloroethane, 0.006mmol of photo-redox catalyst fac- [ Ir (ppy)3]2.0mmol of deionized water, 2.0mmol of triphenylphosphine, 1.0mmol of zinc iodide, and 1.0mmol of potassium phosphate were added to 2.0ml of tetrahydrofuran to carry out a reaction. Under nitrogen atmosphere at 25 deg.CStirred for 12 hours. After the reaction was complete, hydrogen peroxide was added dropwise to the flask until the solution turned purple. Then, ethyl acetate was added to the mixture, and the mixture was washed with saturated sodium thiosulfate and brine. After extraction of the aqueous layer with ethyl acetate, the combined organic layers were dried over anhydrous sodium sulfate and evaporated in vacuo. The residue was purified by flash column chromatography to give 22.1mg of 2,2,7, 7-tetrachloro-1, 1,1,8,8, 8-hexafluoro-4, 5-bis (4-chlorophenyl) octane as a white solid in 38% yield. (2j-1) m.p.91-93 deg.C (uncoated);1H NMR(500MHz,CDCl3)δ7.21(d,J＝8.0Hz,4H),6.85(d,J＝8.0Hz,4H),3.58(d,J＝6.0Hz,2H),2.80(d,J＝15.0Hz,2H),2.62(dd,J＝6.0,15.0Hz,2H)；13C NMR(125MHz,CDCl3)δ138.9,133.9,131.5,129.0,122.7(q,JC-F＝280.5Hz),85.8(q,JC-F＝34.4Hz),47.5,44.2；19F NMR(470MHz,CDCl3)δ-79.7(s,6F)；(2j-2):Colorless oil(12.2mg,21％yield,dr＝1.80:1)；1H NMR(500MHz,CDCl3)δ7.34(d,J＝8.0Hz,4H),7.14(d,J＝8.0Hz,4H),3.38(d,J＝8.5Hz,2H),2.54(dd,J＝8.5,15.0Hz,2H),2.41(d,J＝15.0Hz,2H)；13C NMR(125MHz,CDCl3)δ139.8,134.3,130.8,129.7,122.6(q,JC-F＝280.5Hz),85.4(q,JC-F＝34.8Hz),48.2,43.4；19F NMR(470MHz,CDCl3)δ-79.9(s,6F)；LRMS(EI,70eV)m/z(％):580(M+,1),293(31),291(91),289(100),161(44),159(69)；HRMS(EI+)Calcd for C20H14Cl6F6 +(M+):577.9131,Found:577.9138。
the first specific embodiment: under the irradiation of visible light, 0.2mmol of 3-chlorostyrene, 1.0mmol of trifluorotrichloroethane, 0.006mmol of photo-redox catalyst fac- [ Ir (ppy)3]2.0mmol of deionized water, 2.0mmol of triphenylphosphine, 1.0mmol of zinc iodide, and 1.0mmol of potassium phosphate were added to 2.0ml of tetrahydrofuran to carry out a reaction. The mixture was stirred under nitrogen at 25 ℃ for 12 hours. After the reaction was complete, hydrogen peroxide was added dropwise to the flask until the solution turned purple. Then, ethyl acetate was added to the mixture, and the mixture was washed with saturated sodium thiosulfate and brine. With ethyl acetateAfter extraction of the aqueous layer, the combined organic layers were dried over anhydrous sodium sulfate and evaporated in vacuo. The residue was purified by flash column chromatography to give 25.0mg of 2,2,7, 7-tetrachloro-1, 1,1,8,8, 8-hexafluoro-4, 5-bis (3-chlorophenyl) octane as a white solid in 43% yield. (2k-1) m.p.125-127 deg.C (uncoated);1H NMR(500MHz,CDCl3)δ7.19(d,J＝7.0Hz,2H),7.18-7.15(m,2H),6.87(s,2H),6.83(d,J＝7.0Hz,2H),3.56(d,J＝6.5Hz,2H),2.82(d,J＝15.0Hz,2H),2.68(dd,J＝6.5,15.0Hz,2H)；13C NMR(125MHz,CDCl3)δ142.5,134.8,130.1,130.0,128.3,128.2,122.7(q,JC-F＝280.5Hz),85.7(q,JC-F＝34.6Hz),47.8,43.9；19F NMR(470MHz,CDCl3)δ-79.6(s,6F)；(2k-2):White solid(11.6mg,20％yield,dr＝2.15:1),mp 125-127℃(uncorrected)；1H NMR(500MHz,CDCl3)δ7.32-7.29(m,4H),7.22(s,2H),7.13-7.10(m,2H),3.38(d,J＝7.5Hz,2H),2.57(dd,J＝7.5,14.5Hz,2H),2.40(d,J＝14.5Hz,2H)；13C NMR(125MHz,CDCl3)δ143.4,135.4,130.7,129.7,128.7,127.8,122.6(q,JC-F＝280.4Hz),85.3(q,JC-F＝34.5Hz),48.4,43.4；19F NMR(470MHz,CDCl3)δ-79.9(s,6F)；LRMS(EI,70eV)m/z(％):580(M+,1),295(4),293(33),291(97),289(100),159(50)；HRMS(EI+)Calcd for C20H14Cl6F6 +(M+):577.9131,Found:577.9146。
the specific example twelve: under the irradiation of visible light, 0.2mmol of 2-chlorostyrene, 1.0mmol of trifluorotrichloroethane, 0.006mmol of photo-redox catalyst fac- [ Ir (ppy)3]2.0mmol of deionized water, 2.0mmol of triphenylphosphine, 1.0mmol of zinc iodide, and 1.0mmol of potassium phosphate were added to 2.0ml of tetrahydrofuran to carry out a reaction. The mixture was stirred under nitrogen at 25 ℃ for 12 hours. After the reaction was complete, hydrogen peroxide was added dropwise to the flask until the solution turned purple. Then, ethyl acetate was added to the mixture, and the mixture was washed with saturated sodium thiosulfate and brine. After extraction of the aqueous layer with ethyl acetate, the combined organic layers were dried over anhydrous sodium sulfate and evaporated in vacuo. Purifying the residue by flash column chromatography33.1mg of 2,2,7, 7-tetrachloro-1, 1,1,8,8, 8-hexafluoro-4, 5-bis (2-chlorophenyl) octane as a white solid were obtained in a yield of 57%. m.p.106-108 deg.C (undercorrected);1H NMR(500MHz,CDCl3)δ7.44-7.41(m,2H),7.36-7.33(m,1H),7.24-7.22(m,2H),7.14-7.11(m,2H),7.02-6.99(m,1H),4.26(d,J＝7.5Hz,1H),4.17(d,J＝9.5Hz,1H),2.99(d,J＝15.0Hz,1H),2.85(dd,J＝7.5,15.0Hz,1H),2.74(dd,J＝9.5,15.0Hz,1H),2.33(d,J＝15.0Hz,1H)；13C NMR(125MHz,CDCl3)δ139.8,139.3,136.4,135.2,130.4,130.2,129.9,129.3,129.1,128.7,128.3,127.2,122.8(q,JC-F＝280.8Hz),122.6(q,JC-F＝280.3Hz),85.4(q,JC-F＝34.5Hz),85.3(q,JC-F＝34.5Hz),45.4,43.5,42.8,42.7；19F NMR(470MHz,CDCl3)δ-79.9(s,3F),-80.1(s,3F)；LRMS(EI,70eV)m/z(％):580(M+,1),295(6),293(37),291(94),289(100),159(49)；HRMS(EI+)Calcd for C20H14Cl6F6 +(M+):577.9131,Found:577.9114。
