CN108675935B - Preparation method of 1, 1-diaryl alkane compound - Google Patents

Preparation method of 1, 1-diaryl alkane compound Download PDF

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CN108675935B
CN108675935B CN201810608849.5A CN201810608849A CN108675935B CN 108675935 B CN108675935 B CN 108675935B CN 201810608849 A CN201810608849 A CN 201810608849A CN 108675935 B CN108675935 B CN 108675935B
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CN108675935A (en
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宋仁杰
雍馨
李金恒
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Nanchang Hangkong University
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    • 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
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    • 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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Abstract

The invention relates to a preparation method of a 1, 1-diaryl alkane compound, which takes a p-substituted ethylene compound shown in a formula I, an N, N-disubstituted aniline compound shown in a formula II and a 2-bromo carboxylic ester compound shown in a formula III as reaction raw materials, and the reaction is carried out under the photocatalysis condition to obtain a 1, 1-diaryl alkane compound shown in a formula IV;

Description

Preparation method of 1, 1-diaryl alkane compound
Technical Field
The application belongs to the field of organic synthesis, and particularly relates to a preparation method of a 1, 1-diaryl alkane compound.
Background
1, 1-diarylalkanes have good activity against autoimmune diseases, cancer, inflammation, insomnia and osteoporosis. This skeleton is present in many natural products and well-known drugs with biological activity, including (-) -cyclosporin, (+) -sertraline deoxy, and oxymetafene, among others.
The synthesis of 1, 1-diarylalkanes in the prior art is generally carried out by reacting donor-acceptor (D-A) cyclopropane compounds as raw materials with various nucleophiles such as N, N-dimethylformamide under different catalytic conditions (see the following prior art documents: 1) Tetrahedron 66(2010) 3024-; 2) eur.j.org.chem.2015, 6419-6422; 3) org.Lett.2018,20, 574-577; 4) journal of the Korea Chemical society, 2016, Vol.60, No.5, p.374-377. ).
In recent years, visible light-induced organic synthesis reactions have attracted increasing organic chemists' interest. Under the condition of visible light, the light oxidation reduction catalyst provides an effective way for constructing a new chemical bond in organic synthesis due to the characteristics of environmental friendliness, mild operation condition and the like in the induction of organic reaction, and is also one of the hot spots of organic synthesis reaction research in recent years.
The inventors have made extensive studies and, in the present invention, have proposed a novel method for producing 1, 1-diarylalkane compounds under the condition of photoredox catalysis.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the synthesis method for preparing the 1, 1-diaryl alkane compound, which has the advantages of simple process, greenness, high efficiency, wide application range of reaction substrates and high yield.
The preparation method of the 1, 1-diaryl alkane compound provided by the invention comprises the following steps:
adding a photocatalyst, a copper salt cocatalyst, an alkali and an organic solvent into a reaction raw material p-substituted ethylene compound shown in a formula I, an N, N-disubstituted aniline compound shown in a formula II and a 2-bromo carboxylic ester compound shown in a formula III in a Schlenk tube sealing reactor, reacting under the conditions of inert atmosphere protection, room temperature and illumination, monitoring the completion of the reaction through TLC or GC-MS, and carrying out post-treatment to obtain a 1, 1-diaryl alkane compound shown in a formula IV.
Figure BDA0001695054890000021
In the formula I and the formula IV,
Figure BDA0001695054890000022
is represented by C6-20Aryl of (C)4-20The heteroaryl group of (a);
R1to represent
Figure BDA0001695054890000023
One or more substituents on the ring selected from hydrogen, C1-C20Alkyl of (C)1-C20Alkoxy group of (C)1-C20Alkylthio of, C6-C20Aryl of (C)4-C20Heteroaryl of (A), C3-C20Cycloalkyl, nitro, halogen, -OH, -SH, -CN, -COOR9、-COR10、-OCOR11、-NR12R13(ii) a Wherein R is9、R10、R11、R12、R13Each independently selected from hydrogen and C1-C20Alkyl of (C)6-C20Aryl of (C)4-C20Heteroaryl of (A), C3-C20Any one or more of cycloalkyl groups of (a).
Wherein each R is1The alkyl, aryl, heteroaryl, cycloalkyl moieties in the substituents may optionally be substituted by one or more groups selected from C1-C6Alkyl of (C)1-C6Alkoxy group of (C)1-C6Acyl, halogen, -NO of2、-CN、-OH、C6-C20Aryl of (C)3-C6Cycloalkyl groups of (a).
R2Selected from hydrogen, C1-20Alkyl of (C)6-20Aryl group of (1).
Wherein each R is2The alkyl and aryl moieties in the substituents may optionally be substituted by one or more groups selected from C1-C6Alkyl of (C)1-C6Alkoxy group of (C)1-C6Acyl, halogen, -NO of2、-CN、-OH、C6-C20Aryl of (C)3-C6Cycloalkyl groups of (a).
In the formulae II and IV, R3Represents one or more substituents on the attached phenyl ring selected from hydrogen, C1-C20Alkyl of (C)1-C20Alkoxy group of (C)1-C20Alkylthio of, C6-C20Aryl of (C)4-C20Heteroaryl of (A), C3-C20Cycloalkyl, nitro, halogen, -OH, -SH, -CN, -COOR9、-COR10、-OCOR11、-NR12R13(ii) a Wherein R is9、R10、R11、R12、R13Each independently selected from hydrogen and C1-C20Alkyl of (C)6-C20Aryl of (C)5-C20Heteroaryl of (A), C3-C20Any one or more of cycloalkyl groups of (a).
Wherein each R is3The alkyl, aryl, heteroaryl, cycloalkyl moieties in the substituents may optionally be substituted by one or more groups selected from C1-C6Alkyl of (C)1-C6Alkoxy group of (C)1-C6Acyl, halogen, -NO of2、-CN、-OH、C6-C20Aryl of (C)3-C6Cycloalkyl groups of (a). And, R3The substituents not being in "-NR3R4"para position.
R4,R5Independently of one another, from hydrogen, C1-C20Alkyl of (C)2-C20Alkenyl of, C6-C20Aryl of (C)4-C20Heteroaryl of (A), C3-C20Cycloalkyl groups of (a); or R4,R5Together with the attached N atom, form a heterocyclic group of 5 to 8 ring atoms with or without other heteroatoms.
Wherein each R is4,R5The alkyl, alkenyl, aryl, heteroaryl, cycloalkyl, heterocyclyl moieties in the group may optionally be substituted by one or more groups selected from C1-C6Alkyl of (C)1-C6Alkoxy group of (C)1-C6Acyl, halogen, -NO of2、-CN、-OH、C6-C20Aryl of (C)3-C6Cycloalkyl groups of (a).
