CN102295600A - Method for preparing 5-amino-8-hydroxyquinoline - Google Patents
Method for preparing 5-amino-8-hydroxyquinoline Download PDFInfo
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- CN102295600A CN102295600A CN2011102655748A CN201110265574A CN102295600A CN 102295600 A CN102295600 A CN 102295600A CN 2011102655748 A CN2011102655748 A CN 2011102655748A CN 201110265574 A CN201110265574 A CN 201110265574A CN 102295600 A CN102295600 A CN 102295600A
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- oxine
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Abstract
The invention discloses a method for preparing 5-amino-8-hydroxyquinoline. The method comprises the following steps of: (1) adding a solvent, namely isopropanol into 5-nitro-8-hydroxyquinoline, adding a Pd/C catalyst and raising temperature; (2) adding hydrazine hydrate aqueous solution into a mixed solution obtained in a step (1); and (3) performing reflux reaction, filtering when the solution is hot, and standing filtrate for 8 to 12 hours to precipitate 5-amino-8-hydroxyquinoline columnar crystals. The reaction yield is high. The method is simple and convenient, the tan 5-amino-8-hydroxyquinoline columnar crystals are obtained through reaction and the step of recrystallization is saved, so that a toxic solvent used when a product is recrystallized in the prior art is saved, and the method is low in cost and environment-friendly.
Description
Technical field
The present invention relates to a kind of preparation method of aminocompound, particularly relate to a kind of preparation method of 5-amino-oxine.
Background technology
The oxine metal complexes is a kind of important electroluminescent organic material, and this class title complex has the fluorescence efficiency height, easily purifies and advantage such as stable in properties.By studying the luminescence mechanism of this class title complex, find that the part difference has significant effects to the title complex luminosity.Substituting group is modified, introduced to part normally on phenol oxygen ring or on the pyridine ring, mainly is in the C-5 position, secondly is in the C-2 position.With 5-amino-oxine is raw material, forms Schiff's base with a series of aromatic aldehyde reactions, thereby forms bigger conjugated system, improves the fluorescence property of title complex.In addition, 5-amino-oxine tool anti-herpesvirus and anti-tumor activity; Its derivative has treatment cardiovascular disorder function and anti-mycotic activity.
What obtain that structure is abundant, the 5-amino-oxine derivative complex of excellent performance is the most basic will synthesize purified 5-amino-oxine exactly.
The synthetic method of 5-amino-oxine has bibliographical information at present, and the long Mei Dengren of Wei in 2004 once reported the synthetic method of 5-amino-oxine, this method complicated operation, and the product of generation needs recrystallization, and used recrystallization solvent benzene toxicity is big.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, provide a kind of method simple, the product of generation does not need the synthetic method of the 5-amino-oxine of recrystallization.
Technical scheme of the present invention is summarized as follows:
The preparation method of 5-amino-oxine comprises the steps:
(1) 5-nitro-oxine is added the solvent Virahol, the adding mass content is 5% Pd/C catalyzer, is warming up to 70 ℃; Described mass content is 5% Pd/C catalyzer and the ratio of 5-nitro-oxine is 25g: 1mol.
(2) be that 80% hydrazine hydrate aqueous solution joins in the mixed solution that step (1) obtains with time of 25～35min with mass concentration, described hydrazine hydrate is 1: 1.5～2.0 with the ratio of 5-nitro-oxine amount of substance;
(3) at 80～85 ℃ of back flow reaction 3～5h, filtered while hot, filtrate is left standstill 8～12h, separates out pale brown look 5-amino-oxine styloid.
The described time of step (2) is preferably 30min.
Preferably hydrazine hydrate is 1: 1.8 with the ratio of 5-nitro-oxine amount of substance.
Reflux time is 4h preferably.
The preferred 10h of filtrate time of repose.
The invention has the beneficial effects as follows: reaction yield reaches as high as 70%.The product fusing point is 141.5-143 ℃.Method of the present invention is easy, can obtain pale brown look 5-amino-oxine styloid through reaction of the present invention, does not need the step of recrystallization, has therefore saved prior art used noxious solvent when product is carried out recrystallization, and cost is low, environmental protection.
Embodiment
The preparation method of the 5-amino-oxine of prior art is:
Weighing 5-nitro-oxine and 5%Pd/C, Virahol is made solvent, the 5%Pd/C consumption is the 25g/mol nitro-compound, is warming up to 70 ℃, dropwise slowly drips 80% hydrazine hydrate, hydrazine hydrate is 1: 1.8 with 5-nitro-oxine amount of substance ratio, dropwise the back temperature control and refluxed 4 hours for 80-85 ℃, reaction finishes afterreaction liquid filtered while hot, and filtrate decompression boils off Virahol, get solid benzene recrystallization after the cooling, obtain red-brown solid 5-amino-oxine.
Below in conjunction with embodiment the present invention is described in further detail:
Embodiment 1
The preparation method of 5-amino-oxine comprises the steps:
(1) 5-nitro-oxine is added the solvent Virahol, the adding mass content is 5% Pd/C catalyzer, is warming up to 70 ℃; Described mass content is 5% Pd/C catalyzer and the ratio of 5-nitro-oxine is 25g: 1mol;
(2) be that 80% hydrazine hydrate aqueous solution joins in the mixed solution that step (1) obtains with time of 30min with mass concentration, described hydrazine hydrate is 1: 1.8 with the ratio of 5-nitro-oxine amount of substance;
(3) at 80～85 ℃ of back flow reaction 4h, filtered while hot, filtrate is left standstill 10h, separates out pale brown look 5-amino-oxine styloid, and productive rate is 58.0%.
