CN112047802A - Polysubstituted ethylene compound, preparation method and application thereof - Google Patents

Polysubstituted ethylene compound, preparation method and application thereof Download PDF

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CN112047802A
CN112047802A CN201910485350.4A CN201910485350A CN112047802A CN 112047802 A CN112047802 A CN 112047802A CN 201910485350 A CN201910485350 A CN 201910485350A CN 112047802 A CN112047802 A CN 112047802A
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林国强
唐本忠
冯陈国
秦安军
李梦尧
胡天骄
韩鹏博
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Shanghai Institute of Organic Chemistry of CAS
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Abstract

The invention discloses a polysubstituted ethylene compound, a preparation method and application thereof. The invention specifically discloses a preparation method of a polysubstituted ethylene compound shown as a formula III, which comprises the following steps: in an organic solvent, a compound shown as a formula I and a compound shown as a formula II are subjected to a reaction shown as follows in the presence of a palladium catalyst, a phosphine ligand and alkali to obtain a polysubstituted ethylene compound shown as a formula III. The preparation method can be suitable for various substrates, and the configuration of double bonds is controllable.

Description

Polysubstituted ethylene compound, preparation method and application thereof
Technical Field
The invention relates to the field of chemistry, and particularly relates to a polysubstituted ethylene compound, and a preparation method and application thereof.
Background
Substituted ethenes are widely present in natural products, active pharmaceutical intermediates and luminescent materials. Among them, the polyarylate substituted ethylene skeleton has been widely studied because of having an Aggregation Induced Emission (AIE) effect. In 2001, the Tang group discovered for the first time the aggregation-induced emission properties of silole compounds. Subsequently, cyano-substituted stilbene (CN-BPE), triphenylethylene (trise), and Tetraphenylethylene (TPE) compounds have been extensively studied due to their simple and stable molecular structure, simple synthesis steps, and significant AIE effect.
Figure BDA0002085216040000011
In 2002, subject group of Park et al (j.am. chem.soc.,2002,124,14410.) found that 1-cyano-trans-1, 2-bis (4-methylbiphenyl) ethylene (CN-MBE) had an aggregation-induced fluorescence enhancement (AIEE) effect. Subsequently, the cyanostilbene scaffolds have very broad applications in chemical sensing (Talanta,2013,107,332.), cellular imaging (j.mater.chem.b,2016,4,2614.), and stimulation response (j.am.chem.soc, 2010,132,13675).
Figure BDA0002085216040000012
In 2008, the Tang group (appl. phy. lett.2007,91,011111.) obtained a tetraphenylethylene backbone by Mcmurry olefination and found it to have significant AIE properties. Subsequently, the TPE framework as a light emitting layer has very wide application in deep blue OLED materials. Zhao et al, topic group (chem.commun.,2010,46,686.) butt-jointed two TPEs, and a sky blue OLED material was constructed using a TPE-TPE structure as a light emitting layer. In 2011, the Tang group (chem.mater.2011,23,2536.) introduced triphenylamine and other groups with charge transport properties into TPE, and the compounds were used as both light-emitting layer and hole transport layer to construct deep blue light-emitting OLED material, which is better than OLED material with additional hole transport layer.
Figure BDA0002085216040000021
In 2009, the Chi project group (j. mater. chem.,2009,19,5541.) found that the triphenylethylene (TriPE) -based skeleton was a blue-light material with AIE effect. In 2018, the Tang project group (adv.funct.mater, 2018,28, 1705609) designed and synthesized organic field effect transistor material (OFET) substituted by poly Perylenetetracarboxylic Diimide (PDI) with triphenylethylene (TriPE) as a framework, and the molecules have high quantum efficiency and electron mobility.
Figure BDA0002085216040000022
For multi-substituted ethylene compounds, the cis-trans of the carbon-carbon double bond has a great influence on the luminous properties of the compounds. In 2006, the Ma topic group (j.phys.chem.b., 2006,20999) studied the effect of cis-trans luminescence properties of the double bond of 1, 2-diaryl-substituted olefin compounds (cis-DPDSB/trans-DPDSB).
Figure BDA0002085216040000031
At present, the known method for synthesizing the polysubstituted ethylene mainly comprises a Wittig reaction, a Mcmmurry olefination reaction and a coupling reaction in which a transition metal participates. For the coupling of transition metal, firstly, a metal aryl species is formed by means of oxidation addition of aryl halide, transmetalation of an aryl boron reagent, aryl metal reagent and transition metal, guide group mediated C-H bond activation and the like, and then the metal aryl species and an alkyne compound carry out an alkyne insertion reaction or a Heck reaction with 1, 1-disubstituted olefin and 1, 2-disubstituted olefin, so that a polysubstituted ethylene compound is obtained, but the configuration of double bonds is not easy to control. For multi-substituted ethylene compounds, the Z/E isomers are often similar in polarity and difficult to separate.
Figure BDA0002085216040000032
Disclosure of Invention
The invention aims to solve the technical problem of providing a polysubstituted ethylene compound, and a preparation method and application thereof. The preparation method of the invention can be suitable for various substrates, and the configuration of double bonds is controllable.
The invention provides a preparation method of a polysubstituted ethylene compound shown as a formula III, which comprises the following steps: in an organic solvent, carrying out the following reaction on a compound shown as a formula I and a compound shown as a formula II in the presence of a palladium catalyst, a phosphine ligand and alkali to obtain a polysubstituted ethylene compound shown as a formula III;
Figure BDA0002085216040000041
wherein ring A is C6-16Aromatic rings (e.g. C)6-14An aromatic ring, such as a benzene ring or a naphthalene ring) or a 5-16 membered heteroaromatic ring (e.g., a 5-10 membered heteroaromatic ring, such as a pyridine ring);
each R3Independently of one another is fluorine, chlorine, cyano, C1-6Alkyl (e.g. methyl), C3-6Cycloalkyl radical, C1-6Alkoxy (e.g. methoxy), C3-6Cycloalkoxy or C1-6Haloalkyl (e.g., trifluoromethyl);
m is 0,1, 2, 3 or 4;
x is Br, I or OTf;
R1is C1-6Alkyl (e.g., isopropyl), cyano, and,
Figure BDA0002085216040000042
(e.g. in
Figure BDA0002085216040000043
)、C6-16Aryl (e.g. C)6-14Aryl, e.g. phenyl or naphthyl) or 5-16 membered heteroaryl (e.g. 5-10 membered heteroaryl, e.g. thienyl), C6-16Aryl or 5-16 membered heteroaryl optionally substituted with one or more (e.g. 1,2, 3 or 4) R1-1Substituted, wherein each R1-1Each independently of the others being fluorine, chlorine, cyano, C1-6Alkyl (e.g. methyl), C3-6Cycloalkyl radical, C1-6Alkoxy radicals (e.g. methoxy radicals),C3-6Cycloalkoxy or C1-6Haloalkyl (e.g., trifluoromethyl);
R6is C1-6An alkyl group;
ring B is C6-16Aromatic rings (e.g. C)6-14An aromatic ring, such as a benzene ring, a naphthalene ring, an anthracene ring, or a pyrene ring) or a 5-16 membered heteroaromatic ring (e.g., a 5-10 membered heteroaromatic ring, such as a furan ring, a thiophene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a benzopyridine ring, or a benzofuran ring);
each R5Each independently of the other being fluorine, chlorine, C1-6Alkyl (e.g. methyl), C3-6Cycloalkyl radical, C1-6Alkoxy (e.g. methoxy), C3-6Cycloalkoxy, cyano, nitro, aldehyde, amino,
Figure BDA0002085216040000051
Figure BDA0002085216040000052
(e.g. trimethylsilyl),
Figure BDA0002085216040000053
(e.g. in
Figure BDA0002085216040000054
)、
Figure BDA0002085216040000055
(e.g. in
Figure BDA0002085216040000056
)、
Figure BDA0002085216040000057
(e.g. in
Figure BDA0002085216040000058
)、
Figure BDA0002085216040000059
(e.g. in
Figure BDA00020852160400000510
) Or C1-6Haloalkyl (e.g., trifluoromethyl); wherein R is2-2、R2-3、R2-4、R2 -5、R2-6、R2-7、R2-8、R2-9、R2-10And R2-11Each independently is C1-6An alkyl group;
n is 0,1, 2, 3 or 4;
R4is composed of
Figure BDA00020852160400000511
(e.g. in
Figure BDA00020852160400000512
)、
Figure BDA00020852160400000513
(e.g. in
Figure BDA00020852160400000514
)、
Figure BDA00020852160400000515
Wherein R is51、R52、R53、R54、R55、R56、R57、R58、R59、R60、R61And R62Each independently is hydrogen or C1-6An alkyl group;
the heteroatoms in the heteroaromatic ring or heteroaryl group are each independently nitrogen, oxygen or sulfur, and the number of heteroatoms is independently 1,2, 3 or 4.
At R3、R1、R6、R5、R1-1、R2-2、R2-3、R2-4、R2-5、R2-6、R2-7、R2-8、R2-9、R2-10、R2-11、R51、R52、R53、R54、R55、R56、R57、R58、R59、R60、R61And R62In (b), the C1-6The alkyl groups may each independently be C1-4An alkyl group.
At R3、R5And R1-1In (b), the C1-6The alkoxy groups may each independently be C1-4An alkoxy group.
At R3、R5And R1-1In (b), the C1-6The haloalkyl groups may each independently be C1-4A haloalkyl group. In some embodiments of the invention, the halogen in the haloalkyl is fluorine.
