CN103204863B - 2,2 '-two pyridine amine copper complex and the application in the synthesis of 2-imidazolidine derivatives thereof - Google Patents
2,2 '-two pyridine amine copper complex and the application in the synthesis of 2-imidazolidine derivatives thereof Download PDFInfo
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- CN103204863B CN103204863B CN201310078085.0A CN201310078085A CN103204863B CN 103204863 B CN103204863 B CN 103204863B CN 201310078085 A CN201310078085 A CN 201310078085A CN 103204863 B CN103204863 B CN 103204863B
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Abstract
The invention discloses title complex shown in a kind of structural formula (I), it is by soluble copper salt and 2, and 2 '-two pyridine amine is in interpolation formic acid adjust ph to 5, and reflux obtains.This title complex can be used as the synthesis of catalyzer for 2-imidazoline and its derivative, and have reaction conditions gentleness, productive rate is high, and the reaction times is short, and aftertreatment is easy, and catalyzer is cheap and can reuse, the advantages such as solvent-free intervention.
Description
Technical field
The present invention relates to a kind of 2,2 '-two pyridine amine copper complex and as the application of catalyzer in the synthesis of 2-imidazoline and its derivative, belong to technical field of chemistry and chemical engineering.
Background technology
2-tetrahydroglyoxaline is a kind of important chemical intermediate, is widely used in the industries such as organic synthesis, biomedicine, pharmacy.In synthetic chemistry field, often can be used as the intermediate of natural product synthesis, phase-transfer catalyst design and synthesis, and can be used as achirality or chiral catalyst by after itself and transition-metal coordination; At biomedical sector, 2-tetrahydroglyoxaline can be used as alpha adrenergic receptor antagonist, alpha adrenergic receptor agonist etc., and in pharmaceutical industry, 2-tetrahydroglyoxaline can be used as the main component of multiple antiphlogiston, depressor and cancer therapy drug.2-tetrahydroglyoxaline has multiple synthetic method, and the most frequently used is with carboxylic acid and diamines for the cyclization of heating raw materials vacuum method forms.Though this method technique is simple, long reaction time, productive rate is lower, and has widely applied corrosive raw materials, and environmental pollution is serious.In recent years, the method for catalytic material synthesis 2-tetrahydroglyoxaline based on carboxylic acid derivative and diamines, because it realizes easy and simple to handle, reaction times is short, productive rate is high, and aftertreatment simply receives much concern, but its key problem in technology is the new and effective research of greenization catalyzer and the release of synthesis technique.Therefore, developing simply efficient, recyclable, the environment amenable catalyzer of one is a very important job.
Summary of the invention
An object of the present invention is to provide a kind of 2,2 '-two pyridine amine copper complex.
Another object of the present invention is to provide above-mentioned 2, the application of 2 '-two pyridine amine copper complex in the synthesis of 2-imidazoline and its derivative.
Implementation procedure of the present invention is as follows:
Title complex shown in structural formula (I),
It belongs to oblique system, Cc spacer, and unit cell parameters is
a=11.5409 (7),
b=15.3626 (9),
c=30.2072 (18),
α=90 (deg),
β=90.4940 (10) deg,
γ=90deg.
The preparation method of title complex shown in structural formula (I), comprise the following steps: the soluble copper salt and 2 by mol ratio being 1:1,2 '-two pyridine amine is dissolved in methyl alcohol and water volume ratio is in the solution of 1:1, drips formic acid adjust ph to 5, reflux, cools and obtains product.
Title complex shown in structural formula (I) as the application of catalyzer in the 2-imidazoline and its derivative synthesis shown in equation (II),
Wherein R
1for C
6h
5, p-CH
3c
6h
5, p-FC
6h
5, p-ClC
6h
5, p-BrC
6h
5, p-IC
6h
5, p-CH
3oC
6h
5, p-NH
2c
6h
5, p-NO
2c
6h
5, p-CNC
6h
5, m-CH
3c
6h
5, m-FC
6h
5, m-ClC
6h
5, m-BrC
6h
5, m-IC
6h
5, m-CH
3oC
6h
5, m-NH
2c
6h
5, m-NO
2c
6h
5, m-CNC
6h
5,o-CH
3c
6h
5, o-FC
6h
5, o-ClC
6h
5, o-BrC
6h
5, o-IC
6h
5, o-CH
3oC
6h
5, o-NH
2c
6h
5, o-NO
2c
6h
5, o-CNC
6h
5, 2-C
5h
4n, 3-C
5h
4n, 4-C
5h
4n; R
2for H or CH
2cH
2oH.
