CN104003828A - Preparation method of amine and aromaticnitrile coupling reaction catalyzed by copper complex under visible light - Google Patents
Preparation method of amine and aromaticnitrile coupling reaction catalyzed by copper complex under visible light Download PDFInfo
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Abstract
The invention relates to a preparation method of an amine and aromaticnitrile coupling reaction catalyzed by a copper complex under visible light. The preparation method comprises the following steps: mixing a photocatalyst 2,9-dibutyl-1,10-phenanthroline bis(2-diphenylphosphinophenyl)ether cuprous complex with corresponding amines, aromaticnitrile and sodium acetate in a molar ratio of 0.005:3:1:2, adding a solvent N,N-dimethylacetamide, protecting a reaction system by using argon gas, and placing a fluorescent lamp 2 cm away from a reaction bottle; after corresponding time, diluting the reaction system by using ethyl acetate; and separating liquid, extracting a water layer by using ethyl acetate three times, combining organic layers, drying the obtained product by using anhydrous magnesium sulfate, and carrying out gel column chromatography isolation on the obtained product so as to obtain a corresponding product. The method has the beneficial effects that the used photocatalyst is a cuprous catalyst which is cheap and easily available; the method is simple in step, and high in yield; a great variety of amine and aromaticnitrile couped products are prepared; and visible light is taken as an energy source required for the reaction, therefore, the method is green and environmental-friendly.
Description
The subsidy that present patent application obtains state natural sciences fund (21102101,21172173) and Tianjin Normal University introduces talent's fund (5RL105).
Technical field
The invention belongs to organic chemical synthesis technical field, relate to the preparation method of a kind of univalent copper complex by phenanthroline class part and two (2-diphenylphosphine phenyl) ether mixtures linked reaction of catalytic amine and aromatic nitriles under visible ray.
Background technology
An important direction of organic chemistry development is exactly the synthetic method that finds a kind of mild condition, environmental protection and productive rate higher.Before the general century, gondola Ciamician finds that only a kind of reserves are abundant, clean energy (the G. Ciamician of environmental protection sustainable use catalyzed reaction, Science, 1912,36,385), and the product of light-catalyzed reaction, cannot synthesize through conventional other ordinary methods at all.Since then, photochemistry and light-catalyzed reaction are widely used in Synthetic Organic Chemistry field (N. Hoffmann, Chem. Rev. 2008,108,1052;
M. Fagnoni, D. Dondi, D. Ravelli and A. Albini, Chem. Rev. 2007, 107, 2725） 。But because the main absorption peak of organic compound is less in visible region, so also few with the example of visible light catalytic organic reaction at present, this is also by the developing direction that is organic chemistry forward position.Example that it can be much self-energy by visible light transformation that occurring in nature has (D. Gust and T. A. Moore,
science, 1989,244,35; T. J. Meyer, A
cc. Chem. Res., 1989,22,163; D. Gust, T. A. Moore and A. L. Moore,
acc. Chem. Res., 1993,26,198; V. Balzani, A. Credi andM. Venturi,
chemSusChem, 2008,1,26), this for chemists provide one can understand visible light catalytic transform a platform.
In numerous photocatalysts, photoredox agent is most important one, and it can be applied to photodissociation water, storage of solar energy, numerous Disciplinary Frontiers (K. Kalyanasundaram, the Coord. Chem. Rev. such as prototropy, and solar energy power generating are coupled, 1982,46,159; A. Juris, V. Balzani, F. Barigelletti, S. Campagna, P. Belser and A. von Zelewsky, Coord. Chem. Rev., 1988,84,85; V. Balzani, G. Bergamini, F. Marchioni and P. Ceroni, Coord. Chem. Rev., 2006,250,1254; X. Sala, I. Romero, M. Rodriguez, L. Escriche and A. Llobet, Angew. Chem., Int. Ed., 2009,48,2842; H. Cano-Yelo and A. Deronzier, J. Chem. Soc., Perkin Trans. 2,1984,1093).MacMillan seminar in 2011 reported with three (2-phenylpyridine) iridium as the linked reaction of catalyzer catalytic amine and aromatic nitriles under visible ray (A. McNally, C. K. Prier, D. W. C. MacMillan,
sCIENCE, 2011,334,1114), apply this reaction and can synthesize a lot of useful natural products, and this reaction at all cannot be successful by traditional method.But the catalyzer that this reaction is used is expensive iridium catalyst, this has just greatly hindered the practical application of this reaction and has popularized.
In recent years because copper compound has at a low price, nontoxic, the unrivaled advantages such as abundant Mineral resources, people's concern and interest are more and more caused, find through a large amount of research, can obtain the visible absorption frequency of needs and the stability of compound by the part of adjusting copper complex, thereby obtain good photocatalyst.Therefore, we openly use 2,9-dibutyl-1 here, the achievement in research of two (2-diphenylphosphine phenyl) the ether univalent copper complexs of 10-phenanthroline linked reaction of catalytic amine and aromatic nitriles under visible ray.
Summary of the invention
The present invention further provides dibutyl-1 with 2,9-, the preparation method of two (2-diphenylphosphine phenyl) the ether univalent copper complexs of 10-phenanthroline linked reaction of catalytic amine and aromatic nitriles under visible ray.
The invention discloses for achieving the above object following technology contents:
A kind of 9-dibutyl-1 that adopts, the preparation method of two (2-diphenylphosphine phenyl) the ether univalent copper complexs of 10-phenanthroline linked reaction of catalytic amine and aromatic nitriles under visible ray, it is characterized in that photocatalyst 2, 9-dibutyl-1, two (2-diphenylphosphine phenyl) the ether univalent copper complexs of 10-phenanthroline, corresponding amine, aromatic nitriles and sodium-acetate are according to the mixed in molar ratio of 0.005:3:1:2, add solvent N, N-N,N-DIMETHYLACETAMIDE, reaction system argon shield, place a power saving fluorescent lamp apart from reaction flask 2cm place, after the corresponding time, reaction system is diluted by ethyl acetate, separatory, water layer is extracted with ethyl acetate three times, organic layer merges, with anhydrous magnesium sulfate drying, separate by silica gel column chromatography, obtain corresponding coupled product,
The photocatalyst 2 of wherein said use, 9-dibutyl-1, two (2-diphenylphosphine phenyl) the ether univalent copper complexs of 10-phenanthroline, have the structure of general formula (I):
（I）
Wherein X
-be selected from BF
4 -, CF
3sO
3 -, ClO
4 -, PF
6 -, SbF
6 -, NO
3 -, Cl
-, Br
-, F
-.
The wherein said amine that can prepare and the coupled product of aromatic nitriles have the structure of logical formula II:
（Ⅱ）
Wherein R1-R3: hydrogen atom; The aliphatics substituting group that contains 1 to 20 carbon; The aromatic substituents that contains 1 to 20 carbon;
Containing the aliphatics substituting group of 1 to 20 carbon of aerobic, nitrogen, sulfur heteroatom or containing the aromatic substituents of 1 to 20 carbon of aerobic, nitrogen, sulfur heteroatom;
R1-R3 can be in ring, for containing the aliphatics substituting group of 1 to 20 carbon; The aromatic substituents that contains 1 to 20 carbon;
Containing the aliphatics substituting group of 1 to 20 carbon of aerobic, nitrogen, sulfur heteroatom or containing the aromatic substituents of 1 to 20 carbon of aerobic, nitrogen, sulfur heteroatom;
R1-R3 can be the same or different;
R4, for drawing electron substituent group, is selected from cyano group, carboxylic acid, ethyl ester base, carboxylate methyl ester base, p diethylaminobenzoic acid ester group.