In the formulae III and IV, R6,R7Independently of one another, from hydrogen, halogen, C1-C20Alkyl of R14OCO-, wherein R14Is selected from C1-20Alkyl groups of (a); or R6、R7Together with the carbon atom to which they are attached to formCyclic hydrocarbon groups of 3 to 6 ring atoms.
Wherein R is as defined above6、R7The alkyl, hydrocarbyl moieties in the group may optionally be substituted by one or more groups selected from C1-C6Alkyl of (C)1-C6Alkoxy group of (C)1-C6Acyl, halogen, -NO of2、-CN、-OH、C6-C20Aryl of (C)3-C6Cycloalkyl groups of (a).
R8Is selected from C1-20Alkyl of (C)6-20Aryl group of (1).
Wherein each R is8The alkyl and aryl moieties in the substituents may optionally be substituted by one or more groups selected from C1-C6Alkyl of (C)1-C6Alkoxy group of (C)1-C6Acyl, halogen, -NO of2、-CN、-OH、C6-C20Aryl of (C)3-C6Cycloalkyl groups of (a).
Preferably, in the formula I and the formula IV,
Figure BDA0001695054890000041
is represented by C6-12Aryl of (C)4-12The heteroaryl group of (a);
R1to represent
Figure BDA0001695054890000042
One or more substituents on the ring, preferably selected from hydrogen, C1-C6Alkyl of (C)1-C6Alkoxy group of (C)6-C12Aryl of (C)5-C12Heteroaryl of (A), C3-C6Cycloalkyl, nitro, halogen, -OH, -SH, -CN, -COOR9、-COR10、-OCOR11、-NR12R13(ii) a Wherein R is9、R10、R11、R12、R13Each independently selected from hydrogen and C1-C6Alkyl of (C)6-C12Aryl of (C)4-C12Heteroaryl of (A), C3-C6Cycloalkanes ofAny one or more of the above groups.
Wherein each R is1The alkyl, aryl, heteroaryl, cycloalkyl moieties in the substituents may optionally be substituted by one or more groups selected from C1-C6Alkyl of (C)1-C6Alkoxy group of (C)1-C6Acyl, halogen, -NO of2、-CN、-OH、C6-C12Aryl of (C)3-C6Cycloalkyl groups of (a).
R2Preferably selected from hydrogen, C1-6Alkyl of (C)6-12Aryl group of (1).
Wherein each R is2The alkyl and aryl moieties in the substituents may optionally be substituted by one or more groups selected from C1-C6Alkyl of (C)1-C6Alkoxy group of (C)1-C6Acyl, halogen, -NO of2、-CN、-OH、C6-C12Aryl of (C)3-C6Cycloalkyl groups of (a).
In the formulae II and IV, R3Represents one or more substituents on the attached phenyl ring, preferably selected from hydrogen, C1-C6Alkyl of (C)1-C6Alkoxy group of (C)6-C12Aryl of (C)5-C12Heteroaryl of (A), C3-C6Cycloalkyl, nitro, halogen, -OH, -SH, -CN, -COOR9、-COR10、-OCOR11、-NR12R13(ii) a Wherein R is9、R10、R11、R12、R13Each independently selected from hydrogen and C1-C6Alkyl of (C)6-C12Aryl of (C)4-C12Heteroaryl of (A), C3-C6Any one or more of cycloalkyl groups of (a).
Wherein each R is3The alkyl, aryl, heteroaryl, cycloalkyl moieties in the substituents may optionally be substituted by one or more groups selected from C1-C6Alkyl of (C)1-C6Alkoxy group of (C)1-C6Acyl, halogen, -NO of2、-CN、-OH、C6-C12Aryl of (C)3-C6Cycloalkyl groups of (a). And, R3The substituents not being in "-NR3R4"para position.
Preferably, R4,R5Independently of one another, from hydrogen, C1-C6Alkyl of (C)2-C6Alkenyl of, C6-C12Aryl of (C)4-C12Heteroaryl of (A), C3-C6Cycloalkyl groups of (a); or R4,R5Together with the attached N atom, form a heterocyclic group of 5 to 8 ring atoms with or without other heteroatoms.
Wherein each R is4,R5The alkyl, alkenyl, aryl, heteroaryl, cycloalkyl, heterocyclyl moieties in the radical definitions may optionally be substituted by one or more groups selected from C1-C6Alkyl of (C)1-C6Alkoxy group of (C)1-C6Acyl, halogen, -NO of2、-CN、-OH、C6-C12Aryl of (C)3-C6Cycloalkyl groups of (a).
Preferably, in the formulae III and IV, R6,R7Independently of one another, from hydrogen, halogen, C1-C6Alkyl of R14OCO-, wherein R14Is selected from C1-6Alkyl groups of (a); or R6、R7Together with the carbon atom to which they are attached form a cyclic hydrocarbon group of 3 to 6 ring atoms.
Wherein R is as defined above6、R7The alkyl, hydrocarbyl moieties in the radical definitions may optionally be substituted by one or more groups selected from C1-C6Alkyl of (C)1-C6Alkoxy group of (C)1-C6Acyl, halogen, -NO of2、-CN、-OH、C6-C20Aryl of (C)3-C6Cycloalkyl groups of (a).
R8Is selected from C1-6Alkyl of (C)6-12Aryl group of (1).
Wherein each R is8Alkyl and aryl in the substituentThe moiety may optionally be substituted by one or more groups selected from C1-C6Alkyl of (C)1-C6Alkoxy group of (C)1-C6Acyl, halogen, -NO of2、-CN、-OH、C6-C12Aryl of (C)3-C6Cycloalkyl groups of (a).
Most preferably, in formula I and formula IV,
Figure BDA0001695054890000061
represents phenyl, naphthyl, thienyl, pyridyl;
R1to represent
Figure BDA0001695054890000062
One or more substituents on the ring, more preferably selected from hydrogen and C1-C6Alkyl of (C)1-C6Alkoxy, halogen.
Further preferably, R2Selected from hydrogen and phenyl.
In the formulae II and IV, R3Represents one or more substituents on the attached benzene ring, and is further preferably selected from hydrogen and C1-C6Alkyl of (C)1-C6Alkoxy, halogen. And, R3The substituents not being in "-NR3R4"para position.
Further preferably, R4,R5Independently of one another, from hydrogen, C1-6Alkyl of (C)6-12Aryl of (a); or R4,R5Together with the attached N atom, form a heterocyclic group of 5 to 6 ring atoms with or without other heteroatoms. Wherein each R is4,R5The heterocyclyl moiety in the radical definitions may optionally be substituted by one or more groups selected from C1-C6Alkyl of (C)1-C6Alkoxy group of (C)1-C6Acyl and halogen.
