CN102134197A - Green synthesis method for schiff base compounds - Google Patents
Green synthesis method for schiff base compounds Download PDFInfo
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- CN102134197A CN102134197A CN2010106131925A CN201010613192A CN102134197A CN 102134197 A CN102134197 A CN 102134197A CN 2010106131925 A CN2010106131925 A CN 2010106131925A CN 201010613192 A CN201010613192 A CN 201010613192A CN 102134197 A CN102134197 A CN 102134197A
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- schiff bases
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Abstract
The invention discloses a green synthesis method for schiff base compounds. The synthesis method comprises that ketone and aromatic amine are used as substrates and reacted under the catalysis of carboxylic acid type acidic ionic liquid to obtain the corresponding schiff base compounds. The operation is simple and convenient, the yield of the products is high, the products can be easily separated, and the carboxylic acid type acidic ionic liquid can be directly reused for many times.
Description
(1) technical field
The present invention relates to a kind of is the green method of the synthetic schiff bases compounds of substrate with ketone and aromatic amine.
(2) background technology
Aldehydes or ketones and aromatic amine dehydrating condensation under acid catalysis obtains imines, claims schiff bases again.The schiff bases compounds is important organic synthesis intermediate, in fields such as medicine, agricultural chemicals, spices purposes is widely arranged, and especially in recent years, the schiff bases frequent application was in various kinds of drug is synthetic.Ketone is lower than aldehyde reaction activity, need to divide at high temperature reflux under the condition such as water just to obtain schiff bases with the aromatic amine condensation, and often yield is very low.But adding leaving away of water in the acid accelerated reaction, is the important method of the synthetic schiff bases compounds of catalysis.Comparatively Chang Yong acid has phenylformic acid, p-methyl benzenesulfonic acid, acetate and sodium pyrosulfate etc.
Acid, and Lewis acid and solid acid such as zinc chloride often exist when these traditional catalyst of practical application that consumption is big, strong to equipment corrosion, yield is generally not high and problem such as the difficult repeated use of catalyzer.In the functionalization acidic ionic liquid body owing to have low-steam pressure, higher thermostability, easily reuse and the advantage of liquid acid, be considered to a kind of green catalyst, show good catalytic performance in numerous catalyzed reactions, show important commercial exploitation and be worth.
(3) summary of the invention
Big for the catalyst levels that exists in the prior art that solves preparation schiff bases compounds, be difficult to a series of problems such as repeated use, complex operation, follow a kind of green more and synthetic efficiently theory simultaneously, the invention provides a kind of is the method for the synthetic schiff bases compounds of catalyzer with the carboxylic acid type acidic ion liquid, this method operation is easy, product yield is high and easily separated, and the carboxylic acid type acidic ion liquid can directly be reused repeatedly.
For solving technical problem of the present invention, adopt following technical scheme:
A kind of synthetic method of schiff bases compounds, the structure of described schiff bases compounds is suc as formula shown in (I), formula (II) and the formula (III), it is characterized in that described synthetic method is is substrate suc as formula ketone shown in (IV), formula V or the formula (VI) and structure suc as formula the aromatic amine shown in (VII) with structure, reaction obtains corresponding schiff bases compounds under the carboxylic acid type presence of acidic ionic liquid catalyst; Reaction formula is as follows:
Wherein, R
1And R
2Independently be selected from alkyl or the benzyl of C1～C20 separately;
R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
11, R
12Independently be selected from one of following separately: the alkyl of H, C1～C4, the alkoxyl group of C1～C4, halogen; Perhaps, R
3, R
4, R
5, R
6, R
7In adjacent two group Cheng Huan (such as forming phenyl ring);
n＝1～4；
X represents S, O or N-R
10Or C-R
10, R wherein
10Be selected from one of following: the alkyl of H, C1～C4, the alkoxyl group of C1～C4, halogen.
