CN110305051A - A kind of preparation method of diphenylethyllene thio-ether type compounds - Google Patents

A kind of preparation method of diphenylethyllene thio-ether type compounds Download PDF

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CN110305051A
CN110305051A CN201910540160.8A CN201910540160A CN110305051A CN 110305051 A CN110305051 A CN 110305051A CN 201910540160 A CN201910540160 A CN 201910540160A CN 110305051 A CN110305051 A CN 110305051A
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thio
sulfinic acid
diphenylethyllene
acid sodium
type compounds
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汪朝阳
王柏文
邹波
詹海莺
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Guangdong Pharmaceutical University
South China Normal University
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Guangdong Pharmaceutical University
South China Normal University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/26—Separation; Purification; Stabilisation; Use of additives
    • C07C319/28—Separation; Purification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
    • C07C321/12—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to acyclic carbon atoms
    • C07C321/20—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
    • C07C321/22—Thiols, sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
    • C07C321/24—Thiols, sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
    • C07C321/28—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/01—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and halogen atoms, or nitro or nitroso groups bound to the same carbon skeleton
    • C07C323/09—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and halogen atoms, or nitro or nitroso groups bound to the same carbon skeleton having sulfur atoms of thio groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C323/18—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C07C323/20—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton with singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/62—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D333/30—Hetero atoms other than halogen
    • C07D333/34—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring

Abstract

The invention discloses a kind of preparation methods of diphenylethyllene thio-ether type compounds, the following steps are included: by 1,1- talan, aryl groups per alkyl group sulfinic acid sodium and acidic reduction agent dispersion in a solvent, carry out coupling reaction, obtain diphenylethyllene thio-ether type compounds.The present invention can systematically synthesize a series of talan thio-ether type compounds, not need using transition-metal catalyst, and reaction system is simple, and wide application range of substrates, yield is higher, and reaction raw materials are easy to get, at low cost, pollute small.

Description

A kind of preparation method of diphenylethyllene thio-ether type compounds
Technical field
The present invention relates to a kind of preparation methods of diphenylethyllene thio-ether type compounds.
Background technique
The method of synthesis talan thio-ether type compounds generally comprises following several:
1) 1,1- talan reacts under the action of ethyl alcohol and iodine with unifor, synthesisYield be 86% [Yang F.L., Wang F.X., Wang T.T, et al.Chem Commun, 2014,50(17),2111-2113]；
2) 1,1- talan reacts under the action of TBAI and HBr with paratoluensulfonyl chloride, synthesisYield be 89% [Wang D.Y., Zhang R.X., Lin S., et al.Synlett, 2016,27 (13),2003-2008]；
3) 1,1- talan and toluene-ω-thiol are in TBAI and K2S2O8Under the action of react, synthesizeYield be 32% [Hu B., Zhou P., Zhang Q.H., et al.J Org Chem, 2018,83 (24),14978-14986]；
4) 1,1- talan reacts under the action of copper trifluoromethanesulfcomposite and iodine with Diphenyl disulfide ether, synthesisYield be 65% [Tu H.Y., Hu B.L., Deng, C.L., et al.Chem Commun, 2015,51 (85),15558-15561]；
5) acetylenic acid phenol ester reacts under the action of cumyl peroxide with aryl thiophenol, synthesizes talan thioether class Compound, yield range be 52%~76% [Ni S.Y., Zhang L.J., Zhang W.Z., et al.J Org Chem, 2016,81(19),9470-9475]；
6) organometallic reagent or metal catalytic are used, talan thio-ether type compounds are synthesized, such as: lithium alkylide examination Agent is reacted with benzophenone, synthesisYield is 68% [Watanabe M., Nakamura M., Satoh T.Tetrahedron,2005,61(18),4409-4418]；Chloroethylenes base Grignard Reagent is reacted with toluene-ω-thiol lithium, is closed AtYield is 82% [Ager D.J.J Chem Soc, Perkin Trans 1,1986,183-194]；Pd Metal catalytic vinyl iodide is reacted with phenyl boric acid, synthesisYield be 88% [Lin Y.M., Lu G.P., Cai C.,et al.Org Lett,2015,17(13),3310-3313]。
However, the product of method 1~4 is single, and it is not general talan thio-ether type compounds preparation method, it cannot Prepare talan thio-ether type compounds in a systematic manner, the yield of method 3~5 is lower, the raw material complexity of method 6, expensive reagents, Severe reaction conditions.
Currently, being reacted using aryl groups per alkyl group sulfinic acid sodium with alkene/alkynes/arene compounds to prepare in a systematic manner Thio-ether type compounds are reported, but are not directed to aryl groups per alkyl group sulfinic acid sodium react with talan to prepare talan Thio-ether type compounds, and the generally existing following two disadvantage of method reported:
1) it needs using transition metal-catalyzed, such as: iron is catalyzed [Liu S.W., Tang L.C., Chen, H., et Al.Org Biomol Chem, 2014,12 (32): 6076-6079.], copper catalysis [Gao Y.L., Gao Y., Tang X.D., et al.Org Lett,2016,18(5):1158-1161.]；
2) reaction system needs reducing agent not only to restore sulfinic acid sodium, it is also necessary to which additional oxidant can generate solid Waste (triphenylphosphinc oxide or diethyl phosphate), pollution is big, and processing is difficult, such as: a plus phosphorus reducing agent (triphenyl phosphorus or Asia Diethyl phosphate) it is restored, add elemental iodine to be aoxidized [Lin Y.M., Lu G.P., Wang G.X., et al.Adv Synth Catal,2016,358(24):4100-4105.]、[Guo Y.J.,Lu S.,Tian L.L.,et al.J Org Chem,2018,83(1):338-349.]；B, plus phosphorus reducing agent (triphenyl phosphorus or diethyl phosphite) is restored, and adds iodine list Matter and DMSO carry out synergistic oxidation [Xiao F.H., Xie H., Liu S.W., et al.Adv Synth Catal, 2014,356 (2-3):364-368.]。
Therefore, it is necessary to develop the talan thioether class chemical combination that a kind of yield is high, at low cost, pollution is small, easy to operate Object preparation method.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of diphenylethyllene thio-ether type compounds.
The technical solution used in the present invention is:
A kind of preparation method of diphenylethyllene thio-ether type compounds, comprising the following steps: by 1,1- talan, virtue Base/sodium alkyl-sulfinate and acidic reduction agent dispersion in a solvent, carry out coupling reaction, obtain diphenylethyllene thioether class chemical combination Object.
Preferably, a kind of preparation method of diphenylethyllene thio-ether type compounds, comprising the following steps: by 1,1- hexichol second Alkene, aryl groups per alkyl group sulfinic acid sodium and acidic reduction agent dispersion in a solvent, carry out the coupling reaction of 12~18h at 70~80 DEG C, Quenching reaction, then extracted, liquid separation, drying, decompression are spin-dried for, cross column, obtain diphenylethyllene thio-ether type compounds.
Preferably, 1, the 1- talan, aryl groups per alkyl group sulfinic acid sodium, acidic reduction agent molar ratio be 1:(1.3 ~1.7): (2~4).
It is further preferred that 1, the 1- talan, aryl groups per alkyl group sulfinic acid sodium, acidic reduction agent molar ratio be 1:(1.4~1.6): (2.8~3.2).
Still further preferably, 1, the 1- talan, aryl groups per alkyl group sulfinic acid sodium, acidic reduction agent molar ratio For 1:1.5:3.