Further preferably, in formula III and formula IV, R6,R7Independently of one another, from hydrogen, halogen, C1-C6Alkyl of R14OCO-，Wherein R is14Is selected from C1-6Alkyl groups of (a); or R6、R7Together with the carbon atom to which they are attached form a cyclic hydrocarbon group of 3 to 6 ring atoms.
R8Is selected from C1-6Alkyl group of (1).
According to the preceding radical definitions of the invention, C1-C20Alkyl of (C)1-C6Alkyl of (a), and C1-C20Alkoxy group of (C)1-C6Alkoxy group of (C)1-C6Has C in the definition of acyl and the like1-C20、C1-C6The alkyl moiety of (a) may be selected from, for example, methyl, ethyl, propyl, butyl, pentyl, isopropyl, isobutyl, tert-butyl, n-hexyl, and the like.
According to the preceding radical definitions of the invention, C6-C20Aryl of (C)6-C12The aryl group of (a) may be selected from, for example, phenyl, naphthyl, anthryl, phenanthryl, and the like.
According to the preceding radical definitions of the invention, C4-C20Heteroaryl of (A), C4-C12The heteroatom in the heteroaryl group of (a) may be selected from O, S, N, and specific heteroaryl groups may be selected from, for example, thienyl, furyl, pyridyl, and the like.
According to the preceding radical definitions of the invention, C3-C20Cycloalkyl of, C3-C6Cycloalkyl groups of (a) may be selected from, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl.
According to the reaction of the invention, the photocatalyst is selected from [ Ru (bipy)3]Cl2·6H2O、[Ir(ppy)3]Or Eosin Y. Preferably, the photocatalysis is selected from [ Ru (bipy)3]Cl2·6H2O。
According to the above reaction of the present invention, the copper salt co-catalyst is selected from the group consisting of CuCl, CuOAc, CuI, CuCl2、Cu(OAc)2Any one of them. Preferably, the copper salt promoter is selected from CuCl.
According to the inventionThe aforementioned reaction, said base being selected from K2CO3、Cs2CO3、KOtBu. Preferably, the base is selected from K2CO3。
According to the aforementioned reaction of the present invention, the organic solvent is preferably selected from acetonitrile. The amount of the solvent used is not particularly limited so that each reaction material is sufficiently dispersed.
According to the reaction of the invention, the illumination condition is provided by a 3-5W blue LED light source, preferably a 3W blue LED light source.
According to the reactions of the present invention described above, the reaction time is determined by TLC or GC-MS monitoring, and in general, the reaction is completed in 2 hours.
According to the aforementioned reaction of the present invention, the inert atmosphere is an atmosphere inert to the reaction and is not mechanically considered to be an inert gas. It will be appreciated by those skilled in the art that the inert atmosphere commonly used for organic reactions may be selected from an argon atmosphere or a nitrogen atmosphere.
According to the reaction of the invention, the molar ratio of the p-substituted ethylene compound shown in formula I, the N, N-disubstituted aniline compound shown in formula II, the 2-bromo carboxylic ester compound shown in formula III, the photocatalyst, the copper salt cocatalyst and the base is 1 (1-3), 1-3, (0.01-0.05), 0.05-0.2 and (1-3). Preferably, the molar ratio of the p-substituted ethylene compound shown in the formula I, the N, N-disubstituted aniline compound shown in the formula II, the 2-bromo carboxylic ester compound shown in the formula III-1, the photocatalyst, the copper salt cocatalyst and the alkali is 1:2:2:0.02:0.1: 2.
The aforementioned reaction according to the present invention, wherein the post-treatment operation is as follows: and (3) concentrating the mixed solution after the reaction is finished under reduced pressure to obtain a residue, and separating the residue by column chromatography to obtain the target product of the 1, 1-diaryl alkane compound shown in the formula IV, wherein the eluent separated by the column chromatography is the mixed solution of normal hexane and ethyl acetate.
The invention has the following beneficial effects:
1. the invention reports a synthesis strategy for obtaining a series of 1, 1-diaryl alkane compounds shown in a formula IV by taking a p-substituted ethylene compound shown in a formula I, an N, N-disubstituted aniline compound shown in a formula II and a 2-bromo carboxylic ester compound shown in a formula III as raw materials under a photo-oxidation-reduction catalytic system for the first time, and the method is not reported in the prior art.
2. The method has the advantages of mild reaction conditions, simple operation, wide application range of reaction substrates, low cost of the generation process, capability of recycling the photocatalyst, environmental friendliness and high yield, and can be carried out at room temperature.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Examples 1-19 optimization of reaction conditions
P-methoxystyrene shown as a formula I-1, N-dimethylaniline shown as a formula II-1 and ethyl 2-methyl-2-bromopropionate shown as a formula III-1 are used as reaction raw materials, the influence of different reaction conditions on the optimization result of the synthesis process is discussed, and representative examples 1-19 are selected. The results are shown in table one.
Figure BDA0001695054890000091
A typical experimental procedure for example 1 is as follows:
to a Schlenk closed-tube reactor was added p-methoxystyrene of the formula I-1 (0.2mmol), N-dimethylaniline of the formula II-1 (2 equiv.), ethyl 2-methyl-2-bromopropionate of the formula III-1 (2 equiv.), CuCl (10 mol%), [ Ru (bipy)3]Cl2·6H2O(2mol％),K2CO3(2 equiv.) and MeCN (1mL), then reacting under the protection of argon at room temperature and under the illumination of a 3W blue LED lamp light source, monitoring the completion of the reaction by TLC or GC-MS, distilling under reduced pressure to remove the solvent, and separating the residue by column chromatography (the eluent is n-hexane/ethyl acetate) to obtain the target product of the formula IV-1. The yield is 78%; a colorless oily liquid;1H NMR(400MHz,CDCl3):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)；13CNMR(100MHz,CDCl3):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:
Figure BDA0001695054890000092
Figure BDA0001695054890000101
the specific operations and parameters of examples 2-19 were the same as in example 1, except that the variables listed in Table one above were different from those of example 1.
As can be seen from examples 1 to 19, light irradiation and a photocatalyst are essential factors for enabling the reaction (examples 2, 15), and different photocatalysts such as [ Ir (ppy)3]And Eosin Y have poor catalytic effects [ Ru (bipy) ]3]Cl2·6H2O, and catalyst [ Ru (bipy)3]Cl2·6H2Higher yields of the desired product were still obtained with O as low as 1 mol% (examples 3-6). The use of copper salt cocatalyst and alkali can greatly promote reaction, in which CuCl and K are used2CO3The effect was the best (examples 7 to 14). The power of the blue light source had little effect on the reaction, but the different wavelength sources had a greater effect on the reaction (examples 16-17). The reaction did not proceed smoothly under air conditions and the scale-up under the conditions of example 1 still gave nearly comparable yields to the target product (examples 18-19).
