CN112876507B - Trisubstituted olefin tertiary phosphine compound and preparation method thereof - Google Patents

Trisubstituted olefin tertiary phosphine compound and preparation method thereof Download PDF

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CN112876507B
CN112876507B CN202110344197.0A CN202110344197A CN112876507B CN 112876507 B CN112876507 B CN 112876507B CN 202110344197 A CN202110344197 A CN 202110344197A CN 112876507 B CN112876507 B CN 112876507B
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刘悦进
李明
曾明华
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Hubei University
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Abstract

The invention relates to a tri-substituted olefin tertiary phosphine compound and a preparation method thereof, belonging to the technical field of organic chemistry. Mixing the 2-diphenylphosphine-biphenyl compound, the internal alkyne compound, the ruthenium catalyst, the ligand, the alkali and the organic solvent, uniformly stirring, controlling the reaction to heat to 80-120 ℃ in an argon atmosphere, reacting at constant temperature, cooling to room temperature, and performing suction filtration, reduced pressure distillation and column chromatography separation on the obtained product to obtain the tri-substituted olefin tertiary phosphine compound. The raw materials required by the method are easy to obtain, the product structure is various, and the synthesis yield is up to 90%; in addition, the reaction condition is mild, strong acid and strong base do not need to be added, the requirement on equipment is low, and the production cost is reduced; the method has the advantages of high atom utilization rate in the reaction process, less three wastes, low environmental pollution degree and potential for large-scale potential industrial production.

Description

Trisubstituted olefin tertiary phosphine compound and preparation method thereof
Technical Field
The invention belongs to the technical field of organic chemistry, and relates to a tri-substituted alkene tertiary phosphine compound and a synthesis method thereof, in particular to a high-efficiency and simple method for catalyzing internal alkyne hydrogenation arylation by transition metal ruthenium to synthesize a series of tri-substituted alkene tertiary phosphine compounds.
Background
The tertiary phosphine compound is widely applied to various fields related to the national civilian information, such as organic synthetic chemistry, material chemistry, pharmaceutical chemistry and the like, as an organic micromolecular catalyst, an organic ligand and a photoelectric material due to unique electronic property and space effect. The organic ligand is widely applied to cross-coupling reaction catalyzed by transition metal, and has a very key promotion effect on improving the turnover utilization rate, the reaction conversion rate, the chemical selectivity, the regioselectivity and the enantioselectivity of the catalyst.
In recent years, the design and synthesis of novel monophosphine compounds have been leading edge and hot spot of organic chemistry, and the synthesis of complex tri-substituted olefin tertiary phosphine compounds is extremely challenging and is widely concerned by chemists.
At present, few reports are reported on the synthesis of tri-substituted alkene diaryl hydrocarbon monophosphine compounds, and only two examples of reports (org.Lett.2020,22,5936.) are reported on the synthesis of a series of tri-substituted alkenyl modified biaryl monophosphine compounds through the coupling reaction of alkyne and biaryl monophosphine compounds catalyzed by monovalent rhodium. The method uses symmetrical alkyne as a coupling reagent, and the substrate range is limited; and expensive rhodium is used as an essential catalyst, so that the reaction cost is high.
In the prior art, the method for constructing the tri-substituted olefin biaryl monophosphine compound is only one example, and has the advantages of limited substrate range, less research on application fields, expensive catalyst, high reaction cost and high difficulty in industrial production.
Disclosure of Invention
In view of the above, the present application provides a novel tri-substituted olefin-containing tertiary phosphine compound and a simple preparation method thereof, solves the problems of high production cost, limited substrate range and the like in the prior art, and synthesizes a series of novel tri-substituted alkenyl-substituted tertiary phosphine compounds.
In order to achieve the first object of the present invention, the present invention provides a novel tri-substituted alkene biaryl monophosphine compound, wherein the tri-substituted alkene biaryl monophosphine compound is a compound having the following structural formula III:
Figure BDA0003000300100000011
wherein: r 1 Selected from silicon, alkyl, aryl or heteroaryl; r 2 Selected from alkyl, aryl or heteroaryl; r 3 Selected from hydrogen, alkyl, alkoxy, trifluoromethyl or halogen; r 4 Selected from hydrogen, alkyl, alkoxy, alkylmercapto, trifluoromethyl, halogen, aryl, aryloxy, naphthyl, ester, alkanoyl or cyano.
The second purpose of the invention is to provide a simple preparation method of the novel tri-substituted alkene biaryl monophosphine compound, wherein the synthetic route of the method is shown as the following formula:
Figure BDA0003000300100000021
the simple preparation method of the novel tri-substituted alkene biaryl monophosphine compound comprises the following steps:
taking a compound shown in a structural formula I and a compound shown in a structural formula II as raw materials, reacting at a constant temperature of 80-120 ℃ in an inert atmosphere in the presence of a ruthenium catalyst, a ligand, alkali and an organic solvent, cooling to room temperature, and performing suction filtration, reduced pressure distillation and column chromatography separation on the obtained product to obtain a tri-substituted olefin tertiary phosphine compound III.
Further, in the above technical scheme, the organic solvent is any one or a mixture of more of an alkane solvent, an aromatic hydrocarbon solvent, an alcohol solvent, a nitrile solvent, an ether solvent, a ketone solvent, an amide solvent, a chloroalkane solvent and a sulfoxide solvent; the amount of the organic solvent is not particularly limited, and it is sufficient to ensure that the reaction proceeds normally.