In some embodiments of the invention, X is Br.
In some embodiments of the invention, R1Is C1-6Alkyl, cyano, or,
Figure BDA0002085216040000061
Figure BDA0002085216040000062
Wherein each R6And R1-1Each independently as defined herein, and each z is each independently 0,1, 2, 3, or 4.
In some embodiments of the invention, R1Is any one of the following structures:
Figure BDA0002085216040000063
wherein each R is1-1Each independently as defined herein.
In some embodiments of the invention, R1Is any one of the following structures:
Figure BDA0002085216040000064
in some embodiments of the present invention, the compound of formula I is selected from any of the following structures:
Figure BDA0002085216040000071
wherein each X, R1、R3And m are each independently as defined herein.
In some embodiments of the present invention, the compound of formula I is selected from any of the following structures:
Figure BDA0002085216040000072
wherein each X, R1And R3Each independently as defined herein.
In some embodiments of the present invention, the compound of formula I is selected from any of the following structures:
Figure BDA0002085216040000073
wherein each X, R1And R3Each independently as defined herein.
In some embodiments of the present invention, the compound of formula I is selected from any of the following structures:
Figure BDA0002085216040000081
in some embodiments of the present invention, the compound of formula II is selected from any of the following structures:
Figure BDA0002085216040000091
wherein each R is4、R5And n are each independently as defined herein.
In some embodiments of the present invention, the compound of formula II is selected from any of the following structures:
Figure BDA0002085216040000092
wherein each R is4And R5Each independently as defined herein.
In some embodiments of the present invention, the compound of formula II is selected from any of the following structures:
Figure BDA0002085216040000101
wherein each R is4Each independently as defined herein.
In some embodiments of the invention, R4Is composed of
Figure BDA0002085216040000102
Figure BDA0002085216040000103
In some embodiments of the invention, R4Is composed of
Figure BDA0002085216040000111
In some embodiments of the invention, R4Is composed of
Figure BDA0002085216040000112
In some embodiments of the present invention, the compound of formula II is selected from any of the following structures:
Figure BDA0002085216040000113
in some embodiments of the invention, the compound of formula III is of any of the following structures:
Figure BDA0002085216040000121
Figure BDA0002085216040000131
Figure BDA0002085216040000141
in some embodiments of the invention, the compound of formula I, the compound of formula II, and the corresponding compound of formula III are selected from the following structures:
Figure BDA0002085216040000142
Figure BDA0002085216040000151
Figure BDA0002085216040000161
Figure BDA0002085216040000171
the reaction is preferably carried out under oxygen-free conditions (e.g., the reaction is carried out under an inert gas atmosphere).
The phosphine ligand may be a phosphine ligand conventionally used in the Suzuki reaction in the art.
In some embodiments of the invention, the phosphine ligand is
Figure BDA0002085216040000172
Tris (2-furyl) phosphine, diphenyl-2-pyridylphosphine, benzyldiphenylphosphine, diphenylmethylphosphine, tricyclohexylphosphine tetrafluoroborate, bis-diphenylphosphinomethane1, 2-bis (diphenylphosphino) ethane, 1, 3-bis (diphenylphosphino) propane, 1, 4-bis (diphenylphosphino) butane, 1, 5-bis (diphenylphosphino) pentane, 1, 6-bis (diphenylphosphino) hexane, 2-dicyclohexylphosphine-2 ',6' -dimethoxy-1, 1' -biphenyl
Figure BDA0002085216040000173
1,1' -bis (diphenylphosphino) ferrocene
Figure BDA0002085216040000174
2-dicyclohexylphosphine-2 ',4',6 '-triisopropyl-1, 1' -biphenyl
Figure BDA0002085216040000175
4, 5-bis-diphenylphosphino-9, 9-dimethylxanthene
Figure BDA0002085216040000181
And bis (dicyclohexylphosphinophenyl) ether
Figure BDA0002085216040000182
Wherein R is100Is 0,1, 2, 3, 4 or 5, each R100Each independently is C1-4Alkyl (e.g. methyl), C1-4Alkoxy (e.g., methoxy), fluoro, or trifluoromethyl.
In some embodiments of the invention, the phosphine ligand is triphenylphosphine, tris (2-methoxyphenyl) phosphine, tris (3-methoxyphenyl) phosphine, tris (4-methoxyphenyl) phosphine, tris (2,4, 6-trimethoxyphenyl) phosphine, tris (4-tolyl) phosphine, tris (3-fluorophenyl) phosphine, tris (4-fluorophenyl) phosphine, tris [4- (trifluoromethyl) phenyl ] phosphine, tris (2, 6-dimethoxyphenyl) phosphine, tris (2-furyl) phosphine, diphenyl-2-pyridylphosphine, benzyldiphenylphosphine, diphenylmethylphosphine, tricyclohexylphosphine tetrafluoroborate, bis-diphenylphosphinomethane, 1, 2-bis (diphenylphosphino) ethane, 1, 3-bis (diphenylphosphino) propane, 1, 4-bis (diphenylphosphino) butane, 1, one or more of 5-bis (diphenylphosphino) pentane, 1, 6-bis (diphenylphosphino) hexane, 2-dicyclohexylphosphine-2 ',6' -dimethoxy-1, 1 '-biphenyl, 1' -bis (diphenylphosphino) ferrocene, 2-dicyclohexylphosphine-2 ',4',6 '-triisopropyl-1, 1' -biphenyl, 4, 5-bis-diphenylphosphino-9, 9-dimethylxanthene and bis (dicyclohexylphosphinophenyl) ether.
In some embodiments of the invention, the phosphine ligand is one or more of tris (2-methoxyphenyl) phosphine, tris (4-methoxyphenyl) phosphine, tricyclohexylphosphine tetrafluoroborate, 4, 5-bisdiphenylphosphino-9, 9-dimethylxanthene, and bis (dicyclohexylphosphinophenyl) ether.
In some embodiments of the invention, the phosphine ligand is tris (2-methoxyphenyl) phosphine.
The amount of the phosphine ligand may be an amount conventionally used in the art of phosphine ligands in Suzuki reactions.
In some embodiments of the invention, the molar ratio of the phosphine ligand to the compound of formula I is from 1:10 to 1: 20.
The base may be a base conventionally used in the Suzuki reaction in the art, such as an inorganic base.
In some embodiments of the invention, the base is an alkali metal carbonate (e.g., sodium carbonate, potassium carbonate, cesium carbonate), an alkali metal and C1-4Salts of alkyl-COOH (e.g., salts of alkali metals with acetic acid, salts of alkali metals with pivalic acid, such as sodium acetate, potassium acetate, cesium acetate, salts of alkali metals with pivalic acid, such as sodium pivalate, potassium pivalate, cesium pivalate) and one or more of alkali metal fluorides (e.g., sodium fluoride, potassium fluoride, cesium fluoride).
In some embodiments of the invention, the base is one or more of sodium carbonate, potassium carbonate, cesium carbonate, sodium acetate, potassium acetate, cesium acetate, sodium fluoride, potassium fluoride, cesium fluoride, sodium pivalate, potassium pivalate, and cesium pivalate.
In some embodiments of the invention, the base is cesium with C1-4Salts of alkyl-COOH.
In some embodiments of the invention, the base is cesium pivalate.
The amount of the base may be that conventionally used in the Suzuki reaction in the art.
In some embodiments of the invention, the molar ratio of the base to the compound of formula I may be from 1:1 to 5:1, for example from 1.5:1 to 2: 1.
The organic solvent may be an organic solvent conventionally used in the Suzuki reaction in the art.
In some embodiments of the invention, the organic solvent is one or more of an ether solvent (e.g., tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, ethylene glycol dimethyl ether, methyl tert-butyl ether, anisole, diethyl ether), an alkane solvent (e.g., N-hexane), an alcohol solvent (e.g., ethanol), an aromatic hydrocarbon solvent (e.g., toluene), an ester solvent (e.g., ethyl acetate), a halogenated hydrocarbon solvent (e.g., 1, 2-dichloroethane), a nitrile solvent (e.g., acetonitrile), and an amide solvent (e.g., N-dimethylformamide).
In some embodiments of the invention, the organic solvent is one or more of tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, ethylene glycol dimethyl ether, methyl tert-butyl ether, anisole, diethyl ether, N-hexane, ethanol, toluene, ethyl acetate, 1, 2-dichloroethane, acetonitrile, and N, N-dimethylformamide.
In some embodiments of the invention, the organic solvent is one or more of tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, methyl tert-butyl ether, anisole, diethyl ether, N-hexane, ethanol, ethyl acetate, acetonitrile and N, N-dimethylformamide.
In some embodiments of the invention, the organic solvent is tetrahydrofuran.
The amount of the organic solvent to be used may not be particularly limited as long as the reaction is not affected.
The temperature of the reaction may be a reaction temperature conventional in the Suzuki reaction in the art.
In some embodiments of the invention, the temperature of the reaction is from 50 ℃ to 110 ℃, e.g., from 80 ℃ to 110 ℃.
The molar ratio of the compound shown in the formula II to the compound shown in the formula I can be 1:1-10:1, such as 3:1-5: 1.
The palladium catalyst may be a palladium catalyst conventional in the art for the Suzuki reaction, such as tris (dibenzylideneacetone) dipalladium (Pd)2dba3) Palladium chloride (PdCl)2) Two, two(triphenylphosphine) Palladium dichloride (PdCl)2(PPh3)2) Bis (cyanophenyl) palladium dichloride (PdCl)2(PhCN)2) Diallyl palladium dichloride (PdCl)2(C3H5)2) And palladium bis (acetylacetonate).
