CN1706807A - Direct one-step amination process of synthesizing toluidine from toluene - Google Patents
Direct one-step amination process of synthesizing toluidine from toluene Download PDFInfo
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- CN1706807A CN1706807A CN 200410094518 CN200410094518A CN1706807A CN 1706807 A CN1706807 A CN 1706807A CN 200410094518 CN200410094518 CN 200410094518 CN 200410094518 A CN200410094518 A CN 200410094518A CN 1706807 A CN1706807 A CN 1706807A
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- toluene
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Abstract
The present invention is the one-step direct amination process of synthesizing toluidine with toluene as main material, hydroxylamine hydrochloride as aminating agent and lower fatty acid as solvent and under the catalysis of supported catalyst with vanadium as active component. The present invention has the features of easily prepared catalyst easy to separate from the product and capable of being reused, mild amination condition, high toluidine yield, low cost, high output and environment friendship.
Description
The present invention relates to method by the direct aminated synthesizing toluidine of toluene one-step.
Tolylamine is an important chemical material, all has purposes widely on industry, agricultural and pharmaceutical industries, and along with the development of society, the demand of whole world para-totuidine grows with each passing day.The synthetic main nitrated method that restores of elder generation that adopts toluene of the industry of Tolylamine at present, this method will could realize the synthetic of Tolylamine through two-step reaction, the nitrated nitrotoluene that obtains that at first is toluene and concentrated nitric acid in the presence of 50-60 ℃ and the vitriol oil, second step was that nitrotoluene reduces in the presence of catalyzer and obtains the target product Tolylamine, although this method productive rate is higher, but this method exists reactions steps many, the technical process complexity, equipment corrosion is serious, by product is many, waste of raw materials is big, operational hazards, shortcoming such as big for environment pollution.So in recent years, the c h bond on the direct activation phenyl ring and make the reaction of aromatic hydrocarbons functionalization cause various countries investigators' extensive concern, this is one of the most scabrous problem in the synthetic chemistry.Capture this difficulty, selection of catalysts and preparation are the most key factors.
People such as N.I.Kuznetsova have reported the method for the direct amination synthesizing toluidine of toluene and azanol.The catalyzer that this method is used is NaVO
32H
2O, NaMoO
42H
2O, FeSO
47H
2O and NaPW
11O
39Fe (H
2O) homogeneous catalyst and V such as
2O
5/ SiO
2, MoO
3/ SiO
2Deng heterogeneous catalyst.Used ammoniation agent is NH
2OHH
2SO
4Use V
2O
5/ SiO
2Or MoO
3/ SiO
2When making catalyzer, raw material is easy to get, and catalyzer is made simple, helps separating of catalyzer and product, and catalyzer can reuse, and environmental pollution is little.Use NaPW
11O
39Fe (H
2When O) being catalyzer, make solvent with acetic acid, the Tolylamine yield is higher, has reached 27%, and environmental pollution is little.But these methods also have the place that comes with some shortcomings:
1. use V
2O
5/ SiO
2Or MoO
3/ SiO
2When making catalyzer.Contain H in the solvent for use
2SO
4, to neutralize with NaOH after the reaction, consume a large amount of water, thereby cause raw-material waste, suitability for industrialized production is said it is uneconomic, and productive rate is lower.
2. use V
2O
5/ SiO
2Or MoO
3/ SiO
2When making catalyzer.Because contain strong acid in the solvent for use, active ingredient vanadium and molybdenum will be from V
2O
5/ SiO
2Or MoO
3/ SiO
2Last solution-off, this has influenced the recovery and reuse of catalyzer to a great extent, and the solution-off of active ingredient is to the separation of product and all can exert an adverse impact to environment.
3. use NaPW
11O
39Fe (H
2When O) being catalyzer.Although the productive rate of Tolylamine higher (27%), the making of catalyzer is loaded down with trivial details, and is difficult to separating of post catalyst reaction and product, catalyzer utilize possibility little again.
4. reaction is all carried out in encloses container, also will feed N
2Protect severe reaction conditions.
5. when with other catalyzer, above-mentioned shortcoming is arranged not only, and productive rate is lower.
