CN104003828B - The preparation method of copper complex catalytic amine and aromatic nitriles linked reaction under visible light - Google Patents

The preparation method of copper complex catalytic amine and aromatic nitriles linked reaction under visible light Download PDF

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CN104003828B
CN104003828B CN201410247411.0A CN201410247411A CN104003828B CN 104003828 B CN104003828 B CN 104003828B CN 201410247411 A CN201410247411 A CN 201410247411A CN 104003828 B CN104003828 B CN 104003828B
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cyanobenzene
phenyl
equiv
copper complex
base
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CN104003828A (en
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王斌
阎宇
刘鲲
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Tianjin Normal University
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Abstract

The present invention relates to the method for a kind of copper complex linked reaction of catalytic amine and aromatic nitriles under visible light.Described preparation method is: by photocatalyst 2, 9-dibutyl-1, two (2-diphenylphosphine phenyl) the ether univalent copper complex of 10-phenanthroline, corresponding amine, aromatic nitriles and sodium-acetate according to 0.005: 3: 1: 2 mixed in molar ratio, add solvent N, N-N,N-DIMETHYLACETAMIDE, reaction system argon shield, luminescent lamp is placed at distance reaction flask 2cm place, after the corresponding time, reaction system diluted ethyl acetate, separatory, aqueous layer with ethyl acetate extracts three times, organic layer merges, with anhydrous magnesium sulfate drying, be separated by silica gel column chromatography, obtain corresponding product.The beneficial effect of present method for used photocatalyst be monovalence copper catalyst, cheap and easy to get, step is simple, and productive rate is high, and the kind of prepared amine and the coupled product of aromatic nitriles is a lot, uses visible ray as the energy needed for reacting, environmental protection.

Description

The preparation method of copper complex catalytic amine and aromatic nitriles linked reaction under visible light
Present patent application obtains the subsidy of state natural sciences fund (21102101,21172173) and Tianjin Normal University's technician introduction fund (5RL105).
Technical field
The invention belongs to organic chemical synthesis technical field, the preparation method of the univalent copper complex relating to one phenanthroline class part and two (2-diphenylphosphine phenyl) the ether mixture linked reaction of catalytic amine and aromatic nitriles under visible light.
Background technology
An important direction of organic chemistry development is exactly the synthetic method finding a kind of mild condition, environmental protection and productive rate higher.Before the general century, gondola Ciamician finds only a kind of rich reserves, environmental protection clean energy (the G. Ciamician of sustainable use catalyzed reaction, Science, 1912,36,385), and the product of light-catalyzed reaction, cannot synthesize through other ordinary methods conventional at all.Since then, photochemistry and light-catalyzed reaction are widely used in synthetic organic chemical art (N. Hoffmann, Chem. Rev. 2008,108,1052;
M. Fagnoni, D. Dondi, D. Ravelli and A. Albini, Chem. Rev. 2007, 107, 2725） 。But, because the major absorbance peak of organic compound is less in visible region, so also few with the example of visible light catalytic organic reaction at present, this developing direction also will being organic chemistry forward position.Occurring in nature have can be by visible light transformation much self-energy example (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 is that chemists provide a platform can understood visible light catalytic and transform.
In numerous photocatalysts, photoredox agent is most important one, and it can be applied to photocatalytic water, storage of solar energy, decouple protons shifts, and numerous Disciplinary Frontiers (K. Kalyanasundaram, Coord. Chem. Rev. such as solar energy power generating, 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 report with three (2-phenylpyridine) iridium as catalyzer under visible light catalytic amine and aromatic nitriles linked reaction (A. McNally, C. K. Prier, D. W. C. MacMillan, sCIENCE, 2011,334,1114), apply this reaction and can synthesize much useful natural product, and this reaction at all cannot be successful by traditional method.But the iridium catalyst that the catalyzer that this reaction uses is costliness, this just greatly hinders the practical application of this reaction and popularizes.