Synthetic method of the present invention specifically comprises the steps: and will stir in carboxylic acid type acidic ion liquid, ketone, aromatic amine and the reaction solvent adding reaction vessel, the reflux state divides water, reaction finishes hypsokinesis and goes out reaction solution, and desolventizing promptly obtains described schiff bases compounds.Incline reaction solution after, ionic liquid can directly add ketone, aromatic amine and solvent again and continue to apply mechanically at the reaction vessel bottom.
Further, carboxylic acid type acidic ion liquid of the present invention, its structure is suc as formula shown in (VIII):
In the formula (VIII), R
13For C1～C20 alkyl or-C
xH
2xCOOH, x is selected from 1～4, and m is selected from 1～4, Y
-For one of following: chlorion (Cl
-), bromide anion (Br
-), Tetrafluoroboric acid negatively charged ion (BF
4 -), phosphofluoric acid negatively charged ion (PF
6 -), trifluoromethanesulfonic acid negatively charged ion (CF
3SO
3 -), fluoroform sulfimide negatively charged ion { [(CF
3SO
2)
2N]
-, p-methyl benzenesulfonic acid negatively charged ion (p-MeC
6H
4SO
3 -), dodecyl sodium sulfonate negatively charged ion (C
12H
25SO
3 -), to Witco 1298 Soft Acid negatively charged ion [(p-C
12H
25) C
6H
4SO
3 -], trifluoroacetic acid negatively charged ion (CF
3COO
-), acetate negatively charged ion (CH
3COO
-), phenylformic acid negatively charged ion (PhCOO
-), bisulfate ion negatively charged ion (HSO
4 -).
Further, described reaction with hexanaphthene, toluene or raw ketone as reaction solvent, preferably with raw ketone as reaction solvent.
Further, the molar ratio of described carboxylic acid type acidic ion liquid and described aromatic amine is 0.1%～20%: 1, is preferably 1%～5%: 1.
Further, the molar ratio of described aromatic amine and described ketone is 1: 1～20.When with other organic solvents during as reaction solvent, the molar ratio of preferred described aromatic amine and described ketone is about 1: 1; When with raw ketone as reaction solvent, the molar ratio that is preferably described aromatic amine and described ketone is 1: 10～15.
Generally speaking, the adding volume of reaction solvent is recommended as 1～15ml/mmol in the mole number of described aromatic amine.
Further, the reaction times of reaction of the present invention is 0.5～40h, is preferably 10～20h.
Compared with prior art, beneficial effect of the present invention is: operation is easy, and product yield is high and easily separated, and the carboxylic acid type acidic ion liquid can directly be reused repeatedly.
(4) embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this.
Embodiment 1:
Carboxylic acid type acidic ion liquid 1-carboxymethyl-3-Methylimidazole hydrochloride (9mg, 0.05mmol) add and to fill in the 50ml twoport round-bottomed flask of pimelinketone (20ml), (0.48g is 5mmol) in this reaction vessel, under mechanical stirring to add aniline again, the oil bath reflux is divided water reaction 10h, cool to room temperature, inclining reaction solution, obtains schiff bases N-cyclohexyl imido grpup aniline 0.85g behind the precipitation, yield 98%, the product structure formula is:
Embodiment 2:
Carboxylic acid type acidic ion liquid 1-carboxymethyl-3-butyl imidazole a tetrafluoro borate (14mg, 0.05mmol) add and to fill in the 50ml twoport round-bottomed flask of 3-methyl-2-butanone (20ml), add again that (0.54g is 5mmol) in this reaction vessel, under mechanical stirring to monomethylaniline, the oil bath reflux is divided water reaction 10h, cool to room temperature, inclining reaction solution, obtains schiff bases N-(3-methyl-2 butyl imido grpup)-4-monomethylaniline 0.86g behind the precipitation, yield 98%, the product structure formula is:
Embodiment 3:
Carboxylic acid type acidic ion liquid 1-(4-carboxylic butyl)-3-Methylimidazole tosilate (17mg, 0.05mmol) adding fills in the 50ml twoport round-bottomed flask of propione (20ml), adds 3 again, 4-xylidine (0.61g, 5mmol) in this reaction vessel, under mechanical stirring, the oil bath reflux is divided water reaction 10h, cool to room temperature, inclining reaction solution, obtains schiff bases N-(3-penta butyl imido grpup)-3 behind the precipitation, 4-xylidine 0.90g, yield 95%, the product structure formula is:
Embodiment 4:
Carboxylic acid type acidic ion liquid 1-(4-propyloic)-3-n-octyl imidazoles benzoate (18mg, 0.05mmol) add and to fill in the 50ml twoport round-bottomed flask of 3-heptanone (20ml), (0.62g is 5mmol) in this reaction vessel, under mechanical stirring to add the 4-anisidine again, the oil bath reflux is divided water reaction 10h, cool to room temperature, inclining reaction solution, obtains schiff bases N-(3-heptyl imido grpup)-4-anisidine 0.96g behind the precipitation, yield 88%, the product structure formula is:
Embodiment 5:
Carboxylic acid type acidic ion liquid 1-carboxymethyl-3-N-Methylimidazoleacetic salt (51mg, 0.25mmol) add and to fill in the 50ml twoport round-bottomed flask of hexanaphthene (20ml), cyclopentanone (0.42g, 5mmol) and p-Chlorobenzoic acid amide (0.64g, 5mmol) join successively in this reaction vessel, under mechanical stirring, the oil bath reflux is divided water reaction 10h, cool to room temperature, incline and cyclohexane solution, obtain schiff bases N-cyclopentyl imido grpup-4-chloroaniline 0.82g behind the precipitation, yield 85%, the product structure formula is:
Embodiment 6:
Carboxylic acid type acidic ion liquid 1,3-dicarboxyl Methylimidazole trifluoroacetate (15mg, 0.05mmol) add and to fill in the 50ml twoport round-bottomed flask of toluene (20ml), Tetrahydro-pyran-4-one (0.51g, 5mmol) and o-toluidine (0.54g, 5mmol) join successively in this reaction vessel, under mechanical stirring, the oil bath reflux is divided water reaction 10h, cool to room temperature, inclining toluene solution, obtains schiff bases N-(tetrahydropyrans-4-imido grpup) 2-aminotoluene 0.91g behind the precipitation, yield 96%, the product structure formula is:
Embodiment 7:
Carboxylic acid type acidic ion liquid 1-carboxymethyl-3-Methylimidazole dodecane sulfonate (20mg, 0.05mmol) add and to fill in the 50ml twoport round-bottomed flask of toluene (20ml), 4-methylcyclohexanone (0.56g, 5mmol) and m-bromoaniline (0.86g, 5mmol) join successively in this reaction vessel, under mechanical stirring, the oil bath reflux is divided water reaction 10h, cool to room temperature, incline and toluene solution, obtain schiff bases N-(4-methylcyclohexyl) imido grpup-3-bromaniline 1.12g behind the precipitation, yield 90%, the product structure formula is:
Embodiment 8:
Carboxylic acid type acidic ion liquid 1-carboxymethyl-3-Methylimidazole hexafluorophosphate (15mg, 0.05mmol) add and to fill in the 50ml twoport round-bottomed flask of toluene (20ml), 1-phenyl-acetone (0.67g, 5mmol) with 4-n-butyl aniline (0.75g, 5mmol) join successively in this reaction vessel, under mechanical stirring, the oil bath reflux is divided water reaction 10h, cool to room temperature, incline and toluene solution, obtain schiff bases N-(1-phenyl propyl) imido grpup-4-n-butyl aniline 1.3g behind the precipitation, yield 98%, the product structure formula is:
Embodiment 9:
Carboxylic acid type acidic ion liquid 1-carboxymethyl-3-ethyl base imidazole bisulfate (0.3g, 1mmol) adding fills in the 50ml twoport round-bottomed flask of toluene (20ml), 2-dodecyl ketone (1.0g, 5mmol) with adjacent fluoroaniline (0.56g, 5mmol) join successively in this reaction vessel, under mechanical stirring, the oil bath reflux is divided water reaction 10h, cool to room temperature, incline and toluene solution, obtain schiff bases N-(2-dodecyl) imido grpup-2-fluoroaniline 1.2g behind the precipitation, yield 86%, the product structure formula is:
Embodiment 10:
Carboxylic acid type acidic ion liquid 1-carboxymethyl-3-ethyl base imidazoles hydrobromate (60mg, 0.25mmol) add and to fill in the 50ml twoport round-bottomed flask of toluene (20ml), butanone (0.36g, 5mmol) and naphthylamines (0.72g, 5mmol) join successively in this reaction vessel, under mechanical stirring, the oil bath reflux is divided water reaction 10h, cool to room temperature, incline and toluene solution, obtain schiff bases N-(2-butyl) imido grpup naphthylamines 0.95g behind the precipitation, yield 96%, the product structure formula is:
Embodiment 11: ionic liquid recycles experiment
Reaction solution among the embodiment 1 is inclined to, in this reaction vessel, directly add raw material and can be used for reacting next time.React according to embodiment 1 step, ionic liquid can recycle more than 5 times at least, and gained the results are shown in Table 1.
Table 2:1-carboxymethyl-3-Methylimidazole hydrochloride ionic liquid recycled experiment
| Cycle index | Yield (%) |
| 1 | 96 |
| 2 | 95 |
| 3 | 96 |
| 4 | 93 |
| 5 | 91 |
Claims (10)
1. the synthetic method of a schiff bases compounds, the structure of described schiff bases compounds is suc as formula shown in (I), formula (II) and the formula (III), it is characterized in that described synthetic method is is substrate suc as formula ketone shown in (IV), formula V or the formula (VI) and structure suc as formula the aromatic amine shown in (VII) with structure, reaction obtains corresponding schiff bases compounds under the carboxylic acid type presence of acidic ionic liquid catalyst; Reaction formula is as follows:
Wherein, R
1And R
2Independently be selected from alkyl or the benzyl of C1～C20 separately;
R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
11, R
12Independently be selected from one of following separately: the alkyl of H, C1～C4, the alkoxyl group of C1～C4, halogen; Perhaps, R
3, R
4, R
5, R
6, R
7In two adjacent group Cheng Huan;
n＝1～4；
X represents S, O, N-R
10Or C-R
10, R wherein
10Be selected from one of following: the alkyl of H, C1～C4, the alkoxyl group of C1～C4, halogen.
2. the synthetic method of schiff bases compounds as claimed in claim 1, it is characterized in that described synthetic method specifically comprises the steps: to stir in carboxylic acid type acidic ion liquid, ketone, aromatic amine and the reaction solvent adding reaction vessel, the reflux state divides water, reaction finishes hypsokinesis and goes out reaction solution, and desolventizing promptly obtains described schiff bases compounds.
3. the green synthesis method of schiff bases compounds as claimed in claim 2 is characterized in that: incline reaction solution after, the carboxylic acid type acidic ion liquid can directly add ketone, aromatic amine and reaction solvent again and continue to apply mechanically at the reaction vessel bottom.
4. as the synthetic method of the described schiff bases compounds of one of claim 1～3, it is characterized in that described carboxylic acid type acidic ion liquid, its structure is suc as formula shown in (VIII):
R wherein
13For C1～C20 alkyl or-C
xH
2xCOOH, x is selected from 1～4, and m is 1～4, Y
-For one of following: chlorion, bromide anion, Tetrafluoroboric acid negatively charged ion, phosphofluoric acid negatively charged ion, trifluoromethanesulfonic acid negatively charged ion, fluoroform sulfimide negatively charged ion, p-methyl benzenesulfonic acid negatively charged ion, dodecyl sodium sulfonate negatively charged ion, to Witco 1298 Soft Acid negatively charged ion, trifluoroacetic acid negatively charged ion, acetate negatively charged ion, phenylformic acid negatively charged ion, bisulfate ion negatively charged ion.
