CN108675935A - A kind of preparation method of 1,1- diaryl alkanes hydro carbons compound - Google Patents

A kind of preparation method of 1,1- diaryl alkanes hydro carbons compound Download PDF

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CN108675935A
CN108675935A CN201810608849.5A CN201810608849A CN108675935A CN 108675935 A CN108675935 A CN 108675935A CN 201810608849 A CN201810608849 A CN 201810608849A CN 108675935 A CN108675935 A CN 108675935A
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alkyl
aryl
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halogen
alkoxy
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CN108675935B (en
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宋仁杰
雍馨
李金恒
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Nanchang Hangkong University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/04—Formation of amino groups in compounds containing carboxyl groups
    • C07C227/10—Formation of amino groups in compounds containing carboxyl groups with simultaneously increasing the number of carbon atoms in the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/14—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D295/155—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals with the ring nitrogen atoms and the carbon atoms with three bonds to hetero atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
    • C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
    • C07D295/182—Radicals derived from carboxylic acids
    • C07D295/185—Radicals derived from carboxylic acids from aliphatic carboxylic acids

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention relates to one kind 1, the preparation method of 1 diaryl alkane hydro carbons compound, this method with shown in Formulas I to N shown in substituted ethylene class compound, Formula II, 2 bromo carboxylic acid ester compounds shown in N disubstituted benzenes aminated compounds, formula III are reaction raw materials, 1,1 diaryl alkane hydro carbons compound shown in formula IV is photocatalytically obtained by the reaction.

Description

A kind of preparation method of 1,1- diaryl alkanes hydro carbons compound
Technical field
The application belongs to organic synthesis field, and in particular to the preparation method of one kind 1,1- diaryl alkane hydro carbons compounds.
Background technology
1,1- diaryl alkane hydro carbons compounds have autoimmune disease, cancer, inflammation, insomnia and osteoporosis Good activity.This skeleton is present in many biologically active natural products and famous drug, including (-)-ring Spore rhzomorph, the deoxidation of (+)-Sertraline and Ormeloxifene etc..
Synthesis 1,1- diaryl alkane hydro carbons compounds are typically all by with donor-receptor (D-A) ring third in the prior art Alkyl compound is raw material, is reacted with various nucleopilic reagents such as n,N-Dimethylformamide under different catalytic conditions and carrys out structure It builds (referring to following existing technical literature：1)Tetrahedron 66(2010)3024–3029；2) Eur.J.Org.Chem.2015,6419–6422；3)Org.Lett.2018,20,574-577；4)Journal of the Korean Chemical Society., 2016, Vol.60, No.5, the 374-377 pages.).
In recent years, it is seen that the organic synthesis of photoinduction has attracted the interest of more and more organic chemists.Can Under the conditions of light-exposed, it is environmental-friendly, operating condition is mild due to its in photoredox catalyst inducement organic reaction the features such as, In organic synthesis an effective approach, and the heat of organic synthesis research in recent years are provided to build new chemical bond One of point.
Inventor is by concentrating on studies, and in the present invention, proposes a kind of preparation 1 under photoredox catalytic condition, The new method of 1- diaryl alkane hydro carbons compounds.
Invention content
The purpose of the present invention is to overcome the deficiency in the prior art, and it is suitable to provide one kind simple for process, green high-efficient, reaction substrate It is wide with range, the preparation 1 of high income, the synthetic method of 1- diaryl alkane hydro carbons compounds.
The preparation method of 1,1- diaryl alkanes hydro carbons compound provided by the invention is carried out preparing through the following steps and be obtained ：
Into Schlenk tube sealing reaction devices, with shown in Formulas I to N, N- bis- shown in substituted ethylene class compound, Formula II 2- bromos carboxylic acid ester compound shown in substituted benzene aminated compounds, formula III is reaction raw materials, and photochemical catalyst, mantoquita is added Co-catalyst, alkali and organic solvent react under inert atmosphere protection, room temperature and illumination condition, are monitored by TLC or GC-MS It is post-treated to obtain 1,1- diaryl alkanes hydro carbons compound shown in formula IV after the completion of reaction.
In Formulas I and formula IV,Indicate C6-20Aryl, C4-20Heteroaryl；
R1It indicatesOne or more substituent groups on ring, selected from hydrogen, C1-C20Alkyl, C1-C20Alkoxy, C1- C20Alkylthio group, C6-C20Aryl, C4-C20Heteroaryl, C3-C20Naphthenic base, nitro, halogen ,-OH ,-SH ,-CN ,- COOR9、-COR10、-OCOR11、-NR12R13；Wherein, R9、R10、R11、R12、R13It is each independently selected from hydrogen, C1-C20Alkyl, C6-C20Aryl, C4-C20Heteroaryl, C3-C20Naphthenic base in any one or more.
Wherein, above-mentioned each R1Alkyl, aryl, heteroaryl, cycloalkyl moiety in substituent group can optionally by one or It is multiple to be selected from C1-C6Alkyl, C1-C6Alkoxy, C1-C6Acyl group, halogen ,-NO2、-CN、-OH、C6-C20Aryl, C3- C6Naphthenic base replaced.
R2Selected from hydrogen, C1-20Alkyl, C6-20Aryl.
Wherein, above-mentioned each R2Alkyl, aryl moiety in substituent group optionally can be selected from C by one or more1-C6's Alkyl, C1-C6Alkoxy, C1-C6Acyl group, halogen ,-NO2、-CN、-OH、C6-C20Aryl, C3-C6Naphthenic base taken Generation.
In Formula II and formula IV, R3One or more substituent groups on connected phenyl ring are indicated, selected from hydrogen, C1-C20Alkyl, C1-C20Alkoxy, C1-C20Alkylthio group, C6-C20Aryl, C4-C20Heteroaryl, C3-C20Naphthenic base, nitro, halogen Element ,-OH ,-SH ,-CN ,-COOR9、-COR10、-OCOR11、-NR12R13；Wherein, R9、R10、R11、R12、R13It is each independently selected from Hydrogen, C1-C20Alkyl, C6-C20Aryl, C5-C20Heteroaryl, C3-C20Naphthenic base in any one or more.
Wherein, above-mentioned each R3Alkyl, aryl, heteroaryl, cycloalkyl moiety in substituent group can optionally by one or It is multiple to be selected from C1-C6Alkyl, C1-C6Alkoxy, C1-C6Acyl group, halogen ,-NO2、-CN、-OH、C6-C20Aryl, C3- C6Naphthenic base replaced.Also, R3Substituent group is not at "-NR3R4" contraposition.
R4,R5It is independently from each other hydrogen, C1-C20Alkyl, C2-C20Alkenyl, C6-C20Aryl, C4-C20Heteroaryl Base, C3-C20Naphthenic base；Or R4,R5With formed together with connected N atoms 5-8 cyclic annular atom with or without other miscellaneous originals The heterocycle of son.
Wherein, above-mentioned each R4,R5Alkyl, alkenyl, aryl, heteroaryl, naphthenic base, heterocyclyl moieties in group can appoint Selection of land is selected from C by one or more1-C6Alkyl, C1-C6Alkoxy, C1-C6Acyl group, halogen ,-NO2、-CN、-OH、C6- C20Aryl, C3-C6Naphthenic base replaced.
In formula III and formula IV, R6,R7It is independently from each other hydrogen, halogen, C1-C20Alkyl, R14OCO-, wherein R14Choosing From C1-20Alkyl；Or R6、R7With the cyclic hydrocarbon group for forming 3-6 annular atom together with connected carbon atom.
Wherein above-mentioned R6、R7Alkyl, hydrocarbyl portion in group optionally can be selected from C by one or more1-C6Alkane Base, C1-C6Alkoxy, C1-C6Acyl group, halogen ,-NO2、-CN、-OH、C6-C20Aryl, C3-C6Naphthenic base replaced.
R8Selected from C1-20Alkyl, C6-20Aryl.
Wherein, above-mentioned each R8Alkyl, aryl moiety in substituent group optionally can be selected from C by one or more1-C6's Alkyl, C1-C6Alkoxy, C1-C6Acyl group, halogen ,-NO2、-CN、-OH、C6-C20Aryl, C3-C6Naphthenic base taken Generation.
Preferably, in Formulas I and formula IV,Indicate C6-12Aryl, C4-12Heteroaryl；
R1It indicatesOne or more substituent groups on ring, are preferably selected from hydrogen, C1-C6Alkyl, C1-C6Alkoxy, C6-C12Aryl, C5-C12Heteroaryl, C3-C6Naphthenic base, nitro, halogen ,-OH ,-SH ,-CN ,-COOR9、-COR10、- OCOR11、-NR12R13；Wherein, R9、R10、R11、R12、R13It is each independently selected from hydrogen, C1-C6Alkyl, C6-C12Aryl, C4- C12Heteroaryl, C3-C6Naphthenic base in any one or more.