In recent years because copper compound has at a low price, nontoxic, the unrivaled advantages such as abundant Mineral resources, concern and the interest of people are more and more caused, find through large quantifier elimination, the visible absorption frequency of needs and the stability of compound can be obtained by regulating the part of copper complex, thus obtain excellent photocatalyst.Therefore, we openly use the achievement in research of two (2-diphenylphosphine phenyl) the ether univalent copper complex of 2,9-dibutyl-1,10-phenanthroline linked reaction of catalytic amine and aromatic nitriles under visible light here.
Summary of the invention
Invention further provides the preparation method by two (2-diphenylphosphine phenyl) the ether univalent copper complex of 2,9-dibutyl-1,10-phenanthroline linked reaction of catalytic amine and aromatic nitriles under visible light.
The invention discloses following technology contents for achieving the above object:
A kind of employing 9-dibutyl-1, the preparation method of two (2-diphenylphosphine phenyl) the ether univalent copper complex of 10-phenanthroline linked reaction of catalytic amine and aromatic nitriles under visible light, it is characterized in that photocatalyst 2, 9-dibutyl-1, two (2-diphenylphosphine phenyl) the ether univalent copper complex 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, distance reaction flask 2cm place's placement power saving fluorescent lamp, after the corresponding time, reaction system diluted ethyl acetate, separatory, aqueous layer with ethyl acetate extracts three times, organic layer merges, with anhydrous magnesium sulfate drying, be separated by silica gel column chromatography, obtain corresponding coupled product,
Two (2-diphenylphosphine phenyl) ether univalent copper complex of photocatalyst 2,9-dibutyl-1,10-phenanthroline of wherein said use, has 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; Aliphatic substitution containing 1 to 20 carbon; Aromatic substituents containing 1 to 20 carbon;
Containing the aliphatic substitution of 1 to 20 carbon of aerobic, nitrogen, sulfur heteroatom or the aromatic substituents of 1 to 20 carbon containing aerobic, nitrogen, sulfur heteroatom;
R1-R3 can be in ring, is the aliphatic substitution containing 1 to 20 carbon; Aromatic substituents containing 1 to 20 carbon;
Containing the aliphatic substitution of 1 to 20 carbon of aerobic, nitrogen, sulfur heteroatom or the aromatic substituents of 1 to 20 carbon containing 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, aliphatic substitution containing 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., aromatic substituents containing 1 to 20 carbon, such as: phenyl, tolyl, ethylbenzene, trimethylphenylmethane base, cumyl, naphthyl, first naphthyl, tertiary fourth naphthyl etc., containing aerobic, nitrogen, the aliphatic substitution of 1 to 20 carbon of sulfur heteroatom, such as 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 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, such as pyridyl, substituted pyridinyl, quinolyl, substd quinolines base, furyl, substituted furan base, thienyl, substituted thiophene base etc.
R1-R3 can be in ring, is the aliphatic substitution containing 1 to 20 carbon, such as cyclopentyl, cyclohexyl, substituted ring amyl group base, substituted cyclohexyl etc.; Aromatic substituents containing 1 to 20 carbon, such as: phenyl, tolyl, ethylbenzene, trimethylphenylmethane base, cumyl, naphthyl, first naphthyl, tertiary fourth naphthyl etc.; Containing aliphatic substitution such as tetrahydrofuran base, substituted tetrahydrofuran base, piperidyl, substituted piperidine base, Pyrrolidine base, replacement, Pyrrolidine base, tetrahydro-thienyl, substituted-tetrahydro thienyl or 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 containing aerobic, nitrogen, sulfur heteroatom 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 complex of 10-phenanthroline linked reaction of catalytic amine and aromatic nitriles is under visible light: by photocatalyst 2, 9-dibutyl-1, two (2-diphenylphosphine phenyl) the ether univalent copper complex 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, distance reaction flask 2cm place's placement power saving fluorescent lamp, after the corresponding time, reaction system diluted ethyl acetate, separatory, aqueous layer with ethyl acetate extracts three times, organic layer merges, with anhydrous magnesium sulfate drying, be separated 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 the amine and aromatic nitriles coupling compound that are synthesized by above-mentioned route below, is also the structural formula of compound in embodiment:
Wherein the chemical name of 1 is 4-(1-phenylpyrrole alkyl-2-) cyanobenzene;
Wherein the chemical name of 2 is 4-(1-Phenylpiperidine base-2-) cyanobenzene;
Wherein the chemical name of 3 is 4-(4-phenylmorpholine base-3-) cyanobenzene;
Wherein the chemical name of 4 is 3-(4-cyano-phenyl)-4-phenylpiperazine-1-t-butyl formate;
Wherein the chemical name of 5 is 4-(1-phenylazepan base-2-) cyanobenzene;
Wherein the chemical name of 6 is 4-(1-(ethyl (phenyl (amido) ethyl) cyanobenzene;
Wherein the chemical name of 7 is 4-(1-(p-methylphenyl) pyrrolidyl-2-) cyanobenzene;
Wherein the chemical name of 8 is 4-(1-(4-fluorophenyl) pyrrolidyl-2-) cyanobenzene;
Wherein the chemical name of 9 is 4-(1-(4-bromophenyl) pyrrolidyl-2-) cyanobenzene;
Wherein the chemical name of 10 is 4-(1-(naphthyl-2-) pyrrolidyl-2-) cyanobenzene;
Wherein the chemical name of 11 is 4-(1-(4-p-methoxy-phenyl) pyrrolidyl-2-) cyanobenzene;
Wherein the chemical name of 12 is 4-(1-(4,4-dimethoxybutyl-2-) pyrrolidyl-2-) cyanobenzene;
Wherein the chemical name of 13 is 4-(1-benzylindole base-2-) cyanobenzene;
Wherein the chemical name of 14 is 4-(1-(4-methoxy-benzyl) indyl-2-) cyanobenzene;
Wherein the chemical name of 15 is 4-(1-benzyl-1,2,3,4-tetrahydroquinoline-2-) cyanobenzene;
Wherein the chemical name of 16 is 4-(2-(4-p-methoxy-phenyl)-1,2,3,4-tetrahydro isoquinolyl-1-) cyanobenzene;
Wherein the chemical name of 17 is 4-(1-phenylpyrrole base-2-) ethyl benzoate;
Wherein the chemical name of 18 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, and use visible light catalytic, environmental protection low-carbon (LC), and occurring in nature luminous energy deposit enriches, 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, described these improve and change 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; Two (2-diphenylphosphine phenyl) ether univalent copper complex (the D. G. Cuttell of wherein said photocatalyst 2,9-dibutyl-1,10-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 material (A. McNally, C. K. Prier, D. W. C. MacMillan, sCIENCE, 2011,334,1114) prepare according to literature method.Except particularly pointing out, remaining four acetonitrile cuprous salts, diimine class part and all kinds of SOLVENTS, by commercially available.
Embodiment 1 (4-(1-phenylpyrrole alkyl-2-) cyanobenzene)
4.9 mg photocatalyst tetrafluoroborates 2 are added in the Schlenk bottle of a 25mL, 9-dibutyl-1, two (2-diphenylphosphine phenyl) ether univalent copper complex (the 5.0 μm of ol 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, the power saving fluorescent lamp of distance reaction flask 2cm place's placement 26W, after 12h, reaction system diluted ethyl acetate, separatory, aqueous layer with ethyl acetate extracts three times, organic layer merges, with anhydrous magnesium sulfate drying, be separated by silica gel column chromatography, obtain corresponding coupled product, 225 mg, productive rate: 91%.
1 HNMR (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)
4.9 mg photocatalyst tetrafluoroborates 2 are added in the Schlenk bottle of a 25mL, 9-dibutyl-1, two (2-diphenylphosphine phenyl) ether univalent copper complex (the 5.0 μm of ol 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, the power saving fluorescent lamp of distance reaction flask 2cm place's placement 26W, after 12h, reaction system diluted ethyl acetate, separatory, aqueous layer with ethyl acetate extracts three times, organic layer merges, with anhydrous magnesium sulfate drying, be separated by silica gel column chromatography, obtain corresponding coupled product, 237 mg, productive rate: 90%.