Preferably, the sodium arylsulfinate is C4~C12Sodium arylsulfinate.
It is further preferred that the sodium arylsulfinate is to methyl sodium benzene sulphinate, benzene sulfinic acid sodium salt, to tert-butyl benzene Sulfinic acid sodium, to methoxyl group benzene sulfinic acid sodium salt, to fluorine benzene sulfinic acid sodium salt, to chlorobenzene sulfinic acid sodium, to bromine benzene sulfinic acid sodium salt, to iodine Benzene sulfinic acid sodium salt, p-nitrophenyl sulfinic acid sodium, to trifluoromethyl benzenesulfinic acid sodium, sub- to cyano benzene sulfinic acid sodium salt, o-methyl-benzene Sodium sulfonate, adjacent fluorine benzene sulfinic acid sodium salt, adjacent chlorobenzene sulfinic acid sodium, bromine benzene sulfinic acid sodium salt, m-trifluoromethyl benzene sulfinic acid sodium salt, 2,4, One of 6- trimethyl benzene sulfinic acid sodium salt, 2- naphthalene sulfinic acid sodium, 4- connection benzene sulfinic acid sodium salt, 2- thiophene sulfinic acid sodium.
Preferably, the sodium alkyl-sulfinate is methyl sulfinic acid sodium, in sodium ethanesulfinate, cyclopropyl sulfinic acid sodium It is a kind of.
Preferably, the acidic reduction agent is one of hydrobromic acid, hydroiodic acid, hydrochloric acid.
It is further preferred that the acidic reduction agent is hydroiodic acid.
Preferably, the solvent be toluene, 1,2- dichloroethanes, Isosorbide-5-Nitrae-dioxane, acetonitrile, in nitromethane at least It is a kind of.
Preferably, the quenching reaction is that saturated aqueous sodium thiosulfate is added to be quenched.
Note:
C4~C12Aryl indicate the aryl of carbon atom number 4~12, including phenyl, naphthalene, xenyl, tolyl, tertiary fourth The aryl that phenyl, trimethylphenyl etc. replace without hetero atom, further include nitrobenzophenone, methoxyphenyl, fluorophenyl, chlorphenyl, The aryl that the hetero atoms such as bromophenyl, iodophenyl, trifluoromethyl, cyano-phenyl, 2- thienyl replace；
Aryl groups per alkyl group sulfinic acid sodium indicates sodium arylsulfinate or sodium alkyl-sulfinate.
The beneficial effects of the present invention are: the present invention can systematically synthesize a series of talan thio-ether type compounds, It not needing using transition-metal catalyst, reaction system is simple, and wide application range of substrates, yield is higher, and reaction raw materials are easy to get, at This is low, pollutes small.
Specific embodiment
The present invention will be further explained combined with specific embodiments below and explanation.
Embodiment 1:
A kind of preparation method of diphenylethyllene thio-ether type compounds, comprising the following steps: by 0.3mmol (0.0541g) 1,1- talan, 0.45mmol (0.0802g) the hydrogen iodine to methyl sodium benzene sulphinate and 0.2558g mass fraction 45% Aqueous acid (containing hydroiodic acid 0.9mmol) is dispersed in the toluene of 2mL, and the coupling reaction of 15h is carried out at 75 DEG C, and saturation sulphur is added Sodium thiosulfate aqueous solution is quenched, then is extracted with methylene chloride (15mL × 3), liquid separation, dries organic layer with anhydrous sodium sulfate, Decompression is spin-dried for, cross column, obtain 0.0882g diphenylethyllene thio-ether type compounds (white solid, yield 97%, fusing point 79.5~ 81.0 DEG C), nuclear magnetic resonance spectroscopy, carbon-13 nmr spectra and high resolution mass spectrum characterize data are as follows:
1H NMR(400MHz,CDCl3),δ,ppm:2.31(s,3H,ArCH3-21),6.81(s,1H,CH-2),7.11(d, J=8.0Hz, 2H, ArH-17,19), 7.17-7.25 (m, 5H, ArH-4,5,6,7,8), 7.29-7.43 (m, 5H, ArH-10, 11,12,13,14), 7.41 (d, J=8.0Hz, 2H, ArH-16,20)；
13C NMR(100MHz,CDCl3),δ,ppm:21.2(C-21),125.3(C-2),127.2(C-6,12),127.8 (C-4,8),128.4(C-5,7),128.5(C-10,14),129.9(C-11,13),130.0(C-17,19),130.2(C-16, 20),132.9(C-15),137.0(C-1),139.3(C-3),140.2(C-9),141.6(C-18)；
ESI-HRMS,m/z:Calcd for C21H18S(M+):302.1129,Found:302.1147；
Characterization result shows the structural formula of diphenylethyllene thio-ether type compounds are as follows:
Embodiment 2:
A kind of preparation method of diphenylethyllene thio-ether type compounds, comprising the following steps: by 0.3mmol (0.0541g) 1,1- talan, 0.45mmol (0.0739g) benzene sulfinic acid sodium salt and 0.2558g mass fraction 45% hydroiodic acid it is water-soluble Liquid (containing hydroiodic acid 0.9mmol) is dispersed in the toluene of 2mL, and the coupling reaction of 15h is carried out at 75 DEG C, and saturation thiosulfuric acid is added Sodium water solution is quenched, then is extracted with methylene chloride (15mL × 3), liquid separation, with the dry organic layer of anhydrous sodium sulfate, decompression rotation It is dry, column is crossed, is obtained 0.0739g diphenylethyllene thio-ether type compounds (colourless liquid, yield 85%), nuclear magnetic resonance spectroscopy, Carbon-13 nmr spectra and high resolution mass spectrum characterize data are as follows:
1H NMR(400MHz,CDCl3),δ,ppm:6.85(s,1H,CH-2),7.17-7.25(m,5H,ArH-4,5,6,7, 8),7.27-7.35(m,5H,ArH-10,11,12,13,14),7.36-7.46(m,5H,ArH-16,17,18,19,20)；
13C NMR(100MHz,CDCl3),δ,ppm:124.2(C-2),126.9(C-18),127.3(C-4,8),127.4 (C-6),127.9(C-12),128.4(C-5,7),128.5(C-10,14),129.2(C-11,13),129.6(C-17,19), 129.8(C-16,20),136.6(C-1),139.3(C-15),141.2(C-3),141.5(C-9)；
ESI-HRMS,m/z:Calcd for C20H16S(M+):288.0973,Found:288.0976；
Characterization result shows the structural formula of diphenylethyllene thio-ether type compounds are as follows:
Embodiment 3:
A kind of preparation method of diphenylethyllene thio-ether type compounds, comprising the following steps: by 0.3mmol (0.0541g) 1,1- talan, 0.45mmol (0.0991g) the hydrogen to tert-butyl benzene sulfinic acid sodium salt and 0.2558g mass fraction 45% Acid iodide aqueous solution (containing hydroiodic acid 0.9mmol) is dispersed in the toluene of 2mL, and the coupling reaction of 15h is carried out at 75 DEG C, saturation is added Sodium thiosulfate solution is quenched, then is extracted with methylene chloride (15mL × 3), liquid separation, organic with anhydrous sodium sulfate drying Layer, decompression are spin-dried for, and are crossed column, are obtained 0.0897g diphenylethyllene thio-ether type compounds (colorless solid, yield 87%, fusing point 74.3 ~75.7 DEG C), nuclear magnetic resonance spectroscopy, carbon-13 nmr spectra and high resolution mass spectrum characterize data are as follows:
1H NMR(400MHz,CDCl3),δ,ppm:1.30(s,9H,CH3-22,23,24),6.84(s,1H,CH-2), 7.15-7.24(m,5H,ArH-4,5,6,7,8),7.29-7.36(m,5H,ArH-10,11,12,13,14),7.37-7.42(m, 4H,ArH-16,17,19,20)；
13C NMR(100MHz,CDCl3),δ,ppm:31.4(C-22,23,24),34.6(C-21),125.2(C-2), 126.3(C-17,19),127.2(C-4,8),127.8(C-6,12),128.4(C-10,14),128.5(C-5,7),129.8 (C-11,13),129.9(C-16,20),133.0(C-1),139.3(C-15),140.3(C-3),141.6(C-9),150.2 (C-18)；
ESI-HRMS,m/z:Calcd for C24H24S(M+):344.1599,Found:344.1600；
Characterization result shows the structural formula of diphenylethyllene thio-ether type compounds are as follows:
Embodiment 4:
A kind of preparation method of diphenylethyllene thio-ether type compounds, comprising the following steps: by 0.3mmol (0.0541g) 1,1- talan, 0.45mmol (0.0874g) the hydrogen to methoxyl group benzene sulfinic acid sodium salt and 0.2558g mass fraction 45% Acid iodide aqueous solution (containing hydroiodic acid 0.9mmol) is dispersed in the toluene of 2mL, and the coupling reaction of 15h is carried out at 75 DEG C, saturation is added Sodium thiosulfate solution is quenched, then is extracted with methylene chloride (15mL × 3), liquid separation, organic with anhydrous sodium sulfate drying Layer, decompression are spin-dried for, and are crossed column, are obtained 0.0922g diphenylethyllene thio-ether type compounds (colourless liquid, yield 97%), nuclear-magnetism Hydrogen spectrum, carbon-13 nmr spectra and the high resolution mass spectrum characterize data of resonating are as follows:
1H NMR(400MHz,CDCl3),δ,ppm:3.75(s,3H,OCH3-21),6.75(s,1H,CH-2),6.85(d, 2H, J=8.0Hz, ArH-17,19), 7.17-7.23 (m, 5H, ArH-4,6,8,16,20), 7.30-7.43 (m, 7H, ArH-5, 7,10,11,12,13,14)；
13C NMR(100MHz,CDCl3),δ,ppm:55.4(C-21),114.9(C-17,19),126.7(C-2),126.9 (C-15),127.1(C-6),127.2(C-4,8),127.8(C-12),128.3(C-10,14),128.5(C-5,7),129.9 (C-11,13),132.6(C-1,16,20),139.3(C-3),141.6(C-9),159.3(C-18)；
ESI-HRMS,m/z:Calcd for C21H18OS(M+):318.1078,Found:318.1091；
Characterization result shows the structural formula of diphenylethyllene thio-ether type compounds are as follows:
Embodiment 5:
A kind of preparation method of diphenylethyllene thio-ether type compounds, comprising the following steps: by 0.3mmol (0.0541g) 1,1- talan, 0.45mmol (0.0820g) the hydroiodic acid to fluorine benzene sulfinic acid sodium salt and 0.2558g mass fraction 45% Aqueous solution (containing hydroiodic acid 0.9mmol) is dispersed in the toluene of 2mL, and the coupling reaction of 15h is carried out at 75 DEG C, it is thio that saturation is added Aqueous sodium persulfate solution is quenched, then is extracted with methylene chloride (15mL × 3), liquid separation, with the dry organic layer of anhydrous sodium sulfate, is subtracted Pressure is spin-dried for, cross column, obtain 0.0752g diphenylethyllene thio-ether type compounds (colorless solid, yield 82%, fusing point 53.8~ 55.8 DEG C), nuclear magnetic resonance spectroscopy, carbon-13 nmr spectra, Enantiomeric excess and high resolution mass spectrum characterize data are as follows:
1H NMR(400MHz,CDCl3), δ, ppm:6.75 (s, 1H, CH-2), 7.00 (t, J=8.0Hz, 2H, ArH-6, 12),7.18-7.25(m,4H,ArH-4,5,7,8),7.28-7.36(m,4H,ArH-10,11,13,14),7.38-7.45(m, 4H,ArH-16,17,19,20)；
13C NMR(100MHz,CDCl3), δ, ppm:116.3 (d, J=22Hz, C-17,19), 124.7 (C-2), 127.2 (C-4,8),127.4(C-6),127.9(C-12),128.4(C-10,14),128.5(C-5,7),129.8(C-11,13), 131.6 (d, J=3Hz, C-15), 132.1 (d, J=8Hz, C-16,20), 139.1 (C-1), 140.9 (C-3), 141.4 (C- 9), 162.2 (d, J=246Hz, C-18)；
19F NMR(376MHz,CDCl3),δ,ppm:114.5；
ESI-HRMS,m/z:Calcd for C20H15FS(M+):306.0878,Found:306.0872；
Characterization result shows the structural formula of diphenylethyllene thio-ether type compounds are as follows:
Embodiment 6:
A kind of preparation method of diphenylethyllene thio-ether type compounds, comprising the following steps: by 0.3mmol (0.0541g) 1,1- talan, 0.45mmol (0.0894g) the hydroiodic acid to chlorobenzene sulfinic acid sodium and 0.2558g mass fraction 45% Aqueous solution (containing hydroiodic acid 0.9mmol) is dispersed in the toluene of 2mL, and the coupling reaction of 15h is carried out at 75 DEG C, it is thio that saturation is added Aqueous sodium persulfate solution is quenched, then is extracted with methylene chloride (15mL × 3), liquid separation, with the dry organic layer of anhydrous sodium sulfate, is subtracted Pressure is spin-dried for, cross column, obtain 0.0812g diphenylethyllene thio-ether type compounds (white solid, yield 84%, fusing point 81.2~ 82.4 DEG C), nuclear magnetic resonance spectroscopy, carbon-13 nmr spectra and high resolution mass spectrum characterize data are as follows:
1H NMR(400MHz,CDCl3),δ,ppm:6.76(s,1H,CH-2),7.18-7.25(m,5H,ArH-4,5,6,7, 8),7.27-7.36(m,7H,ArH-10,11,12,13,14,16,20),7.37-7.43(m,2H,ArH-17,19)；
13C NMR(100MHz,CDCl3),δ,ppm:123.3(C-2),127.3(C-4,8),127.6(C-6),128.0 (C-12),128.4(C-10,14),128.5(C-5,7),129.3(C-11,13),129.8(C-17,19),130.7(C-16, 20),132.8(C-1),135.1(C-18),139.0(C-15),141.3(C-3),142.0(C-9)；
ESI-HRMS,m/z:Calcd for C20H15ClS(M+):322.0583,Found:322.0564；
Characterization result shows the structural formula of diphenylethyllene thio-ether type compounds are as follows:
Embodiment 7:
A kind of preparation method of diphenylethyllene thio-ether type compounds, comprising the following steps: by 0.3mmol (0.0541g) 1,1- talan, 0.45mmol (0.1094g) the hydroiodic acid to bromine benzene sulfinic acid sodium salt and 0.2558g mass fraction 45% Aqueous solution (containing hydroiodic acid 0.9mmol) is dispersed in the toluene of 2mL, and the coupling reaction of 15h is carried out at 75 DEG C, it is thio that saturation is added Aqueous sodium persulfate solution is quenched, then is extracted with methylene chloride (15mL × 3), liquid separation, with the dry organic layer of anhydrous sodium sulfate, is subtracted Pressure is spin-dried for, cross column, obtain 0.0895g diphenylethyllene thio-ether type compounds (white solid, yield 81%, fusing point 101.6~ 103.2 DEG C), nuclear magnetic resonance spectroscopy, carbon-13 nmr spectra and high resolution mass spectrum characterize data are as follows:
1H NMR(400MHz,CDCl3),δ,ppm:6.76(s,1H,CH-2),7.19-7.27(m,5H,ArH-4,5,6,7, 8),7.28-7.37(m,5H,ArH-10,11,12,13,14),7.38-7.46(m,4H,ArH-16,17,19,20)；
13C NMR(100MHz,CDCl3),δ,ppm:120.7(C-2),123.0(C-18),127.3(C-4,8),127.6 (C-6),128.0(C-12),128.4(C-10,14),128.5(C-5,7),129.8(C-11,13),130.9(C-16,20), 132.2(C-17,19),135.8(C-1),139.0(C-15),141.3(C-3),142.2(C-9)；
ESI-HRMS,m/z:Calcd for C20H15BrS(M+):366.0078,Found:366.0059；
Characterization result shows the structural formula of diphenylethyllene thio-ether type compounds are as follows:
Embodiment 8:
A kind of preparation method of diphenylethyllene thio-ether type compounds, comprising the following steps: by 0.3mmol (0.0541g) 1,1- talan, 0.45mmol (0.1305g) the hydroiodic acid to iodine benzene sulfinic acid sodium salt and 0.2558g mass fraction 45% Aqueous solution (containing hydroiodic acid 0.9mmol) is dispersed in the toluene of 2mL, and the coupling reaction of 15h is carried out at 75 DEG C, it is thio that saturation is added Aqueous sodium persulfate solution is quenched, then is extracted with methylene chloride (15mL × 3), liquid separation, with the dry organic layer of anhydrous sodium sulfate, is subtracted Pressure is spin-dried for, cross column, obtain 0.0994g diphenylethyllene thio-ether type compounds (white solid, yield 80%, fusing point 103.5~ 105.5 DEG C), nuclear magnetic resonance spectroscopy, carbon-13 nmr spectra and high resolution mass spectrum characterize data are as follows:
1H NMR(400MHz,CDCl3), δ, ppm:6.77 (s, 1H, CH-2), 7.15 (d, J=8.0Hz, 2H, ArH-16, 20),7.21-7.29(m,5H,ArH-4,5,6,7,8),7.30-7.45(m,5H,ArH-10,11,12,13,14),7.63(d,J =8.0Hz, 2H, ArH-17,19)；
13C NMR(100MHz,CDCl3),δ,ppm:91.6(C-18),122.7(C-2),127.2(C-4,8),127.5 (C-6),128.0(C-12),128.4(C-10,14),128.5(C-5,7),129.7(C-11,13),130.9(C-16,20), 136.6(C-1),138.0(C-17,19),139.0(C-15),141.2(C-3),142.3(C-9)；
ESI-HRMS,m/z:Calcd for C20H15IS(M+):413.9939,Found:413.9936；
Characterization result shows the structural formula of diphenylethyllene thio-ether type compounds are as follows:
Embodiment 9:
A kind of preparation method of diphenylethyllene thio-ether type compounds, comprising the following steps: by 0.3mmol (0.0541g) 1,1- talan, the p-nitrophenyl sulfinic acid sodium of 0.45mmol (0.0941g) and the hydrogen iodine of 0.2558g mass fraction 45% Aqueous acid (containing hydroiodic acid 0.9mmol) is dispersed in the toluene of 2mL, and the coupling reaction of 15h is carried out at 75 DEG C, and saturation sulphur is added Sodium thiosulfate aqueous solution is quenched, then is extracted with methylene chloride (15mL × 3), liquid separation, dries organic layer with anhydrous sodium sulfate, Decompression is spin-dried for, cross column, obtain 0.0865g diphenylethyllene thio-ether type compounds (yellow solid, yield 87%, fusing point 110.8~ 112.3 DEG C), nuclear magnetic resonance spectroscopy, carbon-13 nmr spectra and high resolution mass spectrum characterize data are as follows:
1H NMR(400MHz,CDCl3),δ,ppm:6.84(s,1H,CH-2),7.27-7.41(m,10H,ArH-4,5,6, 7,8,10,11,12,13,14), 7.44 (d, J=8.0Hz, 2H, ArH-16,20), 8.13 (d, J=8.0Hz, 2H, ArH-17, 19)；
13C NMR(100MHz,CDCl3),δ,ppm:118.6(C-2),124.2(C-17,19),127.2(C-16,20), 127.5(C-4,8),128.3(C-6),128.4(C-12),128.5(C-10,14),128.6(C-5,7),129.6(C-11, 13),138.6(C-1),140.8(C-3),145.7(C-9),146.3(C-15),146.6(C-18)；
ESI-HRMS,m/z:Calcd for C20H16NO2S([M+H]+):334.0896,Found:334.0889；
Characterization result shows the structural formula of diphenylethyllene thio-ether type compounds are as follows:
Embodiment 10:
A kind of preparation method of diphenylethyllene thio-ether type compounds, comprising the following steps: by 0.3mmol (0.0541g) 1,1- talan, 0.45mmol (0.1045g) to trifluoromethyl benzenesulfinic acid sodium and 0.2558g mass fraction 45% Hydriodic acid aqueous solution (containing hydroiodic acid 0.9mmol) is dispersed in the toluene of 2mL, and the coupling reaction of 15h is carried out at 75 DEG C, is added full It is quenched, then is extracted with methylene chloride (15mL × 3), liquid separation with sodium thiosulfate solution, had with anhydrous sodium sulfate drying Machine layer, decompression are spin-dried for, and are crossed column, are obtained 0.0742g diphenylethyllene thio-ether type compounds (colourless liquid, yield 69%), core Magnetic resonance hydrogen spectrum, carbon-13 nmr spectra, Enantiomeric excess and high resolution mass spectrum characterize data are as follows:
1H NMR(400MHz,CDCl3),δ,ppm:6.83(s,1H,CH-2),7.19-7.30(m,5H,ArH-4,5,6,7, 8), 7.31-7.44 (m, 5H, ArH-10,11,12,13,14), 7.46 (d, J=8.0Hz, 2H, ArH-16,20), 7.54 (d, J =8.0Hz, 2H, ArH-17,19)；
13C NMR(100MHz,CDCl3), δ, ppm:121.0 (C-2), 124.1 (q, J=270Hz, C-21), 125.9 (q, J=4Hz, C-17,19), 127.4 (C-6,12), 128.0 (q, J=31Hz, C-18), 128.3 (C-4,8), 128.4 (C-10, 14),128.5(C-16,20),129.7(C-11,13),138.9(C-1),141.1(C-15),141.8(C-3),144.0(C- 9)；
19F NMR(376MHz,CDCl3),δ,ppm:62.4；
ESI-HRMS,m/z:Calcd for C21H15F3S(M+):356.0847,Found:356.0853；
Characterization result shows the structural formula of diphenylethyllene thio-ether type compounds are as follows:
Embodiment 11:
A kind of preparation method of diphenylethyllene thio-ether type compounds, comprising the following steps: by 0.3mmol (0.0541g) 1,1- talan, 0.45mmol (0.0851g) the hydrogen iodine to cyano benzene sulfinic acid sodium salt and 0.2558g mass fraction 45% Aqueous acid (containing hydroiodic acid 0.9mmol) is dispersed in the toluene of 2mL, and the coupling reaction of 15h is carried out at 75 DEG C, and saturation sulphur is added Sodium thiosulfate aqueous solution is quenched, then is extracted with methylene chloride (15mL × 3), liquid separation, dries organic layer with anhydrous sodium sulfate, Decompression is spin-dried for, cross column, obtain 0.0699g diphenylethyllene thio-ether type compounds (white solid, yield 73%, fusing point 114.3~ 116.0 DEG C), nuclear magnetic resonance spectroscopy, carbon-13 nmr spectra and high resolution mass spectrum characterize data are as follows:
1H NMR(400MHz,CDCl3),δ,ppm:6.81(s,1H,CH-2),7.27-7.39(m,10H,ArH-4,5,6, 7,8,10,11,12,13,14), 7.41 (d, J=8.0Hz, 2H, ArH-17,19), 7.54 (d, J=8.0Hz, 2H, ArH-16, 20)；
13C NMR(100MHz,CDCl3),δ,ppm:109.3(C-21),118.7(C-2),119.1(C-18),127.4 (C-4,8),127.8(C-10,14),128.1(C-6),128.3(C-12),128.5(C-5,7,16,20),129.6(C-11, 13),132.5(C-17,19),138.7(C-1),140.9(C-15),144.0(C-3),145.6(C-9)；
ESI-HRMS,m/z:Calcd for C21H15NS(M+):313.0925,Found:313.0939；
Characterization result shows the structural formula of diphenylethyllene thio-ether type compounds are as follows:
Embodiment 12:
A kind of preparation method of diphenylethyllene thio-ether type compounds, comprising the following steps: by 0.3mmol (0.0541g) 1,1- talan, the o-methyl-benzene sulfinic acid sodium of 0.45mmol (0.0802g) and the hydrogen iodine of 0.2558g mass fraction 45% Aqueous acid (containing hydroiodic acid 0.9mmol) is dispersed in the toluene of 2mL, and the coupling reaction of 15h is carried out at 75 DEG C, and saturation sulphur is added Sodium thiosulfate aqueous solution is quenched, then is extracted with methylene chloride (15mL × 3), liquid separation, dries organic layer with anhydrous sodium sulfate, Decompression is spin-dried for, and is crossed column, is obtained 0.0859g diphenylethyllene thio-ether type compounds (colourless liquid, yield 95%), nuclear magnetic resonance Hydrogen spectrum, carbon-13 nmr spectra and high resolution mass spectrum characterize data are as follows:
1H NMR(400MHz,CDCl3),δ,ppm:2.37(s,3H,ArCH3-21),6.74(s,1H,CH-2),7.10- 7.34(m,10H,ArH-4,5,6,7,8,10,11,12,13,14),7.36-7.43(m,3H,ArH-18,19,20),7.47(d, J=8.0Hz, 1H, ArH-17)；
13C NMR(100MHz,CDCl3),δ,ppm:20.7(C-21),124.3(C-2),126.8(C-18),127.1(C- 19),127.2(C-4,8),127.3(C-6),127.8(C-12),128.4(C-10,14),128.5(C-5,7),129.9(C- 11,13),130.3(C-20),130.4(C-17),135.7(C-1),138.3(C-15),139.3(C-3),141.4(C-9), 141.6(C-16)；
ESI-HRMS,m/z:Calcd for C21H18S(M+):302.1129,Found:302.1116；
Characterization result shows the structural formula of diphenylethyllene thio-ether type compounds are as follows:
Embodiment 13:
A kind of preparation method of diphenylethyllene thio-ether type compounds, comprising the following steps: by 0.3mmol (0.0541g) 1,1- talan, 0.45mmol (0.0820g) adjacent fluorine benzene sulfinic acid sodium salt and 0.2558g mass fraction 45% hydroiodic acid Aqueous solution (containing hydroiodic acid 0.9mmol) is dispersed in the toluene of 2mL, and the coupling reaction of 15h is carried out at 75 DEG C, it is thio that saturation is added Aqueous sodium persulfate solution is quenched, then is extracted with methylene chloride (15mL × 3), liquid separation, with the dry organic layer of anhydrous sodium sulfate, is subtracted Pressure is spin-dried for, and is crossed column, is obtained 0.0780g diphenylethyllene thio-ether type compounds (colourless liquid, yield 85%), hydrogen nuclear magnetic resonance Spectrum, carbon-13 nmr spectra, Enantiomeric excess and high resolution mass spectrum characterize data are as follows:
1H NMR(400MHz,CDCl3),δ,ppm:6.74(s,1H,CH-2),7.02-7.13(m,2H,ArH-17,19), 7.18-7.25(m,5H,ArH-4,5,6,7,8),7.27-7.39(m,5H,ArH-10,11,12,13,14),7.41-7.49(m, 2H,ArH-16,18)；
13C NMR(100MHz,CDCl3), δ, ppm:116.0 (d, J=22Hz, C-19), 122.6 (d, J=2Hz, C-2), 123.4 (d, J=17Hz, C-15), 124.8 (d, J=3Hz, C-16), 127.3 (C-4,8), 127.5 (C-6), 128.0 (C- 12), 128.4 (C-10,14), 128.5 (C-5,7), 129.0 (d, J=8Hz, C-18), 129.8 (C-11,13), 131.9 (d, J =1Hz, C-17), 139.0 (C-1), 141.4 (C-3), 142.0 (C-9), 160.8 (d, J=245Hz, C-20)；
19F NMR(376MHz,CDCl3),δ,ppm:109.6；
ESI-HRMS,m/z:Calcd for C20H15FS(M+):306.0878,Found:306.0871；
Characterization result shows the structural formula of diphenylethyllene thio-ether type compounds are as follows:
Embodiment 14:
A kind of preparation method of diphenylethyllene thio-ether type compounds, comprising the following steps: by 0.3mmol (0.0541g) 1,1- talan, 0.45mmol (0.0940g) adjacent chlorobenzene sulfinic acid sodium and 0.2558g mass fraction 45% hydroiodic acid Aqueous solution (containing hydroiodic acid 0.9mmol) is dispersed in the toluene of 2mL, and the coupling reaction of 15h is carried out at 75 DEG C, it is thio that saturation is added Aqueous sodium persulfate solution is quenched, then is extracted with methylene chloride (15mL × 3), liquid separation, with the dry organic layer of anhydrous sodium sulfate, is subtracted Pressure is spin-dried for, and is crossed column, is obtained 0.0672g diphenylethyllene thio-ether type compounds (colourless liquid, yield 69%), hydrogen nuclear magnetic resonance Spectrum, carbon-13 nmr spectra and high resolution mass spectrum characterize data are as follows:
1H NMR(400MHz,CDCl3), δ, ppm:6.75 (s, 1H, CH-2), 7.14 (t, J=8.0Hz, 1H, ArH-6), 7.20-7.24(m,1H,ArH-18),7.25-7.31(m,5H,ArH-4,5,7,8,12),7.32-7.36(m,4H,Ar-10, 11,13,14), 7.38-7.43 (m, 2H, ArH-16,17), 7.47 (d, J=8.0Hz, 1H, ArH-19)；
13C NMR(100MHz,CDCl3),δ,ppm:121.5(C-2),127.4(C-4,8,18),127.5(C-17), 127.7(C-6),128.0(C-12),128.4(C-10,14),128.5(C-5,7),129.8(C-11,13),129.8(C- 19),129.9(C-16),133.6(C-1),136.0(C-20),138.9(C-15),141.4(C-3),143.9(C-9)；
ESI-HRMS,m/z:Calcd for C20H15ClS(M+):322.0583,Found:322.0635；
Characterization result shows the structural formula of diphenylethyllene thio-ether type compounds are as follows:
Embodiment 15:
A kind of preparation method of diphenylethyllene thio-ether type compounds, comprising the following steps: by 0.3mmol (0.0541g) 1,1- talan, between 0.45mmol (0.1094g) bromine benzene sulfinic acid sodium salt and 0.2558g mass fraction 45% hydroiodic acid Aqueous solution (containing hydroiodic acid 0.9mmol) is dispersed in the toluene of 2mL, and the coupling reaction of 15h is carried out at 75 DEG C, it is thio that saturation is added Aqueous sodium persulfate solution is quenched, then is extracted with methylene chloride (15mL × 3), liquid separation, with the dry organic layer of anhydrous sodium sulfate, is subtracted Pressure is spin-dried for, and is crossed column, is obtained 0.0898g diphenylethyllene thio-ether type compounds (colourless liquid, yield 82%), hydrogen nuclear magnetic resonance Spectrum, carbon-13 nmr spectra and high resolution mass spectrum characterize data are as follows:
1H NMR(400MHz,CDCl3), δ, ppm:6.79 (s, 1H, CH-2), 7.15 (t, J=8.0Hz, 1H, ArH-6), 7.20-7.29(m,5H,ArH-4,5,7,8,19),7.30-7.37(m,5H,ArH-10,11,12,13,14),7.38-7.45 (m,2H,ArH-18,20),7.55(s,1H,ArH-16)；
13C NMR(100MHz,CDCl3),δ,ppm:122.2(C-2),123.0(C-16),127.3(C-4,8),127.7 (C-18,20),128.0(C-6),128.4(C-10,14),128.5(C-5,7),129.7(C-12),129.8(C-11,13), 130.4(C-19),131.6(C-1),138.9(C-17),139.0(C-15),141.2(C-3),142.7(C-9)；
ESI-HRMS,m/z:Calcd for C20H15BrS(M+):366.0078,Found:366.0120；
Characterization result shows the structural formula of diphenylethyllene thio-ether type compounds are as follows:
Embodiment 16:
A kind of preparation method of diphenylethyllene thio-ether type compounds, comprising the following steps: by 0.3mmol (0.0541g) 1,1- talan, 0.45mmol (0.1045g) m-trifluoromethyl benzene sulfinic acid sodium salt and 0.2558g mass fraction 45% Hydriodic acid aqueous solution (containing hydroiodic acid 0.9mmol) is dispersed in the toluene of 2mL, and the coupling reaction of 15h is carried out at 75 DEG C, is added full It is quenched, then is extracted with methylene chloride (15mL × 3), liquid separation with sodium thiosulfate solution, had with anhydrous sodium sulfate drying Machine layer, decompression are spin-dried for, and are crossed column, are obtained 0.0806g diphenylethyllene thio-ether type compounds (colourless liquid, yield 75%), core Magnetic resonance hydrogen spectrum, carbon-13 nmr spectra, Enantiomeric excess and high resolution mass spectrum characterize data are as follows:
1H NMR(400MHz,CDCl3),δ,ppm:6.81(s,1H,CH-2),7.27-7.34(m,6H,ArH-4,5,6,7, 8,19), 7.35-7.46 (m, 5H, ArH-10,11,12,13,14), 7.48 (d, J=8.0Hz, 1H, ArH-18), 7.59 (d, J =8.0Hz, 1H, ArH-20), 7.66 (s, 1H, ArH-16)；
13C NMR(100MHz,CDCl3), δ, ppm:121.7 (C-2), 123.3 (q, J=4Hz, C-18), 123.7 (q, J =271Hz, C-21), 125.6 (q, J=4Hz, C-16), 127.3 (C-4,8), 127.7 (C-6), 128.1 (C-12), 128.4 (C-10,14), 128.5 (C-5,7), 129.5 (C-20), 129.7 (C-11,13), 131.5 (q, J=32Hz, C-17), 132.1 (q, J=1Hz, C-19), 138.1 (C-1), 138.9 (C-15), 141.1 (C-3), 143.2 (C-9)；
19F NMR(376MHz,CDCl3),δ,ppm:62.8；
ESI-HRMS,m/z:Calcd for C21H15F3S(M+):356.0847,Found:356.0848；
Characterization result shows the structural formula of diphenylethyllene thio-ether type compounds are as follows:
Embodiment 17:
A kind of preparation method of diphenylethyllene thio-ether type compounds, comprising the following steps: by 0.3mmol (0.0541g) 1,1- talan, 0.45mmol (0.1151g) 2,4,6- trimethyl benzene sulfinic acid sodium salt and 0.2558g mass fraction 45% Hydriodic acid aqueous solution (contain hydroiodic acid 0.9mmol) be dispersed in the toluene of 2mL, the coupling reaction of 15h is carried out at 75 DEG C, is added Saturated aqueous sodium thiosulfate is quenched, then is extracted with methylene chloride (15mL × 3), liquid separation, dry with anhydrous sodium sulfate Organic layer, decompression are spin-dried for, and are crossed column, are obtained 0.0908g diphenylethyllene thio-ether type compounds (colourless liquid, yield 92%), Nuclear magnetic resonance spectroscopy, carbon-13 nmr spectra and high resolution mass spectrum characterize data are as follows:
1H NMR(400MHz,CDCl3),δ,ppm:2.26(s,3H,CH3-22),2.46(s,6H,CH3-21,23),6.36 (s,1H,CH-2),6.93(s,2H,ArH-17,19),7.11-7.21(m,5H,ArH-4,5,6,7,8),7.30-7.45(m, 5H,ArH-10,11,12,13,14)；
13C NMR(100MHz,CDCl3),δ,ppm:21.1(C-22),22.2(C-21,23),126.8(C-2),126.9 (C-4,8),127.6(C-6),127.7(C-12),128.3(C-17,19),128.5(C-10,14),129.2(C-5,7), 129.8(C-11,13),130.4(C-1),138.6(C-15),138.7(C-18),139.5(C-3),141.7(C-9),142.4 (C-16,20)；
ESI-HRMS,m/z:Calcd for C23H22S(M+):330.1442,Found:330.1468；
Characterization result shows the structural formula of diphenylethyllene thio-ether type compounds are as follows:
Embodiment 18:
A kind of preparation method of diphenylethyllene thio-ether type compounds, comprising the following steps: by 0.3mmol (0.0541g) 1,1- talan, the 2- naphthalene sulfinic acid sodium of 0.45mmol (0.0964g) and the hydroiodic acid water of 0.2558g mass fraction 45% Solution (containing hydroiodic acid 0.9mmol) is dispersed in the toluene of 2mL, and the coupling reaction of 15h is carried out at 75 DEG C, is added and is saturated thio sulphur Acid sodium aqueous solution is quenched, then is extracted with methylene chloride (15mL × 3), liquid separation, with the dry organic layer of anhydrous sodium sulfate, decompression Be spin-dried for, cross column, obtain 0.0921g diphenylethyllene thio-ether type compounds (white solid, yield 91%, fusing point 117.1~ 118.9 DEG C), nuclear magnetic resonance spectroscopy, carbon-13 nmr spectra and high resolution mass spectrum characterize data are as follows:
1H NMR(400MHz,CDCl3),δ,ppm:6.96(s,1H,CH-2),7.21-7.30(m,5H,ArH-4,5,6,7, 8),7.31-7.43(m,5H,ArH-10,11,12,13,14),7.44-7.52(m,3H,ArH-16,20,21),7.73-7.81 (m,3H,ArH-17,19,22),7.88(s,1H,ArH-24)；
13C NMR(100MHz,CDCl3),δ,ppm:123.8(C-2),126.0(C-20),126.7(C-21),127.2 (C-4,8),127.3(C-16),127.4(C-19,22),127.6(C-6),127.8(C-12),127.9(C-17),128.4 (C-10,14),128.5(C-5,7),128.8(C-15),129.8(C-11,13),132.1(C-18),133.7(C-1), 133.9(C-24),139.2(C-23),141.5(C-3),141.6(C-9)；