Based on the above representative condition optimization test results of examples 1 to 19, the reaction conditions of example 1 were selected as the optimum reaction conditions in view of the high price of the photocatalyst. On this basis, the inventors further selected reaction starting materials of different substituents to prepare various target compounds of formula IV.
Example 20
Figure BDA0001695054890000111
To a Schlenk closed-tube reactor was added p-methoxystyrene of the formula I-1 (0.2mmol), N-dimethylaniline of the formula II-1 (2 equiv.), methyl 2-methyl-2-bromopropionate of the formula III-2 (2 equiv.), CuCl (10 mol%), [ Ru (bipy)3]Cl2·6H2O(2mol％),K2CO3(2 equiv.) and MeCN (1mL), then reacting under the protection of argon at room temperature under the illumination of a 3W blue LED lamp light source, monitoring the completion of the reaction by TLC or GC-MS, distilling off the solvent under reduced pressure, and separating the residue by column chromatography (the eluent is n-hexane/ethyl acetate) to obtain the target product of formula IV-2. The yield is 63%; a colorless oily liquid;1H NMR(400MHz,CDCl3):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):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
example 21
Figure BDA0001695054890000112
To a Schlenk closed-tube reactor was added p-methoxystyrene of the formula I-1 (0.2mmol), N-dimethylaniline of the formula II-1 (2 equiv.), ethyl 2, 2-difluoro-2-bromoacetate of the formula III-3 (2 equiv.), CuCl (10 mol%), [ Ru (bipy)3]Cl2·6H2O(2mol％),K2CO3(2 equiv.) and MeCN (1mL), reacting under the protection of argon at room temperature under the illumination of 3W blue LED lamp light source, monitoring the completion of the reaction by TLC or GC-MS, distilling under reduced pressure to remove the solvent, and separating the residue by column chromatography (the eluent is n-hexane/ethyl acetate) to obtain the target compound of formula IV-3And (3) obtaining the product. The yield is 66%; a yellow oily liquid;1H NMR(400MHz,CDCl3):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):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)。
example 22
Figure BDA0001695054890000121
To a Schlenk closed-tube reactor was added p-methoxystyrene of the formula I-1 (0.2mmol), N-dimethylaniline of the formula II-1 (2 equiv.), the compound of the formula III-4 (2 equiv.), CuCl (10 mol%), [ Ru (bipy)3]Cl2·6H2O(2mol％),K2CO3(2 equiv.) and MeCN (1mL), then reacting under the protection of argon at room temperature under the illumination of a 3W blue LED lamp light source, monitoring the completion of the reaction by TLC or GC-MS, distilling off the solvent under reduced pressure, and separating the residue by column chromatography (the eluent is n-hexane/ethyl acetate) to obtain the target product of formula IV-4. The yield is 42%; a colorless oily liquid;1H NMR(400MHz,CDCl3):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):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)。
example 23
Figure BDA0001695054890000131
Adding p-methoxybenzene shown in formula I-1 into a Schlenk tube-sealed reactorEthylene (0.2mmol), N-dimethylaniline of formula II-1 (2 equiv.), methyl 2-bromopropionate of formula III-5 (2 equiv.), CuCl (10 mol%), [ Ru (bipy)3]Cl2·6H2O(2mol％),K2CO3(2 equiv.) and MeCN (1mL), then reacting under the protection of argon at room temperature under the illumination of a 3W blue LED lamp light source, monitoring the completion of the reaction by TLC or GC-MS, distilling off the solvent under reduced pressure, and separating the residue by column chromatography (the eluent is n-hexane/ethyl acetate) to obtain the target product of formula IV-5. The yield is 74 percent; a yellow oily liquid;1H NMR(400MHz,CDCl3):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):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)。
example 24
Figure BDA0001695054890000141
To a Schlenk closed-loop reactor was added p-methoxystyrene of the formula I-1 (0.2mmol), N-dimethylaniline of the formula II-1 (2 equiv.), ethyl 2-bromohexanoate of the formula III-6 (2 equiv.), CuCl (10 mol%), [ Ru (bipy)3]Cl2·6H2O(2mol％),K2CO3(2 equiv.) and MeCN (1mL) were then reacted under argon protection at room temperature under illumination with a 3W blue LED lamp, the completion of the reaction was monitored by TLC or GC-MS, the solvent was distilled off under reduced pressure, and the residue was separated by column chromatography (eluent n-hexane/ethyl acetate) to give the target product of formula IV-6. The yield is 68 percent; a colorless oily liquid;1H NMR(400MHz,CDCl3):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):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)。
example 25
Figure BDA0001695054890000142
To a Schlenk closed-tube reactor was added p-methoxystyrene of the formula I-1 (0.2mmol), N-dimethylaniline of the formula II-1 (2 equiv.), diethyl 2-bromomalonate of the formula III-7 (2 equiv.), CuCl (10 mol%), [ Ru (bipy)3]Cl2·6H2O(2mol％),K2CO3(2 equiv.) and MeCN (1mL) were then reacted under argon protection at room temperature under illumination with a 3W blue LED lamp source, the completion of the reaction was monitored by TLC or GC-MS, the solvent was distilled off under reduced pressure, and the residue was separated by column chromatography (eluent n-hexane/ethyl acetate) to give the target product of formula IV-7. The yield is 45 percent; a colorless oily liquid;1H NMR(400MHz,CDCl3):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):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)。
example 26
Figure BDA0001695054890000151
To a Schlenk closed-tube reactor was added p-methoxystyrene of the formula I-1 (0.2mmol), N-dimethylaniline of the formula II-1 (2 equiv.), dimethyl 2-bromomalonate of the formula III-8 (2 equiv.), CuCl (10 mol%), [ Ru (bipy)3]Cl2·6H2O(2mol％),K2CO3(2 equiv.) and MeCN (1mL), then reacting under the protection of argon at room temperature under the illumination of a 3W blue LED lamp light source, monitoring the completion of the reaction by TLC or GC-MS, distilling off the solvent under reduced pressure, and separating the residue by column chromatography (the eluent is n-hexane/ethyl acetate) to obtain the target product of formula IV-8. The yield is 43%; a colorless oily liquid;1H NMR(400MHz,CDCl3):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):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)。
EXAMPLE 27
Figure BDA0001695054890000161
To a Schlenk closed-tube reactor was added p-methoxystyrene of the formula I-1 (0.2mmol), N-dimethylaniline of the formula II-1 (2 equiv.), ethyl 2-bromoacetate of the formula III-9 (2 equiv.), CuCl (10 mol%), [ Ru (bipy)3]Cl2·6H2O(2mol％),K2CO3(2 equiv.) and MeCN (1mL) were then reacted under argon protection at room temperature under illumination with a 3W blue LED lamp source, the completion of the reaction was monitored by TLC or GC-MS, the solvent was distilled off under reduced pressure, and the residue was separated by column chromatography (eluent n-hexane/ethyl acetate) to give the target product of formula IV-9. The yield is 44%; a colorless oily liquid; 1H NMR (400MHz, CDCl3):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) 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.