Preferably, in the above technical solution, the alkane solvent is selected from any one of alkane solvents such as n-pentane, n-hexane, n-heptane, n-octane, cyclohexane, cycloheptane and cyclooctane; the aromatic hydrocarbon solvent is any one of benzene solvents such as benzene, toluene, xylene, trimethylbenzene, halogenated benzene, benzotrifluoride and the like; the alcohol solvent is selected from any one of alcohol solvents such as methanol, ethanol, propanol, butanol, pentanol, ethylene glycol and propylene glycol; the nitrile solvent is selected from any one of nitrile solvents such as acetonitrile, trimethylacetonitrile, isovaleronitrile, benzonitrile and the like; the ether solvent is any one of ether solvents such as diethyl ether, tetrahydrofuran, methyl tert-butyl ether, anisole, ethylene glycol dimethyl ether and 1, 4-dioxane; the ketone solvent is selected from any one of acetone, butanone, pentanone and other ketone solvents; the amide solvent is selected from any one of amide solvents such as N, N-dimethylformamide, N-dimethylacetamide and the like; the chlorinated alkane solvent is selected from any one of chlorinated alkane solvents such as dichloromethane, trichloromethane, carbon tetrachloride, 1, 2-dichloroethane and the like; the sulfoxide solvent is selected from any one of sulfoxide solvents such as dimethyl sulfoxide.
Further, in the above technical scheme, the compound of structural formula I is selected from any one of hydrogen, alkyl, alkoxy, alkylmercapto, trifluoromethyl, halogen, aryl, aryloxy, naphthyl, ester, alkanoyl or cyano substituted. The compound shown in the structural formula II is selected from any one of silicon base, alkyl, aryl or heteroaryl substituted.
Further, according to the technical scheme, the molar ratio of the compound I to the compound II is 1.0-3.0: 1.
further, in the above technical means, the ligand is selected from the group consisting of Boc-L-glutamic acid, N-acetyl-L-isoleucine, Boc-beta-alanine, N-acetyl-beta-alanine, Boc-1-aminocyclopropanecarboxylic acid, Boc-L-isoleucine, N-acetyl-L-phenylalanine, N-acetyl-L-valine, Boc-1-aminocyclopentanecarboxylic acid, Boc-L-beta-homoalanine, N-acetyl-D-alanine, Boc-L-phenylalanine, Boc-1-aminocyclobutanecarboxylic acid, Boc-glycine, Boc-L-leucine, Boc-D-valine, N-acetyl glycine, Boc-1-aminocyclopropanecarboxylic acid, Boc-L-leucine, Boc-D-valine, N-acetyl glycine, N-acetyl-L-isoleucine, Boc-beta-alanine, N-acetyl-L-alanine, N-acetyl-L-alanine, N-L-alanine, N-acetyl-L-alanine, N-L, Amino acids such as N-acetyl-L-phenylalanine, N-acetyl-D-valine, N-Boc-L-tertiary leucine, Boc-L-proline, N-acetyl-L-leucine, Boc-L-leucine, alanine, valine, phenylalanine, 2-aminoisobutyric acid, serine, cycloleucine, 4-methoxy-L-phenylalanine, tertiary leucine, lysine, glutamic acid, homophenylalanine, isoleucine, leucine, and phenylglycine; 1-adamantanecarboxylic acid, 1-adamantaneacetic acid, 2,4, 6-trimethylbenzoic acid, trimethylacetic acid, 2-adamantanone-5-carboxylic acid, 2-methylbutyric acid, cyclohexylacetic acid, dimethylmalonic acid, cyclopropylcarboxylic acid, 2-diphenylpropionic acid, triphenylacetic acid, and one or more of a large steric hindrance acidic ligand such as diphenyl phosphate and dibenzyl phosphate, and a dicarbonyl ligand such as 2, 5-hexanedione, 3, 5-diheptanone, methyl 2-oxocyclopentanecarboxylate, ethyl acetoacetate, methyl acetoacetate, ethyl 2-methylacetoacetate, cyclopropylacetylacetone, 2-acetylcyclohexanone, benzoyltrifluoroacetone, 1, 3-cyclohexanedione, and 1-phenyl-1, 3-butanedione.
Further, in the above technical scheme, the molar ratio of the ligand to the compound II is 0.05-0.5: 1.
further, in the above technical solution, the ruthenium catalyst is selected from any one or a mixture of a plurality of metal ruthenium catalysts such as bis (4-methylisopropylphenyl) dichloride ruthenium, tris (acetyl acetonate) ruthenium, triphenylphosphine ruthenium chloride, ruthenium trichloride hydrate, dichloro (pentamethylcyclopentadienyl) ruthenium polymer, and bis (triphenylphosphine) ruthenium dichlorodicarbonyl.
Further, according to the technical scheme, the molar ratio of the ruthenium catalyst to the compound II is 0.001-0.1: 1.
further, in the above technical solution, the alkali includes any one of inorganic alkalis such as lithium acetate, sodium acetate, potassium acetate, cesium acetate, lithium trifluoroacetate, sodium trifluoroacetate, potassium trifluoroacetate, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogen carbonate, sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, sodium benzenesulfonate, sodium p-toluenesulfonate, and the like.
Furthermore, in the technical scheme, the dosage of the alkali is 1.0 to 3.0 times of the molar weight of the compound II.
Compared with the prior art, the invention has the following beneficial effects:
(1) the reaction is completed in one step, the steps are simple, other functional groups or complex reaction flows are not required to be introduced in the process to construct a C-C bond, and the method is a simple and efficient synthesis method for the novel tri-substituted alkene biaryl monophosphine compound; (2) the raw materials required in the reaction process are easy to obtain, the yield is up to 90%, the requirement on equipment in the synthesis process is low, and the production cost is reduced; (3) the method has the advantages of high atom utilization rate in the reaction process, less three wastes generation, low environmental pollution degree and potential industrial large-scale production prospect.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments. The embodiment is implemented on the premise of the technical scheme of the invention, and a detailed implementation mode and a specific operation process are given, but the protection scope of the invention is not limited to the following embodiment.