the specific example thirteen: under the irradiation of visible light, 0.2mmol of 2-bromostyrene, 1.0mmol of trifluorotrichloroethane, 0.006mmol of photo-redox catalyst fac- [ Ir (ppy)3]2.0mmol of deionized water, 2.0mmol of triphenylphosphine, 1.0mmol of zinc iodide, and 1.0mmol of potassium phosphate were added to 2.0ml of tetrahydrofuran to carry out a reaction. The mixture was stirred under nitrogen at 25 ℃ for 12 hours. After the reaction was complete, hydrogen peroxide was added dropwise to the flask until the solution turned purple. Then, ethyl acetate was added to the mixture, and the mixture was washed with saturated sodium thiosulfate and brine. After extraction of the aqueous layer with ethyl acetate, the combined organic layers were dried over anhydrous sodium sulfate and evaporated in vacuo. The residue was purified by flash column chromatography to give 29.5mg of 2,2,7, 7-tetrachloro-1, 1,1,8,8, 8-hexafluoro-4, 5-bis (2-bromophenyl) octane as a yellow solid in 44% yield. m.p.87-89 deg.C (uncoated);1H NMR(500MHz,CDCl3)δ7.61(d,J＝8.0Hz,1H),7.42-7.38(m,2H),7.31-7.28(m,2H),7.18-7.16(m,2H),6.94-6.90(m,1H),4.23(d,J＝7.5Hz,1H),4.15(dd,J＝2.5,7.0Hz,1H),3.00(d,J＝15.0Hz,1H),2.86(dd,J＝7.5,15.0Hz,1H),2.78-2.73(m,1H),2.34(d,J＝15.0Hz,1H)；13C NMR(125MHz,CDCl3)δ141.4,140.8,133.7,133.3,130.6,129.6,129.3,129.0,128.9,127.82,127.78,126.8,122.8(q,JC-F＝280.6Hz),122.6(q,JC-F＝280.6Hz),85.3(q,JC-F＝34.5Hz),85.2(q,JC-F＝34.3Hz),46.6,45.62,45.55,42.8；19F NMR(470MHz,CDCl3)δ-79.9(s,3F),-80.2(s,3F)；HRMS(DART Negative Ion)Calcd for C20H13Br2Cl4F6 +(M+):664.8048,Found:664.8062。
the specific embodiment fourteen: under the irradiation of visible light, 0.2mmol of 4-trifluoromethylstyrene, 1.0mmol of trifluorotrichloroethane, and 0.006mmol of photo-redox catalyst fac- [ Ir (ppy)3]2.0mmol of deionized water, 2.0mmol of triphenylphosphine, 1.0mmol of zinc iodide, and 1.0mmol of potassium phosphate were added to 2.0ml of tetrahydrofuran to carry out a reaction. The mixture was stirred under nitrogen at 25 ℃ for 12 hours. After the reaction was complete, hydrogen peroxide was added dropwise to the flask until the solution turned purple. Then, ethyl acetate was added to the mixture, and the mixture was washed with saturated sodium thiosulfate and brine. After extraction of the aqueous layer with ethyl acetate, the combined organic layers were dried over anhydrous sodium sulfate and evaporated in vacuo. The residue was purified by flash column chromatography to give 12.3mg of 2,2,7, 7-tetrachloro-1, 1,1,8,8, 8-hexafluoro-4, 5-bis (4-trifluoromethylphenyl) octane as a yellow solid in 19% yield. (2n-1) m.p.84-86 deg.C (uncoated);1H NMR(500MHz,CDCl3)δ7.48(d,J＝8.0Hz,4H),7.04(d,J＝8.0Hz,4H),3.68(d,J＝7.0Hz,2H),2.88(d,J＝15.0Hz,2H),2.73(dd,J＝7.0,15.0Hz,2H)；13C NMR(125MHz,CDCl3)δ144.5,130.44(q,JC-F＝32.5Hz),130.40,125.8(q,JC-F＝3.75Hz),124.5(q,JC-F＝270.5Hz),122.7(q,JC-F＝280.5Hz),85.6(q,JC-F＝34.6Hz),48.0,44.0；19F NMR(470MHz,CDCl3)δ-62.6(s,6F),-79.6(s,6F)；(2n-2):Yellow solid(11.7mg,18％yield,dr＝1.06:1),m.p.86-88oC(uncorrected)；1H NMR(500MHz,CDCl3)δ7.64(d,J＝7.5Hz,4H),7.34(d,J＝7.5Hz,4H),3.54(d,J＝8.0Hz,2H),2.63(dd,J＝8.0,14.5Hz,2H),2.43(d,J＝14.5Hz,2H)；13C NMR(125MHz,CDCl3)δ145.2,131.0(q,JC-F＝32.6Hz),130.0,126.5(q,JC-F＝3.75Hz),124.5(q,JC-F＝270.4Hz),122.5(q,JC-F＝280.5Hz),85.2(q,JC-F＝34.4Hz),48.5,43.4；19F NMR(470MHz,CDCl3)δ-62.5(s,6F),-80.0(s,6F)；LRMS(EI,70eV)m/z(％):648(M+,13),483(68),481(100),315(76),139(38)；HRMS(EI+)Calcd for C22H14Cl4F12 +(M+):645.9663,Found:645.9658。
the specific embodiment fifteen: under the irradiation of visible light, 0.2mmol of 4-cyanostyrene, 1.0mmol of trifluorotrichloroethane, 0.006mmol of photo-redox catalyst fac- [ Ir (ppy)3]2.0mmol of deionized water, 2.0mmol of triphenylphosphine, 1.0mmol of zinc iodide, and 1.0mmol of potassium phosphate were added to 2.0ml of tetrahydrofuran to carry out a reaction. The mixture was stirred under nitrogen at 25 ℃ for 12 hours. After the reaction was complete, hydrogen peroxide was added dropwise to the flask until the solution turned purple. Then, ethyl acetate was added to the mixture, and the mixture was washed with saturated sodium thiosulfate and brine. After extraction of the aqueous layer with ethyl acetate, the combined organic layers were dried over anhydrous sodium sulfate and evaporated in vacuo. The residue was purified by flash column chromatography to give 22.5mg of 2,2,7, 7-tetrachloro-1, 1,1,8,8, 8-hexafluoro-4, 5-bis (4-cyanophenyl) octane as a white solid in 40% yield. m.p.106-108 deg.C (undercorrected);1H NMR(500MHz,CDCl3)δ7.69(d,J＝8.0Hz,2H),7.50(d,J＝8.0Hz,2H),7.35(d,J＝8.0Hz,2H),7.06(d,J＝8.0Hz,2H),3.59(d,J＝5.5Hz,1H),3.52(d,J＝7.5Hz,1H),2.89(d,J＝15.5Hz,1H),2.79(dd,J＝5.5,15.5Hz,1H),2.62(dd,J＝7.5,15.0Hz,1H),2.37(d,J＝15.0Hz,1H)；13C NMR(125MHz,CDCl3)δ146.3,146.1,133.3,132.8,130.5,130.3,122.6(q,JC-F＝280.6Hz),122.4(q,JC-F＝280.8Hz),118.7,118.6,112.9,112.3,85.4(q,JC-F＝34.8Hz),84.9(q,JC-F＝34.8Hz),48.5,48.3,43.9,43.3；19F NMR(470MHz,CDCl3)δ-79.6(s,3F),-79.9(s,3F)；LRMS(EI,70eV)m/z(％):562(M+,7),285(8),283(43),281(74),150(100),130(36)；HRMS(EI+)Calcd for C22H14N2Cl4F6 +(M+):559.9815,Found:559.9821。