Example 28
Figure BDA0001695054890000171
To a Schlenk closed-tube reactor was added p-methoxystyrene of the formula I-1 (0.2mmol), N-diethylaniline of the formula II-2 (2 equiv.), ethyl 2-methyl-2-bromopropionate of the formula III-1 (2 equiv.), CuCl (10 mol%), [ Ru (bipy)3]Cl2·6H2O(2mol％),K2CO3(2 equiv.) and MeCN (1mL) were then reacted under argon protection at room temperature under illumination with a 3W blue LED lamp source, the completion of the reaction was monitored by TLC or GC-MS, the solvent was distilled off under reduced pressure, and the residue was separated by column chromatography (eluent n-hexane/ethyl acetate) to give the target product of formula IV-10. The yield is 44%; a yellow oily liquid;1H NMR(400MHz,CDCl3):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):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。
example 29
Figure BDA0001695054890000172
To a Schlenk closed-tube reactor was added p-methoxystyrene of the formula I-1 (0.2mmol), N-dipropylaniline of the formula II-3 (2 equiv.), ethyl 2-methyl-2-bromopropionate of the formula III-1 (2 equiv.), CuCl (10 mol%), [ Ru (bipy)3]Cl2·6H2O(2mol％),K2CO3(2 equiv.) and MeCN (1mL) were then reacted under argon protection at room temperature under illumination with a 3W blue LED lamp source, the completion of the reaction was monitored by TLC or GC-MS, the solvent was distilled off under reduced pressure, and the residue was separated by column chromatography (eluent n-hexane/ethyl acetate) to give the target product of formula IV-11. The yield is 62%; a yellow oily liquid;1H NMR(400MHz,CDCl3):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):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。
example 30
Figure BDA0001695054890000181
To a Schlenk closed-tube reactor was added p-methoxystyrene of the formula I-1 (0.2mmol), N-methyl-N-phenylaniline of the formula II-4 (2 equiv.), ethyl 2-methyl-2-bromopropionate of the formula III-1 (2 equiv.), CuCl (10 mol%), [ Ru (bipy)3]Cl2·6H2O(2mol％),K2CO3(2 equiv.) and MeCN (1mL) were then reacted under argon protection at room temperature under illumination with a 3W blue LED lamp, the completion of the reaction was monitored by TLC or GC-MS, the solvent was distilled off under reduced pressure, and the residue was separated by column chromatography (n-hexane/ethyl acetate as eluent) to give the target product of formula IV-12. The yield is 47%; a yellow oily liquid;1H NMR(400MHz,CDCl3):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)；13CNMR(100MHz,CDCl3):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.。
example 31
Figure BDA0001695054890000191
To a Schlenk closed-tube reactor, p-methoxystyrene (0.2mmol) represented by formula I-1, a compound (2 equivalents) represented by formula II-5, and 2-methyl-2-bromo represented by formula III-1 were addedEthyl (2 equiv.) propionate, CuCl (10 mol%), [ Ru (bipy)3]Cl2·6H2O(2mol％),K2CO3(2 equiv.) and MeCN (1mL) were then reacted under argon protection at room temperature under illumination with a 3W blue LED lamp source, the completion of the reaction was monitored by TLC or GC-MS, the solvent was distilled off under reduced pressure, and the residue was separated by column chromatography (eluent n-hexane/ethyl acetate) to give the target product of formula IV-13. The yield is 49%; a yellow oily liquid;1H NMR(400MHz,CDCl3):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)；13CNMR(100MHz,CDCl3):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。
example 32
Figure BDA0001695054890000201
To a Schlenk closed-tube reactor was added p-methoxystyrene of the formula I-1 (0.2mmol), a compound of the formula II-6 (2 equiv.), ethyl 2-methyl-2-bromopropionate of the formula III-1 (2 equiv.), CuCl (10 mol%), [ Ru (bipy)3]Cl2·6H2O(2mol％),K2CO3(2 equiv.) and MeCN (1mL) were then reacted under argon protection at room temperature under illumination with a 3W blue LED lamp source, the completion of the reaction was monitored by TLC or GC-MS, the solvent was distilled off under reduced pressure, and the residue was separated by column chromatography (eluent n-hexane/ethyl acetate) to give the target product of formula IV-14. The yield is 38%; a yellow oily liquid;1H NMR(400MHz,CDCl3):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):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。
example 33
Figure BDA0001695054890000202
To a Schlenk closed-tube reactor was added p-methoxystyrene of the formula I-1 (0.2mmol), a compound of the formula II-2 (2 equiv.), ethyl 2-methyl-2-bromopropionate of the formula III-1 (2 equiv.), CuCl (10 mol%), [ Ru (bipy)3]Cl2·6H2O(2mol％),K2CO3(2 equiv.) and MeCN (1mL), then reacting under the protection of argon at room temperature under the illumination of a 3W blue LED lamp light source, monitoring the completion of the reaction by TLC or GC-MS, distilling off the solvent under reduced pressure, and separating the residue by column chromatography (the eluent is n-hexane/ethyl acetate) to obtain the target product of formula IV-15. The yield is 28%; a yellow oily liquid;1H NMR(400MHz,CDCl3):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)；13CNMR(100MHz,CDCl3):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。
example 34
Figure BDA0001695054890000211
To a Schlenk closed-tube reactor was added p-methoxystyrene of the formula I-1 (0.2mmol), a compound of the formula II-8 (2 equiv.), ethyl 2-methyl-2-bromopropionate of the formula III-1 (2 equiv.), CuCl (10 mol%), [ Ru (bipy)3]Cl2·6H2O(2mol％),K2CO3(2 equiv.) and MeCN (1mL) were then reacted under argon protection at room temperature under illumination with a 3W blue LED lamp source, the completion of the reaction was monitored by TLC or GC-MS, the solvent was distilled off under reduced pressure, and the residue was separated by column chromatography (eluent n-hexane/ethyl acetate) to give the target product of formula IV-16.The yield is 67%; a yellow oily liquid;1H NMR(400MHz,CDCl3):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):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。
example 35
Figure BDA0001695054890000221
To a Schlenk closed-tube reactor was added p-ethoxystyrene of the formula I-2 (0.2mmol), N-dimethylaniline of the formula II-1 (2 equiv.), ethyl 2-methyl-2-bromopropionate of the formula III-1 (2 equiv.), CuCl (10 mol%), [ Ru (bipy)3]Cl2·6H2O(2mol％),K2CO3(2 equiv.) and MeCN (1mL) were then reacted under argon protection at room temperature under illumination with a 3W blue LED lamp, the completion of the reaction was monitored by TLC or GC-MS, the solvent was distilled off under reduced pressure, and the residue was separated by column chromatography (n-hexane/ethyl acetate as eluent) to give the target product of formula IV-17. The yield is 85%; a yellow oily liquid;1H NMR(400MHz,CDCl3):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):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。