Embodiment 2
The preparation method of 5-amino-oxine comprises the steps:
(1) 5-nitro-oxine is added the solvent Virahol, the adding mass content is 5% Pd/C catalyzer, is warming up to 70 ℃; Described mass content is 5% Pd/C catalyzer and the ratio of 5-nitro-oxine is 25g: 1mol;
(2) be that 80% hydrazine hydrate aqueous solution joins in the mixed solution that step (1) obtains with time of 35min with mass concentration, described hydrazine hydrate is 1: 1.5 with the ratio of 5-nitro-oxine amount of substance;
(3) at 80～85 ℃ of back flow reaction 3h, filtered while hot, filtrate is left standstill 10h, separates out pale brown look 5-amino-oxine styloid, and productive rate is 62.8%.
Embodiment 3
The preparation method of 5-amino-oxine comprises the steps:
(1) 5-nitro-oxine is added the solvent Virahol, the adding mass content is 5% Pd/C catalyzer, is warming up to 70 ℃; Described mass content is 5% Pd/C catalyzer and the ratio of 5-nitro-oxine is 25g: 1mol;
(2) be that 80% hydrazine hydrate aqueous solution joins in the mixed solution that step (1) obtains with time of 25min with mass concentration, described hydrazine hydrate is 1: 2.0 with the ratio of 5-nitro-oxine amount of substance;
(3) at 80～85 ℃ of back flow reaction 5h, filtered while hot, filtrate is left standstill 12h, separates out pale brown look 5-amino-oxine styloid, and productive rate is 70.0%.
Embodiment 3
The preparation method of 5-amino-oxine comprises the steps:
(1) 5-nitro-oxine is added the solvent Virahol, the adding mass content is 5% Pd/C catalyzer, is warming up to 70 ℃; Described mass content is 5% Pd/C catalyzer and the ratio of 5-nitro-oxine is 25g: 1mol;
(2) be that 80% hydrazine hydrate aqueous solution joins in the mixed solution that step (1) obtains with time of 25～35min with mass concentration, described hydrazine hydrate is 1: 1.8 with the ratio of 5-nitro-oxine amount of substance;
(3) at 80～85 ℃ of back flow reaction 4h, filtered while hot, filtrate leaves standstill 8, separates out pale brown look 5-amino-oxine styloid, and productive rate is 60.0%.
Claims (5)
1.5-the preparation method of amino-oxine is characterized in that comprising the steps:
(1) 5-nitro-oxine is added the solvent Virahol, the adding mass content is 5% Pd/C catalyzer, is warming up to 70 ℃; Described mass content is 5% Pd/C catalyzer and the ratio of 5-nitro-oxine is 25g: 1mol;
(2) be that 80% hydrazine hydrate aqueous solution joins in the mixed solution that step (1) obtains with time of 25～35min with mass concentration, described hydrazine hydrate is 1: 1.5～2.0 with the ratio of 5-nitro-oxine amount of substance;
(3) at 80～85 ℃ of back flow reaction 3～5h, filtered while hot, filtrate is left standstill 8～12h, separates out pale brown look 5-amino-oxine styloid.
2. the preparation method of 5-amino-oxine according to claim 1 is characterized in that the described time of described step (2) is 30min.
3. the preparation method of 5-amino-oxine according to claim 1 is characterized in that the described hydrazine hydrate and the ratio of 5-nitro-oxine amount of substance are 1: 1.8.
4. the preparation method of 5-amino-oxine according to claim 1 is characterized in that described reflux time is 4h.
5. the preparation method of 5-amino-oxine according to claim 1 is characterized in that the filtrate time of repose is 10h.
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| CN2011102655748A CN102295600A (en) | 2011-09-08 | 2011-09-08 | Method for preparing 5-amino-8-hydroxyquinoline |
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| CN2011102655748A CN102295600A (en) | 2011-09-08 | 2011-09-08 | Method for preparing 5-amino-8-hydroxyquinoline |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004078748A2 (en) * | 2003-02-28 | 2004-09-16 | Bayer Pharmaceuticals Corporation | Novel bicyclic urea derivatives useful in the treatment of cancer and other disorders |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004078748A2 (en) * | 2003-02-28 | 2004-09-16 | Bayer Pharmaceuticals Corporation | Novel bicyclic urea derivatives useful in the treatment of cancer and other disorders |
Non-Patent Citations (2)
| Title |
|---|
| NAVIN B. PATEL, ET AL.: "Synthesis and antimicrobial activity of carbonyl pyridoquinolones containing urea and piperazine residue", 《JOURNAL OF SAUDI CHEMICAL SOCIETY》, vol. 15, 4 August 2010 (2010-08-04), pages 167 - 176, XP028153543, DOI: doi:10.1016/j.jscs.2010.07.004 * |
| 韦长梅等: "Pd/C催化水合肼还原法制备5-氨基-8-羟基喹啉", 《精细化工》, vol. 21, no. 6, 30 June 2004 (2004-06-30), pages 442 - 443 * |
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Application publication date: 20111228 |