United States Patent (USP) Yasuhara US Pat.4 in 1996,545,753 people such as grade have reported their result of study, they have investigated the catalyzer H-152 (Al after differing temps and different time processing
2O
3: 80%, SiO
2: 9.9%, Fe
2O
3: 0.03%, TiO
2: 0.003%, CaO:0.03%, MgO:0.004%, Na
2O:5.4%) exist down, corresponding cresols and Ammoniom-Acetate are 15kg/Cm at pressure
2, the reaction when temperature is 370～390 ℃, preferably transformation efficiency: 99.7%, selectivity: 98.6%.Although this reaction result is better, it is less that reaction product is polluted, severe reaction conditions, and corresponding cresols produce difficulty, thereby the cost height is not suitable for being applied among the industry.And the ammoxidation of benzyl halide and aminating agent not only has above-mentioned shortcoming, and to the seriously corroded of equipment, turnover ratio is lower, does not also meet the thought of Green Chemistry.
United States Patent (USP) Weigert.US Pat.4 in 1977,064,171 grade has been reported hexanaphthene or alkyl cyclohexane and ammonia effect, while aromizing and amidized amination reaction, the author investigates this and is reflected at ZnO/TiO
2/ La
2O
3/, ZnO/TiO
2/ ZrO
2Or ZnO/TiO
2/ ThO
2Catalyzer exists down, and temperature is 450-550 ℃, and at 0.5-20 normal atmosphere, the ratio of ring compound and ammonia was at 5: 1 to 1: 10, and the reaction times, the gained result was best when arriving 8min at 0.1s.Although this reaction of atomic utilization ratio height (68%), unique by product is a hydrogen, the condition harshness, and productive rate is very low.
In addition, prepare in the method for Tolylamine in the direct amination of existing toluene one-step, more representational catalyzer has comprising in the presence of the group VIII metal catalyst of Becker and Hoelderich report, continue aerating oxygen or carbonic acid gas, and the toluene under the continuous reaction stirred condition and the amination reaction of ammonia.People such as H lderich have studied direct synthesizing toluidine in the presence of Pd, Pt, Rh or Ru.People such as thomas then directly generate Tolylamine with Pt at 1000 ℃ of following catalysis toluene and ammonia.Certainly also comprise the catalyzer that some contain transition metal (as: La and Ac) and contain at least a V oxide compound.In addition, people such as Durantel has studied the loaded catalyst that contains transition metal and monobasic, binary nucleation ligand is the Study on Catalytic Amination of Alcohols of catalyzer.But there is the cost height equally in these catalyzer, the not recycling that has, the catalytic reaction condition harshness that has etc.
The method that the purpose of this invention is to provide the direct amination preparing methylbenzene of a kind of simple and effective toluene amine.
The solution of the present invention: with pickling process with NH
4VO
3Being carried on granularity respectively is 20-40 purpose γ-Al
2O
3On, leaving standstill 12-24h, drying with water bath was handled one hour in 100-120 ℃ of baking oven, and under the condition of bubbling air, 380-400 ℃ of roasting adds proper catalyst in the three-necked bottle then, again with a certain amount of NH
2OHHCl is dissolved in medium (V
H2O: V
Lower fatty acid=2: 0.5-2) back adds in the three-necked bottle, adds toluene at last, wherein NH
2OHHCl: toluene (ratio of amount of substance)=1: 0.5-1.5, then normal pressure, 50-95 ℃, under stirring state reacting by heating 2-6 hour, reflux until reaction terminating, separate the product Tolylamine.The Tolylamine yield is up to 56.43%.
This reacts optimum temperature of reaction is 85-95 ℃, and optimum reacting time is 3.5-4.5 hour, and optimum medium is V
H2O: V
Lower fatty acid=2: 0.75-1.25, best NH
2OHHCl: toluene (ratio of amount of substance)=1: 0.75-1.25, best lower fatty acid are acetate.
The present invention is to be active ingredient, γ-Al with the vanadium
2O
3Be the catalyzer of carrier, lower fatty acid is a solvent, NH
2OHHCl is the method for direct amination preparing methylbenzene amine of the toluene of ammoniation agent, has following characteristics:
(1) the catalyzer raw material is easy to get, and is inexpensive, cost is low.
(2) catalyst performance stabilised, the life-span is long, and is reusable.