the specific embodiment is sixteen: under the irradiation of visible light, 0.2mmol of naphthylethylene, 1.0mmol of trichlorotrifluoroethane, and 0.006mmol of photo-redox catalyst fac- [ Ir (ppy)3]2.0mmol of deionized water, 2.0mmol of triphenylphosphine, 1.0mmol of zinc iodide, and 1.0mmol of potassium phosphate were added to 2.0ml of tetrahydrofuran to carry out a reaction. The mixture was stirred under nitrogen at 25 ℃ for 12 hours. After the reaction was complete, hydrogen peroxide was added dropwise to the flask until the solution turned purple. Then, ethyl acetate was added to the mixture, and the mixture was washed with saturated sodium thiosulfate and brine. After extraction of the aqueous layer with ethyl acetate, the combined organic layers were dried over anhydrous sodium sulfate and evaporated in vacuo. The residue was purified by flash column chromatography to give 22.0mg of white solid, 2,7, 7-tetrachloro-1, 1,1,8,8, 8-hexafluoro-4, 5-di (2-naphthyl) octane (2p-1) in 33% yield. m.p.106-108 deg.C (undercorrected);1H NMR(500MHz,CDCl3)δ7.81-7.80(m,2H),7.72-7.68(m,4H),7.48-7.46(m,6H),7.00(d,J＝8.0Hz,2H),3.96(d,J＝5.0Hz,2H),3.01(d,J＝15.0Hz,2H),2.75(dd,J＝5.0,15.0Hz,2H)；13C NMR(125MHz,CDCl3)δ137.8,133.6,133.2,129.7,128.5,128.4,128.2,128.1,126.8,126.7,122.9(q,JC-F＝280.4Hz),86.2(q,JC-F＝34.4Hz),48.2,44.3；19F NMR(470MHz,CDCl3)δ-79.6(s,6F)；(2p-2):White solid(19.0mg,31％yield,dr＝1.06:1),m.p.206-209℃；1H NMR(500MHz,CDCl3)δ7.90-7.83(m,6H),7.76(s,2H),7.54-7.50(m,4H),7.40(d,J＝8.5Hz,2H),3.73(d,J＝8.0Hz,2H),2.76(dd,J＝8.0,14.5Hz,2H),2.57(d,J＝14.5Hz,2H)；13C NMR(125MHz,CDCl3)δ138.9,134.0,133.5,129.3,128.39,128.37,128.3,127.0,126.8,126.7,122.6(q,JC-F＝280.6Hz),85.7(q,JC-F＝34.0Hz),48.9,43.6；19F NMR(470MHz,CDCl3)δ-79.9(s,6F)；LRMS(EI,70eV)m/z(％):612(M+,9),307(57),305(88),253(78),155(100)；HRMS(EI+)Calcd for C28H20Cl4F6 +(M+):610.0223,Found:610.0231。
specific example seventeen: under the irradiation of visible light, 0.2mmol of alpha-methylstyrene, 1.0mmol of trifluorotrichloroethane, 0.006mmol of photo-redox catalyst fac- [ Ir (ppy)3]2.0mmol of deionized water, 2.0mmol of triphenylphosphine, 1.0mmol of zinc iodide, and 1.0mmol of potassium phosphate were added to 2.0ml of tetrahydrofuran to carry out a reaction. The mixture was stirred under nitrogen at 25 ℃ for 12 hours. After the reaction was complete, hydrogen peroxide was added dropwise to the flask until the solution turned purple. Then, ethyl acetate was added to the mixture, and the mixture was washed with saturated sodium thiosulfate and brine. After extraction of the aqueous layer with ethyl acetate, the combined organic layers were dried over anhydrous sodium sulfate and evaporated in vacuo. The residue was purified by flash column chromatography to give 42.1mg of 2,2,7, 7-tetrachloro-1, 1,1,8,8, 8-hexafluoro-4, 5-di (. alpha. -methylphenyl) octane as a white solid in 78% yield. m.p.106-108 deg.C (undercorrected);1H NMR(500MHz,CDCl3)δ7.17-6.97(m,10H),3.27(d,J＝15.0Hz,1H),2.63-2.53(m,2H),2.47(d,J＝15.0Hz,1H),1.75(s,3H),1.68(s,3H)；13C NMR(125MHz,CDCl3)δ141.4,140.8,129.552,129.550,129.2,127.9,127.553,127.552,123.2(q,JC-F＝280.5Hz),123.1(q,JC-F＝280.5Hz),84.41(q,JC-F＝33.0Hz),84.36(q,JC-F＝32.9Hz),49.7,49.2,42.81,42.77,21.2,20.6；19F NMR(470MHz,CDCl3)δ-80.8(s,3F),-81.0(s,3F)；LRMS(EI,70eV)m/z(％):540(M+,1),271(65),269(100),139(38),118(5)；HRMS(EI+)Calcd for C22H20Cl4F6 +(M+):538.0223,Found:538.0229.
the specific embodiment eighteen: under the irradiation of visible light, 0.2mmol of styrene, 1.0mmol of trifluorotrichloroethane, and 0.006mmol of photo-redox catalyst fac- [ Ir (ppy)3]2.0mmol of deionized water, 2.0mmol of triphenylphosphine and 1.0mmol of potassium phosphate were added to 2.0ml of methylene chloride to carry out a reaction. The mixture was stirred under nitrogen at 25 ℃ for 12 hours. After the reaction is finishedHydrogen peroxide was added dropwise to the flask until the solution turned purple. Then, ethyl acetate was added to the mixture, and the mixture was washed with saturated sodium thiosulfate and brine. After extraction of the aqueous layer with ethyl acetate, the combined organic layers were dried over anhydrous sodium sulfate and evaporated in vacuo. The residue was purified by flash column chromatography to give 2,2,7, 7-tetrachloro-1, 1,1,8,8, 8-hexafluoro-4, 5-diphenyloctane as a trace white solid in 15% yield.