For a better understanding of the invention, and not as a limitation on the scope thereof, all numbers expressing quantities, percentages, and other numerical values used in this application are to be understood as being modified in all instances by the term "about". Accordingly, unless expressly indicated otherwise, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
Example 1
The novel trisubstituted alkene biaryl monophosphine compound III-1{ (E) -diphenyl (2'- (1-phenylprop-1-en-2-yl) - [1,1' -biphenyl ] -2-yl) phosphine } of the embodiment has the following synthetic route:
Figure BDA0003000300100000041
the novel tri-substituted alkene biaryl monophosphine compound III-1 is prepared by the following method: 202.8mg of 2-diphenylphosphine-biphenyl (compound I-1, 0.6mmol), 24 μ L of 1-phenylpropylene (compound II-1, 0.2mmol), 3.1mg of p-cymene ruthenium dichloride dimer, 9.1mg of phenylglycine and 1mL of 2-methyltetrahydrofuran are added into a reaction kettle, the mixture is stirred and mixed uniformly, argon is introduced into a reaction system after the reaction is controlled to react for 12 hours at the temperature of 120 ℃ in an argon atmosphere, the reaction system is cooled to room temperature, the mixture is filtered by diatomite, and column chromatography separation is carried out after reduced pressure distillation to obtain 82.6mg of target product, wherein the yield is 91%.
1 H NMR(400MHz,CDCl 3 )δ7.41(dd,J＝7.6Hz,1.2Hz,1H),7.35-7.29(m,7H),7.26-7.04(m,14H),6.83(d,J＝7.6Hz,1H),6.48(s,1H),1.90(d,J＝1.2Hz,3H).
Chemical shift δ 7.41, quartet, ascribed to one hydrogen on the benzene ring; chemical shift delta 7.35-7.29, multiple peaks, belonging to seven hydrogens on benzene ring; chemical shift delta 7.26-7.04, multiple peaks, belonging to fourteen hydrogens on a benzene ring; chemical shift δ 6.83, doublet, ascribed to one hydrogen on the benzene ring; chemical shift δ 6.48, single peak, assigned to one hydrogen on alkenyl; chemical shift δ 1.90, doublet peak, three hydrogens assigned to methyl.
13 C NMR(101MHz,CDCl 3 )δ148.5(d,J＝32.5Hz),144.7,139.6(d,J＝7.3Hz),138.8,138.6(d,J＝13.2Hz),138.3,137.7(d,J＝12.2Hz),136.5(d,J＝12.2Hz),134.7(d,J＝1.7Hz),134.0(d,J＝19.9Hz),133.4(d,J＝19.2Hz),131.4(d,J＝4.2Hz),131.2(d,J＝1.8Hz),130.8(d,J＝5.8Hz),129.0,128.6,128.6(d,J＝2.8Hz),128.5,128.4(d,J＝3.1Hz),128.3,128.1,127.8,127.4,126.4,126.0,19.6(d,J＝2.2Hz).
31 P NMR(162MHz,CDCl 3 )δ-14.4.
HRMS(ESI)m/z:[M+H] + calcd for C 33 H 28 P 455.1915；found 455.1923.
High resolution mass spectrometry gave a true relative molecular mass of 455.1915 for compound hydrogenation, found 455.1923.
From the results of the above-mentioned nuclear magnetic and mass spectrometry tests, it was confirmed that the target compound obtained in this example was { (E) -diphenyl (2'- (1-phenylprop-1-en-2-yl) - [1,1' -biphenyl ] -2-yl) phosphine }.
Example 2
The synthesis route of the novel trisubstituted alkene biaryl monophosphine compound III-2{ (E) - (2'- (1, 2-diphenylvinyl) - [1,1' -biphenyl ] -2-yl) diphenylphosphine }, which is shown in the following example, is as follows:
Figure BDA0003000300100000051
the novel tri-substituted alkene biaryl monophosphine compound III-2 is prepared by the following method: 202.8mg of 2-diphenylphosphine-biphenyl (compound I-1, 0.6mmol), 35.6mg of tolane (compound II-2, 0.2mmol), 3.1mg of p-cymene ruthenium dichloride dimer, 9.1mg of phenylglycine, 39.3mg of potassium acetate and 1mL of 2-methyltetrahydrofuran are added into a reaction kettle, the mixture is stirred and mixed uniformly, argon is introduced into a reaction system, the reaction is controlled to react for 12 hours at 120 ℃ in an argon atmosphere and then cooled to room temperature, the mixture is filtered by diatomite, and after reduced pressure distillation, the target product 93.9mg is obtained by column chromatography separation, wherein the yield is 91%.
1 H NMR(400MHz,CDCl 3 )δ7.45(d,J＝7.6Hz,1H),7.33(td,J＝7.6Hz,1.2Hz,1H),7.25-7.21(m,2H),7.20-7.14(m,5H),7.08-6.95(m,14H),6.93-6.89(m,1H),6.88-6.85(m,1H),6.80(d,J＝7.2Hz,2H),6.76(s,1H),6.69(d,J＝7.6Hz,1H).
13 C NMR(101MHz,CDCl 3 )δ147.7(d,J＝32.1Hz),143.6,143.3,140.7(d,J＝6.7Hz),140.6,138.8(d,J＝13.5Hz),137.7(d,J＝12.9Hz),137.5,136.4,136.2,134.2,134.0,133.8(d,J＝1.7Hz),133.5,133.3,131.8(d,J＝2.3Hz),131.4(d,J＝3.9Hz),130.4(d,J＝3.9Hz),129.8,129.5,128.6,128.4,128.3,128.2,127.9(d,J＝1.2Hz),127.6,127.0,126.7(d,J＝3.4Hz),126.6.