(3) reaction conditions gentleness is carried out under normal pressure.
(4) reaction times is short.
(5) reaction unit is simple.
(6) Tolylamine productive rate height can reach 56.4%.
Therefore, the present invention has considerable application prospect.
Embodiment 1: take by weighing 20 gram 20-40 purpose γ-Al respectively
2O
3Place the beaker of three 150ml, add respectively and contain NH
4VO
31.58 the solution of gram, 1.98 grams, 3.17 grams leaves standstill 24h, drying with water bath was handled one hour in 100 ℃ of baking ovens, and under the condition of bubbling air, 400 ℃ of roastings just obtain catalyzer: 1#, 2#, 3# then.
Embodiment 2: get 1#-3# catalyzer 1.0 respectively and restrain in the three-necked bottle of three 50ml, each adds the NH that is dissolved with 1.5 grams
2Solvent (the V of the 15ml of OHHCl
H2O: V
Acetate=2: 1), add 5ml toluene again, reflux, stir, be heated to 90 ℃, reacted 4 hours, get its aniline productive rate and be respectively 45.2%, 54.8%, 56.4%.
Embodiment 3: do not add catalyzer, other condition is carried out catalyzed reaction by [embodiment 2], and no Tolylamine generates.
Embodiment 4: get in the three-necked bottle of 3# catalyzer 1.0 gram 50ml, add the NH that is dissolved with 1.5 grams
2Solvent (the V of the 15ml of OHHCl
H2O: V
Acetate=2: 1), add 5ml toluene again, reflux, stir, be heated to 90 ℃ of reactions 2 hours, getting its aniline productive rate is 31.3%.
Embodiment 5: get in the three-necked bottle of 3# catalyzer 1.0 gram 50ml, add the NH that is dissolved with 1.5 grams
2Solvent (the V of the 15ml of OHHCl
H2O: V
Acetate=2: 1), add 5ml toluene again, reflux, stir, be heated to 90 ℃, reacted 3 hours, getting its aniline productive rate is 40.3%.
Embodiment 6: get in the three-necked bottle of 3# catalyzer 1.0 gram 50ml, add the NH that is dissolved with 1.5 grams
2Solvent (the V of the 15ml of OHHCl
H2O: V
Acetate=2: 1), add 5ml toluene again, reflux, stir, be heated to 90 ℃, reacted 5 hours, getting its aniline productive rate is 54.5%.
Embodiment 7: get in the three-necked bottle of 3# catalyzer 1.0 gram 50ml, add the NH that is dissolved with 1.5 grams
2Solvent (the V of the 15ml of OHHCl
H2O: V
Acetate=2: 1), add 5ml toluene again, reflux, stir, be heated to 90 ℃, reacted 6 hours, getting its aniline productive rate is 53.0%.
Embodiment 8: get in the three-necked bottle of 3# catalyzer 1.0 gram 50ml, add the NH that is dissolved with 1.5 grams
2Solvent (the V of the 15ml of OHHCl
H2O: V
Acetate=2: 1), add 5ml toluene again, reflux, stir, be heated to 50 ℃, reacted 4 hours, getting its aniline productive rate is 3.2%.
Embodiment 9: get in the three-necked bottle of 3# catalyzer 1.0 gram 50ml, add the NH that is dissolved with 1.5 grams
2Solvent (the V of the 15ml of OHHCl
H2O: V
Acetate=2: 1), add 5ml toluene again, reflux, stir, be heated to 60 ℃, reacted 4 hours, getting its aniline productive rate is 7.8%.
Embodiment 10: get in the three-necked bottle of 3# catalyzer 1.0 gram 50ml, add the NH that is dissolved with 1.5 grams
2Solvent (the V of the 15ml of OHHCl
H2O: V
Acetate=2: 1), add 5ml toluene again, reflux, stir, be heated to 70 ℃, reacted 4 hours, getting its aniline productive rate is 31.5%.
Embodiment 11: get in the three-necked bottle of 3# catalyzer 1.0 gram 50ml, add the NH that is dissolved with 1.5 grams
2Solvent (the V of the 15ml of OHHCl
H2O: V
Acetate=2: 1), add 5ml toluene again, reflux, stir, be heated to 80 ℃, reacted 4 hours, getting its aniline productive rate is 50.2%.
