CN103420851A - Method for preparing 1,5-diaminonaphthalene through naphthalene in one step and application of catalysts - Google Patents
Method for preparing 1,5-diaminonaphthalene through naphthalene in one step and application of catalysts Download PDFInfo
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- CN103420851A CN103420851A CN2013103726167A CN201310372616A CN103420851A CN 103420851 A CN103420851 A CN 103420851A CN 2013103726167 A CN2013103726167 A CN 2013103726167A CN 201310372616 A CN201310372616 A CN 201310372616A CN 103420851 A CN103420851 A CN 103420851A
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Abstract
The invention relates to a method for preparing 1,5-diaminonaphthalene through naphthalene in one step and application of catalysts. The naphthalene generates the 1,5-diaminonaphthalene in one step in an organic solvent under the action of ammonia water, hydrogen peroxide and the catalysts, and the used catalysts are obtained in a manner that one type or several types of Ni, Mn and Mo are loaded on gamma-Al2O3 or a titanium silicon molecular sieve. Under the action of the catalysts, the naphthalene reacts with the ammonia water and the hydrogen peroxide in the solvent to compound the 1,5-diaminonaphthalene in one step. The method is simple in technological process, mild in reaction condition, easy and convenient to operate, and friendly to the environment.
Description
Technical field
The invention belongs to organic chemistry filed, be specifically related to a kind ofly by naphthalene one step, prepare the method for 1,5-diaminonaphthalene and the application of catalyzer.
Background technology
In recent years, 1, the application of 5-diaminonaphthalene in the multiple fine chemical products such as organic synthesis, pigment, dyestuff, medicine, agricultural chemicals, rubber ingredients, resin, sensitive materials increases gradually, particularly along with senior urethane main raw material 1, the demand of 5-naphthalene diisocyanate increases greatly, for the research of its synthetic method, is on the increase.
Mainly containing of preparation method's reported in literature of relevant 1,5-diaminonaphthalene: naphthalene restore nitrification method, cyclization method, ammoniation process, electro-chemical water solution etc.Naphthalene restore nitrification method is the traditional method of producing 1,5-diaminonaphthalene, by naphthalene, after mixed acid nitrification generates 1,5-dinitronaphthalene, is further reduced and generates 1,5-diaminonaphthalene, the method Technology maturation, less investment.At present domestic and international most of manufacturers still adopt this method, and its Technology is being updated, but in nitrifying process, can produce a large amount of 1,8-dinitronaphthalene by product, particularly serious is to produce a large amount of spent acid contaminate environment.And take dinitride that naphthalene or 1-nitro-naphthalene make as raw material all with 1, and 5-dinitronaphthalene and 1, the 8-dinitronaphthalene is main body, also contains the mixture of the impurity such as other dinitrides, trinitro-thing.Because 1,5-dinitronaphthalene and 1,8-dinitronaphthalene character approach, separation difficulty.Traditional iron powder reducing process is used in the reduction of nitro-naphthalene mostly, and its three-waste pollution is serious, and yield is low, and in developed country, this method is superseded.Other main synthetic method is as naphthalene halogenation ammoniation process, and it take naphthalene as raw material, by bromination, prepares 1,5-dibromine naphthalene, then the ammonia solution prepares 1,5-diaminonaphthalene; The shortcoming of this technique is to have a large amount of Isosorbide-5-Nitraes-dibromine naphthalene to generate, separating-purifying difficulty, and the halogenation difficulty of naphthalene, and yield is low.The bisnaphthol ammonolysis process for raw material, prepares 1,5-diaminonaphthalene through the ammonia solution with 1,5-bisnaphthol.This technique is simple, yield is high, however 1,5-bisnaphthol raw material sources difficulty, and ammonia solution process is higher to equipment requirements.Although and electro-chemical water solution technique is simple, can avoid the generation of organic liquid waste and organic sludge, its reaction yield is low, and having relatively high expectations to equipment.The cyclization effect under acidic conditions by adjacent mononitrotoluene and propylene of cyclization method, generate 1-nitro-5-amino naphthalenes, and reduction obtains 1,5-diaminonaphthalene.This technique has been avoided isomer 1 by closed loop, the generation of 8-diaminonaphthalene, but synthesis route complexity, and pilot process is wayward.As seen from the above, existingly take naphthalene and be that the method for the synthetic 1,5-diaminonaphthalene of raw material all needs through a plurality of steps, the process complexity; And often contain the assorted of other in the product obtained
In addition, its preparation process causes larger pollution to environment, causes environmental burden.