The specific examples are nineteen: under the irradiation of visible light, 0.2mmol of styrene, 1.0mmol of trifluorotrichloroethane, and 0.006mmol of photo-redox catalyst fac- [ Ir (ppy)3]2.0mmol of deionized water, 2.0mmol of triphenylphosphine, 1.0mmol of potassium iodide, and 1.0mmol of potassium phosphate were added to 2.0ml of tetrahydrofuran to carry out a reaction. The mixture was stirred under nitrogen at 25 ℃ for 12 hours. After the reaction was complete, hydrogen peroxide was added dropwise to the flask until the solution turned purple. Then, ethyl acetate was added to the mixture, and the mixture was washed with saturated sodium thiosulfate and brine. After extraction of the aqueous layer with ethyl acetate, the combined organic layers were dried over anhydrous sodium sulfate and evaporated in vacuo. The residue was purified by flash column chromatography to give 2,2,7, 7-tetrachloro-1, 1,1,8,8, 8-hexafluoro-4, 5-diphenyloctane as a white solid in 25% yield.
The specific embodiment twenty: under the irradiation of visible light, 0.2mmol of styrene, 1.0mmol of trifluorotrichloroethane, and 0.006mmol of photo-redox catalyst fac- [ Ir (ppy)3]2.0mmol of deionized water, 2.0mmol of triphenylphosphine, 1.0mmol of sodium iodide, and 1.0mmol of potassium phosphate were added to 2.0ml of tetrahydrofuran to carry out a reaction. The mixture was stirred under nitrogen at 25 ℃ for 12 hours. After the reaction was complete, hydrogen peroxide was added dropwise to the flask until the solution turned purple. Then, ethyl acetate was added to the mixture, and the mixture was washed with saturated sodium thiosulfate and brine. After extraction of the aqueous layer with ethyl acetate, the combined organic layers were dried over anhydrous sodium sulfate and evaporated in vacuo. The residue was purified by flash column chromatography to give 2,2,7, 7-tetrachloro-1, 1,1,8,8, 8-hexafluoro-4, 5-diphenyloctane as a white solid in 62% yield.
The specific embodiment twenty one: in at leastUnder the irradiation of light, 0.2mmol of styrene, 1.0mmol of trifluorotrichloroethane, and 0.006mmol of photo-redox catalyst fac- [ Ir (ppy)3]2.0mmol of deionized water, 2.0mmol of triphenylphosphine, 1.0mmol of TBAI, and 1.0mmol of potassium phosphate were added to 2.0ml of tetrahydrofuran to carry out a reaction. The mixture was stirred under nitrogen at 25 ℃ for 12 hours. After the reaction was complete, hydrogen peroxide was added dropwise to the flask until the solution turned purple. Then, ethyl acetate was added to the mixture, and the mixture was washed with saturated sodium thiosulfate and brine. After extraction of the aqueous layer with ethyl acetate, the combined organic layers were dried over anhydrous sodium sulfate and evaporated in vacuo. The residue was purified by flash column chromatography to give 2,2,7, 7-tetrachloro-1, 1,1,8,8, 8-hexafluoro-4, 5-diphenyloctane as a white solid in 63% yield.
The specific embodiment twenty two: under the irradiation of visible light, 0.2mmol of styrene, 1.0mmol of trifluorotrichloroethane, and 0.006mmol of photo-redox catalyst fac- [ Ir (ppy)3]2.0mmol of deionized water, 2.0mmol of triphenylphosphine, 1.0mmol of zinc iodide and 1.0mmol of potassium carbonate were added to 2.0ml of tetrahydrofuran to carry out a reaction. The mixture was stirred under nitrogen at 25 ℃ for 12 hours. After the reaction was complete, hydrogen peroxide was added dropwise to the flask until the solution turned purple. Then, ethyl acetate was added to the mixture, and the mixture was washed with saturated sodium thiosulfate and brine. After extraction of the aqueous layer with ethyl acetate, the combined organic layers were dried over anhydrous sodium sulfate and evaporated in vacuo. The residue was purified by flash column chromatography to give 2,2,7, 7-tetrachloro-1, 1,1,8,8, 8-hexafluoro-4, 5-diphenyloctane as a white solid in 43% yield.
The specific embodiment twenty three: under the irradiation of visible light, 0.2mmol of styrene, 1.0mmol of trifluorotrichloroethane, and 0.006mmol of photo-redox catalyst fac- [ Ir (ppy)3]2.0mmol of deionized water, 2.0mmol of triphenylphosphine, 1.0mmol of zinc iodide, and 1.0mmol of cesium phosphate were added to 2.0ml of tetrahydrofuran to effect a reaction. The mixture was stirred under nitrogen at 25 ℃ for 12 hours. After the reaction was complete, hydrogen peroxide was added dropwise to the flask until the solution turned purple. Then, ethyl acetate was added to the mixture,washed with saturated sodium thiosulfate and brine. After extraction of the aqueous layer with ethyl acetate, the combined organic layers were dried over anhydrous sodium sulfate and evaporated in vacuo. The residue was purified by flash column chromatography to give 2,2,7, 7-tetrachloro-1, 1,1,8,8, 8-hexafluoro-4, 5-diphenyloctane as a white solid in 54% yield.
The specific embodiment twenty four: under the irradiation of visible light, 0.2mmol of styrene, 1.0mmol of trifluorotrichloroethane, and 0.006mmol of photo-redox catalyst fac- [ Ir (ppy)3]2.0mmol of deionized water, 2.0mmol of triphenylphosphine, 1.0mmol of zinc iodide, and 1.0mmol of DBU were added to 2.0ml of tetrahydrofuran to carry out a reaction. The mixture was stirred under nitrogen at 25 ℃ for 12 hours. After the reaction was complete, hydrogen peroxide was added dropwise to the flask until the solution turned purple. Then, ethyl acetate was added to the mixture, and the mixture was washed with saturated sodium thiosulfate and brine. After extraction of the aqueous layer with ethyl acetate, the combined organic layers were dried over anhydrous sodium sulfate and evaporated in vacuo. The residue was purified by flash column chromatography to give 2,2,7, 7-tetrachloro-1, 1,1,8,8, 8-hexafluoro-4, 5-diphenyloctane as a white solid in 43% yield.