example 36
Figure BDA0001695054890000231
To a Schlenk closed-tube reactor was added p-methylstyrene (0.2mmol) represented by formula I-3 and N, N represented by formula II-1-dimethylaniline (2 eq), ethyl 2-methyl-2-bromopropionate of formula III-1 (2 eq), CuCl (10 mol%), [ Ru (bipy)3]Cl2·6H2O(2mol％),K2CO3(2 equiv.) and MeCN (1mL) were then reacted under argon protection at room temperature under illumination with a 3W blue LED lamp, the completion of the reaction was monitored by TLC or GC-MS, the solvent was distilled off under reduced pressure, and the residue was separated by column chromatography (n-hexane/ethyl acetate as eluent) to give the target product of formula IV-18. The yield is 52%; a yellow oily liquid;1H NMR(400MHz,CDCl3):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):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。
example 37
Figure BDA0001695054890000232
To a Schlenk closed-loop reactor was added m-methylstyrene of the formula I-4 (0.2mmol), N-dimethylaniline of the formula II-1 (2 equiv.), ethyl 2-methyl-2-bromopropionate of the formula III-1 (2 equiv.), CuCl (10 mol%), [ Ru (bipy)3]Cl2·6H2O(2mol％),K2CO3(2 equiv.) and MeCN (1mL) were then reacted under argon protection at room temperature under illumination with a 3W blue LED lamp source, the completion of the reaction was monitored by TLC or GC-MS, the solvent was distilled off under reduced pressure, and the residue was separated by column chromatography (eluent n-hexane/ethyl acetate) to give the target product of formula IV-19. The yield is 27%; a yellow oily liquid;1H NMR(400MHz,CDCl3):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):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。
example 38
Figure BDA0001695054890000241
To a Schlenk closed-loop reactor was added o-methylstyrene of the formula I-5 (0.2mmol), N-dimethylaniline of the formula II-1 (2 equiv.), ethyl 2-methyl-2-bromopropionate of the formula III-1 (2 equiv.), CuCl (10 mol%), [ Ru (bipy)3]Cl2·6H2O(2mol％),K2CO3(2 equiv.) and MeCN (1mL) were then reacted under argon protection at room temperature under illumination with a 3W blue LED lamp, the completion of the reaction was monitored by TLC or GC-MS, the solvent was distilled off under reduced pressure, and the residue was separated by column chromatography (n-hexane/ethyl acetate as eluent) to give the target product of formula IV-20. The yield is 43%; a yellow oily liquid;1H NMR(400MHz,CDCl3):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):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。
example 40
Figure BDA0001695054890000251
To a Schlenk closed-tube reactor was added o-methoxystyrene of the formula I-6 (0.2mmol), N-dimethylaniline of the formula II-1 (2 equiv.), ethyl 2-methyl-2-bromopropionate of the formula III-1 (2 equiv.), CuCl (10 mol%), [ Ru (bipy)3]Cl2·6H2O(2mol％),K2CO3(2 equiv.) and MeCN (1mL), then reacting under the protection of argon at room temperature and under the illumination condition of a 3W blue LED lamp light source, monitoring the completion of the reaction by TLC or GC-MS, distilling under reduced pressure to remove the solvent, and separating the residue by column chromatography (the eluent is n-hexane/ethyl acetate) to obtain the formula IV-21, target product of (1). The yield is 68 percent; a yellow oily liquid;1H NMR(400MHz,CDCl3):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):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。
EXAMPLE 41
Figure BDA0001695054890000261
To a Schlenk closed-loop reactor was added 2, 3-dimethoxystyrene of the formula I-7 (0.2mmol), N-dimethylaniline of the formula II-1 (2 equiv.), ethyl 2-methyl-2-bromopropionate of the formula III-1 (2 equiv.), CuCl (10 mol%), [ Ru (bipy)3]Cl2·6H2O(2mol％),K2CO3(2 equiv.) and MeCN (1mL) were then reacted under argon protection at room temperature under illumination with a 3W blue LED lamp source, the completion of the reaction was monitored by TLC or GC-MS, the solvent was distilled off under reduced pressure, and the residue was separated by column chromatography (eluent n-hexane/ethyl acetate) to give the target product of formula IV-22. The yield is 66%; a yellow oily liquid;1H NMR(400MHz,CDCl3):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):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。
example 42
Figure BDA0001695054890000262
2-naphthylethylene (0.2mmol) shown in formula I-8, N-dimethylaniline (2 equivalents) shown in formula II-1 and N, N-dimethylaniline (2 equivalents) shown in formula III-1 are added into a Schlenk tube-sealed reactorShown as ethyl 2-methyl-2-bromopropionate (2 eq.), CuCl (10 mol%), [ Ru (bipy)3]Cl2·6H2O(2mol％),K2CO3(2 equiv.) and MeCN (1mL) were then reacted under argon protection at room temperature under illumination with a 3W blue LED lamp source, the completion of the reaction was monitored by TLC or GC-MS, the solvent was distilled off under reduced pressure, and the residue was separated by column chromatography (eluent n-hexane/ethyl acetate) to give the target product of formula IV-23. 33%; a yellow oily liquid;1H NMR(400MHz,CDCl3):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):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。
example 43
Figure BDA0001695054890000271
To a Schlenk closed-loop reactor was added 1, 1-diphenylethylene (0.2mmol) represented by the formula I-9, N-dimethylaniline (2 equiv.) represented by the formula II-1, ethyl 2-methyl-2-bromopropionate (2 equiv.) represented by the formula III-1, CuCl (10 mol%), [ Ru (bipy)3]Cl2·6H2O(2mol％),K2CO3(2 equiv.) and MeCN (1mL), then reacting under the protection of argon at room temperature under the illumination of a 3W blue LED lamp light source, monitoring the completion of the reaction by TLC or GC-MS, distilling off the solvent under reduced pressure, and separating the residue by column chromatography (the eluent is n-hexane/ethyl acetate) to obtain the target product of formula IV-24. The yield is 46%; a yellow oily liquid;1H NMR(400MHz,CDCl3):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):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。
the embodiments described above are only preferred embodiments of the invention and are not exhaustive of the possible implementations of the invention. Any obvious modifications to the above would be obvious to those of ordinary skill in the art, but would not bring the invention so modified beyond the spirit and scope of the present invention.

