CN110015946B - Preparation method of 1, 5-diaryl-4-pentene-1-alcohol compound - Google Patents
Preparation method of 1, 5-diaryl-4-pentene-1-alcohol compound Download PDFInfo
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Abstract
The invention belongs to the technical field of pharmaceutical and chemical intermediates and related chemistry, and provides a preparation method of a 1, 5-diaryl-4-pentene-1-alcohol compound. From cinnamyl alcohol derivatives in the presence of copper salts, silver salts and
acid as co-catalyst, ligand and additive reacts with styrene compound and water at 80-120 deg.c for 23 hr to obtain 1, 5-diaryl-4-pentene-1-alcohol compound. The method has the advantages of simple and convenient operation, cheap and easily obtained initial raw materials, water resistance of a reaction system, no byproduct generation, copper salt, silver salt and
the acid is catalytic amount, so that the possibility of realizing industrialization is high, and the yield is high; the synthesized 1, 5-diaryl-4-pentene-1-alcohol compound is further functionalized to obtain various compounds, and the compounds are applied to the development and research of natural products, functional materials and fine chemicals.
Description
Technical Field
The invention belongs to the technical field of pharmaceutical and chemical intermediates and related chemistry, and relates to a preparation method of a novel 1, 5-diaryl-4-pentene-1-alcohol compound.
Background
Unsaturated fatty alcohols are an extremely important class of building blocks, which are important in the fields of medicine, pesticides, dyes, functional materials and fragrancesThe required application value. Among them, 1, 5-diaryl-4-penten-1-ol can be used for synthesizing oxygen-containing five-membered and six-membered heterocyclic compounds, such as tetrahydrofuran, tetrahydropyran derivatives [ SchuchD, FriesP.,
PérezB.M.,HartungJ.,J.Am.Chem.Soc.,2009,131,12918]in view of the importance of 1, 5-diaryl-4-penten-1-ol and its derivatized heterocyclic compounds, how to efficiently synthesize 1, 5-diaryl-4-penten-1-ol compounds has attracted considerable attention.
The reported synthesis methods of 1, 5-diaryl-4-pentene-1-alcohol compounds are mainly divided into two major types of reduction reactions and reduction coupling reactions, wherein the reduction reactions comprise reduction reaction of cinnamyl acetophenone under the action of indium trichloride \ sodium borohydride [ Ranu B.C., Samanta S., Tetrahedron,2003,59,7901] and reduction reaction of beta-ketosulfone under the action of sodium amalgam [ Chan C.K., Huang Y.H., Chang M.Y., Tetrahedron,2016,72,5521], raw materials of the two types of methods need special preparation and have the possibility of over-reduction, and the application of the methods is limited; an efficient means for producing 1, 5-diaryl-4-penten-1-ol compounds by reductive coupling reaction of diene compounds with aldehydes is also an effective means for producing 1, 5-diaryl-4-penten-1-ol compounds using nickel as a catalyst and additives requiring diethylzinc or triethylboron as a hydrogen source [ Yang y., Zhu s. -f., Duan h. -f., Zhou c. -y., Wang l. -x., Zhou q. -l., j.am.chem.soc.,2007,129,2248 ]. Under the action of a transition metal catalyst, a target compound is always sought after for high-selectivity synthesis from the simplest raw material, and recently, a cyclic ruthenium catalyst is reported to catalyze alkylation reaction of secondary alcohol and primary alcohol to realize synthesis of 1, 5-diaryl-4-penten-1-ol [ Chang X, Chuan L.W., Li Y., Pularkat S.A., Tetrahedron Lett.2012, 53,1450], wherein the catalyst of the method needs presynthesized and equivalent alkali as an additive, and the efficient synthesis and industrialization of 1, 5-diaryl-4-penten-1-ol are difficult. Along with the continuous deepening of people's understanding of catalytic reaction, the co-catalytic reaction gradually receives wide attention of people, meanwhile, cinnamyl alcohol and styrene derivatives are used as important chemical raw materials, a plurality of useful compounds can be synthesized, if cinnamyl alcohol and styrene derivatives are used as initial raw materials and the synthesis of 1, 5-diaryl-4-pentene-1-alcohol compounds is realized by a co-catalytic method, the synthesis steps can be greatly shortened, the synthesis cost is saved, and the industrial preparation of the 1, 5-diaryl-4-pentene-1-alcohol compounds is facilitated.