Above-mentioned reaction conditions for: with the copper complex shown in structural formula (I) for catalyzer, react under the condition of solvent-free heating, temperature of reaction 60 ~ 120 DEG C, 6 ~ 12 hours reaction times, R in reaction
1-CN and H
2nCH
2cH
2nHR
2mol ratio be 1:1 ~ 1:4, R
1-CN is 1:0.05 ~ 1:0.2 with the mol ratio of catalyzer.
Advantage of the present invention and positively effect:
1. the catalyst preparation process of the present invention's use is simple, synthesizes with low cost, and in reaction, consumption is less, little on the separation impact of product, is conducive to suitability for industrialized production.
2. catalyst system of the present invention, reaction conditions is gentle, and carries out under normal pressure.Operating procedure is simple, adopts the method for the treatment of different things alike and without the need to many more manipulations.
3. the catalyzer that the present invention adopts can reclaim through simple filtration, and washing, can make renewing catalyst activity after drying, after reusing 5 times, decline without obvious productive rate.
Accompanying drawing explanation
Fig. 1 is the single crystal structure figure of title complex shown in structural formula (I).
Embodiment
For a more clear understanding of the present invention, below by embodiment, the present invention is described in further detail.
Embodiment 1: the synthesis of title complex shown in structural formula (I)
Take 0.20g neutralized verdigris and 0.17g2,2 '-two pyridine amine, is dissolved in 100mL methyl alcohol: in the solution of water (V/V)=1:1, drips formic acid adjust ph to 5, reflux 2h, and cross cleaner liquid in Erlenmeyer flask, namely crystallisation by cooling obtains product.Single crystal structure test data is: molecular formula C
54h
49cu
2n
15o
8, it belongs to oblique system, Cc spacer, and unit cell parameters is
a=11.5409 (7),
b=15.3626 (9),
c=30.2072 (18),
α=90 (deg),
β=90.4940 (10) deg,
γ=90deg.
Embodiment 2: with cyanobenzene and quadrol for Material synthesis 2-benzylimidazoline.
Catalyzer prepared by 5mmol cyanobenzene, 20mmol quadrol and 1mmol embodiment 1 is joined in the round-bottomed flask of 50mL, reflux 6h under agitation condition.After reaction terminates, add 20mLCH
2cl
2, after filtration catalizer, by CH
2cl
2evaporate to dryness obtains 2-benzylimidazoline crude product, and post obtains 2-benzylimidazoline sterling 0.63g after being separated (eluent: ethyl acetate/methanol (V/V)=3:1), and yield is 86%.Mass spectrum (m/z): 147 [M+H]
+.Nucleus magnetic resonance:
1hNMR (400MHz, CDCl
3): δ 3.78 (s, 4H, 2CH
2), 4.78 (brs, 1H, NH), 7.39-7.45 (m, 3H, ArH), 7.76-7.80 (m, 2H, ArH).Infrared (KBr): ν/cm
-1: 3201,2929,2867,1611,1571,1508,1469,1344,1269,981,778,696.
Embodiment 3: with p-Cyanochlorobenzene and quadrol for Material synthesis 2-(rubigan) tetrahydroglyoxaline
Catalyzer prepared by 5mmol p-Cyanochlorobenzene, 20mmol quadrol and 1mmol embodiment 1 is joined in the round-bottomed flask of 50mL, reflux 6h under agitation condition.After reaction terminates, add 20mLCH
2cl
2, after filtration catalizer, by CH
2cl
2evaporate to dryness obtains 2-(rubigan) tetrahydroglyoxaline crude product, and post obtains 2-(rubigan) tetrahydroglyoxaline sterling 0.70g after being separated (eluent: ethyl acetate/methanol (V/V)=3:1), and yield is 78%.Mass spectrum (m/z): 181 [M+H]
+.Nucleus magnetic resonance:
1hNMR (CDCl
3, 400MHz) and δ: 3.80 (s, 4H, 2CH
2), 7.38 (d, 2H, ArH), 7.73 (d, 2H, ArH).Infrared (KBr): ν/cm
-1: 3235,2697,2361,1605,1558,1518,1483,1351,1274,1125,1089,986,838,727.