Claims (10)

1. A process for the preparation of a 1, 1-diarylalkane compound of formula IV, characterized in that it is carried out as follows: taking a substituted ethylene compound shown in a formula I, an N, N-disubstituted aniline compound shown in a formula II and a 2-bromo carboxylic ester compound shown in a formula III as reaction raw materials in a Schlenk tube-sealing reactor, adding a photocatalyst, a copper salt cocatalyst, an alkali and an organic solvent, reacting under the conditions of inert atmosphere protection, room temperature and illumination, monitoring the completion of the reaction through TLC or GC-MS, and carrying out post-treatment to obtain a 1, 1-diaryl alkane compound shown in a formula IV;
Figure FDA0002579027010000011
in the formula I and the formula IV,
Figure FDA0002579027010000012
is represented by C6-20Aryl of (C)4-20The heteroaryl group of (a);
R1to represent
Figure FDA0002579027010000013
One or more substituents on the ring selected from hydrogen, C1-C20Alkyl of (C)1-C20Alkoxy group of (C)1-C20Alkylthio of, C6-C20Aryl of (C)4-C20Heteroaryl of (A), C3-C20Cycloalkyl, nitro, halogen, -OH, -SH, -CN, -COOR9、-COR10、-OCOR11、-NR12R13(ii) a Wherein R is9、R10、R11、R12、R13Each independently selected from hydrogen and C1-C20Alkyl of (C)6-C20Aryl of (C)4-C20Heteroaryl of (A), C3-C20Any one or more of cycloalkyl groups of (a);
wherein each R is1The alkyl, aryl, heteroaryl, cycloalkyl moieties in the substituents may optionally be substituted by one or more groups selected from C1-C6Alkyl of (C)1-C6Alkoxy group of (C)1-C6Acyl, halogen, -NO of2、-CN、-OH、C6-C20Aryl of (C)3-C6Cycloalkyl of (a);
R2selected from hydrogen, C1-20Alkyl of (C)6-20Aryl of (a);
wherein each R is2The alkyl and aryl moieties in the substituents may optionally be substituted by one or more groups selected from C1-C6Alkyl of (C)1-C6Alkoxy group of (C)1-C6Acyl, halogen, -NO of2、-CN、-OH、C6-C20Aryl of (C)3-C6Cycloalkyl of (a);
in the formulae II and IV, R3Represents one or more substituents on the attached phenyl ring selected from hydrogen, C1-C20Alkyl of (C)1-C20Alkoxy group of (C)1-C20Alkylthio of, C6-C20Aryl of (C)4-C20Heteroaryl of (A), C3-C20Cycloalkyl, nitro, halogen, -OH, -SH, -CN, -COOR9、-COR10、-OCOR11、-NR12R13；
Wherein R is9、R10、R11、R12、R13Each independently selected from hydrogen and C1-C20Alkyl of (C)6-C20Aryl of (C)5-C20Heteroaryl of (A), C3-C20Any one of the cycloalkyl groups of (1)Or a plurality thereof;
wherein each R is3The alkyl, aryl, heteroaryl, cycloalkyl moieties in the substituents may optionally be substituted by one or more groups selected from C1-C6Alkyl of (C)1-C6Alkoxy group of (C)1-C6Acyl, halogen, -NO of2、-CN、-OH、C6-C20Aryl of (C)3-C6Cycloalkyl of (a); and, R3The substituents not being in "-NR3R4"para position;
R4,R5independently of one another, from hydrogen, C1-C20Alkyl of (C)2-C20Alkenyl of, C6-C20Aryl of (C)4-C20Heteroaryl of (A), C3-C20Cycloalkyl groups of (a); or R4,R5Heterocyclyl with or without other heteroatoms forming 5 to 8 ring atoms with the attached N atom;
wherein each R is4,R5The alkyl, alkenyl, aryl, heteroaryl, cycloalkyl, heterocyclyl moieties in the group may optionally be substituted by one or more groups selected from C1-C6Alkyl of (C)1-C6Alkoxy group of (C)1-C6Acyl, halogen, -NO of2、-CN、-OH、C6-C20Aryl of (C)3-C6Cycloalkyl of (a);
in the formulae III and IV, R6、R7Independently of one another, from hydrogen, halogen, C1-C20Alkyl of R14OCO-, wherein R14Is selected from C1-20Alkyl groups of (a); or R6、R7A cyclic hydrocarbon group forming 3 to 6 ring atoms together with the attached carbon atom;
wherein R is as defined above6、R7The alkyl, hydrocarbyl moieties in the group may optionally be substituted by one or more groups selected from C1-C6Alkyl of (C)1-C6Alkoxy group of (C)1-C6Acyl, halogen, -NO of2、-CN、-OH、C6-C20Aryl of (C)3-C6Cycloalkyl of (a);
R8is selected from C1-20Alkyl of (C)6-20Aryl of (a);
wherein each R is8The alkyl and aryl moieties in the substituents may optionally be substituted by one or more groups selected from C1-C6Alkyl of (C)1-C6Alkoxy group of (C)1-C6Acyl, halogen, -NO of2、-CN、-OH、C6-C20Aryl of (C)3-C6Cycloalkyl of (a);
wherein the photocatalyst is selected from [ Ru (bipy)3]Cl2·6H2O、[Ir(ppy)3]Any one of (a);
the copper salt cocatalyst is selected from any one of CuCl and CuOAc;
the base is selected from K2CO3、Cs2CO3Any one of them.