1 HNMR (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)
4.9 mg photocatalyst tetrafluoroborates 2 are added in the Schlenk bottle of a 25mL, 9-dibutyl-1, two (2-diphenylphosphine phenyl) ether univalent copper complex (the 5.0 μm of ol 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, the power saving fluorescent lamp of distance reaction flask 2cm place's placement 26W, after 12h, reaction system diluted ethyl acetate, separatory, aqueous layer with ethyl acetate extracts three times, organic layer merges, with anhydrous magnesium sulfate drying, be separated by silica gel column chromatography, obtain corresponding coupled product, 239 mg, productive rate: 90%.
1 HNMR (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)
4.9 mg photocatalyst tetrafluoroborates 2 are added in the Schlenk bottle of a 25mL, 9-dibutyl-1, two (2-diphenylphosphine phenyl) ether univalent copper complex (the 5.0 μm of ol 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, the power saving fluorescent lamp of distance reaction flask 2cm place's placement 26W, after 12h, reaction system diluted ethyl acetate, separatory, aqueous layer with ethyl acetate extracts three times, organic layer merges, with anhydrous magnesium sulfate drying, be separated 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-phenylazepan base-2-) cyanobenzene)
4.9 mg photocatalyst tetrafluoroborates 2 are added in the Schlenk bottle of a 25mL, 9-dibutyl-1, two (2-diphenylphosphine phenyl) ether univalent copper complex (the 5.0 μm of ol 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-phenylazepan (3.0 mmol, 3.0 equiv.) and 4.0 mL DMA, reaction system argon shield, the power saving fluorescent lamp of distance reaction flask 2cm place's placement 26W, after 12h, reaction system diluted ethyl acetate, separatory, aqueous layer with ethyl acetate extracts three times, organic layer merges, with anhydrous magnesium sulfate drying, be separated 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)
4.9 mg photocatalyst tetrafluoroborates 2 are added in the Schlenk bottle of a 25mL, 9-dibutyl-1, two (2-diphenylphosphine phenyl) ether univalent copper complex (the 5.0 μm of ol 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, the power saving fluorescent lamp of distance reaction flask 2cm place's placement 26W, after 12h, reaction system diluted ethyl acetate, separatory, aqueous layer with ethyl acetate extracts three times, organic layer merges, with anhydrous magnesium sulfate drying, be separated 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)
4.9 mg photocatalyst tetrafluoroborates 2 are added in the Schlenk bottle of a 25mL, 9-dibutyl-1, two (2-diphenylphosphine phenyl) ether univalent copper complex (the 5.0 μm of ol 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, the power saving fluorescent lamp of distance reaction flask 2cm place's placement 26W, after 12h, reaction system diluted ethyl acetate, separatory, aqueous layer with ethyl acetate extracts three times, organic layer merges, with anhydrous magnesium sulfate drying, be separated 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)
4.9 mg photocatalyst tetrafluoroborates 2 are added in the Schlenk bottle of a 25mL, 9-dibutyl-1, two (2-diphenylphosphine phenyl) ether univalent copper complex (the 5.0 μm of ol 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, the power saving fluorescent lamp of distance reaction flask 2cm place's placement 26W, after 12h, reaction system diluted ethyl acetate, separatory, aqueous layer with ethyl acetate extracts three times, organic layer merges, with anhydrous magnesium sulfate drying, be separated 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)
4.9 mg photocatalyst tetrafluoroborates 2 are added in the Schlenk bottle of a 25mL, 9-dibutyl-1, two (2-diphenylphosphine phenyl) ether univalent copper complex (the 5.0 μm of ol 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, the power saving fluorescent lamp of distance reaction flask 2cm place's placement 26W, after 12h, reaction system diluted ethyl acetate, separatory, aqueous layer with ethyl acetate extracts three times, organic layer merges, with anhydrous magnesium sulfate drying, be separated 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)