Wherein, above-mentioned each R1Alkyl, aryl, heteroaryl, cycloalkyl moiety in substituent group can optionally by one or It is multiple to be selected from C1-C6Alkyl, C1-C6Alkoxy, C1-C6Acyl group, halogen ,-NO2、-CN、-OH、C6-C12Aryl, C3- C6Naphthenic base replaced.
R2It is preferably selected from hydrogen, C1-6Alkyl, C6-12Aryl.
Wherein, above-mentioned each R2Alkyl, aryl moiety in substituent group optionally can be selected from C by one or more1-C6's Alkyl, C1-C6Alkoxy, C1-C6Acyl group, halogen ,-NO2、-CN、-OH、C6-C12Aryl, C3-C6Naphthenic base taken Generation.
In Formula II and formula IV, R3It indicates one or more substituent groups on connected phenyl ring, is preferably selected from hydrogen, C1-C6Alkane Base, C1-C6Alkoxy, C6-C12Aryl, C5-C12Heteroaryl, C3-C6Naphthenic base, nitro, halogen ,-OH ,-SH ,- CN、-COOR9、-COR10、-OCOR11、-NR12R13；Wherein, R9、R10、R11、R12、R13It is each independently selected from hydrogen, C1-C6Alkane Base, C6-C12Aryl, C4-C12Heteroaryl, C3-C6Naphthenic base in any one or more.
Wherein, above-mentioned each R3Alkyl, aryl, heteroaryl, cycloalkyl moiety in substituent group can optionally by one or It is multiple to be selected from C1-C6Alkyl, C1-C6Alkoxy, C1-C6Acyl group, halogen ,-NO2、-CN、-OH、C6-C12Aryl, C3- C6Naphthenic base replaced.Also, R3Substituent group is not at "-NR3R4" contraposition.
Preferably, R4,R5It is independently from each other hydrogen, C1-C6Alkyl, C2-C6Alkenyl, C6-C12Aryl, C4-C12 Heteroaryl, C3-C6Naphthenic base；Or R4,R5With formed together with connected N atoms 5-8 cyclic annular atom with or without it Its heteroatomic heterocycle.
Wherein, above-mentioned each R4,R5Alkyl, alkenyl, aryl, heteroaryl, naphthenic base, heterocyclyl moieties in group definition can To be optionally selected from C by one or more1-C6Alkyl, C1-C6Alkoxy, C1-C6Acyl group, halogen ,-NO2、-CN、- OH、C6-C12Aryl, C3-C6Naphthenic base replaced.
Preferably, in formula III and formula IV, R6,R7It is independently from each other hydrogen, halogen, C1-C6Alkyl, R14OCO-, In, R14Selected from C1-6Alkyl；Or R6、R7With the cyclic hydrocarbon group for forming 3-6 annular atom together with connected carbon atom.
Wherein above-mentioned R6、R7Alkyl, hydrocarbyl portion in group definition optionally can be selected from C by one or more1-C6 Alkyl, C1-C6Alkoxy, C1-C6Acyl group, halogen ,-NO2、-CN、-OH、C6-C20Aryl, C3-C6Naphthenic base institute Substitution.
R8Selected from C1-6Alkyl, C6-12Aryl.
Wherein, above-mentioned each R8Alkyl, aryl moiety in substituent group optionally can be selected from C by one or more1-C6's Alkyl, C1-C6Alkoxy, C1-C6Acyl group, halogen ,-NO2、-CN、-OH、C6-C12Aryl, C3-C6Naphthenic base taken Generation.
Most preferably, in Formulas I and formula IV,Indicate phenyl, naphthalene, thienyl, pyridyl group；
R1It indicatesOne or more substituent groups on ring are further preferably selected from hydrogen, C1-C6Alkyl, C1-C6's Alkoxy, halogen.
It is further preferred that R2Selected from hydrogen, phenyl.
In Formula II and formula IV, R3It indicates one or more substituent groups on connected phenyl ring, is further preferably selected from hydrogen, C1- C6Alkyl, C1-C6Alkoxy, halogen.Also, R3Substituent group is not at "-NR3R4" contraposition.
It is further preferred that R4,R5It is independently from each other hydrogen, C1-6Alkyl, C6-12Aryl；Or R4,R5Be connected N atoms formed together 5-6 cyclic annular atom with or without other heteroatomic heterocycles.Wherein, above-mentioned each R4,R5Group Heterocyclyl moieties in definition optionally can be selected from C by one or more1-C6Alkyl, C1-C6Alkoxy, C1-C6Acyl Base, halogen are replaced.
It is further preferred that in formula III and formula IV, R6,R7It is independently from each other hydrogen, halogen, C1-C6Alkyl, R14OCO-, wherein R14Selected from C1-6Alkyl；Or R6、R7With the ring-type for forming 3-6 annular atom together with connected carbon atom Alkyl.
R8Selected from C1-6Alkyl.
According to present invention group definition above-mentioned, the C1-C20Alkyl, C1-C6Alkyl and C1-C20Alcoxyl Base, C1-C6Alkoxy, C1-C6The group definitions such as acyl group in there is C1-C20、C1-C6Moieties can be selected from for example Methyl, ethyl, propyl, butyl, amyl, isopropyl, isobutyl group, tertiary butyl, n-hexyl etc..
According to present invention group definition above-mentioned, the C6-C20Aryl, C6-C12Aryl can be selected from such as benzene Base, naphthalene, anthryl, phenanthryl etc..
According to present invention group definition above-mentioned, the C4-C20Heteroaryl, C4-C12Heteroaryl in hetero atom It can be selected from O, S, N, specific heteroaryl can be selected from such as thienyl, furyl, pyridyl group.
According to present invention group definition above-mentioned, the C3-C20Naphthenic base, C3-C6Naphthenic base can be selected from for example Cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl.
According to present invention reaction above-mentioned, the photochemical catalyst is selected from [Ru (bipy)3]Cl2·6H2O、[Ir(ppy)3] Or any one of Eosin Y.Preferably, the photocatalysis is selected from [Ru (bipy)3]Cl2·6H2O。
According to present invention reaction above-mentioned, the mantoquita co-catalyst is selected from CuCl, CuOAc, CuI, CuCl2、Cu (OAc)2In any one.Preferably, the mantoquita co-catalyst is selected from CuCl.
According to present invention reaction above-mentioned, the alkali is selected from K2CO3、Cs2CO3、KOtAny one in Bu.Preferably, The alkali is selected from K2CO3。
According to present invention reaction above-mentioned, the organic solvent is preferably selected from acetonitrile.The usage amount of solvent is not made especially Restriction so that each reaction mass is fully dispersed.
According to present invention reaction above-mentioned, the illumination condition is provided by 3-5W blue led light sources, preferably 3W blues LED light source provides.
According to present invention reaction above-mentioned, the reaction determines the reaction time by TLC or GC-MS monitoring, generally For, completion can be reacted within 2 hours.
According to present invention reaction above-mentioned, the inert atmosphere is to reacting inert atmosphere, and not mechanically It is considered inert gas.To those skilled in the art, it is to be understood that the inert atmosphere for being usually used in organic reaction can To be selected from argon gas atmosphere or nitrogen atmosphere.
According to present invention reaction above-mentioned, wherein to substituted ethylene class compound shown in Formulas I, N, N- shown in Formula II 2- bromos carboxylic acid ester compound, photochemical catalyst, mantoquita co-catalyst, alkali shown in disubstituted benzenes aminated compounds, formula III Molar ratio is 1:(1~3):(1~3):(0.01~0.05):(0.05~0.2):(1~3).Preferably, to taking shown in Formulas I For ethylene compounds, N shown in Formula II, 2- bromo carboxylic acid esters shown in N- disubstituted benzenes aminated compounds, formula III -1 Compound, photochemical catalyst, mantoquita co-catalyst, alkali molar ratio be 1:2:2:0.02:0.1:2.
According to present invention reaction above-mentioned, wherein the post-processing operation is as follows：Mixed liquor after the completion of reaction is subtracted Pressure concentration, obtains residue, then by residue through 1,1- diaryl alkane hydro carbons shown in the isolated formula IV of column plastic column chromatography Object target product is closed, the eluent of wherein silica gel column chromatography separation is the mixed liquor of n-hexane and ethyl acetate.
Beneficial effects of the present invention are as follows：
1, the present invention report for the first time with shown in Formulas I to substituted ethylene class compound, N shown in Formula II, N- bis- replaces 2- bromos carboxylic acid ester compound shown in amino benzenes compounds, formula III is that raw material obtains under photoredox catalyst system and catalyzing To the synthesis strategy of 1,1- diaryl alkanes hydro carbons compound shown in a series of formula IV, this method is not seen in prior art report Road.