In some embodiments of the invention, the palladium catalyst is one or more of tetrakis (triphenylphosphine) palladium, palladium acetate, palladium chloride, bis (triphenylphosphine) palladium dichloride, bis (cyanophenyl) palladium dichloride, diallylpalladium dichloride, and bis (acetylacetonato) palladium.
In some embodiments of the invention, the palladium catalyst is palladium acetate.
The amount of the palladium catalyst may be an amount conventionally used for a palladium catalyst in a Suzuki reaction in the art.
In some embodiments of the invention, the molar ratio of the palladium catalyst to the compound of formula I is from 0.025:1 to 0.20:1, such as from 0.05:1 to 0.1: 1.
The progress of the reaction can be monitored by conventional testing methods in the art (e.g., TLC, HPLC, GC, or NMR), and is generally determined as the end point of the reaction when the compound of formula I is no longer reacted.
The present invention also provides a compound selected from any one of the following structures:
Figure BDA0002085216040000201
Figure BDA0002085216040000211
Figure BDA0002085216040000221
the invention also provides application of the compound as an organic electroluminescent material.
The organic electroluminescent material can be applied to the preparation of deep blue light emitting OLED materials, near infrared emitting OFET materials and the like.
In the present invention, unless otherwise indicated, the following terms appearing in the specification and claims have the following meanings:
in the present invention, the term "substituted" or "substituent" means that one or more hydrogen atoms are replaced by the specified group. When the position of substitution is not indicated, the substitution may be at any position, but formation of a stable or chemically feasible chemical is permissible.
In the present invention, the term "optional" or "optionally" means that the subsequently described event or circumstance may, but need not, occur, and that the description includes instances where said event or circumstance occurs and instances where it does not. For example, the term "optionally substituted" means that it may or may not be substituted, and unless otherwise specified, the kind and number of substituents may be arbitrary on the basis that they are chemically realizable.
When any variable (e.g., R) occurs more than one time in the composition or structure of a compound, its definition in each case is independent. Thus, for example, if a group is substituted with 0-2R, the group may optionally be substituted with up to two R, and there are separate options for R in each case. Furthermore, combinations of substituents and/or variants thereof are permissible only if such combinations result in stable compounds.
In the present invention, the term "alkyl" refers to a saturated, straight or branched chain, monovalent hydrocarbon radical having the specified number of carbon atoms. Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl.
In the present invention, the term "alkoxy" refers to an alkyl group attached to the rest of the molecule through an oxygen bridge.
In the present invention, the term "halogen" means fluorine, chlorine, bromine or iodine.
In the present invention, the term "haloalkyl" means an alkyl group in which one or more hydrogen atoms are replaced by halogen, the number of which may be one or more; when the number of the halogen is plural, the halogen may be the same or different. Examples of haloalkyl include, but are not limited to, trifluoromethyl and difluoromethyl.
In the present invention, the term "cycloalkyl" refers to a saturated monovalent cyclic hydrocarbon group having the specified number of ring carbon atoms, and the cycloalkyl group may be monocyclic or polycyclic, and may be a fused ring, spiro ring and bridged ring structure.
In the present invention, the term "cycloalkoxy" refers to a cycloalkyl group attached to the rest of the molecule through an oxygen bridge.
In the present invention, the term "aryl" or "aromatic ring" refers to an aromatic monocyclic or polycyclic (e.g., bicyclic or tricyclic) carbocycle. Examples of aryl groups include, but are not limited to, phenyl and naphthyl.
In the present invention, the term "heteroaryl" or "heteroaromatic ring" refers to an aromatic carbocyclic ring containing at least one heteroatom selected from nitrogen, oxygen and sulfur. Examples of heteroaryl groups include, but are not limited to, furyl, thienyl, benzothienyl, benzofuryl, quinolyl, isoquinolyl, isoxazolyl, and pyrazinyl.
The above preferred conditions can be arbitrarily combined to obtain preferred embodiments of the present invention without departing from the common general knowledge in the art.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows: provides a brand-new preparation method of polysubstituted ethylene compounds. The preparation method of the invention can be suitable for various substrates, and the configuration of double bonds is controllable.
Drawings
FIG. 1 is a single crystal diffractogram of the product 3bc of example 12.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Example 1
Synthesis of compound 3aa:
Figure BDA0002085216040000241
to a dry Schlenk tube, 3.4mg of Pd (OAc) was added under argon atmosphere2，10.6mg P(2-OMe-Ph)378mg 1aa (0.3mmol), 133mg 2aa (0.9mmol), 141mg CsOPiv, 3mL THF, warmed to 110 ℃ and stirred for 3 h. Quenching the reaction with 5mL of saturated ammonium chloride aqueous solution, extracting with 5mL of ethyl acetate for three times, washing the organic phase with saturated NaCl solution, drying the anhydrous sodium sulfate solid, concentrating, performing column chromatography with n-hexane as an eluent, and collecting the product band to obtain 73.0mg of 3aa white solid with a yield of 95%.
1H NMR(400MHz,CDCl3)7.37–7.25(m,8H),7.23–7.18(m,2H),7.16–7.07(m,3H),7.05–6.99(m,2H),6.96(s,1H).
Example 2
Synthesis of compound 3 ab:
Figure BDA0002085216040000242
starting from 1ab, the procedure is as in example 1, with a yield of 74%.
1H NMR(400MHz,CDCl3)7.36–7.26(m,5H),7.22(t,J＝7.4Hz,1H),7.17–7.09(m,4H),7.03(dd,J＝13.9,5.5Hz,4H),6.94(s,1H),2.30(s,3H)；EI-MS m/z(％):270(M+).
Example 3
Synthesis of compound 3 ac:
Figure BDA0002085216040000251
starting from 1ac, the procedure is as in example 1, with a yield of 72%.
1H NMR(400MHz,CDCl3)7.35–7.26(m,5H),7.17–7.02(m,9H),6.92(s,1H),2.38(s,3H)；EI-MS m/z(％):270(M+).
Example 4
Synthesis of compound 3 ad:
Figure BDA0002085216040000252
starting from 1ad, the procedure is as in example 1, with a yield of 78%.
1H NMR(400MHz,CDCl3)7.57(d,J＝8.1Hz,2H),7.38–7.30(m,5H),7.30–7.26(m,2H),7.19–7.12(m,3H),7.05–6.97(m,3H)；EI-MS m/z(％):324(M+).
Example 5
Synthesis of compound 3 ae:
Figure BDA0002085216040000261
starting with 1ae, the procedure is as in example 1, with a yield of 77%.
1H NMR(400MHz,CDCl3)7.36–7.27(m,5H),7.19–7.09(m,5H),7.08–7.04(m,2H),6.90(s,1H),6.89–6.86(m,1H),6.86–6.83(m,1H),3.83(s,3H)；EI-MS m/z(％):286(M+).
Example 6
Synthesis of compound 3 af:
Figure BDA0002085216040000262
starting from 1af, the procedure is described in example 1 with a yield of 85%.
1H NMR(400MHz,CDCl3)7.33–7.28(m,5H),7.16(ddd,J＝15.1,9.4,5.0Hz,5H),7.02(dd,J＝12.1,5.3Hz,4H),6.96(s,1H)；EI-MS m/z(％):274(M+).
Example 7
Synthesis of Compound 3 ag:
Figure BDA0002085216040000271
starting with 1ag, the procedure is as in example 1, 85% yield.
1H NMR(400MHz,CDCl3)7.35–7.26(m,7H),7.20–7.10(m,5H),7.07–7.01(m,2H),6.96(s,1H)；EI-MS m/z(％):290(M+).
Example 8
Synthesis of compound 3 ah:
Figure BDA0002085216040000272
starting from 1ah, the procedure is as in example 1, 91% yield.
1H NMR(400MHz,CDCl3)8.57(d,J＝5.9Hz,2H),7.33(t,J＝5.7Hz,3H),7.30–7.23(m,4H),7.20–7.12(m,5H),7.04(dd,J＝6.8,2.6Hz,3H)；EI-MS m/z(％):257(M+)；HRMS(ESI):m/z C19H16N[M+H]+Calculated value 258.1277, found value 258.1277.
Example 9
Synthesis of compound 3 ai:
Figure BDA0002085216040000273
starting from 1ai, the procedure is as in example 1, with a yield of 40%.
1H NMR(400MHz,CDCl3)7.85(d,J＝7.7Hz,1H),7.79(d,J＝8.4Hz,1H),7.75–7.66(m,2H),7.52–7.42(m,2H),7.32(tt,J＝4.9,3.1Hz,6H),7.06(d,J＝13.6Hz,6H).13C NMR(101MHz,CDCl3)143.78,142.56,138.10,137.43,133.77,132.86,129.72,129.47,128.83,128.75,128.37,128.29,128.24,128.17,127.95,127.86,127.71,126.97,126.16,126.12.
Example 10
Synthesis of Compound 3 ba:
Figure BDA0002085216040000281
see example 1 for operation with 97% yield starting from 1 ba.
1H NMR(400MHz,CDCl3)7.28(dd,J＝6.8,2.0Hz,1H),7.25–7.09(m,13H),6.61(s,1H),2.11(s,3H)；EI-MS m/z(％):270(M+).
Example 11
Synthesis of compound 3 bb:
Figure BDA0002085216040000282
starting from 1bb, the procedure is as in example 1, 69% yield.