Disclosure of Invention
The invention provides a novel preparation method of a 1, 5-diaryl-4-pentene-1-alcohol compound, which has the advantages of short synthetic route, easily obtained substrate, water-resistant reaction system, simple and convenient operation and higher yield.
The technical scheme of the invention is as follows:
a process for preparing 1, 5-diaryl-4-pentene-1-alcohol compound from cinnamyl alcohol derivative as raw material includes reaction between copper salt, silver salt and silver salt
Acid is used as a cocatalyst, a ligand and an additive to react with a styrene compound and water for 23 hours in an organic solvent at the temperature of 80-120 ℃ to obtain a 1, 5-diaryl-4-pentene-1-alcohol compound;
the synthetic route is as follows:
R1selected from hydrogen (H), halogen (halides), methyl (Me) and acetyl (acetyl);
R2selected from hydrogen (H) and alkyl (alkyl);
R3selected from hydrogen (H) and methyl (Me);
R4selected from hydrogen (H) and phenyl (Ph);
R5selected from hydrogen (H), halogen (halides), alkyl (alkyl) and chloromethyl (chloromethyl);
the molar ratio of the cinnamyl alcohol derivative to the copper catalyst is 1: 0.05-1: 0.2;
the molar ratio of the cinnamyl alcohol derivative to the silver catalyst is 1: 0.05-1: 0.2;
the molar ratio of the cinnamyl alcohol derivative to the acid catalyst is 1: 0.05-1: 0.2;
the molar ratio of the cinnamyl alcohol derivative to the styrene compound is 1: 1-1: 10;
the molar ratio of the cinnamyl alcohol derivative to the water is 1: 5-1: 50;
the molar ratio of the cinnamyl alcohol derivative to the additive is 1: 1-1: 5;
the molar concentration of the cinnamyl alcohol derivative is 0.1 mmol/mL-2 mmol/mL;
the organic solvent is tetrahydrofuran, glycol dimethyl ether, dimethyl sulfoxide, carbon tetrachloride, 1, 4-dioxane, toluene and N, N-dimethylformamide. Preferably one or a mixture of two or more of tetrahydrofuran, ethylene glycol dimethyl ether and 1, 4-dioxane.
The copper catalyst is cuprous chloride, cuprous bromide, cuprous iodide, copper tetraacetonitrile hexafluorophosphate, cuprous trifluoromethanesulfonate, copper acetate and copper sulfate. Preferably one or more of cuprous chloride, copper tetraacetonitrile hexafluorophosphate and cuprous trifluoromethanesulfonate.
The ligand is triphenylphosphine, 1, 4-bis (diphenylphosphino) butane, 1, 2-bis (diphenylphosphino) ethane, 1 '-binaphthyl-2, 2' -bisdiphenylphosphine, 1, 10-phenanthroline, bisdiphenylphosphinoferrocene and L-proline. Preferably one or a mixture of two or more of 1,1 '-binaphthyl-2, 2' -bisdiphenylphosphine, 1, 4-bis (diphenylphosphino) butane and 1, 2-bis (diphenylphosphino) ethane.
The silver catalyst is one or more of silver hexafluoroantimonate, silver carbonate, silver fluoride, silver hexafluorophosphate, silver acetate, silver trifluoromethanesulfonate and silver nitrate. Silver triflate or silver hexafluoroantimonate is preferred.
The acid catalyst is one or more of acetic acid, trifluoroacetic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, pivalic acid and 4-nitrobenzoic acid. Preferably one or more of trifluoromethanesulfonic acid, methanesulfonic acid and 4-nitrobenzoic acid.
The additive is one or more of acetonitrile, propionitrile, butyl, hexanenitrile and phenylacetonitrile. Acetonitrile is preferred.