Embodiment 4: with 2-cyanopyridine and quadrol for Material synthesis 2-(2-pyridyl) tetrahydroglyoxaline
Catalyzer prepared by 5mmol2-cyanopyridine, 20mmol quadrol and 1mmol embodiment 1 is joined in the round-bottomed flask of 50mL, reflux 6h under agitation condition.After reaction terminates, add 20mLCH
2cl
2, after filtration catalizer, by CH
2cl
2evaporate to dryness obtains 2-(2-pyridyl) tetrahydroglyoxaline crude product, and post obtains 2-(2-pyridyl) tetrahydroglyoxaline sterling 0.67g after being separated (eluent: ethyl acetate/methanol (V/V)=3:1), and yield is 91%.Mass spectrum (m/z): 148 [M+H]
+.Nucleus magnetic resonance:
1hNMR (CDCl
3, 400MHz) and δ: 3.82 (s, 4H, 2CH
2), 7.33-7.36 (m, 1H, ArH), 8.13-8.15 (m, 1H, ArH), 8.67-8.68 (d, 1H, ArH), 8.98 (s, 1H, ArH).Infrared (KBr): ν/cm
-1: 3159,2940,2854,1609,1587,1513,1467,1412,1277,1191,983,824,706.
Embodiment 5: with cyanobenzene and hydroxyethylethylene diamine for Material synthesis N-hydroxyethyl-2-benzylimidazoline
Catalyzer prepared by 5mmol cyanobenzene, 20mmol hydroxyethylethylene diamine and 1mmol embodiment 1 is joined in the round-bottomed flask of 50mL, reflux 6h under agitation condition.After reaction terminates, add 20mLCH
2cl
2, after filtration catalizer, by CH
2cl
2evaporate to dryness obtains N-hydroxyethyl-2-benzylimidazoline crude product, and post obtains N-hydroxyethyl-2-benzylimidazoline sterling 0.80g after being separated (eluent: ethyl acetate/methanol (V/V)=3:1), and yield is 84%.Mass spectrum (m/z): 191 [M+H]
+.Nucleus magnetic resonance:
1hNMR (CDCl
3, 400MHz) and δ: 2.72 (m, 2H, CH
2), 2.81 (m, 2H, CH
2), 3.17 (s, 1H, OH), 3.50 (m, 2H, CH
2), 3.84 (m, 2H, CH
2), 7.38 (t, 1H, ArH), 7.55 (d, 2H, ArH), 7.82 (d, 2H, ArH).Infrared (KBr): ν/cm
-1: 3306,2934,2869,1639,1613,1592,1499,1447,1065,775,703.
Embodiment 6: with p-Cyanochlorobenzene and hydroxyethylethylene diamine for Material synthesis N-hydroxyethyl-2-(rubigan) tetrahydroglyoxaline
Catalyzer prepared by 5mmol p-Cyanochlorobenzene, 20mmol hydroxyethylethylene diamine and 1mmol embodiment 1 is joined in the round-bottomed flask of 50mL, reflux 6h under agitation condition.After reaction terminates, add 20mLCH
2cl
2, after filtration catalizer, by CH
2cl
2evaporate to dryness obtains N-hydroxyethyl-2-(rubigan) tetrahydroglyoxaline crude product, post obtains N-hydroxyethyl-2-(rubigan) tetrahydroglyoxaline sterling 0.93g after being separated (eluent: ethyl acetate/methanol (V/V)=3:1), and yield is 83%.Mass spectrum (m/z): 225 [M+H]
+.Nucleus magnetic resonance:
1hNMR (CDCl
3, 400MHz) and δ: 3.04 (m, 2H, CH
2), 3.17 (m, 2H, CH
2), 3.84 (s, 1H, OH), 3.99 (m, 2H, CH
2), 4.18 (m, 2H, CH
2), 7.37 (d, 1H, ArH), 7.43 (d, 1H, ArH), 7.85 (d, 1H, ArH), 7.95 (d, 1H, ArH).Infrared (KBr): ν/cm
-1: 3268,2948,1638,1597,1487,1447,1321,1093,1013,843,762.