2, method of the invention is mild with reaction condition, can carry out at room temperature, and easy to operate, reaction substrate is applicable in The advantages of range is wide, generates that process costs are low, photochemical catalyst can recycle and reuse, environmental-friendly, high income.
Specific implementation mode
Below in conjunction with specific embodiment, further detailed description is carried out to the present invention.
Embodiment 1-19 reaction condition optimizations are tested
With shown in Formulas I -1 to N shown in methoxy styrene, Formula II -1, shown in accelerine and formula III -1 2- methyl -2- ethyl bromides be reaction raw materials, inquired into shadow of the differential responses condition for optimization of synthesis result It rings, selects wherein representative embodiment 1-19.As a result as shown in Table 1.
The type testing operation of wherein embodiment 1 is as follows：
It is added shown in Formulas I -1 to methoxy styrene (0.2mmol), -1 institute of Formula II into Schlenk tube sealing reaction devices 2- methyl -2- ethyl bromides (2 equivalent) shown in the n,N-Dimethylaniline (2 equivalent) shown, formula III -1, CuCl (10mol%), [Ru (bipy)3]Cl2·6H2O (2mol%), K2CO3(2 equivalent) and MeCN (1mL), then argon gas protect, It is reacted under the conditions of room temperature and 3W blue LED lamp light source lights are shone, after the completion of TLC or GC-MS monitoring reactions, vacuum distillation removes Solvent is removed, then residue is obtained into the target product of formula IV -1 through column chromatography for separation (eluent is n-hexane/ethyl acetate).Production Rate 78%；Colourless oil liquid；1H NMR(400MHz,CDCl3)δ:7.14 (d, J=8.0Hz, 2H), 7.08 (d, J=8Hz, 2H), 6.77 (d, J=8.4Hz, 2H), 6.63 (d, J=8.0Hz, 2H), 3.87 (t, J=7.2Hz, 1H), 3.74 (s, 3H), 3.70-3.65 (m, 2H), 2.87 (s, 6H), 2.39-2.29 (m, 2H), 1.15 (s, 6H), 1.10 (t, J=7.2Hz, 3H)；13C NMR(100MHz,CDCl3)δ:177.4,157.6,149.0,138.1,133.9,128.7,128.3,113.6,112.8, 60.1,55.2,46.7,46.3,42.0,40.8,26.2,25.9,14.0。
Table one：
Wherein, the concrete operations of embodiment 2-19 and parameter remove the variable listed by above-mentioned table one and differ it with embodiment 1 Outside, remaining operation and parameter are same as Example 1.
Illumination and photochemical catalyst are the necessary factor (embodiments that reaction can carry out it can be seen from embodiment 1-19 2,15), different photochemical catalysts such as [Ir (ppy)3] and Eosin Y catalytic effects be not so good as [Ru (bipy)3]Cl2·6H2O, with And catalyst [Ru (bipy)3]Cl2·6H2The dosage of O (is implemented down to higher target product yield is still obtained when 1mol% Example 3-6).The use of mantoquita co-catalyst and alkali has prodigious facilitation to reaction, wherein with CuCl, K2CO3Effect is best (embodiment 7-14).The power of blue light source influences less reaction, but the light source of different wave length has larger shadow to reaction It rings (embodiment 16-17).Reaction cannot be carried out successfully under air conditions, and amplify production under conditions of embodiment 1 Still it can obtain and be bordering on comparable target product yield (embodiment 18-19).
According to above-mentioned representative condition optimizing test result embodiment 1-19, it is contemplated that photochemical catalyst is expensive, choosing The reaction condition of embodiment 1 is selected as optimum reaction condition.On this basis, inventor further selects the anti-of different substituents Raw material is answered to prepare the target compound of various formula IVs.
Embodiment 20
It is added shown in Formulas I -1 to methoxy styrene (0.2mmol), -1 institute of Formula II into Schlenk tube sealing reaction devices 2- methyl -2- bromo propionic acid A esters (2 equivalent) shown in the n,N-Dimethylaniline (2 equivalent) shown, formula III -2, CuCl (10mol%), [Ru (bipy)3]Cl2·6H2O (2mol%), K2CO3(2 equivalent) and MeCN (1mL), then argon gas protect, It is reacted under the conditions of room temperature and 3W blue LED lamp light source lights are shone, after the completion of TLC or GC-MS monitoring reactions, vacuum distillation removes Solvent is removed, then residue is obtained into the target product of formula IV -2 through column chromatography for separation (eluent is n-hexane/ethyl acetate).It receives Rate 63%；Colourless oil liquid；1H NMR(400MHz,CDCl3)δ:7.14 (d, J=8.0Hz, 2H), 7.08 (d, J=8.4Hz, 2H), 6.77 (d, J=8.4Hz, 2H), 6.64 (d, J=8.4Hz, 2H), 3.87 (t, J=6.8Hz, 1H), 3.74 (s, 3H), 3.24(s,3H),2.87(s,6H),2.39-2.29(m,2H),1.17(s,6H)；13C NMR(100MHz,CDCl3)δ:177.8, 157.6,149.0,138.0,133.8,128.7,128.3,113.6,112.8,55.2,51.3,46.8,46.3,42.0, 40.8,26.2,25.9
Embodiment 21
It is added shown in Formulas I -1 to methoxy styrene (0.2mmol), -1 institute of Formula II into Schlenk tube sealing reaction devices 2,2-, bis- fluoro- 2- bromoethyl acetates (2 equivalent) shown in the n,N-Dimethylaniline (2 equivalent) shown, formula III -3, CuCl (10mol%), [Ru (bipy)3]Cl2·6H2O (2mol%), K2CO3(2 equivalent) and MeCN (1mL), then argon gas protect, It is reacted under the conditions of room temperature and 3W blue LED lamp light source lights are shone, after the completion of TLC or GC-MS monitoring reactions, vacuum distillation removes Solvent is removed, then residue is obtained into the target product of formula IV -3 through column chromatography for separation (eluent is n-hexane/ethyl acetate).It receives Rate 66%；Yellow oily liquid；1H NMR(400MHz,CDCl3)δ:7.13 (d, J=8.4Hz, 2H), 7.07 (d, J=8.4Hz, 2H), 6.79 (d, J=8.4Hz, 2H), 6.66 (d, J=8.4Hz, 2H), 4.13 (t, J=7.2Hz, 1H), 3.88-3.83 (m, 2H), 3.75 (s, 3H), 2.88 (s, 6H), 2.86-2.78 (m, 2H), 1.17 (t, J=7.2Hz, 3H)；13C NMR(100MHz, CDCl3)δ:164.0,158.1,149.2,135.8,131.6,128.6,128.2,113.8,113.0,62.7,55.2,43.1, 40.8,40.7,13.7；LRMS (EI, 70eV) m/z (%):377(M+,25),240(100),225(10)。
Embodiment 22
It is added shown in Formulas I -1 to methoxy styrene (0.2mmol), -1 institute of Formula II into Schlenk tube sealing reaction devices N,N-Dimethylaniline (2 equivalent), -4 compound represented of formula III (2 equivalent) shown, CuCl (10mol%), [Ru (bipy)3]Cl2·6H2O (2mol%), K2CO3(2 equivalent) and MeCN (1mL), then in argon gas protection, in room temperature and 3W blues It is reacted under LED light source illumination condition, after the completion of TLC or GC-MS monitoring reactions, vacuum distillation removes solvent, then will be residual Excess obtains the target product of formula IV -4 through column chromatography for separation (eluent is n-hexane/ethyl acetate).Yield 42%；Colorless oil Shape liquid；1H NMR(400MHz,CDCl3)δ:7.13-7.01 (m, 4H), 6.77 (d, J=8.4Hz, 2H), 6.65 (d, J= 8.8Hz, 2H), 3.80-3.75 (m, 2H), 3.74 (s, 3H), 3.72 (t, J=4Hz, 1H), 2.87 (s, 6H), 2.55 (d, J= 7.2Hz, 2H), 2.34-2.26 (m, 2H), 1.89-1.76 (m, 4H), 1.12 (t, J=7.2Hz, 3H)；13C NMR(100MHz, CDCl3)δ:176.8,157.8,149.1,137.8,133.6,128.8,128.4,113.6,112.8,60.1,55.2,47.8, 46.4,44.4,40.8,22.7,15.9,14.0；LRMS (EI, 70eV) m/z (%):381(M+,12),240(100),121 (2)。