The specific embodiment is twenty five: under the irradiation of visible light, 0.2mmol of styrene, 1.0mmol of trifluorotrichloroethane, and 0.006mmol of photo-redox catalyst fac- [ Ir (ppy)3]2.0mmol of deionized water, 2.0mmol of triphenylphosphine, 1.0mmol of zinc iodide and 1.0mmol of triethylamine were added to 2.0ml of tetrahydrofuran to react. The mixture was stirred under nitrogen at 25 ℃ for 12 hours. After the reaction was complete, hydrogen peroxide was added dropwise to the flask until the solution turned purple. Then, ethyl acetate was added to the mixture, and the mixture was washed with saturated sodium thiosulfate and brine. After extraction of the aqueous layer with ethyl acetate, the combined organic layers were dried over anhydrous sodium sulfate and evaporated in vacuo. The residue was purified by flash column chromatography to give 2,2,7, 7-tetrachloro-1, 1,1,8,8, 8-hexafluoro-4, 5-diphenyloctane as a white solid in 32% yield.
Specific example twenty-six: under the irradiation of visible light, 0.2mmol of styrene, 1.0mmol of trifluorotrichloroethane, and 0.006mmol of photo-redox catalyst fac- [ Ir (ppy)3]2.0mmol of deionized water, 2.0mmol of triphenylphosphine, 1.0mmol of zinc iodide, and 1.0mmol of potassium phosphate were added to 2.0ml of tetrahydrofuran to carry out a reaction. The mixture was stirred at 45 ℃ for 12 hours under a nitrogen atmosphere. After the reaction was complete, hydrogen peroxide was added dropwise to the flask until the solution turned purple. Then, ethyl acetate was added to the mixture, and the mixture was washed with saturated sodium thiosulfate and brine. After extraction of the aqueous layer with ethyl acetate, the combined organic layers were dried over anhydrous sodium sulfate and evaporated in vacuo. The residue was purified by flash column chromatography to give 2,2,7, 7-tetrachloro-1, 1,1,8,8, 8-hexafluoro-4, 5-diphenyloctane as a white solid in 40% yield.
The specific embodiment is twenty-seven: under the irradiation of visible light, 0.2mmol of styrene, 1.0mmol of trifluorotrichloroethane, and 0.006mmol of photo-redox catalyst fac- [ Ir (ppy)3]2.0mmol of deionized water, 2.0mmol of triphenylphosphine, 1.0mmol of zinc iodide, and 1.0mmol of potassium phosphate were added to 2.0ml of tetrahydrofuran to carry out a reaction. The mixture was stirred at 10 ℃ for 12 hours in a nitrogen atmosphere. After the reaction was complete, hydrogen peroxide was added dropwise to the flask until the solution turned purple. Then, ethyl acetate was added to the mixture, and the mixture was washed with saturated sodium thiosulfate and brine. After extraction of the aqueous layer with ethyl acetate, the combined organic layers were dried over anhydrous sodium sulfate and evaporated in vacuo. The residue was purified by flash column chromatography to give 2,2,7, 7-tetrachloro-1, 1,1,8,8, 8-hexafluoro-4, 5-diphenyloctane as a white solid in 30% yield.
The specific embodiment twenty eight: under the irradiation of visible light, 0.2mmol of styrene, 1.0mmol of tetrachloromethane, 0.006mmol of photo-redox catalyst fac- [ Ir (ppy)3]2.0mmol of water, 2.0mmol of triphenylphosphine, 1.0mmol of zinc iodide, and 1.0mmol of potassium phosphate were added to 2.0ml of tetrahydrofuran to carry out a reaction. The mixture was stirred under nitrogen at 25 ℃ for 12 hours. After the reaction was complete, hydrogen peroxide was added dropwise to the flask until the solution turned purple. Then, ethyl acetate was added to the mixture, and the mixture was washed with saturated sodium thiosulfate and brine. After extraction of the aqueous layer with ethyl acetate, the combined organic layers were dried over anhydrous sodium sulfate and evaporated in vacuo. Removing residuesThe residue was purified by flash column chromatography to give 21.8mg of 1,1,1,6,6, 6-hexachloro-3, 4-diphenylhexane as a yellow solid in 49% yield. m.p.96-98 deg.C (undercorrected);1H NMR(500MHz,CDCl3)δ7.31-7.30(m,2H),7.25-7.14(m,6H),6.89-6.87(m,2H),3.54(d,J＝5.0Hz,1H),3.32(d,J＝7.0Hz,1H),3.27(d,J＝15.0Hz,1H),3.10(dd,J＝5.0,15.0Hz,1H),3.03(dd,J＝7.0,15.0Hz,1H),2.82(d,J＝15.0Hz,1H)；13C NMR(125MHz,CDCl3)δ141.5,140.6,130.5,129.8,129.3,128.5,128.1,127.6,99.8,99.5,58.6,58.1,50.8,50.0；LRMS(EI,70eV)m/z(％):444(M+,2),225(9),223(25),221(28),127(68),125(100)；HRMS(EI+)Calcd for C18H16Cl6 +(M+):441.9383,Found:441.9379.
specific example twenty-nine: under the irradiation of visible light, 0.2mmol of 4-methylstyrene, 1.0mmol of tetrachloromethane, 0.006mmol of the photoredox catalyst fac- [ Ir (ppy)3]2.0mmol of water, 2.0mmol of triphenylphosphine, 1.0mmol of zinc iodide, and 1.0mmol of potassium phosphate were added to 2.0ml of tetrahydrofuran to carry out a reaction. The mixture was stirred under nitrogen at 25 ℃ for 12 hours. After the reaction was complete, hydrogen peroxide was added dropwise to the flask until the solution turned purple. Then, ethyl acetate was added to the mixture, and the mixture was washed with saturated sodium thiosulfate and brine. After extraction of the aqueous layer with ethyl acetate, the combined organic layers were dried over anhydrous sodium sulfate and evaporated in vacuo. The residue was purified by flash column chromatography to give 27.0mg of 1,1,1,6,6, 6-hexachloro-3, 4-di (4-methylphenyl) hexane as a yellow solid in a yield of 57%. m.p.103-105 deg.C (undercorrected);1H NMR(500MHz,CDCl3)δ7.16-7.12(m,4H),7.05(d,J＝8.0Hz,2H),6.84(d,J＝8.0Hz,2H),3.60(d,J＝5.5Hz,1H),3.31(d,J＝8.0Hz,1H),3.27(d,J＝15.0Hz,1H),3.08-3.02(m,2H),2.87(d,J＝15.0Hz,1H),2.36(s,3H),2.33(s,3H)；13C NMR(125MHz,CDCl3)δ138.5,137.6,137.3,137.2,130.6,129.9,129.6,129.2,100.0,99.7,58.8,58.2,50.4,49.5,21.7,21.6；LRMS(EI,70eV)m/z(％):472(M+,2),239(9),237(28),235(30),141(31),139(100)；HRMS(EI+)Calcd for C20H20Cl6 +(M+):469.9696,Found:466.9687.