Typical R1-R3: hydrogen atom, the aliphatics substituting group that contains 1 to 20 carbon, such as methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, sec.-propyl, the tertiary butyl, cyclohexyl, vinyl, allyl group etc., the aromatic substituents that contains 1 to 20 carbon, for example: phenyl, tolyl, ethylbenzene, trimethylphenylmethane base, cumyl, naphthyl, first naphthyl, tertiary fourth naphthyl etc., containing aerobic, nitrogen, the aliphatics substituting group of 1 to 20 carbon of sulfur heteroatom, for example methoxyl group, oxyethyl group, positive propoxy, n-butoxy, n-pentyloxy, positive hexyloxy, positive heptan oxygen base, isopropoxy, tert.-butoxy, hexamethylene yloxymethyl, methylamino, ethylamino-, Tri N-Propyl Amine base, n-butylamine-based, n-amylamine base, normal hexyl Amine base, positive heptyl amice base, isopropylamine base, TERTIARY BUTYL AMINE base, cyclohexylamino, first sulfydryl, second sulfydryl, positive the third sulfydryl, positive fourth sulfydryl, positive penta sulfydryl, just own sulfydryl, positive heptan sulfydryl, isopropyl sulfydryl, tertiary fourth sulfydryl, hexamethylene sulfydryl or containing aerobic, nitrogen, the aromatic substituents of 1 to 20 carbon of sulfur heteroatom, for example pyridyl, substituted pyridinyl, quinolyl, substd quinolines base, furyl, substituted furan base, thienyl, substituted thiophene base etc.
R1-R3 can be in ring, for containing the aliphatics substituting group of 1 to 20 carbon, and such as cyclopentyl, cyclohexyl, substituted ring amyl group base, substituted cyclohexyl etc.; The aromatic substituents that contains 1 to 20 carbon, for example: phenyl, tolyl, ethylbenzene, trimethylphenylmethane base, cumyl, naphthyl, first naphthyl, tertiary fourth naphthyl etc.; Containing the aliphatics substituting group of 1 to 20 carbon of aerobic, nitrogen, sulfur heteroatom such as tetrahydrofuran base, substituted tetrahydrofuran base, piperidyl, substituted piperidine base, Pyrrolidine base, replacement, Pyrrolidine base, tetrahydro-thienyl, substituted-tetrahydro thienyl or containing aromatic substituents such as pyridyl, substituted pyridinyl, quinolyl, substd quinolines base, furyl, substituted furan base, thienyl, the substituted thiophene base etc. of 1 to 20 carbon of aerobic, nitrogen, sulfur heteroatom; R1-R3 can be the same or different;
R4, for drawing electron substituent group, is selected from cyano group, carboxylic acid, ethyl ester base, carboxylate methyl ester base, p diethylaminobenzoic acid ester group.
Use 2 of the present invention, 9-dibutyl-1, the preparation method of two (2-diphenylphosphine phenyl) the ether univalent copper complexs of 10-phenanthroline linked reaction of catalytic amine and aromatic nitriles under visible ray is: by photocatalyst 2, 9-dibutyl-1, two (2-diphenylphosphine phenyl) the ether univalent copper complexs of 10-phenanthroline, corresponding amine, aromatic nitriles and sodium-acetate are according to the mixed in molar ratio of 0.005:3:1:2, add solvent N, N-N,N-DIMETHYLACETAMIDE, reaction system argon shield, place a power saving fluorescent lamp apart from reaction flask 2cm place, after the corresponding time, reaction system is diluted by ethyl acetate, separatory, water layer is extracted with ethyl acetate three times, organic layer merges, with anhydrous magnesium sulfate drying, separate by silica gel column chromatography, obtain corresponding coupled product.
Its synthetic route is as follows:
X
-be selected from BF
4 -, CF
3sO
3 -, ClO
4 -, PF
6 -, SbF
6 -, NO
3 -, Cl
-, Br
-, F
-.
1-18 is amine and the aromatic nitriles coupling compound being synthesized by above-mentioned route below, is also the structural formula of compound in embodiment:
Wherein 1 chemical name is 4-(1-phenylpyrrole alkyl-2-) cyanobenzene;
Wherein 2 chemical name is 4-(1-Phenylpiperidine base-2-) cyanobenzene;
Wherein 3 chemical name is 4-(4-phenylmorpholine base-3-) cyanobenzene;
Wherein 4 chemical name is 3-(4-cyano-phenyl)-4-phenylpiperazine-1-t-butyl formate;
Wherein 5 chemical name is 4-(1-phenyl azepan base-2-) cyanobenzene;
Wherein 6 chemical name is 4-(1-(ethyl (phenyl (amido) ethyl) cyanobenzene;
Wherein 7 chemical name is 4-(1-(p-methylphenyl) pyrrolidyl-2-) cyanobenzene;
Wherein 8 chemical name is 4-(1-(4-fluorophenyl) pyrrolidyl-2-) cyanobenzene;
Wherein 9 chemical name is 4-(1-(4-bromophenyl) pyrrolidyl-2-) cyanobenzene;
Wherein 10 chemical name is 4-(1-(naphthyl-2-) pyrrolidyl-2-) cyanobenzene;
Wherein 11 chemical name is 4-(1-(4-p-methoxy-phenyl) pyrrolidyl-2-) cyanobenzene;
Wherein 12 chemical name is 4-(1-(4,4-dimethoxy butyl-2-) pyrrolidyl-2-) cyanobenzene;
Wherein 13 chemical name is 4-(1-benzylindole base-2-) cyanobenzene;
Wherein 14 chemical name is 4-(1-(4-methoxy-benzyl) indyl-2-) cyanobenzene;
Wherein 15 chemical name is 4-(1-benzyl-1,2,3,4-tetrahydroquinoline-2-) cyanobenzene;
Wherein 16 chemical name is 4-(2-(4-p-methoxy-phenyl)-1,2,3,4-tetrahydro isoquinolyl-1-) cyanobenzene;
Wherein 17 chemical name is 4-(1-phenylpyrrole base-2-) ethyl benzoate;
Wherein 18 chemical name is (4-(1-phenylpyrrole base-2-) phenyl) diethyl phosphoric acid.
The beneficial effect of present method is that raw material and catalyzer are cheap and easy to get, and step is simple, and productive rate is high, uses visible light catalytic, environmental protection low-carbon (LC), and occurring in nature luminous energy deposit is abundant, and the kind of the amine that can prepare and the coupled product of aromatic nitriles is a lot.