Embodiment 23
It is added shown in Formulas I -1 to methoxy styrene (0.2mmol), -1 institute of Formula II into Schlenk tube sealing reaction devices 2- bromo propionic acid A esters (2 equivalent) shown in the n,N-Dimethylaniline (2 equivalent) shown, formula III -5, CuCl (10mol%), [Ru(bipy)3]Cl2·6H2O (2mol%), K2CO3(2 equivalent) and MeCN (1mL), then in argon gas protection, in room temperature and 3W Blue LED lamp light source light is reacted under the conditions of shining, and after the completion of TLC or GC-MS monitoring reactions, vacuum distillation removes solvent, then Residue is obtained into the target product of formula IV -5 through column chromatography for separation (eluent is n-hexane/ethyl acetate).Yield 74%；It is yellow Color oily liquids；1H NMR(400MHz,CDCl3)δ:7.05 (t, J=8Hz, 2H), 7.00 (t, J=8.4Hz, 2H), 6.72 (d, J=8Hz, 2H), 6.59 (d, J=8.4Hz, 2H), 3.75 (t, J=8Hz, 1H), 3.67 (s, 3H), 3.54 (s, 3H), 2.81 (s, 6H), 2.40-2.22 (m, 2H), 1.95-1.87 (m, 1H), 1.08 (d, J=6.8Hz, 3H)；13C NMR(100MHz, CDCl3)δ:177.2,157.8,149.1,137.4,137.0,132.8,128.70,128.6,128.3,113.8,112.8, 112.7,55.2,51.5,46.9,40.7,39.8,37.6,37.5,17.3,17.2；LRMS (EI, 70eV) m/z (%):341(M+,10),195(98),167(100),117(49),91(74)。
Embodiment 24
It is added shown in Formulas I -1 to methoxy styrene (0.2mmol), -1 institute of Formula II into Schlenk tube sealing reaction devices 2- bromide ethyl caproates (2 equivalent) shown in the n,N-Dimethylaniline (2 equivalent) shown, formula III -6, CuCl (10mol%), [Ru(bipy)3]Cl2·6H2O (2mol%), K2CO3(2 equivalent) and MeCN (1mL), then in argon gas protection, in room temperature and 3W Blue LED lamp light source light is reacted under the conditions of shining, and after the completion of TLC or GC-MS monitoring reactions, vacuum distillation removes solvent, then Residue is obtained into the target product of formula IV -6 through column chromatography for separation (eluent is n-hexane/ethyl acetate).Yield 68%；Nothing Color oily liquids；1H NMR(400MHz,CDCl3)δ:7.11 (d, J=8.4Hz, 2H), 7.06 (d, J=8.4Hz, 2H), 6.81 (d, J=8Hz, 2H), 6.66 (d, J=8.8Hz, 2H), 3.77 (s, 3H), 3.71 (t, J=7.2Hz, 1H), 3.61 (s, 3H), 2.88(s,6H),2.38-2.26(m,2H),2.10-2.05(m,1H),1.65-1.56(m,2H),1.25-1.22(m,4H), 0.84 (t, J=7.2Hz, 3H)；13C NMR(100MHz,CDCl3)δ:176.8,157.8,149.2,137.1,133.1, 128.8,128.6,128.4,128.2,113.8,112.9,55.2,51.3,47.3,43.7,40.8,38.5,32.4,29.3, 22.6,13.9；LRMS (EI, 70eV) m/z (%):383(M+,17),240(100),225(8)。
Embodiment 25
It is added shown in Formulas I -1 to methoxy styrene (0.2mmol), -1 institute of Formula II into Schlenk tube sealing reaction devices 2- bromo diethyl malonates (2 equivalent) shown in the n,N-Dimethylaniline (2 equivalent) shown, formula III -7, CuCl (10mol%), [Ru (bipy)3]Cl2·6H2O (2mol%), K2CO3(2 equivalent) and MeCN (1mL), then argon gas protect, It is reacted under the conditions of room temperature and 3W blue LED lamp light source lights are shone, after the completion of TLC or GC-MS monitoring reactions, vacuum distillation removes Solvent is removed, then residue is obtained into the target product of formula IV -7 through column chromatography for separation (eluent is n-hexane/ethyl acetate).It receives Rate 45%；Colourless oil liquid；1H NMR(400MHz,CDCl3)δ:7.13 (d, J=8Hz, 2H), 7.07 (d, J=8.4Hz, 2H), 6.81 (d, J=8.4Hz, 2H), 6.66 (d, J=8Hz, 2H), 4.19-4.13 (m, 4H), 3.81 (t, J=8Hz, 1H), 3.76 (s, 3H), 3.24 (t, J=7.2Hz, 1H), 2.90 (s, 6H), 2.57 (t, J=7.6Hz, 2H), 1.24 (t, J= 7.2Hz,6H)；13C NMR(100MHz,CDCl3)δ:169.5,158.0,149.2,136.4,131.7,128.7,128.4, 113.8,112.8,61.2,55.2,50.4,46.8,40.7,34.8,14.1；LRMS (EI, 70eV) m/z (%):413(M+, 17),253(38),240(100)。
Embodiment 26
It is added shown in Formulas I -1 to methoxy styrene (0.2mmol), -1 institute of Formula II into Schlenk tube sealing reaction devices 2- bromomalonic acids dimethyl ester (2 equivalent) shown in the n,N-Dimethylaniline (2 equivalent) shown, formula III -8, CuCl (10mol%), [Ru (bipy)3]Cl2·6H2O (2mol%), K2CO3(2 equivalent) and MeCN (1mL), then argon gas protect, It is reacted under the conditions of room temperature and 3W blue LED lamp light source lights are shone, after the completion of TLC or GC-MS monitoring reactions, vacuum distillation removes Solvent is removed, then residue is obtained into the target product of formula IV -8 through column chromatography for separation (eluent is n-hexane/ethyl acetate).Production Rate 43%；Colourless oil liquid；1H NMR(400MHz,CDCl3)δ:7.13 (d, J=8.4Hz, 2H), 7.07 (d, J=8.4Hz, 2H), 6.81 (d, J=8.4Hz, 2H), 6.67 (d, J=8.4Hz, 2H), 3.79 (t, J=8.4Hz, 1H), 3.76 (s, 3H), 3.69 (s, 6H), 3.29 (t, J=7.2Hz, 1H), 2.90 (s, 6H), 2.58 (t, J=7.6Hz, 2H)；13C NMR(100MHz, CDCl3)δ:169.9,158.0,149.2,136.3,131.6,128.7,128.4,113.9,112.9,55.2,52.4,50.1, 46.9,40.7,34.9；LRMS (EI, 70eV) m/z (%):385(M+,19),253(17),240(100)。
Implementation column 27
It is added shown in Formulas I -1 to methoxy styrene (0.2mmol), -1 institute of Formula II into Schlenk tube sealing reaction devices 2- bromoethyl acetates (2 equivalent) shown in the n,N-Dimethylaniline (2 equivalent) shown, formula III -9, CuCl (10mol%), [Ru(bipy)3]Cl2·6H2O (2mol%), K2CO3(2 equivalent) and MeCN (1mL), then in argon gas protection, in room temperature and 3W Blue LED lamp light source light is reacted under the conditions of shining, and after the completion of TLC or GC-MS monitoring reactions, vacuum distillation removes solvent, then Residue is obtained into the target product of formula IV -9 through column chromatography for separation (eluent is n-hexane/ethyl acetate).Yield 44%；Nothing Color oily liquids；1H NMR(400MHz,CDCl3)δ:7.13 (d, J=8.4Hz, 2H), 7.07 (d, J=8.8Hz, 2H), 6.80 (d, J=8.4Hz, 2H), 6.67 (d, J=8.8Hz, 2H), 4.11-4.06 (m, 2H), 3.78 (t, J=4.8Hz, 1H), 3.76 (s, 3H), 2.89 (s, 6H), 2.33-2.22 (m, 4H), 1.22 (t, J=7.2Hz, 3H)；13C NMR(100MHz,CDCl3)δ: 173.9,157.9,149.2,137.3,132.6,128.7,128.4,113.8,112.9,60.2,55.2,48.8,40.7, 33.0,31.0,14.2。
Embodiment 28
It is added shown in Formulas I -1 to methoxy styrene (0.2mmol), -2 institute of Formula II into Schlenk tube sealing reaction devices 2- methyl -2- ethyl bromides (2 equivalent), CuCl shown in the N shown, N- diethylaniline (2 equivalent), formula III -1 (10mol%), [Ru (bipy)3]Cl2·6H2O (2mol%), K2CO3(2 equivalent) and MeCN (1mL), then argon gas protect, It is reacted under the conditions of room temperature and 3W blue LED lamp light source lights are shone, after the completion of TLC or GC-MS monitoring reactions, vacuum distillation removes Solvent is removed, then residue is obtained into the target product of formula IV -10 through column chromatography for separation (eluent is n-hexane/ethyl acetate). Yield 44%；Yellow oily liquid；1H NMR(400MHz,CDCl3)δ:7.08 (d, J=8.8Hz, 2H), 6.97 (d, J= 8.8Hz, 2H), 6.70 (d, J=8.4Hz, 2H), 6.49 (d, J=8.8Hz, 2H), 3.78 (t, J=7.2Hz, 1H), 3.67 (s, 3H), 3.59-3.57 (m, 2H), 3.23-3.18 (m, 4H), 2.31-2.21 (m, 2H), 1.08 (d, J=6.4Hz, 6H), 1.05- 1.00(m,9H)；13C NMR(100MHz,CDCl3)δ:177.4,157.7,146.2,138.3,132.7,128.8,128.5, 113.6,112.0,60.1,55.2,46.8,46.3,44.3,42.0,26.1,25.9,14.0,12.6。