31 P NMR(162MHz,CDCl 3 )δ-13.2.
HRMS(ESI)m/z:[M+H] + calcd for C 38 H 30 P 517.2074；found 517.2080.
Example 3
The novel trisubstituted alkene biaryl monophosphine compound III-3{ (E) - (2'- (1, 2-bis (4-methoxyphenyl) vinyl) - [1,1' -biphenyl ] -2-yl) diphenylphosphine } of the embodiment has the following synthetic route:
Figure BDA0003000300100000061
the novel tri-substituted alkene biaryl monophosphine compound III-3 is prepared by the following method: 202.8mg of 2-diphenylphosphine-biphenyl (compound I-1, 0.6mmol), 47.6mg of 1, 2-bis (4-methoxyphenyl) acetylene (compound II-3, 0.2mmol), 3.1mg of p-cymene ruthenium dichloride dimer, 9.1mg of phenylglycine, 39.3mg of potassium acetate and 1mL of 2-methyltetrahydrofuran are added into a reaction kettle, the mixture is stirred and mixed uniformly, argon is introduced into a reaction system after the reaction is controlled to react for 12 hours at 120 ℃ in an argon atmosphere, the reaction system is cooled to room temperature, 109.4mg of target product is obtained after the reaction of suction filtration of diatomite and reduced pressure distillation and chromatographic separation of a column layer, and the yield is 95%.
1 H NMR(400MHz,CDCl 3 )δ7.46(d,J＝7.6Hz,1H),7.36(dd,J＝7.6Hz,1.2Hz,1H),7.32-7.27(m,3H),7.24-7.17(m,5H),7.08-7.04(m,3H),6.98-6.91(m,6H),6.75-6.71(m,2H),6.70-6.64(m,4H),6.58-6.55(m,2H),3.75(s,6H).
13 C NMR(101MHz,CDCl 3 )δ158.3(d,J＝5.1Hz),147.9(d,J＝32.2Hz),144.1,141.1,140.7(d,J＝6.9Hz),139.1(d,J＝13.7Hz),137.9(d,J＝12.9Hz),136.1(d,J＝12.1Hz),134.1(d,J＝20.2Hz),134.0(d,J＝1.9Hz),133.4,133.2(d,J＝1.9Hz),131.4(d,J＝4.0Hz),131.0,130.6,130.5,130.4(d,J＝5.2Hz),128.6,128.4(d,J＝7.2Hz),128.2(d,J＝5.7Hz),128.1,127.8,127.6,127.0,126.3,113.4(d,J＝1.1Hz),55.3,55.2.
31 P NMR(162MHz,CDCl 3 )δ-13.6.
HRMS(ESI)m/z:[M+H] + calcd for C 40 H 34 O 2 P 577.2258；found 577.2291.
The inventor changes the reaction raw materials to conform to the compound of the general structural formula I
Figure BDA0003000300100000062
Compounds of structural formula II-3
Figure BDA0003000300100000063
A series of tri-substituted olefin biaryl monophosphine compounds are prepared by the preparation method similar to that of example 3, and are shown in examples 4 to 27.
Example 4
In the preparation method of the novel trisubstituted alkene biaryl monophosphine compound III-4{ (E) - (2'- (1, 2-bis (4-methoxyphenyl) vinyl) -4-methyl- [1,1' -biphenyl ] -2-yl) diphenylphosphine } (shown in the following structural formula), the target product is obtained by using 4-methyl-2-diphenylphosphine-biphenyl as a raw material according to the method of example 3, and the yield of the target product is 82%.
Figure BDA0003000300100000071
Example 5
In the preparation method of the novel tri-substituted alkene biaryl monophosphine compound III-5{ (E) - (2'- (1, 2-bis (4-methoxyphenyl) vinyl) -4-fluoro- [1,1' -biphenyl ] -2-yl) diphenylphosphine } (shown in the following structural formula), 4-fluoro-2-diphenylphosphine-biphenyl was used as a raw material according to the method in example 3 to obtain a target product, and the yield of the target product is 88%.
Figure BDA0003000300100000072
Example 6
In the preparation method of the novel tri-substituted alkene biaryl monophosphine compound III-6{ (E) - (2'- (1, 2-bis (4-methoxyphenyl) vinyl) -4-chloro- [1,1' -biphenyl ] -2-yl) diphenylphosphine } (shown in the following structural formula), the target product is obtained by using 4-chloro-2-diphenylphosphine-biphenyl as a raw material according to the method of example 3, and the yield of the target product is 90%.
Figure BDA0003000300100000073
Example 7
In the preparation method of the novel tri-substituted alkene biaryl monophosphine compound III-7{ (E) - (2'- (1, 2-bis (4-methoxyphenyl) vinyl) -5-methoxy- [1,1' -biphenyl ] -2-yl) diphenylphosphine } (shown in the following structural formula), 5-methoxy-2-diphenylphosphine-biphenyl was used as a raw material according to the method in example 3 to obtain a target product, and the yield of the target product is 73%.
Figure BDA0003000300100000081
Example 8
In the preparation method of the novel trisubstituted alkene biaryl monophosphine compound III-8{ (E) - (2'- (1, 2-bis (4-methoxyphenyl) vinyl) -5-methyl- [1,1' -biphenyl ] -2-yl) diphenylphosphine } (shown in the following structural formula), the target product is obtained by using 5-methyl-2-diphenylphosphine-biphenyl as a raw material according to the method of example 3, and the yield of the target product is 81%.