thirty of the specific embodiments: under the irradiation of visible light, 0.2mmol of 4-tert-butylstyrene, 1.0mmol of tetrachloromethane, and 0.006mmol of photo-redox catalyst fac- [ Ir (ppy)3]2.0mmol of water, 2.0mmol of triphenylphosphine, 1.0mmol of zinc iodide, and 1.0mmol of potassium phosphate were added to 2.0ml of tetrahydrofuran to carry out a reaction. The mixture was stirred under nitrogen at 25 ℃ for 12 hours. After the reaction was complete, hydrogen peroxide was added dropwise to the flask until the solution turned purple. Then, ethyl acetate was added to the mixture, and the mixture was washed with saturated sodium thiosulfate and brine. After extraction of the aqueous layer with ethyl acetate, the combined organic layers were dried over anhydrous sodium sulfate and evaporated in vacuo. The residue was purified by flash column chromatography to give 12.8mg of 1,1,1,6,6, 6-hexachloro-3, 4-di (4-tert-butylphenyl) hexane as a white solid in 44% yield. m.p.171-173 deg.C (undercorrected);1H NMR(500MHz,CDCl3)δ7.20(d,J＝7.5Hz,4H),6.83(d,J＝7.5Hz,4H),3.57(d,J＝5.0Hz,2H),3.28(d,J＝15.0Hz,2H),3.10(dd,J＝5.0,15.0Hz,2H),1.29(s,18H)；13C NMR(125MHz,CDCl3)δ150.4,137.5,130.2,125.2,100.1,58.6,49.5,35.0,32.0；(3c-2):White solid(11.7mg,21％yield,dr＝1.10:1),mp 190-192℃；1H NMR(500MHz,CDCl3)δ7.32(d,J＝8.0Hz,4H),7.13(d,J＝8.0Hz,4H),3.32(d,J＝8.0Hz,2H),3.04(dd,J＝8.0,15.0Hz,2H),2.88(d,J＝15.0Hz,2H),1.32(s,18H)；13C NMR(125MHz,CDCl3)δ151.0,138.4,129.4,126.0,99.7,58.1,50.3,35.1,32.0；LRMS(EI,70eV)m/z(％):556(M+,1),279(26),277(28),183(31),181(100),145(8)；HRMS(EI+)Calcd for C26H32Cl6 +(M+):554.0635,Found:554.0628.
the specific embodiment is thirty-one: under the irradiation of visible light, 0.2mmol of 2-methoxystyrene, 1.0mmol of tetrachloromethane, 0.006mmol of photo-redox catalyst fac- [ Ir (ppy)3]2.0mmol of water, 2.0mmol of triphenylphosphine, 1.0mmol of zinc iodide, and 1.0mmol of potassium phosphate were added to 2.0ml of tetrahydrofuran to carry out a reaction. Stirring for 12 hours under the condition of nitrogen atmosphere and temperature of 25 DEG C. After the reaction was complete, hydrogen peroxide was added dropwise to the flask until the solution turned purple. Then, ethyl acetate was added to the mixture, and the mixture was washed with saturated sodium thiosulfate and brine. After extraction of the aqueous layer with ethyl acetate, the combined organic layers were dried over anhydrous sodium sulfate and evaporated in vacuo. The residue was purified by flash column chromatography to give 22.2mg of 1,1,1,6,6, 6-hexachloro-3, 4-di (4-methoxyphenyl) hexane as a yellow solid in 44% yield. m.p.153-156 deg.C (undercorrected);1H NMR(500MHz,CDCl3)δ7.14(d,J＝7.5Hz,2H),6.88(d,J＝7.5Hz,2H),6.84(d,J＝7.5Hz,2H),6.77(d,J＝7.5Hz,2H),3.82(s,3H),3.79(s,3H),3.56(d,J＝5.0Hz,1H),3.28(d,J＝7.5Hz,1H),3.24(d,J＝15.0Hz,1H),3.04-2.97(m,2H),2.86(d,J＝15.0Hz,1H)；13C NMR(125MHz,CDCl3)δ159.5,159.2,133.5,132.3,131.6,130.7,114.7,113.9,100.0,99.7,59.0,58.2,55.81,55.79,50.1,49.2；LRMS(EI,70eV)m/z(％):504(M+,15),301(44),277(15),275(64),273(100),143(37)；HRMS(EI+)Calcd for C20H20O2Cl6 +(M+):501.9594,Found:501.9599.
the specific embodiment is thirty-two: under the irradiation of visible light, 0.2mmol of 4-fluorostyrene, 1.0mmol of tetrachloromethane, and 0.006mmol of photo-redox catalyst fac- [ Ir (ppy)3]2.0mmol of water, 2.0mmol of triphenylphosphine, 1.0mmol of zinc iodide, and 1.0mmol of potassium phosphate were added to 2.0ml of tetrahydrofuran to carry out a reaction. The mixture was stirred under nitrogen at 25 ℃ for 12 hours. After the reaction was complete, hydrogen peroxide was added dropwise to the flask until the solution turned purple. Then, ethyl acetate was added to the mixture, and the mixture was washed with saturated sodium thiosulfate and brine. After extraction of the aqueous layer with ethyl acetate, the combined organic layers were dried over anhydrous sodium sulfate and evaporated in vacuo. The residue was purified by flash column chromatography to give 13.5mg of 1,1,1,6,6, 6-hexachloro-3, 4-di (4-fluorophenyl) hexane as a white solid in 28% yield. m.p.82-84 deg.C (uncoated);1H NMR(500MHz,CDCl3)δ7.21-7.16(m,2H),7.08-7.03(m,2H,),6.93-6.86(m,4H),3.53(d,J＝5.5Hz,1H),3.35(d,J＝7.5Hz,1H),3.29(d,J＝15.0Hz,1H),3.12(dd,J＝5.5,15.0Hz,1H),3.02(dd,J＝7.5,15.0Hz,1H),2.85(d,J＝15.0Hz,1H)；13C NMR(125MHz,CDCl3)δ162.8(d,JC-F＝245.1Hz),162.5(d,JC-F＝245.3Hz),137.0,136.3,131.7(d,JC-F＝7.6Hz),131.2(d,JC-F＝7.9Hz),116.3(d,JC-F＝21.3Hz),115.6(d,JC-F＝21.3Hz),99.5,99.2,58.9,58.1,50.1,49.4；LRMS(EI,70eV)m/z(％):480(M+,1),243(12),241(38),239(41),145(84),143(100),133(23)；HRMS(EI+)Calcd for C18H14Cl6F2 +(M+):477.9195,Found:477.9206.