1H NMR(400MHz,CDCl3)7.34(dd,J＝5.0,1.7Hz,3H),7.25–7.19(m,3H),7.18–7.09(m,6H),7.06–7.00(m,2H),6.96(s,1H),2.35(s,3H)；EI-MS m/z(％):270(M+).
Example 12
Synthesis of compound 3 bc:
Figure BDA0002085216040000291
starting from 1bc, the procedure is described in example 1, with a yield of 60%. 20mg of 3bc was dissolved in 0.2mL of methylene chloride at 50 ℃ and allowed to stand at-20 ℃. After 24h, white needle-like crystals precipitated, which were filtered off and subjected to single crystal diffraction tests. The single crystal diffractogram is shown in FIG. 1.
1H NMR(400MHz,CDCl3)7.30(s,3H),7.21(d,J＝7.4Hz,4H),7.11(d,J＝8.7Hz,5H),7.01(d,J＝6.6Hz,2H),6.93(s,1H),2.34(s,3H)；EI-MS m/z(％):270(M+).
Example 13
Synthesis of compound 3 bd:
Figure BDA0002085216040000292
starting from 1bd, the procedure is as in example 1, with a yield of 68%.
1H NMR(400MHz,CDCl3)7.28(dd,J＝17.9,11.4Hz,5H),7.15(d,J＝29.4Hz,5H),7.07–6.94(m,4H),6.90(s,1H)；EI-MS m/z(％):274(M+).
Example 14
Synthesis of Compound 3 be:
Figure BDA0002085216040000301
starting from 1be, the procedure is as in example 1, with a yield of 90%.
1H NMR(400MHz,CDCl3)7.33(dd,J＝4.9,1.6Hz,3H),7.29–7.21(m,4H),7.18(dd,J＝6.6,3.0Hz,2H),7.15–7.08(m,3H),7.01(dd,J＝7.4,2.0Hz,2H),6.94(s,1H)；EI-MS m/z(％):290(M+).
Example 15
Synthesis of compound 3 bf:
Figure BDA0002085216040000302
starting from 1bf, the procedure is as in example 1, with a yield of 79%.
1H NMR(400MHz,CDCl3)7.56(d,J＝8.3Hz,2H),7.42(d,J＝8.2Hz,2H),7.38–7.32(m,3H),7.21–7.18(m,2H),7.15(dd,J＝5.2,1.9Hz,3H),7.04(dd,J＝7.0,2.6Hz,2H),7.01(s,1H)；EI-MS m/z(％):324(M+).
Example 16
Synthesis of compound 3 bg:
Figure BDA0002085216040000303
starting from 1bg, the procedure is as in example 1, with a yield of 70%.
1H NMR(400MHz,CDCl3)7.36–7.29(m,3H),7.29–7.23(m,2H),7.23–7.17(m,2H),7.15–7.06(m,3H),7.04–6.97(m,2H),6.89(s,1H),6.87–6.82(m,2H),3.81(s,3H)；EI-MS m/z(％):324(M+).
Example 17
Synthesis of compound 3 bh:
Figure BDA0002085216040000311
starting from 1bh, the procedure is as in example 1, 67% yield.
1H NMR(400MHz,CDCl3)7.38(dd,J＝5.1,1.6Hz,3H),7.30(dd,J＝6.6,2.8Hz,2H),7.21(d,J＝5.1Hz,1H),7.09(t,J＝5.8Hz,3H),7.05(s,1H),6.99–6.90(m,3H),6.72(d,J＝3.5Hz,1H).13C NMR(101MHz,CDCl3)147.91,139.39,136.59,136.23,129.87,129.41,128.78,127.98,127.83,127.45,126.80,126.31,126.08,124.71；EI-MS m/z(％):262(M+)；HRMS(ESI):m/z C18H14S[M+H]+Calculated value 262.0816, found value 262.0821.
Example 18
Synthesis of Compound 3 bi:
Figure BDA0002085216040000312
starting from 1bi, the procedure is as in example 1, with a yield of 71%.
1H NMR(400MHz,CDCl3)7.86–7.72(m,3H),7.70(s,1H),7.52(dd,J＝8.6,1.8Hz,1H),7.48–7.41(m,2H),7.39–7.33(m,3H),7.30–7.22(m,3H),7.13(dd,J＝13.2,5.5Hz,4H),7.09–7.02(m,2H).13C NMR(101MHz,CDCl3)142.54,140.77,140.29,137.38,133.28,132.80,130.48,129.58,128.69,128.24,127.98,127.70,127.52,127.51,126.83,126.79,126.15,125.96,125.59；EI-MS m/z(％):306(M+)；HRMS(ESI):m/z C24H18[M+H]+Calculated value 306.1409, found value 306.1402.
Example 19
Synthesis of compound 3 bj:
Figure BDA0002085216040000321
starting from 1bj, the procedure is as in example 1, with a yield of 94%.
1H NMR(400MHz,CDCl3)8.10(d,J＝8.4Hz,1H),7.83(dd,J＝16.2,7.9Hz,2H),7.45(ddd,J＝10.9,9.6,7.0Hz,3H),7.41–7.33(m,1H),7.29–7.13(m,10H),6.80(s,1H)；EI-MS m/z(％):306(M+).
Example 20
Synthesis of compound 3 bk:
Figure BDA0002085216040000322
starting from 1bk, the procedure is as in example 1, in 88% yield.
1H NMR(400MHz,CDCl3)7.39–7.21(m,4H),7.16–7.08(m,2H),7.08–6.98(m,3H),6.85(d,J＝6.5Hz,2H),6.40(s,1H),3.12–2.44(m,1H),1.11(d,J＝6.8Hz,6H).13C NMR(101MHz,CDCl3)149.56,141.36,137.74,129.12,128.49,127.89,126.82,126.11,124.30,37.52,21.92.
Example 21
Synthesis of compound 3 bl:
Figure BDA0002085216040000331
starting from 1bl, the procedure is as in example 1, 88% yield.
1H NMR(400MHz,CDCl3)7.41–7.32(m,6H),7.31–7.19(m,3H),7.16(d,J＝7.3Hz,2H)；EI-MS m/z(％):205(M+).
Example 22
Synthesis of compound 3 bm:
Figure BDA0002085216040000332
starting from 1bm, the procedure is described in example 1, with a yield of 81%.
1H NMR(400MHz,CDCl3)7.85(s,1H),7.41–7.34(m,3H),7.24–7.10(m,5H),7.03(d,J＝7.2Hz,2H),3.79(s,3H).
Example 23
Synthesis of Compound 3 ca:
Figure BDA0002085216040000341
starting from 2ca, the procedure is described in example 1, with a yield of 76%.
1H NMR(400MHz,CDCl3)7.38(s,1H),7.37–7.28(m,9H),7.21–7.15(m,2H),7.10(d,J＝8.2Hz,2H),6.97(s,1H)；EI-MS m/z(％):324(M+).
Example 24
Synthesis of compound 3 cb:
Figure BDA0002085216040000342
starting from 2cb, the procedure is as in example 1, with a yield of 81%.
1H NMR(400MHz,CDCl3)7.38–7.26(m,8H),7.18(dd,J＝7.0,2.6Hz,2H),6.98(dd,J＝8.6,5.6Hz,2H),6.92(s,1H),6.81(t,J＝8.7Hz,2H)；EI-MS m/z(％):274(M+).
Example 25
Synthesis of compound 3 cc:
Figure BDA0002085216040000343
starting from 2cc, the procedure is as in example 1, with a yield of 76%.
1H NMR(400MHz，CDCl3)7.38–7.27(m，8H)，7.18(dd，J＝6.6，3.0Hz2H),7.09(d,J＝8.5Hz,2H),6.95(s,1H),6.92(s,1H),6.90(s,1H)；EI-MS m/z(％):290(M+).
Example 26
Synthesis of compound 3 cd:
Figure BDA0002085216040000351
starting from 2cd, the procedure is as in example 1, with a yield of 72%.
1H NMR(400MHz,CDCl3)7.36–7.27(m,7H),7.23(ddd,J＝9.3,6.6,1.8Hz,3H),6.95(d,J＝8.7Hz,2H),6.91(s,1H),6.67(d,J＝8.8Hz,2H),3.74(s,3H)；EI-MS m/z(％):286(M+).
Example 27
Synthesis of Compound 3 ce:
Figure BDA0002085216040000352
starting from 2ce, the procedure is described in example 1, yield 79%.
1H NMR(400MHz,CDCl3)7.37–7.26(m,8H),7.23–7.18(m,2H),6.97–6.88(m,5H),2.26(s,3H)；EI-MS m/z(％):270(M+).
Example 28
Synthesis of compound 3 cf:
Figure BDA0002085216040000361
starting from 2cf, the procedure is as in example 1, with a yield of 60%.
1H NMR(400MHz,CDCl3)7.38–7.28(m,5H),7.23–7.18(m,3H),7.15–7.07(m,3H),7.06–7.00(m,1H),6.97(s,1H),6.90–6.79(m,2H),2.33(s,3H)；EI-MS m/z(％):270(M+).
Example 29
Synthesis of compound 3 cg:
Figure BDA0002085216040000362
starting from 2cg, the procedure is as in example 1, with a yield of 44%.
1H NMR(400MHz,CDCl3)7.43–7.31(m,5H),7.18–7.08(m,3H),7.07–6.99(m,1H),6.99–6.90(m,4H),6.83(s,1H),2.12(s,6H).13C NMR(101MHz,CDCl3)144.31,143.41,140.20,136.86,136.13,129.74,128.40,128.13,127.66,127.50,127.40,127.20,127.15,126.69,20.55；EI-MS m/z(％):284(M+)；HRMS(ESI):m/z C20H17N[M+H]+Calculated value 284.1565, found value 284.1572.