5. as the green synthesis method of the described schiff bases compounds of one of claim 1～3, it is characterized in that described reaction with hexanaphthene, toluene or raw ketone as reaction solvent.
6. as the synthetic method of the described schiff bases compounds of one of claim 1～3, the molar ratio that it is characterized in that described carboxylic acid type acidic ion liquid and described aromatic amine is 0.1%～20%: 1.
7. the synthetic method of schiff bases compounds as claimed in claim 6, the molar ratio that it is characterized in that described carboxylic acid type acidic ion liquid and described aromatic amine is 1%～5%: 1.
8. as the synthetic method of the described schiff bases compounds of one of claim 1～3, it is characterized in that the described aromatic amine and the ratio of the amount of substance that feeds intake of described ketone are 1: 1～20.
9. as the synthetic method of the described schiff bases compounds of one of claim 1～3, it is characterized in that the reaction times is 0.5～40h.
10. the synthetic method of schiff bases compounds as claimed in claim 9 is characterized in that the reaction times is 10～20h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898329A (en) * | 2012-09-29 | 2013-01-30 | 西安近代化学研究所 | Method for synthesizing N-aryl ketoimine by acidic catalytic dehydration |
| CN103159644A (en) * | 2013-04-08 | 2013-06-19 | 唐山师范学院 | Curcuminoid condensed aromatic amine Schiff base derivative, as well as preparation method and application thereof in preparation of antibacterial medicaments |
| CN106399686A (en) * | 2016-09-05 | 2017-02-15 | 厦门稀土材料研究所 | Acidic ionic liquid and method for separating and purifying rare earth or rare and precious metals by solvent extraction coupling electrolytic process |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1220988A (en) * | 1997-12-24 | 1999-06-30 | 南京大学 | Method for synthesising schiff base in the absence of solvent |
| EP1177199A1 (en) * | 1999-04-29 | 2002-02-06 | Celanese Chemicals Europe GmbH | Ionic liquids and production and use thereof |
-
2010
- 2010-12-29 CN CN2010106131925A patent/CN102134197B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1220988A (en) * | 1997-12-24 | 1999-06-30 | 南京大学 | Method for synthesising schiff base in the absence of solvent |
| EP1177199A1 (en) * | 1999-04-29 | 2002-02-06 | Celanese Chemicals Europe GmbH | Ionic liquids and production and use thereof |
Non-Patent Citations (2)
| Title |
|---|
| V. D. STYTSENKO 等: "Kinetics and Mechanism of Diphenylamine Synthesis by the Condensation of Aniline with Oxygen-Containing Compounds", 《KINETICS AND CATALYSIS》, vol. 48, no. 2, 31 December 2007 (2007-12-31) * |
| 王敬娴等: "酸性离子液体及其在催化反应中的应用研究进展", 《化工进展》, vol. 27, no. 10, 31 December 2008 (2008-12-31), pages 1574 - 1 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898329A (en) * | 2012-09-29 | 2013-01-30 | 西安近代化学研究所 | Method for synthesizing N-aryl ketoimine by acidic catalytic dehydration |
| CN103159644A (en) * | 2013-04-08 | 2013-06-19 | 唐山师范学院 | Curcuminoid condensed aromatic amine Schiff base derivative, as well as preparation method and application thereof in preparation of antibacterial medicaments |
| CN103159644B (en) * | 2013-04-08 | 2015-04-15 | 唐山师范学院 | Curcuminoid condensed aromatic amine Schiff base derivative and application thereof in preparation of antibacterial medicaments |
| CN106399686A (en) * | 2016-09-05 | 2017-02-15 | 厦门稀土材料研究所 | Acidic ionic liquid and method for separating and purifying rare earth or rare and precious metals by solvent extraction coupling electrolytic process |
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