Embodiment
Below in conjunction with embodiment, the present invention is described, the scheme of embodiment described here, do not limit the present invention, one of skill in the art can make improvements and change according to spirit of the present invention, these described improvement and changing all should be considered as in scope of the present invention, and the requirement of all having the right of scope of the present invention and essence limits; Wherein said photocatalyst 2,9-dibutyl-1, two (2-diphenylphosphine phenyl) ether univalent copper complex (the D. G. Cuttell of 10-phenanthroline, Shan-Ming Kuang, P. E. Fanwick, D. R. McMillin, and R. A. Walton
j. Am. Chem. Soc. 2002,
124, 6), various pyrrolidin derivatives raw material (A. McNally, C. K. Prier, D. W. C. MacMillan,
sCIENCE, 2011,334,1114), various piperidine derivatives raw materials (A. McNally, C. K. Prier, D. W. C. MacMillan,
sCIENCE, 2011,334,1114) prepare according to literature method.Except particularly pointing out, remaining tetrem nitrile cuprous salt, diimine class part and all kinds of SOLVENTS, by commercially available.
Embodiment 1 (4-(1-phenylpyrrole alkyl-2-) cyanobenzene)
In the Schlenk of 25mL bottle, add 4.9 mg photocatalyst tetrafluoroborates 2, 9-dibutyl-1, two (2-diphenylphosphine phenyl) ether univalent copper complex (the 5.0 μ mol of 10-phenanthroline, 0.005 equiv.), 164.1 mg sodium acetate, anhydrous (2.0 mmol, 2.0 equiv.), 128.1 mg para-Phthalonitrile (1.0 mmol, 1.0 equiv.), 433.6 μ L N-Phenylpyrrolidine (3.0 mmol, 3.0 equiv.) and 4.0 mL DMA, reaction system argon shield, place the power saving fluorescent lamp of a 26W apart from reaction flask 2cm place, after 12 hours, reaction system is diluted by ethyl acetate, separatory, water layer is extracted with ethyl acetate three times, organic layer merges, with anhydrous magnesium sulfate drying, separate by silica gel column chromatography, obtain corresponding coupled product, 225 mg, productive rate: 91%.
1 H NMR (400MHz, CDCl
3) δ 7.58 (2H, d), 7.53 (2H, d), 7.14 (2H, dd), 6.66 (1H, m), 6.45-6.41 (2H, m), 4.73 (1H, dd), 3.75-3.69 (1H, m), 3.45-3.38 (1H, m), 2.48-2.38 (1H, m) 2.06-1.86 (3H, m); HRMS (ESI) exact mass calculated for [M+1] (C
17H
17N
2) requires
m/z 249.1392,found
m/z 249.1387.
Embodiment 2 (4-(1-Phenylpiperidine base-2-) cyanobenzene)
In the Schlenk of 25mL bottle, add 4.9 mg photocatalyst tetrafluoroborates 2, 9-dibutyl-1, two (2-diphenylphosphine phenyl) ether univalent copper complex (the 5.0 μ mol of 10-phenanthroline, 0.005 equiv.), 164.1 mg sodium acetate, anhydrous (2.0 mmol, 2.0 equiv.), 128.1 mg para-Phthalonitrile (1.0 mmol, 1.0 equiv.), 483.7 μ L N-Phenylpiperidine (3.0 mmol, 3.0 equiv.) and 4.0 mL DMA, reaction system argon shield, place the power saving fluorescent lamp of a 26W apart from reaction flask 2cm place, after 12 hours, reaction system is diluted by ethyl acetate, separatory, water layer is extracted with ethyl acetate three times, organic layer merges, with anhydrous magnesium sulfate drying, separate by silica gel column chromatography, obtain corresponding coupled product, 237 mg, productive rate: 90%.
1 H NMR (400MHz, CDCl
3) δ 7.47 (2H, d), 7.36 (2H, d), 7.11 (2H, dd), 6.85 (2H, dd), 6.79 (1H, t), 4.37 (1H, dd), 3.39 (1H, ddd), 3.11 (1H, ddd), 1.98-1.92 (1H, m), 1.86-1.65 (4H, m), 1.59-1.48 (1H, m); HRMS (ESI) exact mass calculated for [M+1] (C
18H
19N
2) requires m/z 263.1543, found m/z 263.1544.
Embodiment 3 (4-(4-phenylmorpholine base-3-) cyanobenzene)
In the Schlenk of 25mL bottle, add 4.9 mg photocatalyst tetrafluoroborates 2, 9-dibutyl-1, two (2-diphenylphosphine phenyl) ether univalent copper complex (the 5.0 μ mol of 10-phenanthroline, 0.005 equiv.), 164.1 mg sodium acetate, anhydrous (2.0 mmol, 2.0 equiv.), 128.1 mg para-Phthalonitrile (1.0 mmol, 1.0 equiv.), 489.7 μ L N-phenyl-morpholine (3.0 mmol, 3.0 equiv.) and 4.0 mL DMA, reaction system argon shield, place the power saving fluorescent lamp of a 26W apart from reaction flask 2cm place, after 12 hours, reaction system is diluted by ethyl acetate, separatory, water layer is extracted with ethyl acetate three times, organic layer merges, with anhydrous magnesium sulfate drying, separate by silica gel column chromatography, obtain corresponding coupled product, 239 mg, productive rate: 90%.
1 H NMR (400MHz, CDCl
3) δ 7.48 (2H, d), 7.41 (2H, d), 7.14 (2H, dd), 6.90-6.85 (3H, m), 4.40 (1H, dd), 3.43-3.37 (1H, m), 3.15-3.06 (1H, m), 3.99-3.91 (3H, m), 3.59 (1H, dd); HRMS (ESI) exact mass calculated for [M+1] (C
17H
17N
2O) requires
m/z 265.1335, found
m/z 265.1335.
Embodiment 4 (3-(4-cyano-phenyl)-4-phenylpiperazine-1-t-butyl formate)
In the Schlenk of 25mL bottle, add 4.9 mg photocatalyst tetrafluoroborates 2, 9-dibutyl-1, two (2-diphenylphosphine phenyl) ether univalent copper complex (the 5.0 μ mol of 10-phenanthroline, 0.005 equiv.), 164.1 mg sodium acetate, anhydrous (2.0 mmol, 2.0 equiv.), 128.1 mg para-Phthalonitrile (1.0 mmol, 1.0 equiv.), 787.1 mg 4-phenylpiperazine-1-t-butyl formate (3.0 mmol, 3.0 equiv.) and 4.0 mL DMA, reaction system argon shield, place the power saving fluorescent lamp of a 26W apart from reaction flask 2cm place, after 12 hours, reaction system is diluted by ethyl acetate, separatory, water layer is extracted with ethyl acetate three times, organic layer merges, with anhydrous magnesium sulfate drying, separate by silica gel column chromatography, obtain corresponding coupled product, 328 mg, productive rate: 90%.
1H NMR (400 MHz, CDCl
3) δ 7.51 (2H, d), 7.42 (2H, d,), 7.14 (2H, dd), 6.86-6.75 (3H, m), 4.48 (1H, dd), 4.05-3.67 (2H, br m), 3.65-3.10 (4H, br m), 1.39 (9H, s); HRMS (ESI) exact mass calculated for [M+1] (C
22H
26N
3O
2) requires m/z 364.2020, found m/z 364.2020.