4.9 mg photocatalyst tetrafluoroborates 2 are added in the Schlenk bottle of a 25mL, 9-dibutyl-1, two (2-diphenylphosphine phenyl) ether univalent copper complex (the 5.0 μm of ol 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, the power saving fluorescent lamp of distance reaction flask 2cm place's placement 26W, after 12h, reaction system diluted ethyl acetate, separatory, aqueous layer with ethyl acetate extracts three times, organic layer merges, with anhydrous magnesium sulfate drying, be separated 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)
4.9 mg photocatalyst tetrafluoroborates 2 are added in the Schlenk bottle of a 25mL, 9-dibutyl-1, two (2-diphenylphosphine phenyl) ether univalent copper complex (the 5.0 μm of ol 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, the power saving fluorescent lamp of distance reaction flask 2cm place's placement 26W, after 12h, reaction system diluted ethyl acetate, separatory, aqueous layer with ethyl acetate extracts three times, organic layer merges, with anhydrous magnesium sulfate drying, be separated 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-dimethoxybutyl-2-) pyrrolidyl-2-) cyanobenzene)
4.9 mg photocatalyst tetrafluoroborates 2 are added in the Schlenk bottle of a 25mL, 9-dibutyl-1, two (2-diphenylphosphine phenyl) ether univalent copper complex (the 5.0 μm of ol 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-dimethoxybutyl-2-) tetramethyleneimine (3.0 mmol, 3.0 equiv.) and 4.0 mL DMA, reaction system argon shield, the power saving fluorescent lamp of distance reaction flask 2cm place's placement 26W, after 24 hours, reaction system diluted ethyl acetate, separatory, aqueous layer with ethyl acetate extracts three times, organic layer merges, with anhydrous magnesium sulfate drying, be separated 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)
4.9 mg photocatalyst tetrafluoroborates 2 are added in the Schlenk bottle of a 25mL, 9-dibutyl-1, two (2-diphenylphosphine phenyl) ether univalent copper complex (the 5.0 μm of ol 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, the power saving fluorescent lamp of distance reaction flask 2cm place's placement 26W, after 12h, reaction system diluted ethyl acetate, separatory, aqueous layer with ethyl acetate extracts three times, organic layer merges, with anhydrous magnesium sulfate drying, be separated 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)
4.9 mg photocatalyst tetrafluoroborates 2 are added in the Schlenk bottle of a 25mL, 9-dibutyl-1, two (2-diphenylphosphine phenyl) ether univalent copper complex (the 5.0 μm of ol 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, the power saving fluorescent lamp of distance reaction flask 2cm place's placement 26W, after 24 hours, reaction system diluted ethyl acetate, separatory, aqueous layer with ethyl acetate extracts three times, organic layer merges, with anhydrous magnesium sulfate drying, be separated 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)
4.9 mg photocatalyst tetrafluoroborates 2 are added in the Schlenk bottle of a 25mL, 9-dibutyl-1, two (2-diphenylphosphine phenyl) ether univalent copper complex (the 5.0 μm of ol 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-benzyls-1, 2, 3, 4-tetrahydroquinoline (3.0 mmol, 3.0 equiv.) and 4.0 mL DMA, reaction system argon shield, the power saving fluorescent lamp of distance reaction flask 2cm place's placement 26W, after 14 hours, reaction system diluted ethyl acetate, separatory, aqueous layer with ethyl acetate extracts three times, organic layer merges, with anhydrous magnesium sulfate drying, be separated 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)
4.9 mg photocatalyst tetrafluoroborates 2 are added in the Schlenk bottle of a 25mL, 9-dibutyl-1, two (2-diphenylphosphine phenyl) ether univalent copper complex (the 5.0 μm of ol 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-methoxyphenyls-1, 2, 3, 4-tetrahydroquinoline (3.0 mmol, 3.0 equiv.) and 4.0 mL DMA, reaction system argon shield, the power saving fluorescent lamp of distance reaction flask 2cm place's placement 26W, after 12h, reaction system diluted ethyl acetate, separatory, aqueous layer with ethyl acetate extracts three times, organic layer merges, with anhydrous magnesium sulfate drying, be separated 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)