Embodiment 29
It is added shown in Formulas I -1 to methoxy styrene (0.2mmol), -3 institute of Formula II into Schlenk tube sealing reaction devices 2- methyl -2- ethyl bromides (2 equivalent), CuCl shown in the N shown, N- dipropyl aniline (2 equivalent), formula III -1 (10mol%), [Ru (bipy)3]Cl2·6H2O (2mol%), K2CO3(2 equivalent) and MeCN (1mL), then argon gas protect, It is reacted under the conditions of room temperature and 3W blue LED lamp light source lights are shone, after the completion of TLC or GC-MS monitoring reactions, vacuum distillation removes Solvent is removed, then residue is obtained into the target product of formula IV -11 through column chromatography for separation (eluent is n-hexane/ethyl acetate). Yield 62%；Yellow oily liquid；1H NMR(400MHz,CDCl3)δ:7.16 (d, J=8.4Hz, 2H), 7.03 (d, J= 8.8Hz, 2H), 6.77 (d, J=8.4Hz, 2H), 6.51 (d, J=8.4Hz, 2H), 3.84 (t, J=6.8Hz, 1H), 3.74 (s, 3H), 3.68-3.63 (m, 2H), 3.16 (t, J=3.6Hz, 4H), 2.38-2.28 (m, 2H), 1.60-1.50 (m, 6H), 1.16 (s, 2H), 1.14 (s, 2H), 1.09 (t, J=5.2Hz, 3H), 0.89 (t, J=7.6Hz, 6H)；13C NMR(100MHz, CDCl3)δ:177.5,157.6,146.5,138.2,132.3,128.8,128.3,113.6,111.7,60.1,53.0,46.3, 42.0,26.1,26.0,20.4,14.0,11.4。
Embodiment 30
It is added shown in Formulas I -1 to methoxy styrene (0.2mmol), -4 institute of Formula II into Schlenk tube sealing reaction devices 2- methyl -2- ethyl bromides (2 equivalent) shown in the N- Methyl-N-phenyls aniline (2 equivalent) that shows, formula III -1, CuCl (10mol%), [Ru (bipy)3]Cl2·6H2O (2mol%), K2CO3(2 equivalent) and MeCN (1mL), then argon gas protect, It is reacted under the conditions of room temperature and 3W blue LED lamp light source lights are shone, after the completion of TLC or GC-MS monitoring reactions, vacuum distillation removes Solvent is removed, then residue is obtained into the target product of formula IV -12 through column chromatography for separation (eluent is n-hexane/ethyl acetate). Yield 47%；Yellow oily liquid；1H NMR(400MHz,CDCl3)δ:7.24-7.13(m,6H),6.94-6.87(m,5H), 6.80 (d, J=8.8Hz, 2H), 3.92 (t, J=6.8Hz, 1H), 3.76 (s, 3H), 3.73-3.68 (m, 2H), 3.25 (s, 3H), 2.36 (d, J=6.4Hz, 2H), 1.26 (s, 3H), 1.16 (d, J=5.6Hz, 3H), 1.12 (t, J=6.8Hz, 3H)；13C NMR(100MHz,CDCl3)δ:177.3,157.9,149.1,146.9,139.2,137.6,129.1,128.8,128.5, 121.3,120.5,119.3,113.7,60.2,55.2,46.8,46.6,42.0,40.2,26.1,26.0,14.0.。
Embodiment 31
It is added shown in Formulas I -1 to methoxy styrene (0.2mmol), -5 institute of Formula II into Schlenk tube sealing reaction devices 2- methyl -2- ethyl bromides (2 equivalent) shown in the compound (2 equivalent) shown, formula III -1, CuCl (10mol%), [Ru (bipy)3]Cl2·6H2O (2mol%), K2CO3(2 equivalent) and MeCN (1mL), then in argon gas protection, in room temperature and 3W blues It is reacted under LED light source illumination condition, after the completion of TLC or GC-MS monitoring reactions, vacuum distillation removes solvent, then will be residual Excess obtains the target product of formula IV -13 through column chromatography for separation (eluent is n-hexane/ethyl acetate).Yield 49%；Yellow Oily liquids；1H NMR(400MHz,CDCl3)δ:7.16-7.07 (m, 4H), 6.83-6.75 (m, 4H), 3.87 (t, J= 7.2Hz, 1H), 3.74 (s, 3H), 3.70-3.65 (m, 2H), 3.06 (t, J=5.2Hz, 4H), 2.38-2.29 (m, 2H), 1.70-1.64 (m, 4H), 1.56-1.50 (m, 2H), 1.14 (d, J=2.0Hz, 6H), 1.10 (t, J=7.2Hz, 3H)；13C NMR(100MHz,CDCl3)δ:177.4,157.8,150.5,138.0,136.4,128.8,128.3,116.5,113.6, 60.1,55.2,50.9,46.5,42.1,26.2,25.9,25.9,24.3,14.0。
Embodiment 32
It is added shown in Formulas I -1 to methoxy styrene (0.2mmol), -6 institute of Formula II into Schlenk tube sealing reaction devices 2- methyl -2- ethyl bromides (2 equivalent) shown in the compound (2 equivalent) shown, formula III -1, CuCl (10mol%), [Ru (bipy)3]Cl2·6H2O (2mol%), K2CO3(2 equivalent) and MeCN (1mL), then in argon gas protection, in room temperature and 3W blues It is reacted under LED light source illumination condition, after the completion of TLC or GC-MS monitoring reactions, vacuum distillation removes solvent, then will be residual Excess obtains the target product of formula IV -14 through column chromatography for separation (eluent is n-hexane/ethyl acetate).Yield 38%；Yellow Oily liquids；1H NMR(400MHz,CDCl3)δ:7.15-7.12 (m, 4H), 6.80-6.76 (m, 4H), 3.89 (t, J= 7.2Hz, 1H), 3.82 (t, J=4.8Hz, 4H), 3.74 (s, 3H), 3.71-3.65 (m, 2H), 3.08 (t, J=4.8Hz, 4H), 2.39-2.29 (m, 2H), 1.14 (s, 6H), 1.10 (t, J=7.2Hz, 3H)；13C NMR(100MHz,CDCl3)δ:177.3, 157.8,149.5,137.8,137.3,128.7,128.4,115.7,113.7,66.9,60.1,55.2,49.5,46.6, 46.5,42.0,26.1,25.9,14.0。
Embodiment 33
It is added shown in Formulas I -1 to methoxy styrene (0.2mmol), -2 institute of Formula II into Schlenk tube sealing reaction devices 2- methyl -2- ethyl bromides (2 equivalent) shown in the compound (2 equivalent) shown, formula III -1, CuCl (10mol%), [Ru (bipy)3]Cl2·6H2O (2mol%), K2CO3(2 equivalent) and MeCN (1mL), then in argon gas protection, in room temperature and 3W blues It is reacted under LED light source illumination condition, after the completion of TLC or GC-MS monitoring reactions, vacuum distillation removes solvent, then will be residual Excess obtains the target product of formula IV -15 through column chromatography for separation (eluent is n-hexane/ethyl acetate).Yield 28%；Yellow Oily liquids；1H NMR(400MHz,CDCl3)δ:7.16-7.12 (m, 4H), 6.83-6.76 (m, 4H), 3.89 (t, J= 7.2Hz, 1H), 3.77-3.73 (m, 5H), 3.70-3.65 (m, 2H), 3.58 (t, J=5.2Hz, 2H), 3.10-3.05 (m, 4H), 2.40-2.33 (m, 4H), 1.18 (t, J=18.0Hz, 3H), 1.14 (s, 6H), 1.10 (t, J=7.2Hz, 3H)；13C NMR(100MHz,CDCl3)δ:177.3,172.3,157.8,149.1,137.9,137.7,128.7,128.5,116.7, 113.7,60.1,55.2,49.9,49.6,46.5,45.6,45.4,42.0,41.5,26.5,26.1,26.0,14.0,9.5。
Embodiment 34
It is added shown in Formulas I -1 to methoxy styrene (0.2mmol), -8 institute of Formula II into Schlenk tube sealing reaction devices 2- methyl -2- ethyl bromides (2 equivalent) shown in the compound (2 equivalent) shown, formula III -1, CuCl (10mol%), [Ru (bipy)3]Cl2·6H2O (2mol%), K2CO3(2 equivalent) and MeCN (1mL), then in argon gas protection, in room temperature and 3W blues It is reacted under LED light source illumination condition, after the completion of TLC or GC-MS monitoring reactions, vacuum distillation removes solvent, then will be residual Excess obtains the target product of formula IV -16 through column chromatography for separation (eluent is n-hexane/ethyl acetate).Yield 67%；Yellow Oily liquids；1H NMR(400MHz,CDCl3)δ:7.07 (d, J=8.8Hz, 2H), 6.76 (d, J=8.0Hz, 2H), 6.40 (s, 2H), 4.36-4.33 (m, 1H), 3.88-3.80 (m, 1H), 3.75 (d, J=1.2Hz, 3H), 3.72-3.61 (m, 1H), 2.89 (d, J=0.8Hz, 6H), 2.56-2.17 (m, 6H), 2.09 (d, J=12.8Hz, 2H), 1.26 (s, 3H), 1.13 (s, 3H), 1.11-1.07(m,3H)；13C NMR(100MHz,CDCl3)δ:177.6,157.2,148.6,137.1,130.7,128.2, 113.2,60.3,55.2,44.2,42.6,40.7,39.1,26.3,26.0,22.1,13.9。