Summary of the invention
The object of the present invention is to provide a kind of method that is prepared 1,5-diaminonaphthalene by naphthalene one step, this law is bright, and to have technique simple, the reaction conditions gentleness, and advantages of environment protection, and be conducive to carry out suitability for industrialized production.
Another object of the present invention is to provide a kind of for the above-mentioned catalyzer that is prepared the method for 1,5-diaminonaphthalene by naphthalene one step.
Preparation method by naphthalene one-step synthesis 1,5-diaminonaphthalene of the present invention is, naphthalene is under the effect of ammoniacal liquor, hydrogen peroxide and catalyzer, and in organic solvent, a step generates 1,5-diaminonaphthalene; Temperature of reaction is 60～120 ℃; Described catalyzer is by loading on carrier γ-Al by one or more in Ni, Mn, Mo
2O
3Or obtain on HTS.
The mol ratio of ammoniacal liquor and naphthalene is preferably 5～15:1.
The mol ratio of hydrogen peroxide and naphthalene is preferably 10～25:1.
In described catalyzer, one or more in Ni, Mn, Mo are at carrier γ-Al
2O
3Or the charge capacity on HTS is preferably 5%～30%.
The consumption of described catalyzer is preferably 5%～20% of naphthalene quality.
Described organic solvent is preferably DMF, triethylamine or 1,2-ethylene dichloride.
Temperature of reaction is preferably 65-100 ℃.
Reaction times is preferably 1～5 hour.
The mode that adds of hydrogen peroxide is preferably in 1～3 hour and evenly adds.
The invention still further relates to the application of catalyzer, one or more that are about in Ni, Mn, Mo load on carrier γ-Al
2O
3Or on HTS as catalyzer for prepared the method for 1,5-diaminonaphthalene by naphthalene one step.
The effect of invention
The present inventor is through deep research, successfully realized first preparing 1 by naphthalene by single stage method, the 5-diaminonaphthalene, with existing 1, the preparation method of 5-diaminonaphthalene compares, and the present invention only just can make 1,5-diaminonaphthalene by a step, not only preparation technology is simple, and the reaction conditions gentleness.In addition, by by γ-Al
2O
3Or one or both the catalyzer in HTS load Ni, Mn, Mo is applied in this preparation process, reaction can be carried out at a lower temperature, easy and simple to handle.After reaction completes and filters out solid catalyst, raw naphthalene material, solvent and excess of ammonia water reusable edible after rectifying separation, continue to prepare 1,5-diaminonaphthalene, to improve yield.Prepare 1,5-diaminonaphthalene by of the present invention by the naphthalene single stage method, not only realized the simplification of technique, and the basic thought that also meets Green Chemistry, environmental friendliness, and, because remaining raw material and solvent after reaction can recycle, suitability for industrialized production is had important practical significance.
Embodiment
Following examples are intended to illustrate the present invention, rather than limitation of the present invention.
Embodiment 1
Take respectively 2.04g (NH
4)
6Mo
7O
244H
2O, 5.51gNi (NO)
26H
2O, the Mn (NO that the 7.24g mass concentration is 50%
3)
2Solution.Flood 10g γ-Al after getting appropriate water dissolution
2O
3Flood after 24 hours gained solution dryly under vacuum, calcining, finally by hydrogen reducing, obtain respectively γ-Al
2O
3The catalyzer of load Mo, Ni, Mn.
The Ni of HTS load, Mn, the catalyst based preparation method of Mo are the same.
Take the there-necked flask that the 0.50g naphthalene is placed in 100ml, add 20.00g DMF (hereinafter to be referred as DMF), add the Ni/ HTS of 0.08g massfraction 20% simultaneously.Start constant flow pump, heated and stirred after 20 minutes under the environment of 50 ℃, to the ammoniacal liquor that adds 5.00g massfraction 25% in there-necked flask, slowly drip the hydrogen peroxide of 5.11g massfraction 30% with constant flow pump.Under 65 ℃, the condition of normal pressure, condensing reflux, reaction, after 2 hours, obtains sample solution through suction filtration.Through liquid phase analysis, with the 1,5-diaminonaphthalene calculated, be 15.00mg.