Embodiment 5 (4-(1-phenyl azepan base-2-) cyanobenzene)
In the Schlenk of 25mL bottle, add 4.9 mg photocatalyst tetrafluoroborates 2, 9-dibutyl-1, two (2-diphenylphosphine phenyl) ether univalent copper complex (the 5.0 μ mol of 10-phenanthroline, 0.005 equiv.), 164.1 mg sodium acetate, anhydrous (2.0 mmol, 2.0 equiv.), 128.1 mg para-Phthalonitrile (1.0 mmol, 1.0 equiv.), 526 mg 1-phenyl azepan (3.0 mmol, 3.0 equiv.) and 4.0 mL DMA, reaction system argon shield, place the power saving fluorescent lamp of a 26W apart from reaction flask 2cm place, after 12 hours, reaction system is diluted by ethyl acetate, separatory, water layer is extracted with ethyl acetate three times, organic layer merges, with anhydrous magnesium sulfate drying, separate by silica gel column chromatography, obtain corresponding coupled product, 226 mg, productive rate: 82%.
1H NMR (400 MHz, CDCl
3) δ 7.58 (2H, d), 7.29 (2H, d), 7.14 (2H, dd), 6.64 (1H, t), 6.54 (2H, d), 4.61 (1H, dd), 3.88-3.81 (1H, m), 3.46(1H, ddd), 2.47-2.38 (1H, m), 2.00-1.63 (5H, m), 1.52-1.28 (2H, m); HRMS (ESI) exact mass calculated for [M+1](C
19H
21N
2) requires m/z 277.1699, found m/z 263.1700.
Embodiment 6(4-(1-(ethyl (phenyl (amido) ethyl) cyanobenzene)
In the Schlenk of 25mL bottle, add 4.9 mg photocatalyst tetrafluoroborates 2, 9-dibutyl-1, two (2-diphenylphosphine phenyl) ether univalent copper complex (the 5.0 μ mol of 10-phenanthroline, 0.005 equiv.), 164.1 mg sodium acetate, anhydrous (2.0 mmol, 2.0 equiv.), 128.1 mg para-Phthalonitrile (1.0 mmol, 1.0 equiv.), 489.7 μ L N, N-Diethyl Aniline (3.0 mmol, 3.0 equiv.) and 4.0 mL DMA, reaction system argon shield, place the power saving fluorescent lamp of a 26W apart from reaction flask 2cm place, after 12 hours, reaction system is diluted by ethyl acetate, separatory, water layer is extracted with ethyl acetate three times, organic layer merges, with anhydrous magnesium sulfate drying, separate by silica gel column chromatography, obtain corresponding coupled product, 228 mg, productive rate: 91%.
1H NMR (400 MHz, CDCl
3) δ 7.64 (2H, d ), 7.46 (2H, d ), 7.30-7.21 (2H, m ), 6.84-6.71 (3H, m ), 5.06 (1H, q ), 3.26 (2H, t ), 1.63 (3H, d ), 1.15(3H, t ); HRMS (ESI) exact mass calculated for [M+1](C
17H
19N
2) requires m/z 251.1543, found m/z 251.1542.
Embodiment 7(4-(1-(p-methylphenyl) pyrrolidyl-2-) cyanobenzene)
In the Schlenk of 25mL bottle, add 4.9 mg photocatalyst tetrafluoroborates 2, 9-dibutyl-1, two (2-diphenylphosphine phenyl) ether univalent copper complex (the 5.0 μ mol of 10-phenanthroline, 0.005 equiv.), 164.1 mg sodium acetate, anhydrous (2.0 mmol, 2.0 equiv.), 128.1 mg para-Phthalonitrile (1.0 mmol, 1.0 equiv.), 483.7 mg N-p-methylphenyl tetramethyleneimine (3.0 mmol, 3.0 equiv.) and 4.0 mL DMA, reaction system argon shield, place the power saving fluorescent lamp of a 26W apart from reaction flask 2cm place, after 12 hours, reaction system is diluted by ethyl acetate, separatory, water layer is extracted with ethyl acetate three times, organic layer merges, with anhydrous magnesium sulfate drying, separate by silica gel column chromatography, obtain corresponding coupled product, 239 mg, productive rate: 91%.
1H NMR (400 MHz, CDCl
3) δ 7.57 (2H, d), 7.33 (2H, d), 6.95 (2H, d), 6.34 (2H, d), 4.68 (1H, dd), 3.75-3.68 (1H, m), 3.42-3.34 (1H, m), 2.47-2.36 (1H, m), 2.20 (3H, s), 2.04-1.84 (3H, m); HRMS (ESI) exact mass calculated for [M+1] (C
18H
19N
2) requires m/z 263.1543, found m/z 263.1543.
Embodiment 8(4-(1-(4-fluorophenyl) pyrrolidyl-2-) cyanobenzene)
In the Schlenk of 25mL bottle, add 4.9 mg photocatalyst tetrafluoroborates 2, 9-dibutyl-1, two (2-diphenylphosphine phenyl) ether univalent copper complex (the 5.0 μ mol of 10-phenanthroline, 0.005 equiv.), 164.1 mg sodium acetate, anhydrous (2.0 mmol, 2.0 equiv.), 128.1 mg para-Phthalonitrile (1.0 mmol, 1.0 equiv.), 510.6 mg N-(4-fluorophenyls) tetramethyleneimine (3.0 mmol, 3.0 equiv.) and 4.0 mL DMA, reaction system argon shield, place the power saving fluorescent lamp of a 26W apart from reaction flask 2cm place, after 12 hours, reaction system is diluted by ethyl acetate, separatory, water layer is extracted with ethyl acetate three times, organic layer merges, with anhydrous magnesium sulfate drying, separate by silica gel column chromatography, obtain corresponding coupled product, 241 mg, productive rate: 91%.
1H NMR (400 MHz, CDCl
3) δ 7.58 (2H, d), 7.32 (2H, d), 6.89-6.80 (2H, m), 6.37-6.28 (2H, m), 4.65 (1H, dd), 3.73-3.66 (1H, m), 3.40-3.33 (1H, m), 2.50-2.38 (1H, m),2.10-1.84 (3H, m); HRMS (ESI) exact mass calculated for [M+1] (C
17H
16FN
2)requires m/z 267.1292, found m/z 267.1293.
Embodiment 9(4-(1-(4-bromophenyl) pyrrolidyl-2-) cyanobenzene)
In the Schlenk of 25mL bottle, add 4.9 mg photocatalyst tetrafluoroborates 2, 9-dibutyl-1, two (2-diphenylphosphine phenyl) ether univalent copper complex (the 5.0 μ mol of 10-phenanthroline, 0.005 equiv.), 164.1 mg sodium acetate, anhydrous (2.0 mmol, 2.0 equiv.), 128.1 mg para-Phthalonitrile (1.0 mmol, 1.0 equiv.), 510.6 mg N-(4-bromophenyls) tetramethyleneimine (3.0 mmol, 3.0 equiv.) and 4.0 mL DMA, reaction system argon shield, place the power saving fluorescent lamp of a 26W apart from reaction flask 2cm place, after 12 hours, reaction system is diluted by ethyl acetate, separatory, water layer is extracted with ethyl acetate three times, organic layer merges, with anhydrous magnesium sulfate drying, separate by silica gel column chromatography, obtain corresponding coupled product, 262 mg, productive rate: 80%.