The separation method comprises recrystallization, column chromatography and the like.
The solvent used in the recrystallization method comprises benzene, ethanol, petroleum ether, acetonitrile, tetrahydrofuran, chloroform, n-hexane, acetone, ethyl acetate and dichloromethane.
When the product is separated by column chromatography, silica gel or alumina can be used as stationary phase, and the developing agent is generally polar and nonpolar mixed solvent, such as ethyl acetate-petroleum ether, ethyl acetate-n-hexane, dichloromethane-petroleum ether, and methanol-petroleum ether.
The invention has the advantages of simple operation, cheap and easily obtained initial raw materials, water resistance of a reaction system, no by-product generation, copper salt, silver salt and
the acid is catalytic amount, so that the method has the possibility of realizing industrialization, and the 1, 5-diaryl-4-pentene-1-alcohol compound is obtained with high yield; the 1, 5-diaryl-4-pentene-1-alcohol compound synthesized by the method can be further functionalized to obtain various compounds, and is applied to the development and research of natural products, functional materials and fine chemicals.
Drawings
FIG. 1 is a diagram of trans-1, 5-diphenyl-4-penten-1-ol of example 11H nuclear magnetic spectrum.
FIG. 2 is a diagram of trans-1, 5-diphenyl-4-penten-1-ol of example 113C nuclear magnetic spectrum.
FIG. 3 is a scheme showing the preparation of trans-5- (4-chlorophenyl) -1-phenyl-4-penten-1-ol in example 21H nuclear magnetic spectrum.
FIG. 4 is a drawing of trans-5- (4-chlorophenyl) -1-phenyl-4-penten-1-ol from example 213C nuclear magnetic spectrum.
FIG. 5 is a drawing showing the preparation of trans-3-methyl-1, 5-diphenyl-4-penten-1-ol in example 31H nuclear magnetic spectrum.
FIG. 6 is a drawing showing the preparation of trans-3-methyl-1, 5-diphenyl-4-penten-1-ol in example 313C nuclear magnetic spectrum.
FIG. 7 shows trans-1-phenyl-5- (p-acetophenone) in example 4Of yl) -4-penten-1-ol1H nuclear magnetic spectrum.
FIG. 8 is a drawing showing the preparation of trans-1-phenyl-5- (p-acetylphenyl) -4-penten-1-ol in example 413C nuclear magnetic spectrum.
FIG. 9 is a drawing showing the preparation of trans-5- (4-fluorophenyl) -4-methyl-1-phenyl-4-penten-1-ol in example 51H nuclear magnetic spectrum.
FIG. 10 is a drawing showing the preparation of trans-5- (4-fluorophenyl) -4-methyl-1-phenyl-4-penten-1-ol in example 513C nuclear magnetic spectrum.
FIG. 11 is a drawing of trans-4-benzylidene-1-phenyl-1-nonanol from example 61H nuclear magnetic spectrum.
FIG. 12 is a drawing of trans-4-benzylidene-1-phenyl-1-nonanol from example 613C nuclear magnetic spectrum.
FIG. 13 is a drawing of trans-1- (4-tert-butylphenyl) -5-phenyl-4-penten-1-ol from example 71H nuclear magnetic spectrum.
FIG. 14 is a drawing of trans-1- (4-tert-butylphenyl) -5-phenyl-4-penten-1-ol from example 713C nuclear magnetic spectrum.
FIG. 15 is a scheme showing the preparation of trans-1- (4-chloromethylphenyl) -5-phenyl-4-penten-1-ol in example 81H nuclear magnetic spectrum.
FIG. 16 is a scheme showing the preparation of trans-1- (4-chloromethylphenyl) -5-phenyl-4-penten-1-ol in example 813C nuclear magnetic spectrum.
Detailed Description
The preparation method of the 1, 5-diaryl-4-pentene-1-alcohol compound has the advantages of cheap and easily obtained raw materials, few reaction steps, water resistance of a system, no byproduct generation, convenience in operation, high reaction yield and the like.