Example 30
Synthesis of Compound 3 ch:
Figure BDA0002085216040000371
starting from 2ch, the procedure is described in example 1 with a yield of 83%.
1H NMR(400MHz,CDCl3)7.39(d,J＝8.3Hz,2H),7.37–7.30(m,8H),7.17(s,2H),7.08(d,J＝8.4Hz,2H),6.94(s,1H)；EI-MS m/z(％):281(M+).
Example 31
Synthesis of compound 3 ci:
Figure BDA0002085216040000372
starting from 2ci, the procedure is as in example 1, with a yield of 74%.
1H NMR(400MHz,CDCl3)7.98(d,J＝8.8Hz,2H),7.40–7.30(m,8H),7.17(dd,J＝7.1,2.3Hz,2H),7.13(d,J＝8.8Hz,2H),7.00(s,1H)；EI-MS m/z(％):301(M+).
Example 32
Synthesis of compound 3 cj:
Figure BDA0002085216040000373
starting from 2cj, the procedure is as in example 1, with a yield of 74%.
1H NMR(400MHz,CDCl3)7.31(dd,J＝6.7,2.8Hz,8H),7.22–7.16(m,4H),7.04(d,J＝8.1Hz,2H),6.95(s,1H),3.01(s,6H).13C NMR(101MHz,CDCl3)171.57,144.01,143.26,140.11,138.93,134.29,130.45,129.49,128.86,128.38,127.90,127.80,127.77,127.36,127.09.
Example 33
Synthesis of Compound 3 ck:
Figure BDA0002085216040000381
starting from 2ck, the procedure is described in example 1, with a yield of 63%.
1H NMR(400MHz,CDCl3)7.37–7.27(m,8H),7.23–7.19(m,2H),6.93(t,J＝7.8Hz,1H),6.88(s,1H),6.45(d,J＝7.8Hz,2H),6.33(s,1H),3.43(s,2H)；EI-MS m/z(％):271(M+)；HRMS(ESI):m/z C20H17N[M+H]+Calculated value 271.1361, found value 271.1362.
Example 34
Synthesis of compound 3 cl:
Figure BDA0002085216040000382
starting from 2cl, the procedure is described in example 1 with a yield of 76%.
1H NMR(400MHz,CDCl3)7.38–7.25(m,10H),7.25–7.19(m,2H),7.00(d,J＝7.9Hz,2H),6.95(s,1H),0.21(s,9H).13C NMR(101MHz,CDCl3)143.56,142.81,140.59,139.19,137.77,133.16,130.42,128.90,128.85,128.33,128.29,127.70,127.64,127.57,-1.01.
Example 35
Synthesis of Compound 3 cm:
Figure BDA0002085216040000391
starting from 2cm, the procedure is described in example 1 with a yield of 77%.
1H NMR(400MHz,CDCl3)9.89(s,1H),7.64(d,J＝8.2Hz,2H),7.40–7.29(m,8H),7.22–7.10(m,4H),7.00(s,1H).13C NMR(101MHz,CDCl3)191.83,146.06,143.95,142.87,139.79,134.48,130.37,130.10,129.57,128.95,128.46,128.32,128.11,127.94,126.96；EI-MS m/z(％):284(M+)；HRMS(ESI):m/z C21H16O[M+H]+Calculated value 284.1201, found value 284.1207.
Example 36
Synthesis of compound 3 cn:
Figure BDA0002085216040000392
starting from 2cn, the procedure is as in example 1, 84% yield.
1H NMR(400MHz,CDCl3)7.72(d,J＝8.4Hz,2H),7.38–7.29(m,8H),7.19(dd,J＝6.5,2.9Hz,2H),7.09(d,J＝8.3Hz,2H),6.99(s,1H),2.53(s,3H).13C NMR(101MHz,CDCl3)197.73,145.36,142.98,142.47,139.94,135.11,130.38,129.70,128.92,128.43,128.21,128.18,127.98,127.88,127.08,26.69；EI-MS m/z(％):298(M+)；HRMS(ESI):m/z C22H18O[M+H]+Calculated value 298.1358, found value 298.1364.
Example 37
Synthesis of compound 3 co:
Figure BDA0002085216040000401
starting from 2co, the procedure is described in example 1 with a yield of 65%.
1H NMR(400MHz,CDCl3)7.79(d,J＝8.4Hz,2H),7.33(d,J＝5.2Hz,8H),7.18(dd,J＝6.6,3.0Hz,2H),7.07(d,J＝8.3Hz,2H),6.98(s,1H),3.86(s,3H).13C NMR(101MHz,CDCl3)166.88,145.00,142.89,142.12,139.78,130.26,129.38,129.22,128.73,128.27,127.97,127.92,127.78,127.74,127.05,51.99；EI-MS m/z(％):314(M+)；HRMS(ESI):m/z C22H18O2[M+H]+Calculated value 314.1307, found value 314.1310.
Example 38
Synthesis of Compound 3 cp:
Figure BDA0002085216040000402
starting from 2cp, the procedure is as in example 1, 81% yield.
1H NMR(400MHz,CDCl3)7.37–7.26(m,3H),7.20(dd,J＝7.1,2.1Hz,1H),7.00(d,J＝8.4Hz,1H),6.96–6.88(m,1H),2.41(s,1H)；EI-MS m/z(％):302(M+).
Example 39
Synthesis of compound 3 cq:
Figure BDA0002085216040000411
starting from 2cq, the procedure is as in example 1, with a yield of 99%.
1H NMR(400MHz,CDCl3)7.68(d,J＝8.5Hz,2H),7.40–7.31(m,8H),7.21–7.13(m,4H),6.98(s,1H),3.01(s,3H).13C NMR(101MHz,CDCl3)146.43,143.15,142.54,139.41,137.94,130.20,130.19,129.00,128.43,128.39,128.18,127.85,127.08,125.99,44.51；EI-MS m/z(％):334(M+)；
Example 40
Synthesis of Compound 3 da:
Figure BDA0002085216040000412
starting from 2da, the procedure is as in example 1, with a yield of 66%.
1H NMR(400MHz,CDCl3)7.46–7.38(m,3H),7.34–7.28(m,4H),7.28–7.23(m,4H),7.14(d,J＝3.4Hz,2H),6.88(s,1H),5.61(d,J＝1.1Hz,1H).13C NMR(101MHz,CDCl3)142.61,142.56,142.31,141.01,140.76,130.04,128.97,128.36,127.71,127.34,126.98,123.56,117.69,110.18.
EXAMPLE 41
Synthesis of Compound 3 db:
Figure BDA0002085216040000421
starting from 2db, the procedure is described in example 1, with a yield of 76%.
1H NMR(400MHz,CDCl3)7.51–7.44(m,3H),7.37–7.27(m,7H),7.27–7.23(m,2H),7.04(d,J＝5.0Hz,1H),6.93(d,J＝3.2Hz,1H),6.87(dd,J＝5.0,3.7Hz,1H)；EI-MS m/z(％):262(M+)；HRMS(ESI):m/z C18H14S[M+H]+Calculated value 262.0816, found value 262.0822.
Example 42
Synthesis of Compound 3 dc:
Figure BDA0002085216040000422
starting from 2dc, the procedure is as in example 1, with a yield of 87%.
1H NMR(400MHz,CDCl3)8.90(s,1H),8.32(s,2H),7.42–7.30(m,8H),7.18(dd,J＝6.5,3.0Hz,2H),6.83(s,1H).13C NMR(101MHz,CDCl3)156.77,156.04,147.42,141.90,138.89,131.57,129.92,129.33,128.61,128.52,128.50,127.71,120.24.
Example 43
Synthesis of Compound 3 dd:
Figure BDA0002085216040000431
starting from 2dd, the procedure is described in example 1 with a yield of 70%.
1H NMR(400MHz,CDCl3)8.36(d,J＝1.8Hz,1H),8.32(dd,J＝4.7,1.3Hz,1H),7.39–7.29(m,8H),7.21–7.14(m,3H),7.01(dd,J＝7.9,4.8Hz,1H),6.93(s,1H)；EI-MS m/z(％):256(M-H)-.
Example 44
Synthesis of Compound 3 de:
Figure BDA0002085216040000432
starting from 2de, the procedure is as in example 1, with a yield of 65%.
1H NMR(400MHz,CDCl3)7.54–7.37(m,3H),7.37–7.15(m,7H),7.02(s,1H),6.89(s,1H),6.57(s,1H),3.72(s,3H)；EI-MS m/z(％):260(M+)；HRMS(ESI):m/z C18H17N2[M+H]+Calculated value 261.1386, found value 261.1386.
Example 45
Synthesis of compound 3 df:
Figure BDA0002085216040000433
starting from 2df, the procedure is as in example 1, with a yield of 97%.
1H NMR(400MHz,CDCl3)8.59(d,J＝2.1Hz,1H),8.03(d,J＝8.4Hz,1H),7.69(d,J＝1.9Hz,1H),7.62(ddd,J＝8.4,6.8,1.4Hz,1H),7.54(d,J＝8.1Hz,1H),7.50–7.42(m,1H),7.41–7.30(m,8H),7.28–7.19(m,3H),7.10(s,1H)；EI-MS m/z(％):307(M+)；HRMS(ESI):m/z C23H18N[M+H]+Calculated value 308.1434, found value 308.1433.
Example 46
Synthesis of compound 3 dg:
Figure BDA0002085216040000441
starting from 2dg, the procedure is as in example 1, with a yield of 63%.