1H NMR (400 MHz, CDCl
3) δ7.58 (2H, d), 7.28 (2H, d), 7.27 (2H, d), 7.19 (2H, d) 4.68 (1H, dd), 3.70-3.64 (1H, m), 3.40-3.34 (1H, m), 2.48-2.38 (1H, m), 2.06-1.86 (3H, m); HRMS (ESI) exact mass calculated for [M+1] (C
17H
16BrN
2) requires m/z 327.0491, found m/z 327.0492.
Embodiment 10(4-(1-(naphthyl-2-) pyrrolidyl-2-) cyanobenzene)
In the Schlenk of 25mL bottle, add 4.9 mg photocatalyst tetrafluoroborates 2, 9-dibutyl-1, two (2-diphenylphosphine phenyl) ether univalent copper complex (the 5.0 μ mol of 10-phenanthroline, 0.005 equiv.), 164.1 mg sodium acetate, anhydrous (2.0 mmol, 2.0 equiv.), 128.1 mg para-Phthalonitrile (1.0 mmol, 1.0 equiv.), 591.8 mg N-(naphthyl-2-) tetramethyleneimine (3.0 mmol, 3.0 equiv.) and 4.0 mL DMA, reaction system argon shield, place the power saving fluorescent lamp of a 26W apart from reaction flask 2cm place, after 12 hours, reaction system is diluted by ethyl acetate, separatory, water layer is extracted with ethyl acetate three times, organic layer merges, with anhydrous magnesium sulfate drying, separate by silica gel column chromatography, obtain corresponding coupled product, 253mg, productive rate: 85%.
1H NMR (400 MHz, CDCl
3) δ 7.67-7.49 (5H, m), 7.38-7.27 (3H, m), 7.14 (1H, ddd), 6.77 (1H, dd), 6.66 (1H, d), 4.89 (1H, dd), 3.86-3.80 (1H, m), 3.58-3.50 (1H, m), 2.53-2.42 (1H, m), 2.12-1.87 (3H, m); HRMS (ESI) exact mass calculated for [M+1] (C
21H
19N
2) requires m/z 299.1543, found m/z 299.1543.
Embodiment 11(4-(1-(4-p-methoxy-phenyl) pyrrolidyl-2-) cyanobenzene)
In the Schlenk of 25mL bottle, add 4.9 mg photocatalyst tetrafluoroborates 2, 9-dibutyl-1, two (2-diphenylphosphine phenyl) ether univalent copper complex (the 5.0 μ mol of 10-phenanthroline, 0.005 equiv.), 164.1 mg sodium acetate, anhydrous (2.0 mmol, 2.0 equiv.), 128.1 mg para-Phthalonitrile (1.0 mmol, 1.0 equiv.), 531.6 mg N-p-methoxyphenyl tetramethyleneimine (3.0 mmol, 3.0 equiv.) and 4.0 mL DMA, reaction system argon shield, place the power saving fluorescent lamp of a 26W apart from reaction flask 2cm place, after 12 hours, reaction system is diluted by ethyl acetate, separatory, water layer is extracted with ethyl acetate three times, organic layer merges, with anhydrous magnesium sulfate drying, separate by silica gel column chromatography, obtain corresponding coupled product, 236mg, productive rate: 85%.
1H NMR (400 MHz, CDCl
3) δ7.57 (2H, d), 7.34 (2H, d), 6.74 (2H, d), 6.36 (2H, d), 4.63 (1H, dd), 3.73-3.63 (4H, m), 3.39-3.31 (1H, m), 2.47-2.36 (1H, m), 2.02-1.91 (2H, m), 1.91-1.83 (1H, m); HRMS (ESI) exact mass calculated for [M+1] (C
18H
19N
2O) requires m/z 279.1492, found m/z 279.1491.
Embodiment 12(4-(1-(4,4-dimethoxy butyl-2-) pyrrolidyl-2-) cyanobenzene)
In the Schlenk of 25mL bottle, add 4.9 mg photocatalyst tetrafluoroborates 2, 9-dibutyl-1, two (2-diphenylphosphine phenyl) ether univalent copper complex (the 5.0 μ mol of 10-phenanthroline, 0.005 equiv.), 164.1 mg sodium acetate, anhydrous (2.0 mmol, 2.0 equiv.), 128.1 mg para-Phthalonitrile (1.0 mmol, 1.0 equiv.), 562 mg 1-(4, 4-dimethoxy butyl-2-) tetramethyleneimine (3.0 mmol, 3.0 equiv.) and 4.0 mL DMA, reaction system argon shield, place the power saving fluorescent lamp of a 26W apart from reaction flask 2cm place, after 24 hours, reaction system is diluted by ethyl acetate, separatory, water layer is extracted with ethyl acetate three times, organic layer merges, with anhydrous magnesium sulfate drying, separate by silica gel column chromatography, obtain corresponding coupled product, 218mg, productive rate: 76%.
1H NMR (400 MHz, CDCl
3) δ7.56 (2H, d), 7.45 (2H, d), 4.28 (1H, dd), 3.80 (1H, dd), 3.25 (3H, s), 3.14-3.08 (4H, m), 2.74-2.65 (1H, m), 2.61 (1H, q), 2.18-2.07 (1H, m), 1.89-1.68 (3H, m), 1.61-1.36 (2H, m), 1.04 (3H, d); HRMS (ESI) exact mass calculated for [M+1] (C
17H
25N
2O
2) requires m/z 289.1911, found m/z 289.1911.
Embodiment 13(4-(1-benzylindole base-2-) cyanobenzene)
In the Schlenk of 25mL bottle, add 4.9 mg photocatalyst tetrafluoroborates 2, 9-dibutyl-1, two (2-diphenylphosphine phenyl) ether univalent copper complex (the 5.0 μ mol of 10-phenanthroline, 0.005 equiv.), 164.1 mg sodium acetate, anhydrous (2.0 mmol, 2.0 equiv.), 128.1 mg para-Phthalonitrile (1.0 mmol, 1.0 equiv.), 629 mg N-benzylindole (3.0 mmol, 3.0 equiv.) and 4.0 mL DMA, reaction system argon shield, place the power saving fluorescent lamp of a 26W apart from reaction flask 2cm place, after 12 hours, reaction system is diluted by ethyl acetate, separatory, water layer is extracted with ethyl acetate three times, organic layer merges, with anhydrous magnesium sulfate drying, separate by silica gel column chromatography, obtain corresponding coupled product, 278mg, productive rate: 90%.