Embodiment 35
It is added shown in Formulas I -2 to ethoxystyrene (0.2mmol), -1 institute of Formula II into Schlenk tube sealing reaction devices 2- methyl -2- ethyl bromides (2 equivalent) shown in the n,N-Dimethylaniline (2 equivalent) shown, formula III -1, CuCl (10mol%), [Ru (bipy)3]Cl2·6H2O (2mol%), K2CO3(2 equivalent) and MeCN (1mL), then argon gas protect, It is reacted under the conditions of room temperature and 3W blue LED lamp light source lights are shone, after the completion of TLC or GC-MS monitoring reactions, vacuum distillation removes Solvent is removed, then residue is obtained into the target product of formula IV -17 through column chromatography for separation (eluent is n-hexane/ethyl acetate). Yield 85%；Yellow oily liquid；1H NMR(400MHz,CDCl3)δ:7.13 (d, J=8.4Hz, 2H), 7.08 (d, J= 12.0Hz, 2H), 676 (d, J=8.8Hz, 2H), 6.64 (d, J=8.8Hz, 2H), 3.99-3.94 (m, 2H), 3.86 (t, J= 7.2Hz, 1H), 3.71-3.66 (m, 2H), 2.87 (s, 6H), 2.35-2.30 (m, 2H), 1.36 (t, J=6.8Hz, 3H), 1.14 (d, J=3.2Hz, 6H), 1.10 (t, J=7.2Hz, 3H)；13C NMR(100MHz,CDCl3)δ:177.4,157.1,149.0, 138.1,134.0,128.7,128.3,114.3,112.9,63.4,60.1,46.7,46.4,42.0,40.8,26.2,25.9, 14.9,14.0。
Embodiment 36
P-methylstyrene (0.2mmol) shown in Formulas I -3 is added into Schlenk tube sealing reaction devices, shown in Formula II -1 N,N-Dimethylaniline (2 equivalent), 2- methyl -2- ethyl bromides (2 equivalent) shown in formula III -1, CuCl (10mol%), [Ru (bipy)3]Cl2·6H2O (2mol%), K2CO3(2 equivalent) and MeCN (1mL), then argon gas protect, It is reacted under the conditions of room temperature and 3W blue LED lamp light source lights are shone, after the completion of TLC or GC-MS monitoring reactions, vacuum distillation removes Solvent is removed, then residue is obtained into the target product of formula IV -18 through column chromatography for separation (eluent is n-hexane/ethyl acetate). Yield 52%；Yellow oily liquid；1H NMR(400MHz,CDCl3)δ:7.06-6.95 (m, 6H), 6.56 (d, J=8.8Hz, 2H), 3.80 (t, J=6.8Hz, 1H), 3.63-3.57 (m, 2H), 2.79 (s, 6H), 2.28 (t, J=3.6Hz, 2H), 2.18 (s, 3H), 1.07 (s, 6H), 1.02 (t, J=7.2Hz, 3H)；13C NMR(100MHz,CDCl3)δ:177.4,149.1, 143.1,136.4,135.1,133.8,128.9,128.4,127.6,112.9,60.1,46.9,46.5,42.1,40.8, 26.1,26.0,20.9,13.9。
Embodiment 37
It is added into Schlenk tube sealing reaction devices shown in m-methyl styrene (0.2mmol), Formula II -1 shown in Formulas I -4 N,N-Dimethylaniline (2 equivalent), 2- methyl -2- ethyl bromides (2 equivalent) shown in formula III -1, CuCl (10mol%), [Ru (bipy)3]Cl2·6H2O (2mol%), K2CO3(2 equivalent) and MeCN (1mL), then argon gas protect, It is reacted under the conditions of room temperature and 3W blue LED lamp light source lights are shone, after the completion of TLC or GC-MS monitoring reactions, vacuum distillation removes Solvent is removed, then residue is obtained into the target product of formula IV -19 through column chromatography for separation (eluent is n-hexane/ethyl acetate). Yield 27%；Yellow oily liquid；1H NMR(400MHz,CDCl3)δ:7.13-7.04 (m, 5H), 6.91 (d, J=7.2Hz, 1H), 6.64 (d, J=8.8Hz, 2H), 3.87 (t, J=7.2Hz, 1H), 3.69-3.64 (m, 2H), 2.87 (s, 6H), 2.37- 2.35 (m, 2H), 2.28 (s, 3H), 1.15 (s, 6H), 1.09 (t, J=7.2Hz, 3H)；13C NMR(100MHz,CDCl3)δ: 177.4,149.1,146.0,137.7,133.6,128.6,128.4,128.1,126.6,124.8,112.9,60.1,47.2, 46.5,42.1,40.8,26.0,21.5,14.0。
Embodiment 38
It is added into Schlenk tube sealing reaction devices shown in o-methyl styrene (0.2mmol), Formula II -1 shown in Formulas I -5 N,N-Dimethylaniline (2 equivalent), 2- methyl -2- ethyl bromides (2 equivalent) shown in formula III -1, CuCl (10mol%), [Ru (bipy)3]Cl2·6H2O (2mol%), K2CO3(2 equivalent) and MeCN (1mL), then argon gas protect, It is reacted under the conditions of room temperature and 3W blue LED lamp light source lights are shone, after the completion of TLC or GC-MS monitoring reactions, vacuum distillation removes Solvent is removed, then residue is obtained into the target product of formula IV -20 through column chromatography for separation (eluent is n-hexane/ethyl acetate). Yield 43%；Yellow oily liquid；1H NMR(400MHz,CDCl3)δ:7.39 (d, J=7.6Hz, 1H), 7.15 (t, J= 7.2Hz, 1H), 7.09-7.03 (m, 4H), 6.62 (d, J=8.4Hz, 2H), 4.16 (t, J=8.4Hz, 1H), 3.70-3.58 (m, 2H), 2.88 (d, J=12.0Hz, 6H), 2.36-2.33 (m, 2H), 2.31 (s, 3H), 1.15 (d, J=10.8Hz, 6H), (1.09 t, J=7.2Hz, 3H)；13C NMR(100MHz,CDCl3)δ:177.4,149.0,143.6,135.6,132.6, 130.4,129.4,128.7,126.8,125.8,125.7,112.8,60.1,47.0,42.2,42.1,40.9,40.7,26.4, 25.8,20.0,14.0。
Embodiment 40
O-methoxystyrene (0.2mmol), -1 institute of Formula II shown in Formulas I -6 are added into Schlenk tube sealing reaction devices 2- methyl -2- ethyl bromides (2 equivalent) shown in the n,N-Dimethylaniline (2 equivalent) shown, formula III -1, CuCl (10mol%), [Ru (bipy)3]Cl2·6H2O (2mol%), K2CO3(2 equivalent) and MeCN (1mL), then argon gas protect, It is reacted under the conditions of room temperature and 3W blue LED lamp light source lights are shone, after the completion of TLC or GC-MS monitoring reactions, vacuum distillation removes Solvent is removed, then residue is obtained into the target product of formula IV -21 through column chromatography for separation (eluent is n-hexane/ethyl acetate). Yield 68%；Yellow oily liquid；1H NMR(400MHz,CDCl3)δ:7.25-7.22(m,1H),7.16-7.06(m,3H), 6.87-6.77 (m, 2H), 6.64 (d, J=8.8Hz, 2H), 4.49 (t, J=7.2Hz, 1H), 3.80 (s, 3H), 3.65-3.60 (m, 2H), 2.87 (s, 6H), 2.37-2.27 (m, 2H), 2.28 (s, 3H), 1.15 (s, 6H), 1.09 (t, J=7.2Hz, 3H)；13C NMR(100MHz,CDCl3)δ:177.6,156.5,148.9,134.5,133.3,128.8,128.0,126.7,120.3, 112.7,110.7,60.0,55.4,45.7,42.1,40.8,38.5,25.9,25.8,13.9。
Embodiment 41
2,3- dimethoxy styrenes (0.2mmol), Formula II-shown in Formulas I -7 are added into Schlenk tube sealing reaction devices 2- methyl -2- ethyl bromides (2 equivalent), CuCl shown in n,N-Dimethylaniline shown in 1 (2 equivalent), formula III -1 (10mol%), [Ru (bipy)3]Cl2·6H2O (2mol%), K2CO3(2 equivalent) and MeCN (1mL), then argon gas protect, It is reacted under the conditions of room temperature and 3W blue LED lamp light source lights are shone, after the completion of TLC or GC-MS monitoring reactions, vacuum distillation removes Solvent is removed, then residue is obtained into the target product of formula IV -22 through column chromatography for separation (eluent is n-hexane/ethyl acetate). Yield 66%；Yellow oily liquid；1H NMR(400MHz,CDCl3)δ:7.16 (d, J=8.8Hz, 2H), 7.00-6.95 (m, 2H), 6.71-6.62 (m, 3H), 4.48 (t, J=7.2Hz, 1H), 3.81 (s, 3H), 3.72 (s, 3H), 3.71-3.62 (m, 2H), 2.86 (s, 6H), 2.41-2.21 (m, 2H), 1.15 (d, J=7.6Hz, 6H), 1.10 (t, J=7.2Hz, 3H)；13C NMR (100MHz,CDCl3)δ:177.5,152.7,149.0,146.3,139.9,133.3,128.8,123.5,120.0,112.8, 109.9,60.5,60.1,55.6,46.1,42.1,40.8,39.1,26.2,25.5,13.9。