Embodiment 2
Take the there-necked flask that the 0.50g naphthalene is placed in 100ml, add 20.00gDMF, add the Mo/ γ-Al of 0.11g massfraction 10% simultaneously
2O
3.Start constant flow pump, heated and stirred after 20 minutes under the environment of 50 ℃, to the ammoniacal liquor that adds 5.03g massfraction 25% in there-necked flask, slowly drip the hydrogen peroxide of 5.01g massfraction 30% with constant flow pump.Under 65 ℃, the condition of normal pressure, condensing reflux, reaction, after 2 hours, obtains sample solution through suction filtration.Through liquid phase analysis, with the 1,5-diaminonaphthalene calculated, be 11.65mg.
Embodiment 3
Take the there-necked flask that the 0.50g naphthalene is placed in 100ml, add 20.01gDMF, add the Mo/ γ-Al of 0.11g massfraction 10% simultaneously
2O
3.Start constant flow pump, heated and stirred after 20 minutes under the environment of 50 ℃, to the ammoniacal liquor that adds 5.05g massfraction 25% in there-necked flask, slowly drip the hydrogen peroxide of 10.03g massfraction 30% with constant flow pump.Under 65 ℃, the condition of normal pressure, condensing reflux, reaction, after 2 hours, obtains sample solution through suction filtration.Through liquid phase analysis, with the 1,5-diaminonaphthalene calculated, be 21.42mg.
Embodiment 4
Take the there-necked flask that the 0.50g naphthalene is placed in 100ml, add 20.04gDMF, add the Mn/ γ-Al of 0.09g massfraction 10% simultaneously
2O
3.Start constant flow pump, heated and stirred after 20 minutes under the environment of 50 ℃, to the ammoniacal liquor that adds 5.01g massfraction 25% in there-necked flask, slowly drip the hydrogen peroxide of 5.04g massfraction 30% with constant flow pump.Under 65 ℃, the condition of normal pressure, condensing reflux, reaction, after 2 hours, obtains sample solution through suction filtration.Through liquid phase analysis, with the 1,5-diaminonaphthalene calculated, be 5.65mg.
Embodiment 5
Take the there-necked flask that the 0.50g naphthalene is placed in 100ml, add 20.04gDMF, add the Mn-Mo/ γ-Al of 0.09g massfraction 10% simultaneously
2O
3, the massfraction 5% of Mn wherein, the massfraction 5% of Mo.Start constant flow pump, heated and stirred after 20 minutes under the environment of 50 ℃, to the ammoniacal liquor that adds 5.01g massfraction 25% in there-necked flask, slowly drip the hydrogen peroxide of 5.04g massfraction 30% with constant flow pump.Under 70 ℃, the condition of normal pressure, condensing reflux, reaction, after 2 hours, obtains sample solution through suction filtration.Through liquid phase analysis, with the 1,5-diaminonaphthalene calculated, be 19.76mg.
Comparative Examples 1
Take the there-necked flask that the 0.50g naphthalene is placed in 100ml, add 20.04gDMF, start constant flow pump, under the environment of 50 ℃, heated and stirred is after 20 minutes, to the ammoniacal liquor that adds 5.01g massfraction 25% in there-necked flask, slowly drip the hydrogen peroxide of 5.04g massfraction 30% with constant flow pump.Under 70 ℃, the condition of normal pressure, condensing reflux, reaction, after 2 hours, obtains sample solution through suction filtration.Through liquid phase analysis, without 1,5-diaminonaphthalene, generate.
Claims (10)
1. one kind prepares 1 by naphthalene one step, the method of 5-diaminonaphthalene, it is characterized in that, naphthalene is under the effect of ammoniacal liquor, hydrogen peroxide and catalyzer, in organic solvent, a step generates 1, the 5-diaminonaphthalene, wherein temperature of reaction is 60～120 ℃, described catalyzer is that one or more in Ni, Mn, Mo load on carrier γ-Al
2O
3Or HTS.
2. method according to claim 1, is characterized in that, the mol ratio of ammoniacal liquor and naphthalene is 5～15:1.