1H NMR (400 MHz, CDCl
3) δ 7.58 (2H, d), 7.49 (2H, d), 7.28-7.14 (5H, m), 7.09-7.02 (2H, m), 6.71, (1H, dd), 6.46 (1H, d, J = 8.0 Hz), 4.65 (1H, t), 4.34 (1H, d), 3.96 (1H, d), 3.41 (1H, dd), 2.92 (1H, dd) HRMS (ESI) exact mass calculated for [M+1] (C
22H
19N
2) requires m/z 311.1543,found m/z 311.1544.
Embodiment 14(4-(1-(4-methoxy-benzyl) indyl-2-) cyanobenzene)
In the Schlenk of 25mL bottle, add 4.9 mg photocatalyst tetrafluoroborates 2, 9-dibutyl-1, two (2-diphenylphosphine phenyl) ether univalent copper complex (the 5.0 μ mol of 10-phenanthroline, 0.005 equiv.), 164.1 mg sodium acetate, anhydrous (2.0 mmol, 2.0 equiv.), 128.1 mg para-Phthalonitrile (1.0 mmol, 1.0 equiv.), 717.8 mg N-are to methoxy-benzyl indoles (3.0 mmol, 3.0 equiv.) and 4.0 mL DMA, reaction system argon shield, place the power saving fluorescent lamp of a 26W apart from reaction flask 2cm place, after 24 hours, reaction system is diluted by ethyl acetate, separatory, water layer is extracted with ethyl acetate three times, organic layer merges, with anhydrous magnesium sulfate drying, separate by silica gel column chromatography, obtain corresponding coupled product, 318mg, productive rate: 94%.
1H NMR (400 MHz, CDCl
3) δ 7.61 (2H, d), 7.49 (2H, d), 7.10-7.01 (4H, m), 6.77 (2H, d), 6.70, (1H, dd), 6.50 (1H, d), 4.61 (1H, t), 4.31 (1H, d), 3.88 (1H, d), 3.76 (3H, s), 3.39 (1H, dd), 2.89 (1H, dd); HRMS (ESI) exact mass calculated for [M+1] (C
23H
21N
2O) requires m/z 341.1654, found m/z 341.1650.
Embodiment 15 4-(1-benzyl-1,2,3,4-tetrahydroquinoline-2-) cyanobenzene)
In the Schlenk of 25mL bottle, add 4.9 mg photocatalyst tetrafluoroborates 2, 9-dibutyl-1, two (2-diphenylphosphine phenyl) ether univalent copper complex (the 5.0 μ mol of 10-phenanthroline, 0.005 equiv.), 164.1 mg sodium acetate, anhydrous (2.0 mmol, 2.0 equiv.), 128.1 mg para-Phthalonitrile (1.0 mmol, 1.0 equiv.), 669.6 mg N-benzyl-1, 2, 3, 4-tetrahydroquinoline (3.0 mmol, 3.0 equiv.) and 4.0 mL DMA, reaction system argon shield, place the power saving fluorescent lamp of a 26W apart from reaction flask 2cm place, after 14 hours, reaction system is diluted by ethyl acetate, separatory, water layer is extracted with ethyl acetate three times, organic layer merges, with anhydrous magnesium sulfate drying, separate by silica gel column chromatography, obtain corresponding coupled product, 285mg, productive rate: 88%.
1H NMR (400 MHz, CDCl
3) δ 7.58 (2H, d), 7.33-7.14 (7H, m), 7.07-6.97 (2H, m), 6.64 (1H, dd), 6.59 (1H, d), 4.77-4.68 (2H, m), 4.13 (1H, d), 2.63 (1H, ddd), 2.50 (1H, ddd), 2.37-2.25 (1H, m), 2.10-2.01 (1H, m); HRMS (ESI) exact mass calculated for [M+1] (C
23H
21N
2) requires m/z 325.1699, found m/z 325.1701.
Embodiment 16(4-(2-(4-p-methoxy-phenyl)-1,2,3,4-tetrahydro isoquinolyl-1-) cyanobenzene)
In the Schlenk of 25mL bottle, add 4.9 mg photocatalyst tetrafluoroborates 2, 9-dibutyl-1, two (2-diphenylphosphine phenyl) ether univalent copper complex (the 5.0 μ mol of 10-phenanthroline, 0.005 equiv.), 164.1 mg sodium acetate, anhydrous (2.0 mmol, 2.0 equiv.), 128.1 mg para-Phthalonitrile (1.0 mmol, 1.0 equiv.), 718 mg N-p-methoxyphenyl-1, 2, 3, 4-tetrahydroquinoline (3.0 mmol, 3.0 equiv.) and 4.0 mL DMA, reaction system argon shield, place the power saving fluorescent lamp of a 26W apart from reaction flask 2cm place, after 12 hours, reaction system is diluted by ethyl acetate, separatory, water layer is extracted with ethyl acetate three times, organic layer merges, with anhydrous magnesium sulfate drying, separate by silica gel column chromatography, obtain corresponding coupled product, 276mg, productive rate: 81%.
1H NMR (400 MHz, CDCl
3) δ7.48 (2H, d), 7.30-7.13 (5H, m), 7.10-7.04 (1H, m), 6.77 (4H, s), 5.62 (1H, s), 3.73 (3H, s), 3.54-3.45 (1H, m), 3.42-3.33 (1H, m), 2.99-2.88 (2H, m); HRMS (ESI) exact mass calculated for [M+1] (C
21H
22N
2O) requires m/z 341.1648, found m/z 341.1648.
Embodiment 17(4-(1-phenylpyrrole base-2-) ethyl benzoate)
In the Schlenk of 25mL bottle, add 4.9 mg photocatalyst tetrafluoroborates 2, 9-dibutyl-1, two (2-diphenylphosphine phenyl) ether univalent copper complex (the 5.0 μ mol of 10-phenanthroline, 0.005 equiv.), 164.1 mg sodium acetate, anhydrous (2.0 mmol, 2.0 equiv.), 175.2 mg 4-cyanobenzoic acid ethyl ester (1.0 mmol, 1.0 equiv.), 433.6 μ L N-Phenylpyrrolidine (3.0 mmol, 3.0 equiv.) and 4.0 mL DMA, reaction system argon shield, place the power saving fluorescent lamp of a 26W apart from reaction flask 2cm place, after 16 hours, reaction system is diluted by ethyl acetate, separatory, water layer is extracted with ethyl acetate three times, organic layer merges, with anhydrous magnesium sulfate drying, separate by silica gel column chromatography, obtain corresponding coupled product, 255mg, productive rate: 86%.
1H NMR (400 MHz, CDCl
3) δ 7.95 (2H, d), 7.28 (2H, d), 7.12 (2H, dd), 6.66 (1H, t), 6.44 (2H, d), 4.73 (1H, dd), 4.33 (2H, q, 3.75-3.68 (1H, m), 3.44-3.36 (1H, m), 2.45-2.35 (1H, m), 2.02-1.95 (2H, m), 1.94-1.87 (1H, m), 1.35 (3H, d); HRMS (ESI) exact mass calculated for [M+1] (C
19H
22NO
2) requires m/z 296.1645, found m/z 296.1645.