Embodiment 7: with 2-cyanopyridine and hydroxyethylethylene diamine for Material synthesis N-hydroxyethyl-2-(2-pyridyl) tetrahydroglyoxaline
Catalyzer prepared by 5mmol2-cyanopyridine, 20mmol hydroxyethylethylene diamine and 1mmol embodiment 1 is joined in the round-bottomed flask of 50mL, reflux 6h under agitation condition.After reaction terminates, add 20mLCH
2cl
2, after filtration catalizer, by CH
2cl
2evaporate to dryness obtains N-hydroxyethyl-2-(2-pyridyl) tetrahydroglyoxaline crude product, post obtains N-hydroxyethyl-2-(2-pyridyl) tetrahydroglyoxaline sterling 0.87g after being separated (eluent: ethyl acetate/methanol (V/V)=3:1), and yield is 91%.Mass spectrum (m/z): 192 [M+H]
+.Nucleus magnetic resonance:
1hNMR (CDCl
3, 400MHz) and δ: 2.90 (m, 2H, CH
2), 2.99 (m, 2H, CH
2), 3.47 (s, 1H, OH), 3.67 (m, 2H, CH
2), 3.72 (m, 2H, CH
2), 7.43 (m, 1H, ArH), 7.84 (m, 1H, ArH), 8.17 (d, 1H, ArH), 8.55 (d, 1H, ArH).Infrared (KBr): ν/cm
-1: 3372,2943,1659,1532,1460,1434,1052,750,692.
Embodiment 8: with cyanobenzene and quadrol for Material synthesis 2-benzylimidazoline
Similar to Example 1, difference is: the catalyzer using 3 times adding recovery in the process of the 2-benzylimidazoline of preparation, remaining reaction condition is identical.2-benzylimidazoline yield is 81%.
Embodiment 9: with cyanobenzene and quadrol for Material synthesis 2-benzylimidazoline
Similar to Example 1, difference is: the catalyzer using 5 times adding recovery in the process of the 2-benzylimidazoline of preparation, remaining reaction condition is identical.2-benzylimidazoline yield is 78%.
Claims (4)
1. title complex shown in structural formula (I),
It belongs to oblique system, Cc spacer, and unit cell parameters is
a=11.5409 (7),
b=15.3626 (9),
c=30.2072 (18),
α=90o,
β=90.4940 (10) o,
γ=90o.
2. the preparation method of title complex described in claim 1, comprise the following steps: the soluble copper salt and 2 by mol ratio being 1:1,2 '-two pyridine amine is dissolved in methyl alcohol and water volume ratio is in the solution of 1:1, drips formic acid adjust ph to 5, reflux, cools and obtains product.
3. title complex described in claim 1 is as the application of catalyzer in the 2-imidazoline and its derivative synthesis shown in equation (II),
Wherein R
1for C
6h
5, p-CH
3c
6h
5, p-FC
6h
5, p-ClC
6h
5, p-BrC
6h
5, p-IC
6h
5, p-CH
3oC
6h
5, p-NH
2c
6h
5, p-NO
2c
6h
5, p-CNC
6h
5, m-CH
3c
6h
5, m-FC
6h
5, m-ClC
6h
5, m-BrC
6h
5, m-IC
6h
5, m-CH
3oC
6h
5, m-NH
2c
6h
5, m-NO
2c
6h
5, m-CNC
6h
5,o-CH
3c
6h
5, o-FC
6h
5, o-ClC
6h
5, o-BrC
6h
5, o-IC
6h
5, o-CH
3oC
6h
5, o-NH
2c
6h
5, o-NO
2c
6h
5, o-CNC
6h
5, 2-C
5h
4n, 3-C
5h
4n, 4-C
5h
4n; R
2for H or CH
2cH
2oH.
4. apply according to claim 3, it is characterized in that: with the copper complex shown in structural formula (I) for catalyzer, react under the condition of solvent-free heating, temperature of reaction 60 ~ 120 DEG C, 6 ~ 12 hours reaction times, R in reaction
1-CN and H
2nCH
2cH
2nHR
2mol ratio be 1:1 ~ 1:4, R
1-CN is 1:0.05 ~ 1:0.2 with the mol ratio of catalyzer.
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CN101698672A (en) * | 2009-11-06 | 2010-04-28 | 南京大学 | Tricarbonal rhenium (I) complexes containing carrier-transporting groups (oxadiazole or carbazole), preparation method and application thereof |
CN102180877A (en) * | 2011-03-24 | 2011-09-14 | 浙江工业大学 | Synthetic process of imidazo phenanthroline compound |
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CN101698672A (en) * | 2009-11-06 | 2010-04-28 | 南京大学 | Tricarbonal rhenium (I) complexes containing carrier-transporting groups (oxadiazole or carbazole), preparation method and application thereof |
CN102180877A (en) * | 2011-03-24 | 2011-09-14 | 浙江工业大学 | Synthetic process of imidazo phenanthroline compound |
Non-Patent Citations (1)
Title |
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Complex formation reactions of (2,2¢-dipyridylamine)copper(II) with various biologically relevant ligands. The kinetics of hydrolysis of amino acid esters;Azza A. Shoukry et al.;《Transition Metal Chemistry》;20051231;第30卷;814-827 * |
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