1H NMR(400MHz,CDCl3)7.47(q,J＝5.0Hz,3H),7.37(dd,J＝7.9,1.3Hz,2H),7.31(dt,J＝8.2,5.4Hz,7H),7.19(t,J＝7.7Hz,1H),7.11(t,J＝7.4Hz,1H),7.07(s,1H),5.80(s,1H).13C NMR(101MHz,CDCl3)154.96,154.10,144.13,141.57,140.11,129.68,129.09,129.05,128.51,128.16,128.08,127.31,124.40,122.83,120.95,116.29,110.93,105.36；EI-MS m/z(％):296(M+)；HRMS(ESI):m/z C22H17O[M+H]+Calculated value 297.1274, found value 297.1274.
Example 47
Synthesis of compound 3 dh:
Figure BDA0002085216040000442
starting from 2dh, the procedure is as in example 1, 93% yield.
1H NMR(400MHz,CDCl3)8.15(dd,J＝6.2,3.4Hz,1H),7.82(dt,J＝6.8,3.6Hz,1H),7.64(d,J＝8.1Hz,1H),7.51–7.44(m,3H),7.42(dd,J＝7.9,1.6Hz,2H),7.39–7.30(m,3H),7.19–7.11(m,4H),7.08(dd,J＝7.7,1.8Hz,2H),7.04(d,J＝7.2Hz,1H)；EI-MS m/z(％):306(M+).
Example 48
Synthesis of Compound 3 di:
Figure BDA0002085216040000451
starting from 2di, the procedure is as in example 1, 53% yield.
1H NMR(400MHz,CDCl3)7.70(dd,J＝6.0,3.4Hz,1H),7.63(dd,J＝6.0,3.3Hz,1H),7.57(s,1H),7.53(d,J＝8.6Hz,1H),7.44–7.29(m,9H),7.27–7.21(m,3H),7.13(s,1H),7.05(dd,J＝8.6,1.4Hz,1H)；EI-MS m/z(％):306(M+)。
Example 49:
Figure BDA0002085216040000452
starting from 2dj, the procedure is as in example 1, 67% yield.
1H NMR(400MHz,Tol)8.27–8.17(m,2H),8.05(s,1H),7.75–7.66(m,2H),7.52–7.43(m,3H),7.26–7.13(m,7H),6.97–6.89(m,2H),6.63–6.52(m,3H)；13C NMR(100MHz,Tol)147.69,143.41,140.30,132.99,131.88,130.03,129.94,129.00,128.78,128.61,128.07,127.82,127.32,126.95,126.64,125.62,125.26,125.23。
EI-MS(m/z,％)::356(M+,100),278(44.53),279(35.6),276(31.8)；HRMS(EI):m/z C28H20[M]+Calculated 356.1565, found 356.1567.
Example 50
Figure BDA0002085216040000461
Starting from 2dj, the procedure is as in example 1, 67% yield.
1H NMR(400MHz,Tol)8.27–8.17(m,2H),8.05(s,1H),7.75–7.66(m,2H),7.52–7.43(m,3H),7.26–7.13(m,7H),6.97–6.89(m,2H),6.63–6.52(m,3H)；13C NMR(100MHz,Tol)147.69,143.41,140.30,132.99,131.88,130.03,129.94,129.00,128.78,128.61,128.07,127.82,127.32,126.95,126.64,125.62,125.26,125.23。
EI-MS(m/z,％)::356(M+,100),278(44.53),279(35.6),276(31.8)；HRMS(EI):m/z C28H20[M]+Calculated 356.1565, found 356.1567.
Example 51: investigating different arylboron compounds
In a dry Schlenk tube, 2.3mg of Pd (OAc) were added under argon atmosphere2，7.1mg P(2-OMe-Ph)352mg of 1aa (0.2mmol), an arylboron compound shown below (0.6mmol), 77mg of CsOAc, 2mL of THF, were heated to 110 ℃ and stirred for 3 h. Diluting with 10mL of dichloromethane, adding 25 μ L of dodecane internal standard, and determining yield and ratio by GC-FID (gasifying injection at 320 deg.C, initial temperature 50 deg.C, increasing by 15 deg.C per minute, increasing to 300 deg.C, and retaining10 minutes).
Figure BDA0002085216040000471
Figure BDA0002085216040000472
The percentage is the yield of compound 3aa, and the ratio in parentheses is the 3aa to 4aa yield ratio.
Various types of boronic acid groups are suitable for use in this reaction.
Example 52: investigating different phosphine ligands
In a dry Schlenk tube, 2.3mg of Pd (OAc) were added under argon atmosphere25 mol% or 10 mol% of ligand (for monophosphine ligands, e.g. L)1-15、L22-23Using 10 mol% for bisphosphine ligands, e.g. L16-21、L24-265 mol%), 52mg 1aa (0.2mmol), 2aa (0.6mmol), 77mg CsOAc, 2mL THF were used, warmed to 110 ℃ and stirred for 3 h. 10mL of dichloromethane was added for dilution, 25. mu.L of dodecane internal standard was added, and the yield and ratio were determined by GC-FID.
Figure BDA0002085216040000473
Figure BDA0002085216040000481
Figure BDA0002085216040000482
Figure BDA0002085216040000491
Various types of phosphine ligands are suitable for use in the present invention.
Example 53: investigating different solvents
In a dry Schlenk tube, 2.3mg of Pd (OAc) were added under argon atmosphere2，7.1mg P(2-OMe-Ph)352mg of 1aa (0.2mmol), 2aa (0.3mmol), 77mg of CsOAc, 2mL of the solvents mentioned in the table below, are stirred at 110 ℃ for 3 h. 10mL of dichloromethane was added for dilution, 25. mu.L of dodecane internal standard was added, and the yield and ratio were determined by GC-FID.
Figure BDA0002085216040000492
Figure BDA0002085216040000493
Various types of solvents are suitable for this reaction.
Example 54: investigating different palladium sources
In a dry Schlenk tube, 5 mol% of a palladium source shown in the following table, 7.1mg of P (2-OMe-Ph) were added under protection of argon352mg of 1aa (0.2mmol), 2aa (0.3mmol), 77mg of CsOAc, 2mL of THF, warm to 110 ℃ and stir for 3 h. 10mL of dichloromethane was added for dilution, 25. mu.L of dodecane internal standard was added, and the yield and ratio were determined by GC-FID.
Figure BDA0002085216040000501
Figure BDA0002085216040000502
Various types of palladium sources are suitable for this reaction.
Example 55: investigating different bases
In a dry Schlenk tube, 2.3mg of Pd (OAc) were added under argon atmosphere2，7.1mg P(2-OMe-Ph)352mg of 1aa (0.2mmol), 2aa (0.6mmol), a base as shown in the following table, 2mL of THF, was heated to 110 ℃ and stirred for 3 h. 10mL of dichloromethane was added for dilution, 25. mu.L of dodecane internal standard was added, and the yield and ratio were determined by GC-FID.
Figure BDA0002085216040000511
Figure BDA0002085216040000512
Various types of bases are suitable for this reaction, among which the alkali metal salts of organic acids work better.
Example 56: investigating boron ester equivalent
In a dry Schlenk tube, 2.3mg of Pd (OAc) were added under argon atmosphere2，7.1mg P(2-OMe-Ph)352mg of 1aa (0.2mmol), 2aa equivalents as shown in the table below, 94mg of CsOPiv, 2mL of THF, were heated to 110 ℃ and stirred for 3 h. 10mL of dichloromethane was added for dilution, 25. mu.L of dodecane internal standard was added, and the yield and ratio were determined by GC-FID.
Figure BDA0002085216040000513
Figure BDA0002085216040000521
Example 57: investigation of reaction temperature
In a dry Schlenk tube, 2.3mg of Pd (OAc) were added under argon atmosphere2，7.1mg P(2-OMe-Ph)352mg of 1aa (0.2mmol), 2aa (0.6mmol), 94mg of CsOPiv, 2mL of THF, were heated to the temperature indicated in the following table and stirred for 3 h. 10mL of dichloromethane was added for dilution, 25. mu.L of dodecane internal standard was added, and the yield and ratio were determined by GC-FID.
Figure BDA0002085216040000522
Figure BDA0002085216040000523
Example 58
Figure BDA0002085216040000531
In a dry Schlenk tube, 1.67g of boric acid (10mmol), 0.56mL of ethylene glycol (11mmol), 1.80g of anhydrous magnesium sulfate (15mmol), 50mL of dry dichloromethane were added under argon atmosphere, and the mixture was stirred at room temperature for 4 h. The solid was filtered off with suction, the filtrate was retained, the solvent was removed by rotation and dried in vacuo to give 1.57g of an off-white solid in 81% yield.
1H NMR(400MHz,CDCl3)8.22(d,J＝8.6Hz,2H),7.98(d,J＝8.5Hz,2H),4.44(s,4H).
Example 59
Figure BDA0002085216040000532
See example 58 for operation in 86% yield.
1H NMR(400MHz,CDCl3)7.84(d,J＝8.0Hz,2H),7.42(d,J＝8.1Hz,2H),4.39(s,4H),3.11(s,3H),2.95(s,3H).
Example 60
Figure BDA0002085216040000533
See example 58 for operation in 90% yield.
1H NMR(400MHz,CDCl3)7.78(d,J＝7.7Hz,2H),7.55(d,J＝7.8Hz,2H),4.38(s,4H),0.27(s,9H).
Example 61
Figure BDA0002085216040000541
See example 58 for operation in 87% yield.