4.9 mg photocatalyst tetrafluoroborates 2 are added in the Schlenk bottle of a 25mL, 9-dibutyl-1, two (2-diphenylphosphine phenyl) ether univalent copper complex (the 5.0 μm of ol 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, the power saving fluorescent lamp of distance reaction flask 2cm place's placement 26W, after 16 hours, reaction system diluted ethyl acetate, separatory, aqueous layer with ethyl acetate extracts three times, organic layer merges, with anhydrous magnesium sulfate drying, be separated 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)
4.9 mg photocatalyst tetrafluoroborates 2 are added in the Schlenk bottle of a 25mL, 9-dibutyl-1, two (2-diphenylphosphine phenyl) ether univalent copper complex (the 5.0 μm of ol 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, the power saving fluorescent lamp of distance reaction flask 2cm place's placement 26W, after 24 hours, reaction system diluted ethyl acetate, separatory, aqueous layer with ethyl acetate extracts three times, organic layer merges, with anhydrous magnesium sulfate drying, be separated 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)
5.2 mg photocatalyst hexafluoro-phosphate radicals 2 are added in the Schlenk bottle of a 25mL, 9-dibutyl-1, two (2-diphenylphosphine phenyl) ether univalent copper complex (the 5.0 μm of ol 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, the power saving fluorescent lamp of distance reaction flask 2cm place's placement 26W, after 12h, reaction system diluted ethyl acetate, separatory, aqueous layer with ethyl acetate extracts three times, organic layer merges, with anhydrous magnesium sulfate drying, be separated by silica gel column chromatography, obtain corresponding coupled product, 218 mg, productive rate: 88%.
1 HNMR (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)
4.8 mg photocatalyst nitrate radicals 2 are added in the Schlenk bottle of a 25mL, 9-dibutyl-1, two (2-diphenylphosphine phenyl) ether univalent copper complex (the 5.0 μm of ol 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, the power saving fluorescent lamp of distance reaction flask 2cm place's placement 26W, after 12h, reaction system diluted ethyl acetate, separatory, aqueous layer with ethyl acetate extracts three times, organic layer merges, with anhydrous magnesium sulfate drying, be separated by silica gel column chromatography, obtain corresponding coupled product, 209 mg, productive rate: 84%.
1 HNMR (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)
5.0 mg photocatalyst perchlorates 2 are added in the Schlenk bottle of a 25mL, 9-dibutyl-1, two (2-diphenylphosphine phenyl) ether univalent copper complex (the 5.0 μm of ol 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, the power saving fluorescent lamp of distance reaction flask 2cm place's placement 26W, after 12h, reaction system diluted ethyl acetate, separatory, aqueous layer with ethyl acetate extracts three times, organic layer merges, with anhydrous magnesium sulfate drying, be separated by silica gel column chromatography, obtain corresponding coupled product, 220 mg, productive rate: 89%.
1 HNMR (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 (1)

1. one kind adopts 9-dibutyl-1, the preparation method of two (2-diphenylphosphine phenyl) the ether univalent copper complex of 10-phenanthroline linked reaction of catalytic amine and aromatic nitriles under visible light, it is characterized in that photocatalyst 2, 9-dibutyl-1, two (2-diphenylphosphine phenyl) the ether univalent copper complex 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, distance reaction flask 2cm place's placement power saving fluorescent lamp, after the corresponding time, reaction system diluted ethyl acetate, separatory, aqueous layer with ethyl acetate extracts three times, organic layer merges, with anhydrous magnesium sulfate drying, be separated by silica gel column chromatography, obtain corresponding coupled product,
Two (2-diphenylphosphine phenyl) ether univalent copper complex of photocatalyst 2,9-dibutyl-1,10-phenanthroline of wherein said use, has the structure of general formula (I):
Wherein X -be selected from BF 4 -, CF 3sO 3 -, ClO 4 -, PF 6 -, SbF 6 -, NO 3 -;
The described coupled product can preparing amine and aromatic nitriles is:
(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-phenylazepan 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-dimethoxybutyl-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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