Embodiment 42
N shown in 2- naphthalenes ethylene (0.2mmol), Formula II -1 shown in Formulas I -8 is added into Schlenk tube sealing reaction devices, 2- methyl -2- ethyl bromides (2 equivalent) shown in accelerine (2 equivalent), formula III -1, CuCl (10mol%), [Ru(bipy)3]Cl2·6H2O (2mol%), K2CO3(2 equivalent) and MeCN (1mL), then in argon gas protection, in room temperature and 3W Blue LED lamp light source light is reacted under the conditions of shining, and after the completion of TLC or GC-MS monitoring reactions, vacuum distillation removes solvent, then Residue is obtained into the target product of formula IV -23 through column chromatography for separation (eluent is n-hexane/ethyl acetate).33%；Yellow Oily liquids；1H NMR(400MHz,CDCl3)δ:7.77-7.67(m,4H),7.40-7.35(m,2H),7.17-7.14(m, 2H), 6.66-6.62 (m, 2H), 4.09 (t, J=7.6Hz, 1H), 3.60-3.54 (m, 2H), 2.87 (s, 6H), 2.54-2.42 (m, 2H), 1.18 (d, J=7.6Hz, 6H), 1.02 (t, J=7.2Hz, 3H)；13C NMR(100MHz,CDCl3)δ:177.4, 149.1,143.5,133.5,133.3,132.0,128.6,127.8,127.7,127.6,126.9,125.7,125.6, 125.1,112.8,60.1,47.3,46.2,42.1,40.7,26.2,26.0,13.9。
Embodiment 43
1,1- diphenylethlenes (0.2mmol), -1 institute of Formula II shown in Formulas I -9 are added into Schlenk tube sealing reaction devices 2- methyl -2- ethyl bromides (2 equivalent) shown in the n,N-Dimethylaniline (2 equivalent) shown, formula III -1, CuCl (10mol%), [Ru (bipy)3]Cl2·6H2O (2mol%), K2CO3(2 equivalent) and MeCN (1mL), then argon gas protect, It is reacted under the conditions of room temperature and 3W blue LED lamp light source lights are shone, after the completion of TLC or GC-MS monitoring reactions, vacuum distillation removes Solvent is removed, then residue is obtained into the target product of formula IV -24 through column chromatography for separation (eluent is n-hexane/ethyl acetate). Yield 46%；Yellow oily liquid；1H NMR(400MHz,CDCl3)δ:7.29 (d, J=7.2Hz, 4H), 7.19 (s, 1H), 7.14-7.10 (m, 5H), 7.03 (t, J=7.2Hz, 2H), 6.52 (d, J=8.8Hz, 2H), 3.41-3.35 (m, 2H), 2.83 (s, 6H), 1.19 (s, 2H), 1.01 (s, 6H), 0.91 (t, J=7.2Hz, 3H)；13C NMR(100MHz,CDCl3)δ:177.1, 148.3,147.8,134.7,129.4,127.4,125.5,111.6,60.1,55.1,47.8,42.0,40.5,28.1,13.7。
Embodiment described above is merely a preferred embodiment of the present invention, and the simultaneously exhaustion of the feasible implementation of non-present invention.For It is any apparent to made by it under the premise of without departing substantially from the principle of the invention and spirit for those skilled in the art Change, should all be contemplated as falling with the present invention claims within.

Claims (9)

1. the preparation method of 1,1- diaryl alkanes hydro carbons compound shown in a kind of formula IV, which is characterized in that the method operates It is as follows：Into Schlenk tube sealing reaction devices, with N, N- disubstituted benzenes shown in substituted ethylene class compound, Formula II shown in Formulas I 2- bromos carboxylic acid ester compound shown in aminated compounds, formula III is reaction raw materials, and photochemical catalyst, mantoquita co-catalysis is added Agent, alkali and organic solvent react under inert atmosphere protection, room temperature and illumination condition, have been reacted by TLC or GC-MS monitorings Cheng Hou, it is post-treated to obtain 1,1- diaryl alkanes hydro carbons compound shown in formula IV；
In Formulas I and formula IV,Indicate C6-20Aryl, C4-20Heteroaryl；
R1It indicatesOne or more substituent groups on ring, selected from hydrogen, C1-C20Alkyl, C1-C20Alkoxy, C1-C20's Alkylthio group, C6-C20Aryl, C4-C20Heteroaryl, C3-C20Naphthenic base, nitro, halogen ,-OH ,-SH ,-CN ,-COOR9、- COR10、-OCOR11、-NR12R13；Wherein, R9、R10、R11、R12、R13It is each independently selected from hydrogen, C1-C20Alkyl, C6-C20's Aryl, C4-C20Heteroaryl, C3-C20Naphthenic base in any one or more；
Wherein, above-mentioned each R1Alkyl, aryl, heteroaryl, cycloalkyl moiety in substituent group can be selected optionally by one or more From C1-C6Alkyl, C1-C6Alkoxy, C1-C6Acyl group, halogen ,-NO2、-CN、-OH、C6-C20Aryl, C3-C6Ring Alkyl is replaced；
R2Selected from hydrogen, C1-20Alkyl, C6-20Aryl；
Wherein, above-mentioned each R2Alkyl, aryl moiety in substituent group optionally can be selected from C by one or more1-C6Alkyl, C1-C6Alkoxy, C1-C6Acyl group, halogen ,-NO2、-CN、-OH、C6-C20Aryl, C3-C6Naphthenic base replaced；
In Formula II and formula IV, R3One or more substituent groups on connected phenyl ring are indicated, selected from hydrogen, C1-C20Alkyl, C1-C20 Alkoxy, C1-C20Alkylthio group, C6-C20Aryl, C4-C20Heteroaryl, C3-C20Naphthenic base, nitro, halogen ,- OH、-SH、-CN、-COOR9、-COR10、-OCOR11、-NR12R13；Wherein, R9、R10、R11、R12、R13Be each independently selected from hydrogen, C1-C20Alkyl, C6-C20Aryl, C5-C20Heteroaryl, C3-C20Naphthenic base in any one or more；
Wherein, above-mentioned each R3Alkyl, aryl, heteroaryl, cycloalkyl moiety in substituent group can be selected optionally by one or more From C1-C6Alkyl, C1-C6Alkoxy, C1-C6Acyl group, halogen ,-NO2、-CN、-OH、C6-C20Aryl, C3-C6Ring Alkyl is replaced；Also, R3Substituent group is not at "-NR3R4" contraposition；
R4,R5It is independently from each other hydrogen, C1-C20Alkyl, C2-C20Alkenyl, C6-C20Aryl, C4-C20Heteroaryl, C3-C20Naphthenic base；Or R4,R5With formed together with connected N atoms 5-8 cyclic annular atom with or without other hetero atoms Heterocycle；
Wherein, above-mentioned each R4,R5Alkyl, alkenyl, aryl, heteroaryl, naphthenic base, heterocyclyl moieties in group can be optionally C is selected from by one or more1-C6Alkyl, C1-C6Alkoxy, C1-C6Acyl group, halogen ,-NO2、-CN、-OH、C6-C20's Aryl, C3-C6Naphthenic base replaced；
In formula III and formula IV, R6、R7It is independently from each other hydrogen, halogen, C1-C20Alkyl, R14OCO-, wherein R14It is selected from C1-20Alkyl；Or R6、R7With the cyclic hydrocarbon group for forming 3-6 annular atom together with connected carbon atom；
Wherein above-mentioned R6、R7Alkyl, hydrocarbyl portion in group optionally can be selected from C by one or more1-C6Alkyl, C1- C6Alkoxy, C1-C6Acyl group, halogen ,-NO2、-CN、-OH、C6-C20Aryl, C3-C6Naphthenic base replaced；
R8Selected from C1-20Alkyl, C6-20Aryl；
Wherein, above-mentioned each R8Alkyl, aryl moiety in substituent group optionally can be selected from C by one or more1-C6Alkyl, C1-C6Alkoxy, C1-C6Acyl group, halogen ,-NO2、-CN、-OH、C6-C20Aryl, C3-C6Naphthenic base replaced；
Wherein, the photochemical catalyst is selected from [Ru (bipy)3]Cl2·6H2O、[Ir(ppy)3] or Eosin Y any one；
The mantoquita co-catalyst is selected from CuCl, CuOAc, CuI, CuCl2、Cu(OAc)2In any one；
The alkali is selected from K2CO3、Cs2CO3、KOtAny one in Bu.