the specific embodiment is thirty-three: under the irradiation of visible light, 0.2mmol of 4-chlorostyrene, 1.0mmol of tetrachloromethane, 0.006mmol of the photoredox catalyst fac- [ Ir (ppy)3]2.0mmol of water, 2.0mmol of triphenylphosphine, 1.0mmol of zinc iodide, and 1.0mmol of potassium phosphate were added to 2.0ml of tetrahydrofuran to carry out a reaction. The mixture was stirred under nitrogen at 25 ℃ for 12 hours. After the reaction was complete, hydrogen peroxide was added dropwise to the flask until the solution turned purple. Then, ethyl acetate was added to the mixture, and the mixture was washed with saturated sodium thiosulfate and brine. After extraction of the aqueous layer with ethyl acetate, the combined organic layers were dried over anhydrous sodium sulfate and evaporated in vacuo. The residue was purified by flash column chromatography to give 18.0mg of 1,1,1,6,6, 6-hexachloro-3, 4-di (4-chlorophenyl) hexane as a white solid in 35% yield. m.p.106-108 deg.C (undercorrected);1H NMR(500MHz,CDCl3)δ7.33(d,J＝7.5Hz,2H),7.20(d,J＝7.5Hz,2H),7.15(d,J＝7.5Hz,2H),6.86(d,J＝7.5Hz,2H),3.53(d,J＝5.5Hz,1H),3.35(d,J＝7.5Hz,1H),3.28(d,J＝15.0Hz,1H),3.10(dd,J＝5.5,15.0Hz,1H),3.03(dd,J＝7.5,15.0Hz,1H),2.85(d,J＝15.0Hz,1H)；13C NMR(125MHz,CDCl3)δ139.7,138.9,134.1,133.8,131.6,131.0,129.6,128.9,99.3,99.0,58.7,57.9,50.1,49.4；LRMS(EI,70eV)m/z(％):514(M+,1),259(8),257(21),161(64),159(100)；HRMS(EI+)Calcd for C18H14Cl8 +(M+):509.8604,Found:509.8606.
comparative example one: under the irradiation of visible light, 0.2mmol of styrene,1.0mmol of trifluorotrichloroethane, 0.006mmol of the photoredox catalyst fac- [ Ir (ppy)3]2.0mmol of deionized water, 2.0mmol of triphenylphosphine and 1.0mmol of potassium phosphate were added to 2.0ml of methanol to carry out a reaction. The mixture was stirred at 25 ℃ for 12 hours under a nitrogen atmosphere, and as a result, no reaction occurred.
Comparative example two: under the irradiation of visible light, 0.2mmol of styrene, 1.0mmol of trifluorotrichloroethane, and 0.006mmol of photo-redox catalyst fac- [ Ir (ppy)3]2.0mmol of deionized water, 2.0mmol of triphenylphosphine and 1.0mmol of potassium phosphate were added to 2.0ml of acetonitrile to carry out a reaction. The mixture was stirred at 25 ℃ for 12 hours under a nitrogen atmosphere, and as a result, no reaction occurred.
In the first embodiment of the invention, styrene and derivatives thereof and trichlorotrifluoroethane are taken as substrates, and fac- [ Ir (ppy) is added into the substrates at the temperature of 25 DEG C3]As a catalyst, potassium phosphate as a base and zinc iodide as an iodine source were reacted in an aqueous solution of tetrahydrofuran as a solvent. In one of the examples one to seventeen, aryl alkene is used as variable to perform chloroalkylation reaction with trifluorotrichloroethane. It is worth noting that styrene substituted by strong electron-withdrawing groups can also be well adapted to the process of the present invention; the first example, the eighteen example, the first comparative example and the second comparative example take a solvent as a variable; the first and nineteen to twenty-one examples take iodine salt as variable; in the first embodiment, twenty-two to twenty-five embodiments take different bases as variables; examples twenty-six to twenty-seven are temperature dependent.
Example twenty eight reaction was carried out at room temperature of 25 ℃ using styrene and carbon tetrachloride as substrates by adding fac- [ Ir (ppy)3] as a catalyst, potassium phosphate as a base, and zinc iodide as an iodine source to the substrates in an aqueous solution of tetrahydrofuran as a solvent. Where examples twenty eight to thirty three are variable with aryl alkenes.
The general formula of the reaction equation of the invention is as follows:
Figure GDA0002886671250000261
the R is1Is one of hydrogen atom, 4-methyl, 3-methyl, 2, 4-dimethyl, 4-tert-butyl, 4-methoxy, 4-acetoxyl, 4-fluoro, 4-chloro, 3-chloro, 2-bromo, 4-trifluoromethyl and 4-cyano. The styrene derivative may be a vinyl naphthalene or an alpha-methylstyrene. The R is2Is-chloro or trifluoromethyl. The reaction mechanism of the present invention: referring to fig. 1, the following description is made by taking the first embodiment as an example:
first, CF3CCl3And reacted with triphenylphosphine (chemical formula: PPh3) to produce (dichlorotrifluoroethyl) phosphine salt A. Then, halide ion (Cl)-) And ZnI2Exchanging to obtain intermediate iodonium salt B, and irradiating with visible light to obtain iridium tris (2-phenylpyridine) face (formula: fac- [ ir (Ppy)3]) Is a photo-redox catalyst and is used in the presence of H2O and K3PO4In the presence of Hydrogen Iodide (HI) and triphenylphosphine oxide (Ph)3P ═ O), generating free radical CF3CCl2H; wherein visible light plays an initiating role; h2O is used to provide protons; potassium phosphate acts as a base, leaving the entire system in an alkaline environment, so that hydrogen iodide and triphenylphosphine oxide are more easily removed. Then, CF3CCl2Reaction of the free radical with styrene 1 gives the new free radical intermediate C. And finally, carrying out tail-to-tail dimerization reaction on the free radical intermediate C to obtain a target product 2. Wherein the two carbons of the vinyl group in styrene, the carbon connecting the benzene ring is the "tail", and the carbon far away from the benzene ring is the "head". The products prepared by the invention are tail-to-tail dimerization products, and meanwhile, the invention can provide multi-branch fluorine-containing dimerization products.