2. The method of claim 1, wherein in formula I and formula IV,
Figure FDA0002579027010000021
is represented by C6-12Aryl of (C)4-12The heteroaryl group of (a);
R1to represent
Figure FDA0002579027010000022
One or more substituents on the ring selected from hydrogen, C1-C6Alkyl of (C)1-C6Alkoxy group of (C)6-C12Aryl of (C)5-C12Heteroaryl of (A), C3-C6Cycloalkyl, nitro, halogen, -OH, -SH, -CN, -COOR9、-COR10、-OCOR11、-NR12R13(ii) a Wherein R is9、R10、R11、R12、R13Each independently selected from hydrogen and C1-C6Alkyl of (C)6-C12Aryl of (C)4-C12Heteroaryl of (A), C3-C6Any one or more of cycloalkyl groups of (a);
wherein each R is1The alkyl, aryl, heteroaryl, cycloalkyl moieties in the substituents may optionally be substituted by one or more groups selected from C1-C6Alkyl of (C)1-C6Alkoxy group of (C)1-C6Acyl, halogen, -NO of2、-CN、-OH、C6-C12Aryl of (C)3-C6Cycloalkyl of (a);
R2selected from hydrogen, C1-6Alkyl of (C)6-12Aryl of (a);
wherein each R is2The alkyl and aryl moieties in the substituents may optionally be substituted by one or more groups selected from C1-C6Alkyl of (C)1-C6Alkoxy group of (C)1-C6Acyl, halogen, -NO of2、-CN、-OH、C6-C12Aryl of (C)3-C6Cycloalkyl of (a);
in the formulae II and IV, R3Represents one or more substituents on the attached phenyl ring selected from hydrogen, C1-C6Alkyl of (C)1-C6Alkoxy group of (C)6-C12Aryl of (C)5-C12Heteroaryl of (A), C3-C6Cycloalkyl, nitro, halogen, -OH, -SH, -CN, -COOR9、-COR10、-OCOR11、-NR12R13(ii) a Wherein R is9、R10、R11、R12、R13Each independently selected from hydrogen and C1-C6Alkyl of (C)6-C12Aryl of (C)4-C12Heteroaryl of (A), C3-C6Any one or more of cycloalkyl groups of (a);
wherein each R is3The alkyl, aryl, heteroaryl, cycloalkyl moieties in the substituents may optionally be substituted by one or more groups selected from C1-C6Alkyl of (C)1-C6Alkoxy group of (C)1-C6Acyl, halogen, -NO of2、-CN、-OH、C6-C12Aryl of (C)3-C6Cycloalkyl of (a); and, R3The substituents not being in "-NR3R4"para position;
R4,R5independently of one another, from hydrogen, C1-C6Alkyl of (C)2-C6Alkenyl of, C6-C12Aryl of (C)4-C12Heteroaryl of (A), C3-C6Cycloalkyl groups of (a); or R4,R5Heterocyclyl with or without other heteroatoms forming 5 to 8 ring atoms with the attached N atom;
wherein each R is4,R5The alkyl, alkenyl, aryl, heteroaryl, cycloalkyl, heterocyclyl moieties in the radical definitions may optionally be substituted by one or more groups selected from C1-C6Alkyl of (C)1-C6Alkoxy group of (C)1-C6Acyl, halogen, -NO of2、-CN、-OH、C6-C12Aryl of (C)3-C6Cycloalkyl of (a);
in the formulae III and IV, R6,R7Independently of one another, from hydrogen, halogen, C1-C6Alkyl of R14OCO-, wherein R14Is selected from C1-6Alkyl groups of (a); or R6、R7A cyclic hydrocarbon group forming 3 to 6 ring atoms together with the attached carbon atom;
wherein R is as defined above6、R7The alkyl, hydrocarbyl moieties in the radical definitions may optionally be substituted by one or more groups selected from C1-C6Alkyl of (C)1-C6Alkoxy group of (C)1-C6Acyl, halogen, -NO of2、-CN、-OH、C6-C20Aryl of (C)3-C6Cycloalkyl of (a);
R8is selected from C1-6Alkyl of (C)6-12Aryl of (a);
wherein each R is8The alkyl and aryl moieties in the substituents may optionally be substituted by one or more groups selected from C1-C6Alkyl of (C)1-C6Alkoxy group of (C)1-C6Acyl, halogen, -NO of2、-CN、-OH、C6-C12Aryl of (C)3-C6Cycloalkyl groups of (a).
3. The method of claim 2, wherein in formula I and formula IV,
Figure FDA0002579027010000041
represents phenyl, naphthyl, thienyl, pyridyl;
R1to represent
Figure FDA0002579027010000042
One or more substituents on the ring selected from hydrogen, C1-C6Alkyl of (C)1-C6Alkoxy, halogen of (a);
R2selected from hydrogen and phenyl.
In the formulae II and IV, R3Represents one or more substituents on the attached phenyl ring selected from hydrogen, C1-C6Alkyl of (C)1-C6Alkoxy, halogen of (a); and, R3The substituents not being in "-NR3R4"para position;
R4,R5independently of one another, from hydrogen, C1-6Alkyl of (C)6-12Aryl of (a); or R4,R5Heterocyclyl with or without other heteroatoms forming 5 to 6 ring atoms with the attached N atom; wherein each R is4,R5The heterocyclyl moiety in the radical definitions may optionally be substituted by one or more groups selected from C1-C6Alkyl of (C)1-C6Alkoxy group of (C)1-C6Acyl and halogen of (a);
in the formulae III and IV, R6,R7Independently of one another, from hydrogen, halogen, C1-C6Alkyl of R14OCO-, wherein R14Is selected from C1-6Alkyl groups of (a); or R6、R7A cyclic hydrocarbon group forming 3 to 6 ring atoms together with the attached carbon atom;
R8is selected from C1-6Alkyl group of (1).
4. The method according to any one of claims 1 to 3, wherein the photocatalyst is [ Ru (bipy) ]3]Cl2·6H2O, the copper salt cocatalyst is selected from CuCl, and the alkali is selected from K2CO3。
5. A process according to any one of claims 1 to 3, wherein the organic solvent is selected from acetonitrile; the illumination condition is provided by a 3-5W blue LED light source.
6. The method of claim 5, wherein the lighting conditions are provided by a 3W blue LED light source.
7. The method according to any one of claims 1 to 3, wherein the inert atmosphere is a nitrogen atmosphere or an argon atmosphere.
8. The method according to any one of claims 1 to 3, wherein the molar ratio of the p-substituted ethylene compound of formula I, the N, N-disubstituted aniline compound of formula II, the 2-bromo carboxylic ester compound of formula III, the photocatalyst, the copper salt cocatalyst and the base is 1 (1-3): 0.01-0.05): 0.05-0.2): 1-3.
9. The method according to claim 7, wherein the molar ratio of the p-substituted ethylene compound shown in formula I, the N, N-disubstituted aniline compound shown in formula II, the 2-bromo carboxylic ester compound shown in formula III-1, the photocatalyst, the copper salt cocatalyst and the base is 1:2:2:0.02:0.1: 2.
10. The method of claim 1, wherein the post-processing operation is as follows: and (3) concentrating the mixed solution after the reaction is finished under reduced pressure to obtain a residue, and separating the residue by using column chromatography to obtain the target product shown in the formula IV, wherein the eluent separated by using the column chromatography is the mixed solution of normal hexane and ethyl acetate.
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