The invention will be further illustrated with reference to the following specific examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. The simple replacement or improvement of the present invention by those skilled in the art is within the technical scheme of the present invention.
Example 1: synthesis of trans-1, 5-diphenyl-4-penten-1-ol
In a 25mL reactor, cuprous chloride (1.49mg,0.015mmol), silver hexafluoroantimonate (20.6mg,0.06mmol), 1, 4-bis (diphenylphosphino) butane (7.68mg,0.018mmol), cinnamyl alcohol (0.040g, 0.3mmol), 4-nitrobenzoic acid (10.02mg, 0.06mmol) were charged, and after 3 times of nitrogen substitution, acetonitrile (31.3. mu.L, 0.6mmol), 0.3mL tetrahydrofuran and water (54. mu.L, 3.0mmol) were added, and after stirring at room temperature for 10 minutes, styrene (0.094g,0.9mmol) was added, and stirring was carried out at 100 ℃ for 23 hours. Column chromatography (silica gel, 200 mesh; developing solvent, petroleum ether/ethyl acetate: 5/1) gave trans-1, 5-diphenyl-4-penten-1-ol 0.060g, a yield of 84%.
A colorless oily liquid;1H NMR(400MHz,CDCl3):δ7.34–7.16(m,10H),6.38(d,J＝15.8Hz,1H),6.21(dt,J＝15.8,6.8Hz,1H),4.70(t,J＝6.6Hz,1H),2.31–2.23(m,2H),2.04(bs,1H),2.01–1.83(m,2H).13C NMR(100MHz,CDCl3):δ144.5,137.6,130.3,130.0,128.4,127.6,126.9,125.9,125.9,73.9,38.4,29.2.
example 2: synthesis of trans-5- (4-chlorophenyl) -1-phenyl-4-penten-1-ol
The same procedure as in example 1 was repeated, except for reacting trans-3- (4-chlorophenyl) -2-propen-1-ol with styrene to give trans-5- (4-chlorophenyl) -1-phenyl-4-penten-1-ol 0.069g in 85% yield.
A colorless oily liquid;1H NMR(400MHz,CDCl3):δ7.37–7.20(m,9H),6.33(d,J＝15.9Hz,1H),6.17(dt,J＝15.9,7.3Hz,1H),4.70(t,J＝6.6Hz,1H),2.34–2.19(m,2H),2.08(bs,1H),1.97–1.81(m,2H).13C NMR(100MHz,CDCl3):δ144.5,136.2,132.4,130.8,129.2,128.6,128.5,128.4,127.6,127.1,125.9,73.9,38.3,29.2.IR(neat):3381,3062,3028,2928,1491,1452,1091,1059,966,763,701cm-1.HRMS(EI):calcd for C17H17ClO[M]+:272.0968,Found 272.0965.
example 3: synthesis of trans-3-methyl-1, 5-diphenyl-4-penten-1-ol
The same procedure as in example 1 was repeated, except that trans-4-phenyl-3-buten-2-ol was reacted with styrene to give 0.064g of trans-3-methyl-1, 5-diphenyl-4-penten-1-ol in an yield of 84%.
A colorless oily liquid;1H NMR(400MHz,CDCl3):δ7.36–7.31(m,6H),7.29–7.20(m,4H),6.34(d,J＝15.9Hz,1H),6.14(dd,J＝15.9,8.2Hz,1H),4.73(t,J＝7.0Hz,1H),2.41–2.30(m,1H),1.96(bs,1H),1.95–1.88(m,1H),1.78–1.72(m,1H).13C NMR(100MHz,CDCl3):δ144.6,137.6,136.2,128.7,128.5,127.6,127.0,126.1,126.0,73.0,46.1,34.5,20.8.IR(neat):3376,3062,3029,2927,2853,1493,1470,1052,965,751,701cm-1.HRMS(EI):calcd for C18H20O[M]+:252.1514,found 252.1511.