Figure BDA0003000300100000082
Example 9
In the preparation method of the novel tri-substituted alkene biaryl monophosphine compound III-9{ (E) - (2'- (1, 2-bis (4-methoxyphenyl) vinyl) -5-fluoro- [1,1' -biphenyl ] -2-yl) diphenylphosphine } (shown in the following structural formula), 5-fluoro-2-diphenylphosphine-biphenyl was used as a raw material according to the method in example 3 to obtain a target product, and the yield of the target product is 68%.
Figure BDA0003000300100000083
Example 10
In the preparation method of the novel trisubstituted alkene biaryl monophosphine compound III-10{ (E) - (2'- (1, 2-bis (4-methoxyphenyl) vinyl) -5-chloro- [1,1' -biphenyl ] -2-yl) diphenylphosphine } (shown in the following structural formula), the target product is obtained by taking 5-chloro-2-diphenylphosphine-biphenyl as a raw material and referring to the method in example 3, and the yield of the target product is 72%.
Figure BDA0003000300100000084
Example 11
In the preparation method of the novel trisubstituted alkene biaryl monophosphine compound III-11{ (E) - (2' - (1, 2-bis (4-methoxyphenyl) vinyl) -6' -methoxy- [1,1' -biphenyl ] -2-yl) diphenylphosphine } (shown in the following structural formula), 2-methoxy-2-diphenylphosphine-biphenyl was used as a raw material according to the method of example 3, so as to obtain a target product, wherein the yield of the target product is 46%.
Figure BDA0003000300100000091
Example 12
In the preparation method of the novel tri-substituted alkene biaryl monophosphine compound III-12{ (E) - (2' - (1, 2-bis (4-methoxyphenyl) vinyl) -6' -methyl- [1,1' -biphenyl ] -2-yl) diphenylphosphine } (shown in the following structural formula), 2-methyl-2-diphenylphosphine-biphenyl was used as a raw material according to the method in example 3 to obtain a target product, and the yield of the target product is 37%.
Figure BDA0003000300100000092
Example 13
In the preparation method of the novel trisubstituted alkene biaryl monophosphine compound III-13{ (E) - (2' - (1, 2-bis (4-methoxyphenyl) vinyl) -5' -methoxy- [1,1' -biphenyl ] -2-yl) diphenylphosphine } (shown in the following structural formula), 3-methoxy-2-diphenylphosphine-biphenyl was used as a raw material according to the method of example 3, so as to obtain a target product, wherein the yield of the target product is 50%.
Figure BDA0003000300100000093
Example 14
In the preparation method of the novel trisubstituted alkene biaryl monophosphine compound III-14{ (E) - (2' - (1, 2-bis (4-methoxyphenyl) vinyl) -5' -methyl- [1,1' -biphenyl ] -2-yl) diphenylphosphine } (shown in the following structural formula), 3-methyl-2-diphenylphosphine-biphenyl was used as a raw material according to the method of example 3, so as to obtain a target product, wherein the yield of the target product is 92%.
Figure BDA0003000300100000101
Example 15
In the preparation method of the novel tri-substituted alkene biaryl monophosphine compound III-15{ (E) - (2' - (1, 2-bis (4-methoxyphenyl) vinyl) -4' -methoxy- [1,1' -biphenyl ] -2-yl) diphenylphosphine } (shown in the following structural formula), 4-methoxy-2-diphenylphosphine-biphenyl was used as a raw material according to the method in example 3 to obtain a target product, and the yield of the target product is 67%.
Figure BDA0003000300100000102
Example 16
In the preparation method of the novel trisubstituted alkene biaryl monophosphine compound III-16{ (E) - (2' - (1, 2-bis (4-methoxyphenyl) vinyl) -4' -methylmercapto- [1,1' -biphenyl ] -2-yl) diphenylphosphine } (shown in the following structural formula), the target product is obtained by using 4-methylmercapto-2-diphenylphosphine-biphenyl as a raw material according to the method of example 3, and the yield of the target product is 81%.
Figure BDA0003000300100000103
Example 17
In the preparation method of the novel tri-substituted alkene biaryl monophosphine compound III-17{ (E) - (2' - (1, 2-bis (4-methoxyphenyl) vinyl) -4' -phenoxy- [1,1' -biphenyl ] -2-yl) diphenylphosphine } (shown in the following structural formula), the target product was obtained by using 4-phenoxy-2-diphenylphosphine-biphenyl as a raw material according to the method of example 3, and the yield of the target product was 94%.
Figure BDA0003000300100000111
Example 18
In the preparation method of the novel trisubstituted alkene biaryl monophosphine compound III-18{ (E) - (2' - (1, 2-bis (4-methoxyphenyl) vinyl) -4' -methyl- [1,1' -biphenyl ] -2-yl) diphenylphosphine } (shown in the following structural formula), the target product is obtained by using 4-methyl-2-diphenylphosphine-biphenyl as a raw material and referring to the method of example 3, and the yield of the target product is 76%.
Figure BDA0003000300100000112
Example 19
In the preparation method of the novel tri-substituted alkene biaryl monophosphine compound III-19{ (E) - (2' - (1, 2-bis (4-methoxyphenyl) vinyl) -4' -phenyl- [1,1' -biphenyl ] -2-yl) diphenylphosphine } (shown in the following structural formula), 4-phenyl-2-diphenylphosphine-biphenyl was used as a raw material according to the method in example 3 to obtain a target product, and the yield of the target product is 62%.