Embodiment 18((4-(1-phenylpyrrole base-2-) phenyl) diethyl phosphoric acid)
In the Schlenk of 25mL bottle, add 4.9 mg photocatalyst tetrafluoroborates 2, 9-dibutyl-1, two (2-diphenylphosphine phenyl) ether univalent copper complex (the 5.0 μ mol of 10-phenanthroline, 0.005 equiv.), 164.1 mg sodium acetate, anhydrous (2.0 mmol, 2.0 equiv.), 216.2 mg 4-(morpholinyl-4-carbonyls) cyanobenzene (1.0 mmol, 1.0 equiv.), 433.6 μ L N-Phenylpyrrolidine (3.0 mmol, 3.0 equiv.) and 4.0 mL DMA, reaction system argon shield, place the power saving fluorescent lamp of a 26W apart from reaction flask 2cm place, after 24 hours, reaction system is diluted by ethyl acetate, separatory, water layer is extracted with ethyl acetate three times, organic layer merges, with anhydrous magnesium sulfate drying, separate by silica gel column chromatography, obtain corresponding coupled product, 243mg, productive rate: 68%.
1H NMR (400 MHz, CDCl
3) δ7.32 (2H, d), 7.25 (2H, d), 7.13 (2H, dd), 6.63 (1H, t), 6.45 (2H, d), 4.71 (1H, dd),3.86-3.32 (10H, m), 2.44-2.31 (1H, m), 2.02-1.95 (3H, m); HRMS (ESI) exact mass calculated for [M+1] (C
21H
25N
2O) requires m/z 337.1911, found m/z 337.1912.
Embodiment 19 (4-(1-phenylpyrrole alkyl-2-) cyanobenzene)
In the Schlenk of 25mL bottle, add 5.2 mg photocatalyst hexafluoro-phosphate radicals 2, 9-dibutyl-1, two (2-diphenylphosphine phenyl) ether univalent copper complex (the 5.0 μ mol of 10-phenanthroline, 0.005 equiv.), 164.1 mg sodium acetate, anhydrous (2.0 mmol, 2.0 equiv.), 128.1 mg para-Phthalonitrile (1.0 mmol, 1.0 equiv.), 433.6 μ L N-Phenylpyrrolidine (3.0 mmol, 3.0 equiv.) and 4.0 mL DMA, reaction system argon shield, place the power saving fluorescent lamp of a 26W apart from reaction flask 2cm place, after 12 hours, reaction system is diluted by ethyl acetate, separatory, water layer is extracted with ethyl acetate three times, organic layer merges, with anhydrous magnesium sulfate drying, separate by silica gel column chromatography, obtain corresponding coupled product, 218 mg, productive rate: 88%.
1 H NMR (400MHz, CDCl
3) δ 7.58 (2H, d), 7.53 (2H, d), 7.14 (2H, dd), 6.66 (1H, m), 6.45-6.41 (2H, m), 4.73 (1H, dd), 3.75-3.69 (1H, m), 3.45-3.38 (1H, m), 2.48-2.38 (1H, m) 2.06-1.86 (3H, m); HRMS (ESI) exact mass calculated for [M+1] (C
17H
17N
2) requires
m/z 249.1392,found
m/z 249.1387.
Embodiment 20 (4-(1-phenylpyrrole alkyl-2-) cyanobenzene)
In the Schlenk of 25mL bottle, add 4.8 mg photocatalyst nitrate radicals 2, 9-dibutyl-1, two (2-diphenylphosphine phenyl) ether univalent copper complex (the 5.0 μ mol of 10-phenanthroline, 0.005 equiv.), 164.1 mg sodium acetate, anhydrous (2.0 mmol, 2.0 equiv.), 128.1 mg para-Phthalonitrile (1.0 mmol, 1.0 equiv.), 433.6 μ L N-Phenylpyrrolidine (3.0 mmol, 3.0 equiv.) and 4.0 mL DMA, reaction system argon shield, place the power saving fluorescent lamp of a 26W apart from reaction flask 2cm place, after 12 hours, reaction system is diluted by ethyl acetate, separatory, water layer is extracted with ethyl acetate three times, organic layer merges, with anhydrous magnesium sulfate drying, separate by silica gel column chromatography, obtain corresponding coupled product, 209 mg, productive rate: 84%.
1 H NMR (400MHz, CDCl
3) δ 7.58 (2H, d), 7.53 (2H, d), 7.14 (2H, dd), 6.66 (1H, m), 6.45-6.41 (2H, m), 4.73 (1H, dd), 3.75-3.69 (1H, m), 3.45-3.38 (1H, m), 2.48-2.38 (1H, m) 2.06-1.86 (3H, m); HRMS (ESI) exact mass calculated for [M+1] (C
17H
17N
2) requires
m/z 249.1392,found
m/z 249.1387.
Embodiment 21 (4-(1-phenylpyrrole alkyl-2-) cyanobenzene)
In the Schlenk of 25mL bottle, add 5.0 mg photocatalyst perchlorates 2, 9-dibutyl-1, two (2-diphenylphosphine phenyl) ether univalent copper complex (the 5.0 μ mol of 10-phenanthroline, 0.005 equiv.), 164.1 mg sodium acetate, anhydrous (2.0 mmol, 2.0 equiv.), 128.1 mg para-Phthalonitrile (1.0 mmol, 1.0 equiv.), 433.6 μ L N-Phenylpyrrolidine (3.0 mmol, 3.0 equiv.) and 4.0 mL DMA, reaction system argon shield, place the power saving fluorescent lamp of a 26W apart from reaction flask 2cm place, after 12 hours, reaction system is diluted by ethyl acetate, separatory, water layer is extracted with ethyl acetate three times, organic layer merges, with anhydrous magnesium sulfate drying, separate by silica gel column chromatography, obtain corresponding coupled product, 220 mg, productive rate: 89%.
1 H NMR (400MHz, CDCl
3) δ 7.58 (2H, d), 7.53 (2H, d), 7.14 (2H, dd), 6.66 (1H, m), 6.45-6.41 (2H, m), 4.73 (1H, dd), 3.75-3.69 (1H, m), 3.45-3.38 (1H, m), 2.48-2.38 (1H, m) 2.06-1.86 (3H, m); HRMS (ESI) exact mass calculated for [M+1] (C
17H
17N
2) requires
m/z 249.1392,found
m/z 249.1387。
Claims (6)
1. one kind adopts 9-dibutyl-1, the preparation method of two (2-diphenylphosphine phenyl) the ether univalent copper complexs of 10-phenanthroline linked reaction of catalytic amine and aromatic nitriles under visible ray, it is characterized in that photocatalyst 2, 9-dibutyl-1, two (2-diphenylphosphine phenyl) the ether univalent copper complexs of 10-phenanthroline, corresponding amine, aromatic nitriles and sodium-acetate are according to the mixed in molar ratio of 0.005:3:1:2, add solvent N, N-N,N-DIMETHYLACETAMIDE, reaction system argon shield, place a power saving fluorescent lamp apart from reaction flask 2cm place, after the corresponding time, reaction system is diluted by ethyl acetate, separatory, water layer is extracted with ethyl acetate three times, organic layer merges, with anhydrous magnesium sulfate drying, separate by silica gel column chromatography, obtain corresponding coupled product,
The photocatalyst 2 of wherein said use, 9-dibutyl-1, two (2-diphenylphosphine phenyl) the ether univalent copper complexs of 10-phenanthroline, have the structure of general formula (I):
（I）
Wherein X
-be selected from BF
4 -, CF
3sO
3 -, ClO
4 -, PF
6 -, SbF
6 -, NO
3 -;
The wherein said amine that can prepare and the coupled product of aromatic nitriles have the structure of logical formula II:
（Ⅱ）
Wherein R1-R3: hydrogen atom; The aliphatics substituting group that contains 1 to 20 carbon; The aromatic substituents that contains 1 to 20 carbon;
Containing the aliphatics substituting group of 1 to 20 carbon of aerobic, nitrogen, sulfur heteroatom or containing the aromatic substituents of 1 to 20 carbon of aerobic, nitrogen, sulfur heteroatom;
R1-R3 can be in ring, for containing the aliphatics substituting group of 1 to 20 carbon; The aromatic substituents that contains 1 to 20 carbon;
Containing the aliphatics substituting group of 1 to 20 carbon of aerobic, nitrogen, sulfur heteroatom or containing the aromatic substituents of 1 to 20 carbon of aerobic, nitrogen, sulfur heteroatom;
R1-R3 can be the same or different;
R4, for drawing electron substituent group, is selected from cyano group, carboxylic acid, ethyl ester base, carboxylate methyl ester base, p diethylaminobenzoic acid ester group.