example 4: synthesis of trans-1-phenyl-5- (p-acetylphenyl) -4-penten-1-ol
In a 25mL reactor, copper tetraacetonitrileate hexafluorophosphate (5.59mg,0.015mmol), silver trifluoromethanesulfonate (15.4mg,0.06mmol), 1,1 '-binaphthyl-2, 2' -bisdiphenylphosphine (11.21mg,0.018mmol), trans-1- (4- (3-hydroxy-1-propenyl) -1-acetophenone (0.053g, 0.3mmol), methanesulfonic acid (5.77mg, 0.06mmol) were charged, after 3 times of replacement with nitrogen, acetonitrile (31.3. mu.L, 0.6mmol), 0.3mL1, 4-dioxane and water (54. mu.L, 3.0mmol) were added, after stirring at room temperature for 10 minutes, styrene (0.094g,0.9mmol) was added, stirring at 120 ℃ for 23 hours, column chromatography (silica gel, 200 mesh 300 mesh; developing solvent, petroleum ether/ethyl acetate 3/1) was performed to give trans-1-phenyl-5- (p-acetylphenyl) -4-pentene 0.052g of 1-alcohol, yield 62%.
A light yellow liquid;1H NMR(400MHz,CDCl3):δ7.88(d,J＝8.4Hz,2H),7.40–7.29(m,7H),6.49–6.33(m,2H),4.74(d,J＝6.4Hz,1H),2.57(s,3H),2.40–2.28(m,2H),2.03(bs,1H),2.00–1.86(m,2H).13C NMR(100MHz,CDCl3):δ197.6,144.5,142.4,135.6,133.4,131.2,129.6,128.8,128.6,127.7,126.6,126.0,125.9,74.0,38.2,29.4,26.5.IR(neat):3386,3060,3023,2929,2851,1683,1635,1570,1520,1465,1068,1021,965,886cm-1.HRMS(EI):calcd for C19H20O2[M]+:280.1463,found 280.1461.
example 5: synthesis of trans-5- (4-fluorophenyl) -4-methyl-1-phenyl-4-penten-1-ol
The same procedure as in example 4 was repeated, except for reacting trans-3- (4-fluorophenyl) -2-methyl-2-propen-1-ol with styrene to give trans-5- (4-fluorophenyl) -4-methyl-1-phenyl-4-penten-1-ol 0.064g, in 79% yield.
A light brown oily liquid;1H NMR(400MHz,CDCl3):δ7.36–7.24(m,5H),7.15(t,J＝8.0Hz,2H),6.98(t,J＝8.0Hz,2H),6.23(s,1H),4.71(t,J＝6.4Hz,1H),2.33–2.15(m,2H),2.08–2.02(m,1H),2.02(bs,1H),1.96–1.88(s,1H),1.82(s,3H),13C NMR(100MHz,CDCl3):δ161.07(d,1JC–F＝244.9Hz),144.6,138.3,134.4(d,4JC–F＝3.3Hz),130.2(d,3JC–F＝7.8Hz),128.5,127.6,125.9,124.1,114.8(d,2JC–F＝21.2Hz),74.2,37.2,36.8,17.7.IR(neat):3384,3029,2932,1508,1452,1228,1157,966,850,763,701cm-1.HRMS(ESI):calcd for C18H18FO[M-H]-:269.1347,Found 269.1345.
example 6: synthesis of trans-4-benzylidene-1-phenyl-1-nonanol
The same procedure as in example 4 was repeated, except for reacting trans-2-benzylidene-1-heptanol with styrene to give 0.068g of trans-4-benzylidene-1-phenyl-1-nonanol in 73% yield.
A colorless oily liquid;1H NMR(400MHz,CDCl3):δ7.38–7.34(m,4H),7.32–7.27(m,3H),7.19–7.16(m,3H),6.27(s,1H),4.72(t,J＝7.8Hz,1H),2.34–2.14(m,4H),2.06–2.02(m,1H),1.99(bs,1H),1.94–1.89(m,1H),1.47–1.39(m,2H),1.30–1.21(m,4H),0.85(t,J＝6.9Hz,3H).13C NMR(100MHz,CDCl3):δ144.7,143.0,138.5,128.6,128.5,128.1,127.7,126.0,126.0,125.3,74.4,37.5,33.4,32.0,30.7,28.0,22.5,14.1.IR(neat):3363,3060,3026,2954,2928,2858,1493,1453,1058,1028,915,747,699cm-1.HRMS(EI):calcd for C22H28O[M]+:308.2140,Found 308.2142.