With reference to fig. 2, details are made by taking an example of twenty-eight:
first, CCl4With triphenylphosphine (formula: PPh)3) The reaction produces (trichloromethyl) phosphonium salt A. Then, halide ion (Cl)-) And ZnI2Exchanging to obtain intermediate iodonium salt B, irradiating with visible light to obtain iridium tris (2-phenylpyridine) complex (structural formula: fac- [ ir (Ppy)3]) Is a photo-redox catalyst and is used in the presence of H2O andK3PO4in the presence of Hydrogen Iodide (HI) and triphenylphosphine oxide (Ph)3P ═ O), generating free radical CCl3To prepare the compound. Wherein visible light plays an initiating role; h2O is used to provide protons; potassium phosphate acts as a base, leaving the entire system in an alkaline environment, so that hydrogen iodide and triphenylphosphine oxide are more easily removed. Subsequently, CCl3Reaction of the free radical with styrene 1 gives the new free radical intermediate C. And finally, carrying out tail-to-tail dimerization reaction on the free radical intermediate C to obtain a target product 2. The products prepared by the invention are tail-to-tail dimerization products, and meanwhile, the invention can provide multi-branch chlorine-containing dimerization products.
The halogenated alkane synthesized by styrene and derivatives thereof and trichloroalkane and the preparation method thereof, disclosed by the invention, are used for preparing the trifluorodichloroalkane by taking the styrene and the derivatives thereof and the trichloroalkane as substrates, wherein the trichloroalkane is carbon tetrachloride or trifluorotrichloroethane, and performing chloroalkylation/dimerization reaction for 10-14 hours under the illumination condition; wherein the reaction temperature is 10-45 ℃, preferably 25 ℃, and the reaction is carried out under normal pressure, and the reaction condition is mild and easy to achieve; the illumination condition is preferably blue LED light which can play a good initiating role in the invention and promote the reaction; the reaction is carried out with tris (2-phenylpyridine) iridium (fac- [ Ir (ppy)3]) As a catalyst, the reaction speed can be accelerated, so that the reaction time is shortened; simultaneously, adding alkali, an iodine source, triphenylphosphine and deionized water into the whole reaction system; the whole reaction is carried out in a solvent, wherein the solvent is preferably tetrahydrofuran, and each reactant can be uniformly dispersed in the tetrahydrofuran, so that the reaction is more complete, and the yield is improved; meanwhile, the whole reaction needs to be carried out in a nitrogen atmosphere, and the nitrogen plays a role in protection, so that the product is not easily oxidized by oxygen. After the reaction is finished, hydrogen peroxide is added into the reaction vessel, the solution color is changed into purple, and the purpose of adding the hydrogen peroxide is to oxidize the triphenylphosphine into the triphenoxyphosphate, so that the redundant triphenylphosphine can be removed. Then, ethyl acetate was used as an extract to conduct extraction and liquid separation, and after completion of extraction and liquid separation, the organic layer was again charged with saturated sodium thiosulfate and brineWashing, namely, the brine is saturated sodium chloride solution, and the purpose of washing is to remove the hydrogen peroxide remained in the organic layer; the aqueous layer was then extracted once with ethyl acetate in order to collect the product that may remain in the aqueous layer, thereby increasing the yield; and combining the organic layers, drying the organic layers by using anhydrous sodium sulfate, performing vacuum evaporation after complete drying, performing column layer separation by using a silica gel column after evaporation is finished, wherein the elution liquid is a mixed liquid of petroleum ether and ethyl acetate, and obtaining the required product after a series of purification treatments. The product is a tail-to-tail dimerization product formed by taking styrene and derivatives thereof as reactants.
The method can directly synthesize the target product, does not need to separate intermediate products, can obtain the target product only by stirring and reacting under normal pressure, has the highest yield of 77 percent, greatly simplifies the process, reduces the energy consumption, and has the advantage of higher yield. And in the reaction process, the waste solution is less, and other polluted gases and liquid are not discharged, so that the method reduces the discharge of the waste solution, and has the advantages of protecting the environment and ensuring the health of operators. In addition, a series of chloroalkylated and dimeric derivatives of styrene can be prepared, and the method has strong substrate universality. Therefore, the invention fills the blank of chloroalkylation and dimerization organic matters of styrene prepared at the present stage, promotes the development of polysubstituted derivatives, and can provide powerful guarantee for developing chlorinated alkane-containing biological medicines.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.

Claims (3)

1. A preparation method of halogenated alkane synthesized by styrene and derivatives thereof and trichloroalkane is characterized in that: the molecular structural formula of the halogenated alkane is
Figure FDA0002886671240000011
The halogenated alkane is formed by reacting styrene and derivatives thereof with trichloroalkane; simultaneously adding triphenylphosphine, an iodine source, a catalyst, alkali and deionized water; the styrene and the derivatives thereof have molecular structural formulas
Figure FDA0002886671240000012
Or a naphthylethylene or alpha-methylstyrene; the molecular structural formula of the trichloroalkane is CCl3R2；
The R is1Is any one of hydrogen atom, 4-methyl, 3-methyl, 2, 4-dimethyl, 4-tertiary butyl, 4-methoxy, 4-acetoxyl, 4-fluorine, 4-chlorine, 3-chlorine, 2-bromine, 4-trifluoromethyl and 4-cyano; the R is2Is-chloro or trifluoromethyl;
the preparation method comprises the steps of adding styrene and derivatives thereof, trichloroalkane, a catalyst, deionized water, triphenylphosphine, an iodine source and alkali into a reaction vessel filled with a solvent under visible light, and reacting under nitrogen; then extracting, separating liquid, washing, drying an organic phase, evaporating in vacuum, and finally separating and purifying through a column layer to obtain halogenated alkane;
the catalyst is surface-type tris (2-phenylpyridine) iridium;
the solvent is any one of dichloromethane and tetrahydrofuran;
the iodine source is any one of sodium iodide, potassium iodide, TBAI and zinc iodide;
the alkali is any one of cesium carbonate, potassium carbonate, triethylamine, DBU and potassium phosphate.
2. The method for preparing haloalkanes according to claim 1, which comprises the steps of: the molar parts of the materials added into the reaction vessel are as follows:
1 part of styrene and derivatives thereof;
5 parts of trichloroalkane;
0.03 part of catalyst;
5 parts of alkali;
5 parts of an iodine source;
10 parts of triphenylphosphine;
10 parts of deionized water.
3. The method for preparing haloalkanes according to claim 1, which comprises the steps of: when styrene and derivatives thereof react with trichloroalkane, the reaction temperature is 10-45 ℃, and the reaction time is 10-14 h; before extraction and liquid separation, adding hydrogen peroxide into a reaction vessel, and then adding an extraction liquid to perform extraction and liquid separation; the extract is ethyl acetate.
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