3. method according to claim 1, is characterized in that, the mol ratio of hydrogen peroxide and naphthalene is 10～25:1.
4. method according to claim 1, is characterized in that, one or more in the Ni in catalyzer, Mn, Mo are at carrier γ-Al
2O
3Or the charge capacity on HTS is 5%～30%.
5. method according to claim 4, is characterized in that, the consumption of described catalyzer is 10%～25% of naphthalene quality.
6. method according to claim 1, is characterized in that, described organic solvent is DMF, triethylamine or 1,2-ethylene dichloride.
7. method according to claim 1, is characterized in that, described temperature of reaction is 65-100 ℃.
8. method according to claim 1, is characterized in that, the mode that adds of described hydrogen peroxide evenly added in 1～3 hour.
9. according to the described method of claim 1-8 any one, it is characterized in that, the described reaction times is 1～5 hour.
10. one or more in Ni, Mn, Mo are loaded on to carrier γ-Al
2O
3Or be used for the described method that is prepared 1,5-diaminonaphthalene by naphthalene one step of claim 1-8 any one as catalyzer on HTS.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104829462A (en) * | 2015-05-20 | 2015-08-12 | 湘潭大学 | Method for synthesizing 1,5-diaminonaphthalene by one step with naphthalene |
| CN104829463A (en) * | 2015-05-20 | 2015-08-12 | 湘潭大学 | Environment-friendly synthesis method of 1-naphthylamine |
| CN105801423A (en) * | 2016-03-31 | 2016-07-27 | 常州大学 | Synthetic method of 2-amino-2-(3-amino-5-cyanocyclohexane)acetic acid |
| WO2017020401A1 (en) * | 2015-08-03 | 2017-02-09 | 南开大学 | Hydrogenation isomerization and cracking catalyst for preparing biological aviation kerosene from castor oil |
| WO2017020400A3 (en) * | 2015-05-20 | 2018-02-22 | 南开大学 | Catalyst used for castor oil to prepare biological aviation kerosene, preparation method, and application |
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| CN101906045A (en) * | 2010-07-06 | 2010-12-08 | 四川大学 | Method for directly synthesizing aniline from benzene and ammonia by one step |
| CN102020568A (en) * | 2010-11-04 | 2011-04-20 | 常州介孔催化材料有限公司 | Method for preparing 1,5-diaminonaphthalene and 1,8-diaminonaphthalene |
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2013
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101906045A (en) * | 2010-07-06 | 2010-12-08 | 四川大学 | Method for directly synthesizing aniline from benzene and ammonia by one step |
| CN102020568A (en) * | 2010-11-04 | 2011-04-20 | 常州介孔催化材料有限公司 | Method for preparing 1,5-diaminonaphthalene and 1,8-diaminonaphthalene |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104829462A (en) * | 2015-05-20 | 2015-08-12 | 湘潭大学 | Method for synthesizing 1,5-diaminonaphthalene by one step with naphthalene |
| CN104829463A (en) * | 2015-05-20 | 2015-08-12 | 湘潭大学 | Environment-friendly synthesis method of 1-naphthylamine |
| WO2017020400A3 (en) * | 2015-05-20 | 2018-02-22 | 南开大学 | Catalyst used for castor oil to prepare biological aviation kerosene, preparation method, and application |
| WO2017020401A1 (en) * | 2015-08-03 | 2017-02-09 | 南开大学 | Hydrogenation isomerization and cracking catalyst for preparing biological aviation kerosene from castor oil |
| CN106391107A (en) * | 2015-08-03 | 2017-02-15 | 南开大学 | Hydroisomerization and cracking catalyst for preparation of biological aviation kerosene from castor oil |
| CN106391107B (en) * | 2015-08-03 | 2019-02-12 | 南开大学 | The hydroisomerizing and Cracking catalyst of biological aviation kerosine are prepared for castor oil |
| US10399069B2 (en) | 2015-08-03 | 2019-09-03 | Nankai University | Hydroisomerization and cracking catalyst for preparing biological aviation kerosene from castor oil |
| CN105801423A (en) * | 2016-03-31 | 2016-07-27 | 常州大学 | Synthetic method of 2-amino-2-(3-amino-5-cyanocyclohexane)acetic acid |
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