example 7: synthesis of trans-1- (4-tert-butylphenyl) -5-phenyl-4-penten-1-ol
In a 25mL reactor, tetraacetonitrilocucupper hexafluorophosphate (5.59mg,0.015mmol), silver hexafluoroantimonate (20.6mg,0.06mmol), 1, 2-bis (diphenylphosphino) ethane (7.17mg,0.018mmol), cinnamyl alcohol (0.040g, 0.3mmol), trifluoromethanesulfonic acid (9.00mg, 0.06mmol) were charged, and after 3 times of nitrogen substitution, acetonitrile (31.3. mu.L, 0.6mmol), 0.3mL ethylene glycol dimethyl ether and water (54. mu.L, 3.0mmol) were added, and after stirring at room temperature for 10 minutes, 4-tert-butylstyrene (0.144g,0.9mmol) was added, and stirring was carried out at 100 ℃ for 23 hours. Column chromatography (silica gel, 200 mesh; developing solvent, petroleum ether/ethyl acetate: 10/1) gave trans-1- (4-tert-butylphenyl) -5-phenyl-4-penten-1-ol 0.065g, 73% yield.
A colorless oily liquid;1H NMR(400MHz,CDCl3):δ7.35(d,J＝8.1Hz,2H),7.34–7.24(m,6H),7.19–7.14(m,1H),6.38(d,J＝15.8Hz,1H),6.18(dt,J＝15.8,7.2Hz,1H),4.65(t,J＝6.0Hz,1H),2.32–2.21(m,2H),2.12(bs,1H),2.00–1.82(m,2H),1.31(s,9H).13C NMR(100MHz,CDCl3):δ150.4,141.5,137.7,130.2,130.1,128.4,126.8,125.9,125.6,125.3,73.7,38.2,34.4,31.3,29.3.IR(neat):3377,3082,3031,2957,2843,1578,1491,1443,1418,1083,1022,967,789,713cm-1.HRMS(EI):calcd forC21H26O[M]+:294.1984,Found 294.1984.
example 8: synthesis of trans-1- (4-chloromethylphenyl) -5-phenyl-4-penten-1-ol
The same procedure as in example 7 was repeated, except that cinnamyl alcohol was reacted with 4-chloromethylstyrene to give trans-1- (4-chloromethylphenyl) -5-phenyl-4-penten-1-ol in an amount of 0.067g and a yield of 78%.
A yellow oily liquid;1H NMR(400MHz,CDCl3):δ7.39–7.32(m,5H),7.27–7.17(m,4H),6.38(d,J＝15.8Hz,1H),6.18(dt,J＝15.8,8.3Hz,1H),4.71(t,J＝6.4Hz,1H),4.56(s,2H),2.31–2.24(m,2H),2.08(bs,1H),1.97–1.83(m,2H).13C NMR(100MHz,CDCl3):144.9,137.6,136.7,130.5,129.8,128.7,128.4,126.9,126.3,125.9,73.5,45.9,38.4,29.1.IR(neat):3381,3080,3056,3024,2933,2863,1494,1446,1266,1070,965,744,692cm-1.HRMS(EI):calcd for C18H19ClO[M]+:286.1124,Found 286.1128.