ESI-HRMS,m/z:Calcd for C24H18S(M+):338.1129,Found:338.1107；
Characterization result shows the structural formula of diphenylethyllene thio-ether type compounds are as follows:
Embodiment 19:
A kind of preparation method of diphenylethyllene thio-ether type compounds, comprising the following steps: by 0.3mmol (0.0541g) 1,1- talan, 0.45mmol (0.1081g) 4- connection benzene sulfinic acid sodium salt and 0.2558g mass fraction 45% hydroiodic acid Aqueous solution (containing hydroiodic acid 0.9mmol) is dispersed in the toluene of 2mL, and the coupling reaction of 15h is carried out at 75 DEG C, it is thio that saturation is added Aqueous sodium persulfate solution is quenched, then is extracted with methylene chloride (15mL × 3), liquid separation, with the dry organic layer of anhydrous sodium sulfate, is subtracted Pressure is spin-dried for, cross column, obtain 0.0748g diphenylethyllene thio-ether type compounds (white solid, yield 68%, fusing point 122.0~ 123.2 DEG C), nuclear magnetic resonance spectroscopy, carbon-13 nmr spectra and high resolution mass spectrum characterize data are as follows:
1H NMR(400MHz,CDCl3),δ,ppm:6.88(s,1H,CH-2),7.15-7.28(m,5H,ArH-4,5,6,7, 8), 7.29-7.38 (m, 5H, ArH-10,11,12,13,14), 7.39-7.44 (m, 3H, ArH-23,24,25), 7.47 (d, J= 8.0Hz,2H,ArH-16,20),7.50-7.58(m,4H,ArH-17,19,22,26)；
13C NMR(100MHz,CDCl3),δ,ppm:124.0(C-2),127.0(C-22,26),127.3(C-17,19), 127.4(C-24),127.6(C-6),127.8(C-4,8),127.9(C-12),128.4(C-10,14),128.5(C-5,7), 128.9(C-23,25),129.8(C-11,13),129.9(C-16,20),135.6(C-1),139.2(C-15),139.8(C- 18),140.3(C-3),141.4(C-9),141.5(C-21)；
ESI-HRMS,m/z:Calcd for C21H12S(M+):364.1286,Found:364.1273；
Characterization result shows the structural formula of diphenylethyllene thio-ether type compounds are as follows:
Embodiment 20:
A kind of preparation method of diphenylethyllene thio-ether type compounds, comprising the following steps: by 0.3mmol (0.0541g) 1,1- talan, 0.45mmol (0.0766g) 2- thiophene sulfinic acid sodium and 0.2558g mass fraction 45% hydroiodic acid Aqueous solution (containing hydroiodic acid 0.9mmol) is dispersed in the toluene of 2mL, and the coupling reaction of 15h is carried out at 75 DEG C, it is thio that saturation is added Aqueous sodium persulfate solution is quenched, then is extracted with methylene chloride (15mL × 3), liquid separation, with the dry organic layer of anhydrous sodium sulfate, is subtracted Pressure is spin-dried for, cross column, obtain 0.00342g diphenylethyllene thio-ether type compounds (faint yellow solid, yield 40%, fusing point 90.2~ 92.2 DEG C), nuclear magnetic resonance spectroscopy, carbon-13 nmr spectra and high resolution mass spectrum characterize data are as follows:
1H NMR(400MHz,CDCl3),δ,ppm:6.71(s,1H,CH-2),6.96-7.00(m,1H,ArH-17), 7.15-7.25(m,5H,ArH-4,5,6,7,8),7.27-7.38(m,5H,Ar-10,11,12,13,14),7.39-7.46(m, 2H,ArH-16,18)；
13C NMR(100MHz,CDCl3),δ,ppm:127.2(C-2,4,8),127.3(C-18),127.7(C-6), 127.9(C-12),128.3(C-10,14),128.5(C-5,7),129.4(C-17),129.7(C-11,13),132.8(C- 16),133.9(C-15),138.8(C-1),139.2(C-3),141.1(C-9)；
ESI-HRMS,m/z:Calcd for C18H15S2([M+H]+):295.0610,Found:295.0642；
Characterization result shows the structural formula of diphenylethyllene thio-ether type compounds are as follows:
Embodiment 21:
A kind of preparation method of diphenylethyllene thio-ether type compounds, comprising the following steps: by 0.3mmol (0.0541g) 1,1- talan, the methyl sulfinic acid sodium of 0.45mmol (0.0459g) and the hydroiodic acid water of 0.2558g mass fraction 45% Solution (containing hydroiodic acid 0.9mmol) is dispersed in the toluene of 2mL, and the coupling reaction of 15h is carried out at 75 DEG C, is added and is saturated thio sulphur Acid sodium aqueous solution is quenched, then is extracted with methylene chloride (15mL × 3), liquid separation, with the dry organic layer of anhydrous sodium sulfate, decompression It is spin-dried for, crosses column, obtain 0.0672g diphenylethyllene thio-ether type compounds (colourless liquid, yield 99%), hydrogen nuclear magnetic resonance Spectrum, carbon-13 nmr spectra and high resolution mass spectrum characterize data are as follows:
1H NMR(400MHz,CDCl3),δ,ppm:2.33(s,3H,SCH3-15),6.53(s,1H,CH-2),7.15- 7.25(m,5H,ArH-4,5,6,7,8),7.27-7.41(m,5H,ArH-10,11,12,13,14)；
13C NMR(100MHz,CDCl3),δ,ppm:18.1(C-15),126.9(C-2),127.0(C-4,8),127.6 (C-6),127.7(C-12),128.3(C-10,14),128.4(C-5,7),129.7(C-11,13),138.4(C-1),139.5 (C-3),141.8(C-9)；
ESI-HRMS,m/z:Calcd for C15H15S([M+H]+):227.0889,Found:227.0873；
Characterization result shows the structural formula of diphenylethyllene thio-ether type compounds are as follows:
Embodiment 22:
A kind of preparation method of diphenylethyllene thio-ether type compounds, comprising the following steps: by 0.3mmol (0.0541g) 1,1- talan, the sodium ethanesulfinate of 0.45mmol (0.0522g) and the hydroiodic acid water of 0.2558g mass fraction 45% Solution (containing hydroiodic acid 0.9mmol) is dispersed in the toluene of 2mL, and the coupling reaction of 15h is carried out at 75 DEG C, is added and is saturated thio sulphur Acid sodium aqueous solution is quenched, then is extracted with methylene chloride (15mL × 3), liquid separation, with the dry organic layer of anhydrous sodium sulfate, decompression It is spin-dried for, crosses column, obtain 0.0707g diphenylethyllene thio-ether type compounds (colourless liquid, yield 98%), hydrogen nuclear magnetic resonance Spectrum, carbon-13 nmr spectra and high resolution mass spectrum characterize data are as follows:
1H NMR(400MHz,CDCl3), δ, ppm:1.33 (t, J=8.0Hz, 3H, CH3- 16), 2.76 (q, 2H, J= 8.0Hz,SCH2-15),6.59(s,1H,CH-2),7.16-7.25(m,5H,ArH-4,5,6,7,8),7.27-7.40(m,5H, ArH-10,11,12,13,14)；
13C NMR(100MHz,CDCl3),δ,ppm:15.6(C-16),28.9(C-15),125.9(C-2),126.9(C- 6),127.1(C-4,8),127.5(C-12),128.3(C-10,14),128.4(C-5,7),129.8(C-11,13),138.7 (C-1),139.7(C-3),142.0(C-9)；
ESI-HRMS,m/z:Calcd for C16H17S([M+H]+):241.1045,Found:241.1035；