Figure BDA0003000300100000113
Example 20
In the preparation method of the novel trisubstituted alkene biaryl monophosphine compound III-20{ (E) - (2' - (1, 2-bis (4-methoxyphenyl) vinyl) -4' -fluoro- [1,1' -biphenyl ] -2-yl) diphenylphosphine } (shown in the following structural formula), the target product is obtained by using 4-fluoro-2-diphenylphosphine-biphenyl as a raw material according to the method of example 3, and the yield of the target product is 81%.
Figure BDA0003000300100000114
Example 21
In the preparation method of the novel trisubstituted alkene biaryl monophosphine compound III-21{ (E) - (2' - (1, 2-bis (4-methoxyphenyl) vinyl) -4' -chloro- [1,1' -biphenyl ] -2-yl) diphenylphosphine } (shown in the following structural formula), the target product is obtained by using 4-chloro-2-diphenylphosphine-biphenyl as a raw material according to the method of example 3, and the yield of the target product is 80%.
Figure BDA0003000300100000121
Example 22
In the preparation method of the novel trisubstituted alkene biaryl monophosphine compound III-22{ (E) - (2' - (1, 2-bis (4-methoxyphenyl) vinyl) -4' -bromo- [1,1' -biphenyl ] -2-yl) diphenylphosphine } (shown in the following structural formula), the target product was obtained by using 4-bromo-2-diphenylphosphine-biphenyl as a raw material according to the method of example 3, and the yield of the target product was 75%.
Figure BDA0003000300100000122
Example 23
In the preparation method of the novel trisubstituted alkene biaryl monophosphine compound III-23{ (E) -1- (2- (1, 2-bis (4-methoxyphenyl) vinyl) -2'- (diphenylphosphino) - [1,1' -biphenyl ] -4-yl) ethan-1-one } (represented by the following structural formula), the target product was obtained in 88% yield by the method of example 3 using 4-acetyl-2-diphenylphosphine-biphenyl as a raw material.
Figure BDA0003000300100000123
Example 24
In the preparation method of the novel tri-substituted alkene biaryl monophosphine compound III-24{ (E) -2- (1, 2-bis (4-methoxyphenyl) vinyl) -2'- (diphenylphosphine alkyl) - [1,1' -biphenyl ] -4-carboxylic acid methyl ester } (shown in the following structural formula), 4-carbomethoxy-2-diphenylphosphine-biphenyl was used as a raw material according to the method in example 3 to obtain a target product, and the yield of the target product is 97%.
Figure BDA0003000300100000131
Example 25
In this example, according to the method for preparing the novel trisubstituted alkene biaryl monophosphine compound III-25{ (E) -2- (1, 2-bis (4-methoxyphenyl) vinyl) -2'- (diphenylphosphino) - [1,1' -biphenyl ] -4-carbonitrile } (represented by the following structural formula), 4-cyano-2-diphenylphosphino-biphenyl was used as a raw material in accordance with the method in example 3, and the yield of the target product was 94%.
Figure BDA0003000300100000132
Example 26
In the preparation method of the novel tri-substituted alkene biaryl monophosphine compound III-26{ (E) - (2' - (1, 2-bis (4-methoxyphenyl) vinyl) -4' -trifluoromethyl- [1,1' -biphenyl ] -2-yl) diphenylphosphine } (shown in the following structural formula), the target product is obtained by using 4-trifluoromethyl-2-diphenylphosphine-biphenyl as a raw material according to the method in example 3, and the yield of the target product is 82%.
Figure BDA0003000300100000133
Example 27
In the preparation method of the novel trisubstituted alkene biaryl monophosphine compound III-27{ (E) - (2- (3- (1, 2-bis (4-methoxyphenyl) vinyl) naphthalen-2-yl) phenyl) diphenylphosphine } (shown in the following structural formula), the target product was obtained in 54% yield by using 2-diphenylphosphine-phenylnaphthalene as a raw material and referring to the method of example 3.
Figure BDA0003000300100000141
In addition, the inventor also changes the reaction raw materials to obtain the compound of the structural formula I
Figure BDA0003000300100000142
A compound of the general structural formula II
Figure BDA0003000300100000143
A series of tri-substituted olefin diaryl monophosphine compounds, as shown in examples 28-50, were prepared using the similar preparation methods as in example 1 or example 2.
Example 28
In the preparation method of the novel trisubstituted alkene biaryl monophosphine compound III-28{ (E) - (2'- (1- (4- (methoxyphenyl) prop-1-en-2-yl) - [1,1' -biphenyl ] -2-yl) diphenylphosphine } (represented by the following structural formula), the target product was obtained in a yield of 77% by using (4-methoxyphenyl) propyne as a raw material according to the method of example 1.
Figure BDA0003000300100000144
Example 29
In the preparation method of the novel trisubstituted alkene biaryl monophosphine compound III-29{ (E) - (2'- (1- (4- (methylphenyl) prop-1-en-2-yl) - [1,1' -biphenyl ] -2-yl) diphenylphosphine } (represented by the following structural formula), the target product was obtained in a yield of 71% by using (4-methylphenyl) propyne as a raw material according to the method of example 1.
Figure BDA0003000300100000145
Example 30
In this example, a process for producing a novel trisubstituted alkene biaryl monophosphine compound III-30{ (E) - (2'- (1- (4- (fluorophenyl) prop-1-en-2-yl) - [1,1' -biphenyl ] -2-yl) diphenylphosphine } (represented by the following structural formula) was performed by using (4-fluorophenyl) propyne as a starting material in accordance with the process of example 1 to obtain the desired compound in a yield of 68%.