Claims (8)
1. a method for preparing a 1, 5-diaryl-4-pentene-1-ol compound, comprising the steps of: from cinnamyl alcohol derivatives in the presence of copper salts, silver salts and
action of acids as co-catalysts, ligands and additivesReacting with styrene compound and water in organic solvent at 80-120 deg.c for 23 hr to obtain 1, 5-diaryl-4-pentene-1-alcohol compound;
the synthetic route is as follows:
R1selected from hydrogen, halogen, methyl and acetyl;
R2selected from hydrogen and alkyl;
R3selected from hydrogen and methyl;
R4selected from hydrogen and phenyl;
R5selected from hydrogen, halogen, alkyl and chloromethyl;
the molar ratio of the cinnamyl alcohol derivative to the copper catalyst is 1: 0.05-1: 0.2;
the molar ratio of the cinnamyl alcohol derivative to the silver catalyst is 1: 0.05-1: 0.2;
the molar ratio of the cinnamyl alcohol derivative to the acid catalyst is 1: 0.05-1: 0.2;
the molar ratio of the cinnamyl alcohol derivative to the styrene compound is 1: 1-1: 10;
the molar ratio of the cinnamyl alcohol derivative to the water is 1: 5-1: 50;
the molar ratio of the cinnamyl alcohol derivative to the additive is 1: 1-1: 5;
the molar concentration of the cinnamyl alcohol derivative is 0.1 mmol/mL-2 mmol/mL;
the copper catalyst is one or more of cuprous chloride, cuprous bromide, cuprous iodide, copper tetraacetonitrile hexafluorophosphate, cuprous trifluoromethanesulfonate, copper acetate and copper sulfate;
the ligand is one or more of triphenylphosphine, 1, 4-bis (diphenylphosphino) butane, 1, 2-bis (diphenylphosphino) ethane, 1 '-binaphthyl-2, 2' -bis-diphenylphosphine and bis-diphenylphosphine ferrocene;
the silver catalyst is one or more of silver hexafluoroantimonate, silver carbonate, silver fluoride, silver hexafluorophosphate, silver acetate, silver trifluoromethanesulfonate and silver nitrate;
the acid catalyst is one or more of acetic acid, trifluoroacetic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, pivalic acid and 4-nitrobenzoic acid;
the additive is one or more of acetonitrile, propionitrile, hexanenitrile and phenylacetonitrile.
2. The method according to claim 1, wherein the organic solvent is one or more of tetrahydrofuran, ethylene glycol dimethyl ether, and 1, 4-dioxane.
3. The process according to claim 1 or 2, wherein the copper catalyst is one or a mixture of two or more of cuprous chloride, copper tetraacetonitrile hexafluorophosphate and cuprous trifluoromethanesulfonate.
4. The method according to claim 3, wherein the ligand is one or more selected from the group consisting of 1,1 '-binaphthyl-2, 2' -bisdiphenylphosphine, 1, 4-bis (diphenylphosphino) butane, and 1, 2-bis (diphenylphosphino) ethane.
5. The process according to claim 1,2 or 4, wherein the silver catalyst is silver triflate or silver hexafluoroantimonate.
6. The method according to claim 5, wherein the acid catalyst is one or a mixture of two or more of trifluoromethanesulfonic acid, methanesulfonic acid and 4-nitrobenzoic acid.
7. The method of claim 1,2, 4 or 6, wherein the additive is acetonitrile.
8. The method according to claim 7, wherein the separation method is recrystallization or column chromatography; the solvent used in the recrystallization method is benzene, ethanol, petroleum ether, acetonitrile, tetrahydrofuran, chloroform, n-hexane, acetone, ethyl acetate or dichloromethane; when the product is separated by column chromatography, silica gel or alumina is used as the stationary phase, and the developing agent is a mixed solvent of polarity and non-polarity.
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| CN104926594A (en) * | 2015-05-04 | 2015-09-23 | 西安近代化学研究所 | Preparation method for 2,4- dichloro-2-fluorobutane derivative |
| CN107556153A (en) * | 2017-09-15 | 2018-01-09 | 大连理工大学 | A kind of preparation method of conjugated diene compound |
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| CN104326862A (en) * | 2014-11-20 | 2015-02-04 | 西安近代化学研究所 | Preparation method of 2,4-dichloro-1,1,1-trifluorobutane derivative |
| CN104926594A (en) * | 2015-05-04 | 2015-09-23 | 西安近代化学研究所 | Preparation method for 2,4- dichloro-2-fluorobutane derivative |
| CN107556153A (en) * | 2017-09-15 | 2018-01-09 | 大连理工大学 | A kind of preparation method of conjugated diene compound |
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