1H NMR(400MHz,CDCl3)7.92(ddd,J＝13.4,7.8,3.6Hz,4H),4.40(s,4H),2.61(d,J＝2.4Hz,3H).
Example 62
Figure BDA0002085216040000542
See example 58 for operation in 72% yield.
1H NMR(400MHz,CDCl3)7.71(d,J＝8.2Hz,1H),7.36–7.09(m,4H),4.37(s,4H),2.50(s,3H).
Example 63
Figure BDA0002085216040000543
See example 58 for operation in 97% yield.
1H NMR(400MHz,CDCl3)7.97(dd,J＝23.0,8.2Hz,4H),4.43(s,4H),3.07(s,3H).
Example 64
Figure BDA0002085216040000544
See example 58 for operation in 75% yield.
1H NMR(400MHz,CDCl3)8.50(s,1H),8.44(d,J＝8.6Hz,2H),8.00(d,J＝7.8Hz,2H),7.55–7.39(m,4H),4.63(s,4H)；13C NMR(100MHz,CDCl3)136.03,131.12,129.88,128.79,128.57,125.83,124.96,66.11.
Example 65
Figure BDA0002085216040000551
See example 58 for operation in 50% yield.
1H NMR(400MHz,CDCl3)9.05(d,J＝9.2Hz,1H),8.56(d,J＝7.7Hz,1H),8.27–8.10(m,5H),8.07(d,J＝8.9Hz,1H),8.01(t,J＝7.6Hz,1H),4.56(s,4H)；13C NMR(101MHz,cdcl3)136.47,134.08,133.64,131.07,130.69,128.71,127.90,127.79,127.43,125.76,125.45,125.32,124.54,124.39,124.13,66.05。
Effect example 1
(1) Preparation of compound mother liquor:
weighing 0.01mmol of compound, dissolving in 1mL of chromatographic pure THF, and mixing well by ultrasonic oscillation to obtain 10-2mmol solution; taking 100 μ L of the above solution with a pipette, adding 900 μ L of chromatographically pure THF to dissolve, and ultrasonically oscillating to obtain 10-3mmol solution; taking 40 μ L of the above solution with a pipette, adding 3mL +960 μ L of chromatographically pure THF, dissolving, and ultrasonic oscillating to obtain 10-5mmol of the solution.
(2) Determination of the maximum absorption wavelength of a Compound
2mL of the solution prepared in the step (1) was taken, and the maximum absorption peak of each compound was measured by a UV/Vis spectrometer (Shimadzu UV-2600spectrophotometer) at 25 ℃.
(3) Measurement of Absolute Quantum efficiency of Compound (solution State)
Taking 2mL of the solution prepared in the step (1), testing the solution in an absolute quantum efficiency tester (Hamamatsu absolute PL quaternary yield quantum meter C11347Quantaurus _ QY) at 25 ℃, setting the excitation wavelength as the maximum absorption wavelength of each compound respectively, and determining the absolute quantum efficiency.
(4) Determination of the Absolute Quantum efficiency of Compounds (solid State)
2mg of the compound was measured at 25 ℃ in an absolute quantum efficiency tester (Hamamatsu absolute PL quaternary yield quantum meter C11347Quantaurus _ QY), and the excitation wavelength was set to the maximum absorption wavelength of each compound, respectively, to measure the absolute quantum efficiency.
Figure BDA0002085216040000561
Figure BDA0002085216040000571

Claims (10)

1. A preparation method of polysubstituted ethylene compounds shown as a formula III comprises the following steps: in an organic solvent, carrying out the following reaction on a compound shown as a formula I and a compound shown as a formula II in the presence of a palladium catalyst, a phosphine ligand and alkali to obtain a polysubstituted ethylene compound shown as a formula III;
Figure FDA0002085216030000011
wherein ring A is C6-16An aromatic or 5-16 membered heteroaromatic ring;
each R3Independently of one another is fluorine, chlorine, cyano, C1-6Alkyl radical, C3-6Cycloalkyl radical, C1-6Alkoxy radical, C3-6Cycloalkoxy or C1-6A haloalkyl group;
m is 0,1, 2, 3 or 4;
x is Br, I or OTf;
R1is C1-6Alkyl, cyano, or,
Figure FDA0002085216030000012
C6-16Aryl or 5-16 membered heteroaryl, said C6-16Aryl or 5-16 membered heteroaryl optionally substituted with one or more R1-1Substituted, wherein each R1-1Each independently of the others being fluorine, chlorine, cyano, C1-6Alkyl radical, C3-6Cycloalkyl radical, C1-6Alkoxy radical, C3-6Cycloalkoxy or C1-6A haloalkyl group;
R6is C1-6An alkyl group;
ring B is C6-16An aromatic or 5-16 membered heteroaromatic ring;
each R5Each independently of the other being fluorine, chlorine, C1-6Alkyl radical, C3-6Cycloalkyl radical, C1-6Alkoxy radical, C3-6Cycloalkoxy, cyano, nitro, aldehyde, amino,
Figure FDA0002085216030000013
Figure FDA0002085216030000014
Or C1-6A haloalkyl group; wherein R is2-2、R2-3、R2-4、R2-5、R2-6、R2-7、R2-8、R2-9、R2-10And R2-11Each independently is C1-6An alkyl group;
n is 0,1, 2, 3 or 4;
R4is composed of
Figure FDA0002085216030000021
Wherein R is51、R52、R53、R54、R55、R56、R57、R58、R59、R60、R61And R62Each independently is hydrogen or C1-6An alkyl group;
the heteroatoms in the heteroaromatic ring or heteroaryl group are each independently nitrogen, oxygen or sulfur, and the number of heteroatoms is independently 1,2, 3 or 4.
2. The method of claim 1, wherein: at R3、R1、R6、R5、R1-1、R2-2、R2-3、R2-4、R2-5、R2-6、R2-7、R2-8、R2-9、R2-10、R2-11、R51、R52、R53、R54、R55、R56、R57、R58、R59、R60、R61And R62In (b), the C1-6Each alkyl group is independently C1-4An alkyl group;
and/or, at R3、R5And R1-1In (b), the C1-6Alkoxy is each independently C1-4Alkoxy radicalA group;
and/or, at R3、R5And R1-1In (b), the C1-6Haloalkyl is each independently C1-4A haloalkyl group;
and/or, at R3、R5And R1-1In (b), the C1-6Halogen in haloalkyl is fluorine;
and/or, when ring A is C6-16When it is an aromatic ring, said C6-16The aromatic ring being C6-14An aromatic ring;
and/or, when ring a is a 5-16 membered heteroaryl ring, said 5-16 membered heteroaryl ring is a 5-10 membered heteroaryl ring;
and/or when R1Is C6-16Aryl is said to C6-16Aryl is C6-14An aryl group;
and/or when R1When it is a 5-16 membered heteroaryl group, said 5-16 membered heteroaryl group is a 5-10 membered heteroaryl group;
and/or, when ring B is a 5-16 membered heteroaryl ring, the 5-16 membered heteroaryl ring is a 5-10 membered heteroaryl ring;
and/or, the reaction is carried out under oxygen-free conditions;
and/or the phosphine ligand is
Figure FDA0002085216030000022
One or more of tris (2-furanyl) phosphine, diphenyl-2-pyridylphosphine, benzyldiphenylphosphine, diphenylmethylphosphine, tricyclohexylphosphine tetrafluoroborate, bisdiphenylphosphinomethane, 1, 2-bis (diphenylphosphino) ethane, 1, 3-bis (diphenylphosphino) propane, 1, 4-bis (diphenylphosphino) butane, 1, 5-bis (diphenylphosphino) pentane, 1, 6-bis (diphenylphosphino) hexane, 2-dicyclohexylphosphine-2 ',6' -dimethoxy-1, 1 '-biphenyl, 1' -bis (diphenylphosphino) ferrocene, 2-dicyclohexylphosphine-2 ',4',6 '-triisopropyl-1, 1' -biphenyl, 4, 5-bisdiphenylphosphino-9, 9-dimethylxanthene and bis (dicyclohexylphosphinophenyl) ether, wherein R is100Is 0,1, 2, 3, 4 or 5, each R100Each independently is C1-4Alkyl radical, C1-4Alkoxy, fluoro or trifluoromethyl;
and/or the molar ratio of the phosphine ligand to the compound shown in the formula I is 1:10-1: 20;
and/or the base is alkali metal carbonate, alkali metal and C1-4One or more of a salt of alkyl-COOH and an alkali metal fluoride;
and/or the molar ratio of the alkali to the compound shown in the formula I is 1:1-5: 1;
and/or the organic solvent is one or more of an ether solvent, an alkane solvent, an alcohol solvent, an aromatic hydrocarbon solvent, an ester solvent, a halogenated hydrocarbon solvent, a nitrile solvent and an amide solvent;
and/or the temperature of the reaction is 50-110 ℃;
and/or the molar ratio of the compound shown in the formula II to the compound shown in the formula I is 1:1-10: 1;
and/or the palladium catalyst is one or more of tris (dibenzylideneacetone) dipalladium, palladium chloride, bis (triphenylphosphine) palladium dichloride, bis (cyanobenzene) palladium dichloride, diallyl palladium dichloride and bis (acetylacetonato) palladium;
and/or the molar ratio of the palladium catalyst to the compound shown in the formula I is 0.025-0.20: 1.