Figure BDA0003000300100000151
Example 31
In this example, a process for producing a novel trisubstituted alkene biaryl monophosphine compound III-31{ (E) - (2'- (1- (4- (chlorophenyl) prop-1-en-2-yl) - [1,1' -biphenyl ] -2-yl) diphenylphosphine } (represented by the following structural formula) was carried out using (4-chlorophenyl) propyne as a starting material in accordance with the process in example 1 to obtain the desired compound in a yield of 61%.
Figure BDA0003000300100000152
Example 32
In this example, according to the method for preparing the novel trisubstituted alkene biaryl monophosphine compound III-32{ (E) - (2'- (1- (4- (bromophenyl) prop-1-en-2-yl) - [1,1' -biphenyl ] -2-yl) diphenylphosphine } (represented by the following structural formula), using (4-bromophenyl) propyne as a raw material and referring to the method in example 1, the target product was obtained in a yield of 64%.
Figure BDA0003000300100000153
Example 33
In the preparation method of the novel trisubstituted alkene biaryl monophosphine compound III-33{ (E) - (2'- (1- (3- (methoxyphenyl) prop-1-en-2-yl) - [1,1' -biphenyl ] -2-yl) diphenylphosphine } (represented by the following structural formula), the target product was obtained in a yield of 67% using (3-methoxyphenyl) propyne as a raw material according to the method of example 1.
Figure BDA0003000300100000154
Example 34
In the preparation method of the novel trisubstituted alkene biaryl monophosphine compound III-34{ (E) - (2'- (1- (3- (methylphenyl) prop-1-en-2-yl) - [1,1' -biphenyl ] -2-yl) diphenylphosphine } (represented by the following structural formula), the target product was obtained in the yield of 81% by using (3-methylphenyl) propyne as a raw material according to the method of example 1.
Figure BDA0003000300100000161
Example 35
In the preparation method of the novel trisubstituted alkene biaryl monophosphine compound III-35{ (E) - (2'- (1- (3- (fluorophenyl) prop-1-en-2-yl) - [1,1' -biphenyl ] -2-yl) diphenylphosphine } (represented by the following structural formula), the target product was obtained in a yield of 70% by using (3-fluorophenyl) propyne as a raw material according to the method of example 1.
Figure BDA0003000300100000162
Example 36
In this example, a process for producing a novel trisubstituted alkene biaryl monophosphine compound III-36{ (E) - (2'- (1- (3- (chlorophenyl) prop-1-en-2-yl) - [1,1' -biphenyl ] -2-yl) diphenylphosphine } (represented by the following structural formula) was performed by using (3-chlorophenyl) propyne as a starting material in accordance with the process in example 1 to obtain the desired product in a yield of 67%.
Figure BDA0003000300100000163
Example 37
In the preparation method of the novel tri-substituted alkene biaryl monophosphine compound III-37{ (E) - (2'- (1- (3- (bromophenyl) prop-1-en-2-yl) - [1,1' -biphenyl ] -2-yl) diphenylphosphine } (shown in the following structural formula), the target product was obtained in 84% yield by using (3-bromophenyl) propyne as a raw material according to the method in example 1.
Figure BDA0003000300100000171
Example 38
In the preparation method of the novel trisubstituted alkene biaryl monophosphine compound III-38{ (E) - (2'- (1- (4-methoxyphenyl) -2- (trimethylsilyl) vinyl) - [1,1' -biphenyl ] -2-yl) diphenylphosphine } (shown in the following structural formula), the target product was obtained in a yield of 63% by using ((4-methoxyphenyl) ethynyl) trimethylsilane as a raw material and referring to the method of example 2.
Figure BDA0003000300100000172
Example 39
In the preparation method of the novel trisubstituted alkene biaryl monophosphine compound III-39{ (E) - (2'- (1- (4-cyanophenyl) -2- (trimethylsilyl) ethenyl) - [1,1' -biphenyl ] -2-yl) diphenylphosphine } (represented by the following structural formula), the target product was obtained in a yield of 70% by using ((4-cyanophenyl) ethynyl) trimethylsilane as a raw material according to the method of example 2.
Figure BDA0003000300100000173
Example 40
In the preparation method of the novel trisubstituted alkene biaryl monophosphine compound III-40{ (Z) - (2'- (1, 2-bis (2-methoxyphenyl) vinyl) - [1,1' -biphenyl ] -2-yl) diphenylphosphine } (shown in the following structural formula), the target product was obtained in 26% yield by using (2-methoxyphenyl) acetylene as a raw material and referring to the method of example 2.
Figure BDA0003000300100000181
EXAMPLE 41
In the preparation method of the novel trisubstituted alkene biaryl monophosphine compound III-41{ (E) - (2'- (1, 2-bis (3-methoxyphenyl) vinyl) - [1,1' -biphenyl ] -2-yl) diphenylphosphine } (shown in the following structural formula), the target product was obtained in 77% yield by using (3-methoxyphenyl) acetylene as a raw material and referring to the method of example 2.
Figure BDA0003000300100000182
Example 42
In the preparation method of the novel trisubstituted alkene biaryl monophosphine compound III-42{ (E) - (2'- (1, 2-bis (3-methylphenyl) vinyl) - [1,1' -biphenyl ] -2-yl) diphenylphosphine } (shown in the following structural formula), the target product was obtained in 79% yield by using (3-methylphenyl) acetylene as a raw material according to the method of example 2.
Figure BDA0003000300100000183
Example 43
In the preparation method of the novel trisubstituted alkene biaryl monophosphine compound III-43{ (E) - (2'- (1, 2-bis (3-fluorophenyl) vinyl) - [1,1' -biphenyl ] -2-yl) diphenylphosphine } (shown in the following structural formula), the target product was obtained in 88% yield by the method of example 2 using (3-fluorophenyl) acetylene as a raw material.