2. according to the method described in claim 1, it is characterized in that, in Formulas I and formula IV,Indicate C6-12Aryl, C4-12's Heteroaryl；
R1It indicatesOne or more substituent groups on ring, selected from hydrogen, C1-C6Alkyl, C1-C6Alkoxy, C6-C12Virtue Base, C5-C12Heteroaryl, C3-C6Naphthenic base, nitro, halogen ,-OH ,-SH ,-CN ,-COOR9、-COR10、-OCOR11、- NR12R13；Wherein, R9、R10、R11、R12、R13It is each independently selected from hydrogen, C1-C6Alkyl, C6-C12Aryl, C4-C12It is miscellaneous Aryl, C3-C6Naphthenic base in any one or more；
Wherein, above-mentioned each R1Alkyl, aryl, heteroaryl, cycloalkyl moiety in substituent group can be selected optionally by one or more From C1-C6Alkyl, C1-C6Alkoxy, C1-C6Acyl group, halogen ,-NO2、-CN、-OH、C6-C12Aryl, C3-C6Ring Alkyl is replaced；
R2Selected from hydrogen, C1-6Alkyl, C6-12Aryl；
Wherein, above-mentioned each R2Alkyl, aryl moiety in substituent group optionally can be selected from C by one or more1-C6Alkyl, C1-C6Alkoxy, C1-C6Acyl group, halogen ,-NO2、-CN、-OH、C6-C12Aryl, C3-C6Naphthenic base replaced；
In Formula II and formula IV, R3One or more substituent groups on connected phenyl ring are indicated, selected from hydrogen, C1-C6Alkyl, C1-C6 Alkoxy, C6-C12Aryl, C5-C12Heteroaryl, C3-C6Naphthenic base, nitro, halogen ,-OH ,-SH ,-CN ,- COOR9、-COR10、-OCOR11、-NR12R13；Wherein, R9、R10、R11、R12、R13It is each independently selected from hydrogen, C1-C6Alkyl, C6-C12Aryl, C4-C12Heteroaryl, C3-C6Naphthenic base in any one or more；
Wherein, above-mentioned each R3Alkyl, aryl, heteroaryl, cycloalkyl moiety in substituent group can be selected optionally by one or more From C1-C6Alkyl, C1-C6Alkoxy, C1-C6Acyl group, halogen ,-NO2、-CN、-OH、C6-C12Aryl, C3-C6Ring Alkyl is replaced；Also, R3Substituent group is not at "-NR3R4" contraposition；
R4,R5It is independently from each other hydrogen, C1-C6Alkyl, C2-C6Alkenyl, C6-C12Aryl, C4-C12Heteroaryl, C3- C6Naphthenic base；Or R4,R5With formed together with connected N atoms 5-8 cyclic annular atom with or without other heteroatomic miscellaneous Ring group；
Wherein, above-mentioned each R4,R5Alkyl, alkenyl, aryl, heteroaryl, naphthenic base, heterocyclyl moieties in group definition can appoint Selection of land is selected from C by one or more1-C6Alkyl, C1-C6Alkoxy, C1-C6Acyl group, halogen ,-NO2、-CN、-OH、C6- C12Aryl, C3-C6Naphthenic base replaced；
In formula III and formula IV, R6,R7It is independently from each other hydrogen, halogen, C1-C6Alkyl, R14OCO-, wherein R14Selected from C1-6 Alkyl；Or R6、R7With the cyclic hydrocarbon group for forming 3-6 annular atom together with connected carbon atom；
Wherein above-mentioned R6、R7Alkyl, hydrocarbyl portion in group definition optionally can be selected from C by one or more1-C6Alkane Base, C1-C6Alkoxy, C1-C6Acyl group, halogen ,-NO2、-CN、-OH、C6-C20Aryl, C3-C6Naphthenic base replaced；
R8Selected from C1-6Alkyl, C6-12Aryl；
Wherein, above-mentioned each R8Alkyl, aryl moiety in substituent group optionally can be selected from C by one or more1-C6Alkyl, C1-C6Alkoxy, C1-C6Acyl group, halogen ,-NO2、-CN、-OH、C6-C12Aryl, C3-C6Naphthenic base replaced.
3. according to the method described in claim 2, it is characterized in that, in Formulas I and formula IV,Indicate phenyl, naphthalene, thiophene Base, pyridyl group；
R1It indicatesOne or more substituent groups on ring, selected from hydrogen, C1-C6Alkyl, C1-C6Alkoxy, halogen；
R2Selected from hydrogen, phenyl.
In Formula II and formula IV, R3One or more substituent groups on connected phenyl ring are indicated, selected from hydrogen, C1-C6Alkyl, C1-C6 Alkoxy, halogen；Also, R3Substituent group is not at "-NR3R4" contraposition；
R4,R5It is independently from each other hydrogen, C1-6Alkyl, C6-12Aryl；Or R4,R55- is formed with together with connected N atoms 6 cyclic annular atoms with or without other heteroatomic heterocycles；Wherein, above-mentioned each R4,R5Heterocyclyl moieties in group definition Can C be optionally selected from by one or more1-C6Alkyl, C1-C6Alkoxy, C1-C6Acyl group, halogen replaced；
In formula III and formula IV, R6,R7It is independently from each other hydrogen, halogen, C1-C6Alkyl, R14OCO-, wherein R14Selected from C1-6 Alkyl；Or R6、R7With the cyclic hydrocarbon group for forming 3-6 annular atom together with connected carbon atom；
R8Selected from C1-6Alkyl.
4. according to the method described in claim 1-3 any one, which is characterized in that the photochemical catalyst is [Ru (bipy)3] Cl2·6H2O, the mantoquita co-catalyst is to be selected from K selected from CuCl, the alkali2CO3。
5. according to the method described in claim 1-3 any one, which is characterized in that the organic solvent is selected from acetonitrile；Institute The illumination condition stated is provided by 3-5W blue led light sources, and preferably 3W blue leds light source provides.
6. according to the method for claim 1-3 any one, which is characterized in that the inert atmosphere is nitrogen atmosphere Or argon gas atmosphere.
7. according to the method described in claim 1-3 any one, which is characterized in that substituted ethylene class chemical combination shown in Formulas I Object, N shown in Formula II, 2- bromos carboxylic acid ester compound, photocatalysis shown in N- disubstituted benzenes aminated compounds, formula III Agent, mantoquita co-catalyst, alkali molar ratio be 1:(1~3):(1~3):(0.01~0.05):(0.05~0.2):(1~3).
8. the method according to the description of claim 7 is characterized in that substituted ethylene class compound shown in Formulas I, Formula II institute 2- bromos carboxylic acid ester compound, photochemical catalyst, mantoquita shown in the N shown, N- disubstituted benzenes aminated compounds, formula III -1 help Catalyst, alkali molar ratio be 1:2:2:0.02:0.1:2.
9. method according to any one of claims 1 to 8, which is characterized in that the post-processing operation is as follows：It will be anti- Mixed liquor after the completion of answering is concentrated under reduced pressure, and obtains residue, then by target of the residue through the isolated formula IV of column plastic column chromatography The eluent of product, wherein silica gel column chromatography separation is the mixed liquor of n-hexane and ethyl acetate.
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