3. The method of claim 2, wherein: when ring A is C6-16When it is aromatic, the C6-16The aromatic ring is a benzene ring or a naphthalene ring;
and/or, when ring a is a 5-16 membered heteroaryl ring, said 5-16 membered heteroaryl ring is a pyridine ring;
and/or when R3Is C1-6When alkyl, said C1-6Alkyl is methyl;
and/or when R3Is C1-6At alkoxy, the C1-6Alkoxy is methoxy;
and/or when R3Is C1-6When halogenated alkyl, said C1-6Haloalkyl is trifluoromethyl;
and/or when R1Is C1-6When alkyl, said C1-6Alkyl is isopropyl;
and/or when R1Is composed of
Figure FDA0002085216030000041
The above-mentioned
Figure FDA0002085216030000042
Is composed of
Figure FDA0002085216030000043
And/or when R1Is C6-16Aryl is said to C6-16Aryl is phenyl or naphthyl;
and/or when R1When 5-16 membered heteroaryl, said 5-16 membered heteroaryl is thienyl;
and/or when R1-1Is C1-6When alkyl, said C1-6Alkyl is methyl;
and/or when R1-1Is C1-6At alkoxy, the C1-6Alkoxy is methoxy;
and/or when R1-1Is C1-6When halogenated alkyl, said C1-6Haloalkyl is trifluoromethyl;
and/or, when ring B is C6-16When it is aromatic, the C6-16The aromatic ring is a benzene ring, a naphthalene ring, an anthracene ring or a pyrene ring;
and/or, when ring B is a 5-16 membered heteroaromatic ring, said 5-16 membered heteroaromatic ring is a furan, thiophene, pyridine, pyrimidine, imidazole, benzopyridine or benzofuran ring;
and/or when R5Is C1-6When alkyl, said C1-6Alkyl is methyl;
and/or when R5Is C1-6At alkoxy, the C1-6Alkoxy is methoxy;
and/or when R5Is composed of
Figure FDA0002085216030000044
When is in use, the
Figure FDA0002085216030000045
Is trimethylsilyl;
and/or when R5Is composed of
Figure FDA0002085216030000046
When is in use, the
Figure FDA0002085216030000047
Is composed of
Figure FDA0002085216030000048
And/or when R5Is composed of
Figure FDA0002085216030000049
When is in use, the
Figure FDA00020852160300000410
Is composed of
Figure FDA00020852160300000411
And/or when R5Is composed of
Figure FDA00020852160300000412
When is in use, the
Figure FDA00020852160300000413
Is composed of
Figure FDA00020852160300000414
And/or when R5Is composed of
Figure FDA00020852160300000415
When is in use, the
Figure FDA00020852160300000416
Is composed of
Figure FDA00020852160300000417
And/or when R5Is C1-6When halogenated alkyl, said C1-6Haloalkyl is trifluoromethyl;
and/or when R4Is composed of
Figure FDA00020852160300000418
When is in use, the
Figure FDA00020852160300000419
Is composed of
Figure FDA00020852160300000420
And/or when R4Is composed of
Figure FDA0002085216030000051
When is in use, the
Figure FDA0002085216030000052
Is composed of
Figure FDA0002085216030000053
And/or when R100Is C1-4When alkyl, said C1-4Alkyl is methyl;
and/or when R100Is C1-4At alkoxy, the C1-4Alkoxy is methoxy;
and/or, when the base is an alkali metal carbonate, the alkali metal carbonate is one or more of sodium carbonate, potassium carbonate and cesium carbonate;
and/or, when the base is an alkali metal with C1-4When the alkyl-COOH is a salt, the salt is a salt of an alkali metal and acetic acid, and/or a salt of an alkali metal and pivalic acid;
and/or, when the base is an alkali metal fluoride, the alkali metal fluoride is one or more of sodium fluoride, potassium fluoride and cesium fluoride;
and/or the molar ratio of the alkali to the compound shown in the formula I is 1.5-2: 1;
and/or, when the organic solvent is an ether solvent, the ether solvent is one or more of tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, ethylene glycol dimethyl ether, methyl tert-butyl ether, anisole and diethyl ether;
and/or when the organic solvent is an alkane solvent, the alkane solvent is n-hexane;
and/or, when the organic solvent is an alcohol solvent, the alcohol solvent is ethanol;
and/or, when the organic solvent is an aromatic solvent, the aromatic solvent is toluene;
and/or, when the organic solvent is an ester solvent, the ester solvent is ethyl acetate;
and/or, when the organic solvent is a halogenated hydrocarbon solvent, the halogenated hydrocarbon solvent is 1, 2-dichloroethane;
and/or, when the organic solvent is a nitrile solvent, the nitrile solvent is acetonitrile;
and/or, when the organic solvent is an amide solvent, the amide solvent is N, N-dimethylformamide;
and/or the temperature of the reaction is 80-110 ℃;
and/or the molar ratio of the compound shown in the formula II to the compound shown in the formula I is 3-5: 1;
and/or the palladium catalyst is one or more of tetrakis (triphenylphosphine) palladium, palladium acetate, palladium chloride, bis (triphenylphosphine) palladium dichloride, bis (cyanophenyl) palladium dichloride, diallyl palladium dichloride and bis (acetylacetonato) palladium;
and/or the molar ratio of the palladium catalyst to the compound shown in the formula I is 0.05-0.1: 1.
4. The method of claim 1, wherein: r1Is C1-6Alkyl, cyano, or,
Figure FDA0002085216030000061
Each z is independently 0,1, 2, 3 or 4;
and/or, R4Is composed of
Figure FDA0002085216030000062
And/or, the compound shown in the formula I is selected from any one of the following structures:
Figure FDA0002085216030000063
and/or the compound shown in the formula II is selected from any one of the following structures:
Figure FDA0002085216030000064
and/or the phosphine ligand is triphenylphosphine, tris (2-methoxyphenyl) phosphine, tris (3-methoxyphenyl) phosphine, tris (4-methoxyphenyl) phosphine, tris (2,4, 6-trimethoxyphenyl) phosphine, tris (4-tolyl) phosphine, tris (3-fluorophenyl) phosphine, tris (4-fluorophenyl) phosphine, tris [4- (trifluoromethyl) phenyl ] phosphine, tris (2, 6-dimethoxyphenyl) phosphine, tris (2-furyl) phosphine, diphenyl-2-pyridylphosphine, benzyldiphenylphosphine, diphenylmethylphosphine, tricyclohexylphosphine tetrafluoroborate, bisdiphenylphosphinomethane, 1, 2-bis (diphenylphosphino) ethane, 1, 3-bis (diphenylphosphino) propane, 1, 4-bis (diphenylphosphino) butane, 1, 5-bis (diphenylphosphino) pentane, One or more of 1, 6-bis (diphenylphosphino) hexane, 2-dicyclohexylphosphine-2 ',6' -dimethoxy-1, 1 '-biphenyl, 1' -bis (diphenylphosphino) ferrocene, 2-dicyclohexylphosphine-2 ',4',6 '-triisopropyl-1, 1' -biphenyl, 4, 5-bisdiphenylphosphino-9, 9-dimethylxanthene and bis (dicyclohexylphosphinophenyl) ether;
and/or the base is one or more of sodium carbonate, potassium carbonate, cesium carbonate, sodium acetate, potassium acetate, cesium acetate, sodium fluoride, potassium fluoride, cesium fluoride, sodium pivalate, potassium pivalate and cesium pivalate;
and/or the organic solvent is one or more of tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, ethylene glycol dimethyl ether, methyl tert-butyl ether, anisole, diethyl ether, N-hexane, ethanol, toluene, ethyl acetate, 1, 2-dichloroethane, acetonitrile and N, N-dimethylformamide.
5. The method of claim 1, wherein: r1Is any one of the following structures:
Figure FDA0002085216030000071
and/or, X is Br;
and/or, R4Is composed of
Figure FDA0002085216030000072
And/or, the compound shown in the formula I is selected from any one of the following structures:
Figure FDA0002085216030000081
and/or the compound shown in the formula II is selected from any one of the following structures:
Figure FDA0002085216030000082
and/or the phosphine ligand is one or more of tri (2-methoxyphenyl) phosphine, tri (4-methoxyphenyl) phosphine, tricyclohexylphosphine tetrafluoroborate, 4, 5-bis (diphenylphosphino) -9, 9-dimethylxanthene and bis (dicyclohexylphosphinophenyl) ether;
and/or, the alkali is cesium and C1-4Salts of alkyl-COOH;
and/or the organic solvent is tetrahydrofuran;
and/or the palladium catalyst is palladium acetate.
6. The method of claim 1, wherein: r1Is any one of the following structures:
Figure FDA0002085216030000091
and/or, the compound shown in the formula I is selected from any one of the following structures:
Figure FDA0002085216030000092
and/or the compound shown in the formula II is selected from any one of the following structures:
Figure FDA0002085216030000101
and/or, R4Is composed of
Figure FDA0002085216030000102
And/or the phosphine ligand is tri (2-methoxyphenyl) phosphine;
and/or, the base is cesium pivalate.
7. The method of claim 1, wherein: the compound shown in the formula I is selected from any one of the following structures:
Figure FDA0002085216030000111
and/or the compound shown in the formula II is selected from any one of the following structures:
Figure FDA0002085216030000121
8. the method of claim 1, wherein: the compound shown in the formula III is of any one structure as follows:
Figure FDA0002085216030000122
Figure FDA0002085216030000131
Figure FDA0002085216030000141
9. a compound selected from any one of the following structures:
Figure FDA0002085216030000142
Figure FDA0002085216030000151
Figure FDA0002085216030000161
10. use of a compound according to claim 9 as an organic electroluminescent material.
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