2. preparation method claimed in claim 1, wherein R1-R3 is the aliphatics substituting group that contains 1 to 20 carbon, refers to: methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, sec.-propyl, the tertiary butyl, cyclohexyl, vinyl or allyl group, the aromatic substituents that contains 1 to 20 carbon refers to phenyl, tolyl, ethylbenzene, trimethylphenylmethane base, cumyl, naphthyl, first naphthyl or tertiary fourth naphthyl, containing aerobic, nitrogen, the aliphatics substituting group of 1 to 20 carbon of sulfur heteroatom refers to methoxyl group, oxyethyl group, positive propoxy, n-butoxy, n-pentyloxy, positive hexyloxy, positive heptan oxygen base, isopropoxy, tert.-butoxy, hexamethylene yloxymethyl, methylamino, ethylamino-, Tri N-Propyl Amine base, n-butylamine-based, n-amylamine base, normal hexyl Amine base, positive heptyl amice base, isopropylamine base, TERTIARY BUTYL AMINE base, cyclohexylamino, first sulfydryl, second sulfydryl, positive the third sulfydryl, positive fourth sulfydryl, positive penta sulfydryl, just own sulfydryl, positive heptan sulfydryl, isopropyl sulfydryl, tertiary fourth sulfydryl, hexamethylene sulfydryl.
3. preparation method claimed in claim 1, wherein R1-R3 is that the aromatic substituents that contains 1 to 20 carbon of aerobic, nitrogen, sulfur heteroatom refers to pyridyl, substituted pyridinyl, quinolyl, substd quinolines base, furyl, substituted furan base, thienyl or substituted thiophene base.
4. preparation method claimed in claim 1,, wherein R1-R3 is in the aliphatics substituting group encircling as containing 1 to 20 carbon and refers to cyclopentyl, cyclohexyl, substituted ring amyl group base or substituted cyclohexyl; The aromatic substituents that contains 1 to 20 carbon refers to phenyl, tolyl, ethylbenzene, trimethylphenylmethane base, cumyl, naphthyl, first naphthyl or tertiary fourth naphthyl; The aliphatics substituting group that contains 1 to 20 carbon of aerobic, nitrogen, sulfur heteroatom refers to tetrahydrofuran base, substituted tetrahydrofuran base, piperidyl, substituted piperidine base, Pyrrolidine base, substituted-tetrahydro pyrryl, tetrahydro-thienyl or substituted-tetrahydro thienyl.
5. preparation method claimed in claim 1, the aromatic substituents that wherein contains 1 to 20 carbon of aerobic, nitrogen, sulfur heteroatom refers to pyridyl, substituted pyridinyl, quinolyl, substd quinolines base, furyl, substituted furan base, thienyl or substituted thiophene base.
6. preparation method claimed in claim 1, wherein typical coupled product comprises:
(1) 4-(1-phenylpyrrole alkyl-2-) cyanobenzene;
(2) 4-(1-Phenylpiperidine base-2-) cyanobenzene;
(3) 4-(4-phenylmorpholine base-3-) cyanobenzene;
(4) 3-(4-cyano-phenyl)-4-phenylpiperazine-1-t-butyl formate;
(5) 4-(1-phenyl azepan base-2-) cyanobenzene;
(6) 4-(1-(ethyl (phenyl (amido) ethyl) cyanobenzene;
(7) 4-(1-(p-methylphenyl) pyrrolidyl-2-) cyanobenzene;
(8) 4-(1-(4-fluorophenyl) pyrrolidyl-2-) cyanobenzene;
(9) 4-(1-(4-bromophenyl) pyrrolidyl-2-) cyanobenzene;
(10) 4-(1-(naphthyl-2-) pyrrolidyl-2-) cyanobenzene;
(11) 4-(1-(4-p-methoxy-phenyl) pyrrolidyl-2-) cyanobenzene;
(12) 4-(1-(4,4-dimethoxy butyl-2-) pyrrolidyl-2-) cyanobenzene;
(13) 4-(1-benzylindole base-2-) cyanobenzene;
(14) 4-(1-(4-methoxy-benzyl) indyl-2-) cyanobenzene;
(15) 4-(1-benzyl-1,2,3,4-tetrahydroquinoline-2-) cyanobenzene;
(16) 4-(2-(4-p-methoxy-phenyl)-1,2,3,4-tetrahydro isoquinolyl-1-) cyanobenzene;
(17) 4-(1-phenylpyrrole base-2-) ethyl benzoate;
(18) (4-(1-phenylpyrrole base-2-) phenyl) diethyl phosphoric acid.
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| CN110433861B (en) * | 2019-08-30 | 2022-01-04 | 济南大学 | Preparation method and application of self-supporting MOF (Metal organic framework) nano-array composite catalyst |
| CN112778184A (en) * | 2021-01-29 | 2021-05-11 | 绍兴文理学院 | Method for arylating alpha position of tertiary amine |
| CN112812060A (en) * | 2021-01-29 | 2021-05-18 | 绍兴文理学院 | Arylation method of tetrahydroquinoline |
| CN112898191A (en) * | 2021-01-29 | 2021-06-04 | 绍兴文理学院 | Arylation method of indoline |
| CN112898191B (en) * | 2021-01-29 | 2022-04-26 | 绍兴文理学院 | Arylation method of indoline |
| CN112812060B (en) * | 2021-01-29 | 2022-04-29 | 绍兴文理学院 | Arylation method of tetrahydroquinoline |
| CN116041220A (en) * | 2022-12-31 | 2023-05-02 | 浙江工业大学 | Preparation method of aryl substituted amide compound |
| CN116041220B (en) * | 2022-12-31 | 2024-05-03 | 浙江工业大学 | Preparation method of aryl substituted amide compound |
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