Characterization result shows the structural formula of diphenylethyllene thio-ether type compounds are as follows:
Embodiment 23:
A kind of preparation method of diphenylethyllene thio-ether type compounds, comprising the following steps: by 0.3mmol (0.0541g) 1,1- talan, the cyclopropyl sulfinic acid sodium of 0.45mmol (0.0576g) and the hydroiodic acid of 0.2558g mass fraction 45% Aqueous solution (containing hydroiodic acid 0.9mmol) is dispersed in the toluene of 2mL, and the coupling reaction of 15h is carried out at 75 DEG C, it is thio that saturation is added Aqueous sodium persulfate solution is quenched, then is extracted with methylene chloride (15mL × 3), liquid separation, with the dry organic layer of anhydrous sodium sulfate, is subtracted Pressure is spin-dried for, and is crossed column, is obtained 0.0294g diphenylethyllene thio-ether type compounds (colourless liquid, yield 39%), hydrogen nuclear magnetic resonance Spectrum, carbon-13 nmr spectra and high resolution mass spectrum characterize data are as follows:
1H NMR(400MHz,CDCl3),δ,ppm:0.66-0.95(m,4H,CH2-16,17),2.11-2.18(m,1H, SCH-15),7.17-7.25(m,5H,ArH-4,5,6,7,8),7.27-7.40(m,5H,ArH-10,11,12,13,14)；
13C NMR(100MHz,CDCl3),δ,ppm:8.3(C-16,17),14.6(C-15),126.8(C-2),127.0 (C-4,8),127.1(C-6),127.5(C-12),128.2(C-10,14),128.3(C-5,7),129.7(C-11,13), 138.1(C-1),139.5(C-3),141.8(C-9)；
ESI-HRMS,m/z:Calcd for C17H17S([M+H]+):253.1045,Found:253.1048；
Characterization result shows the structural formula of diphenylethyllene thio-ether type compounds are as follows:
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention, It should be equivalent substitute mode, be included within the scope of the present invention.

Claims (10)

1. a kind of preparation method of diphenylethyllene thio-ether type compounds, it is characterised in that: the following steps are included: by 1,1- hexichol Ethylene, aryl groups per alkyl group sulfinic acid sodium and acidic reduction agent dispersion in a solvent, carry out coupling reaction, obtain diphenylethyllene sulphur Ether compound.
2. the preparation method of diphenylethyllene thio-ether type compounds according to claim 1, it is characterised in that: including following Step: it in a solvent by 1,1- talan, aryl groups per alkyl group sulfinic acid sodium and acidic reduction agent dispersion, is carried out at 70~80 DEG C The coupling reaction of 12~18h, quenching reaction, then extracted, liquid separation, drying, decompression are spin-dried for, cross column, obtain diphenylethyllene Thio-ether type compounds.
3. the preparation method of diphenylethyllene thio-ether type compounds according to claim 1 or 2, it is characterised in that: described 1,1- talan, aryl groups per alkyl group sulfinic acid sodium, acidic reduction agent molar ratio be 1:(1.3~1.7): (2~4).
4. the preparation method of diphenylethyllene thio-ether type compounds according to claim 3, it is characterised in that: described 1,1- Talan, aryl groups per alkyl group sulfinic acid sodium, acidic reduction agent molar ratio be 1:(1.4~1.6): (2.8~3.2).
5. the preparation method of diphenylethyllene thio-ether type compounds according to claim 1 or 2, it is characterised in that: described Sodium arylsulfinate is C4~C12Sodium arylsulfinate；The sodium alkyl-sulfinate is methyl sulfinic acid sodium, ethyl sulfinic acid One of sodium, cyclopropyl sulfinic acid sodium.
6. the preparation method of diphenylethyllene thio-ether type compounds according to claim 5, it is characterised in that: the aryl Sulfinic acid sodium be to methyl sodium benzene sulphinate, benzene sulfinic acid sodium salt, to tert-butyl benzene sulfinic acid sodium salt, to methoxyl group benzene sulfinic acid sodium salt, To fluorine benzene sulfinic acid sodium salt, to chlorobenzene sulfinic acid sodium, to bromine benzene sulfinic acid sodium salt, to iodine benzene sulfinic acid sodium salt, p-nitrophenyl sulfinic acid sodium, To trifluoromethyl benzenesulfinic acid sodium, to cyano benzene sulfinic acid sodium salt, o-methyl-benzene sulfinic acid sodium, adjacent fluorine benzene sulfinic acid sodium salt, adjacent chlorobenzene Sulfinic acid sodium, bromine benzene sulfinic acid sodium salt, m-trifluoromethyl benzene sulfinic acid sodium salt, 2,4,6- trimethyl benzene sulfinic acid sodium salt, 2- naphthalene Asia sulphur One of sour sodium, 4- connection benzene sulfinic acid sodium salt, 2- thiophene sulfinic acid sodium.
7. the preparation method of diphenylethyllene thio-ether type compounds according to claim 1 or 2, it is characterised in that: described Acidic reduction agent is one of hydrobromic acid, hydroiodic acid, hydrochloric acid.
8. the preparation method of diphenylethyllene thio-ether type compounds according to claim 7, it is characterised in that: the acidity Reducing agent is hydroiodic acid.
9. the preparation method of diphenylethyllene thio-ether type compounds according to claim 1 or 2, it is characterised in that: described Solvent is at least one of toluene, 1,2- dichloroethanes, 1,4- dioxane, acetonitrile, nitromethane.
10. the preparation method of diphenylethyllene thio-ether type compounds according to claim 2, it is characterised in that: described to quench Reaction of going out is quenched for saturated aqueous sodium thiosulfate is added.
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CN114656380A (en) * 2022-03-10 2022-06-24 南阳师范学院 Method for simply synthesizing allyl methyl sulfide
CN115819301A (en) * 2022-11-23 2023-03-21 湖南大学 Method for preparing alkynyl sulfur (selenium) ether by coupling zinc-promoted disulfide (selenium) ether with alkynyl bromide
CN115819301B (en) * 2022-11-23 2024-03-29 湖南大学 Method for preparing alkynyl sulfur (selenium) ether by coupling zinc-promoted disulfide (selenium) ether with alkynyl bromine

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Application publication date: 20191008