Figure BDA0003000300100000191
Example 44
In the preparation method of the novel trisubstituted alkene biaryl monophosphine compound III-44{ (E) - (2'- (1, 2-bis (3-chlorophenyl) vinyl) - [1,1' -biphenyl ] -2-yl) diphenylphosphine } (represented by the following structural formula), the target product was obtained in 82% yield by using (3-chlorophenyl) acetylene as a raw material and referring to the method of example 2.
Figure BDA0003000300100000192
Example 45
In the preparation method of the novel trisubstituted alkene biaryl monophosphine compound III-45{ (E) - (2'- (1, 2-bis (3-bromophenyl) vinyl) - [1,1' -biphenyl ] -2-yl) diphenylphosphine } (shown in the following structural formula), the target product was obtained in 77% yield by using (3-bromophenyl) acetylene as a raw material and referring to the method of example 2.
Figure BDA0003000300100000193
Example 46
In the preparation method of the novel trisubstituted alkene biaryl monophosphine compound III-46{ (E) - (2'- (1, 2-bis (4-methylphenyl) vinyl) - [1,1' -biphenyl ] -2-yl) diphenylphosphine } (shown in the following structural formula), the target product was obtained in 88% yield by using (4-methylphenyl) acetylene as a raw material according to the method of example 2.
Figure BDA0003000300100000201
Example 47
In the preparation method of the novel trisubstituted alkene biaryl monophosphine compound III-47{ (E) - (2'- (1, 2-bis (4-chlorophenyl) vinyl) - [1,1' -biphenyl ] -2-yl) diphenylphosphine } according to the method of example 2, using (4-chlorophenyl) acetylene as a raw material, the objective compound was obtained in a yield of 81%.
Figure BDA0003000300100000202
Example 48
In the preparation method of the novel trisubstituted alkene biaryl monophosphine compound III-48{ (E) - (2'- (1, 2-bis (4-bromophenyl) vinyl) - [1,1' -biphenyl ] -2-yl) diphenylphosphine } (shown in the following structural formula), the target product was obtained in 74% yield by using (4-bromophenyl) acetylene as a raw material and referring to the method of example 2.
Figure BDA0003000300100000203
Example 49
In the preparation method of the novel tri-substituted alkene biaryl monophosphine compound III-49{ (Z) - (2'- (1, 2-bis (thiophen-3-yl) vinyl) - [1,1' -biphenyl ] -2-yl) diphenylphosphine } (shown in the following structural formula), 1, 2-bis (thiophen-3-yl) acetylene is used as a raw material, and the method is referred to the method in example 2, so that the target product is obtained, and the yield of the target product is 58%.
Figure BDA0003000300100000204
Example 50
In the preparation method of the novel tri-substituted alkene biaryl monophosphine compound III-50{ (E) - (2'- (decyl-5-en-5-yl) - [1,1' -biphenyl ] -2-yl) diphenylphosphine } (shown in the following structural formula), the target product was obtained in a yield of 64% by using 5-decyne as a raw material according to the method of example 2.
Figure BDA0003000300100000211
From the above examples and the measured data, it can be seen that the method for preparing the novel tri-substituted olefin biaryl monophosphine compound by using the method of the present application is simple and convenient to operate, the required raw materials are cheap and easy to obtain, the production cost is reduced, the production efficiency is improved, the requirement on equipment in the synthesis process is low, and the method is suitable for industrial production.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.

Claims (6)

1. The synthesis method of the tri-substituted alkene biaryl monophosphine compound is characterized by comprising the following steps: the synthetic route is shown as follows,
Figure FDA0003709317590000011
wherein: r 1 Selected from silicon, alkyl, aryl or heteroaryl; r 2 Selected from alkyl, aryl or heteroaryl; r 3 Selected from hydrogen, alkyl, alkoxy, trifluoromethyl or halogen; r 4 Selected from the group consisting of hydrogen, alkyl, alkoxy, alkylmercapto, trifluoromethyl, halogen, aryloxy, naphthyl, ester, alkanoyl or nitrile groups; the ruthenium catalyst is p-cymene ruthenium dichloride dimer, the ligand is phenylglycine, and the alkali is potassium acetate.
2. The method for synthesizing the tri-substituted alkene biaryl monophosphine compound according to claim 1, wherein: the method specifically comprises the steps of taking a compound with a structural formula I and a compound with a structural formula II as raw materials, reacting at a constant temperature of 80-120 ℃ in an inert atmosphere in the presence of a ruthenium catalyst, a ligand, alkali and an organic solvent, cooling to room temperature, carrying out suction filtration, reduced pressure distillation and column chromatography separation on the obtained product, and obtaining the tri-substituted olefin tertiary phosphine compound III.
3. The method for synthesizing the tri-substituted alkene biaryl monophosphine compound according to claim 2, wherein: the molar ratio of the compound I to the compound II is 1.0-3.0: 1.
4. the method for synthesizing the tri-substituted alkene biaryl monophosphine compound according to claim 2, wherein: the organic solvent is any one or a mixture of more of alkane solvents, aromatic solvents, alcohol solvents, nitrile solvents, ether solvents, ketone solvents, amide solvents, chloralkane solvents and sulfoxide solvents.
5. The method for synthesizing the tri-substituted alkene biaryl monophosphine compound according to claim 2, wherein the method comprises the following steps: the molar ratio of the ligand to the compound II is 0.05-0.5: 1.
6. the method for synthesizing the tri-substituted alkene biaryl monophosphine compound according to claim 2, wherein: the molar ratio of the ruthenium catalyst to the compound II is 0.001-0.1: 1.
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