Embodiment 12: get in the three-necked bottle of 3# catalyzer 1.0 gram 50ml, add the NH that is dissolved with 1.5 grams
2Solvent (the V of the 15ml of OHHCl
H2O: V
Acetate=2: 1), add 5ml toluene again, reflux, stir, be heated to 95 ℃, reacted 2 hours, getting the Tolylamine productive rate is 50.2%.
Embodiment 13: with the 3# catalyst recovery in [embodiment 2], carry out catalyzed reaction by the condition in [embodiment 2], reuse four times, get the Tolylamine productive rate and be respectively 56.4%, 52.5%, 50.3%, 49.6%.
Embodiment 14: the 3# catalyzer is not being added NH
2Under the OHHCl situation, carry out catalyzed reaction by the condition in [embodiment 2], after the separation, (1) adds people 1.5 gram NH in liquid phase
2OHHCl is undertaken by the reaction conditions in [embodiment 2] then, and getting the Tolylamine productive rate is 2.6%; (2) solid phase is carried out catalyzed reaction by the condition in [embodiment 2], and getting the Tolylamine productive rate is 54.3%.
Claims (9)
1. the method by the direct amination system aniline of toluene one-step is characterized in that with pickling process NH
4VO
3Being carried on granularity is 20-40 purpose γ-Al
2O
3On, leaving standstill 12-24h, drying with water bath was handled one hour in 100-120 ℃ of baking oven, and under the condition of bubbling air, it is standby to make catalyzer after the 380-400 ℃ of roasting then.
2. proper catalyst is added in the reactor, again with a certain amount of NH
2OHHCl is dissolved in medium (V
H2O: V
Lower fatty acid=2: 0.5-2) back adds in the three-necked bottle, adds toluene at last, wherein NH
2OHHCl: toluene (ratio of amount of substance)=1: 0.5-1.5, then normal pressure, 50-95 ℃, under stirring state reacting by heating 2-6 hour, reflux until reaction terminating, separate the product Tolylamine.
3. according to claims 1 described method, it is characterized in that with the vanadium being active centre, γ-Al
2O
3Loaded catalyst for carrier.
4. according to claims 1 described method, be characterised in that γ-Al
2O
3Granularity be the 20-40 order.
5. according to claims 1 described method, be characterised in that said lower fatty acid is formic acid, acetate, propionic acid or butyric acid.
6. according to claims 1 described method, be characterised in that V
H2O: V
Lower fatty acid=2: 1.
7. according to claims 1 described method, be characterised in that NH
2OHHCl: toluene (ratio of amount of substance)=1: 1.
8. according to claims 1 described method, be characterised in that temperature of reaction is 50-95 ℃.
9. according to claims 1 described method, be characterised in that the reaction times is 2-6 hour.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100945182A CN100551899C (en) | 2004-06-09 | 2004-10-30 | A kind of method by direct one-step aminating synthesis of toluidine from toluene |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200410022748.8 | 2004-06-09 | ||
| CN200410022748 | 2004-06-09 | ||
| CNB2004100945182A CN100551899C (en) | 2004-06-09 | 2004-10-30 | A kind of method by direct one-step aminating synthesis of toluidine from toluene |
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| Publication Number | Publication Date |
|---|---|
| CN1706807A true CN1706807A (en) | 2005-12-14 |
| CN100551899C CN100551899C (en) | 2009-10-21 |
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|---|---|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008009668A1 (en) * | 2006-07-21 | 2008-01-24 | Basf Se | Direct amination of hydrocarbons |
| CN101870656A (en) * | 2010-07-20 | 2010-10-27 | 陈虎魁 | Method for preparing 2,4-dimethylaniline by direct amination of m-xylene |
| CN104447353A (en) * | 2014-12-10 | 2015-03-25 | 河北工业大学 | Method for directly preparing aniline by virtue of reaction between benzene and hydroxylammonium salt |
| CN104829463A (en) * | 2015-05-20 | 2015-08-12 | 湘潭大学 | Environment-friendly synthesis method of 1-naphthylamine |
| CN104829462A (en) * | 2015-05-20 | 2015-08-12 | 湘潭大学 | Method for synthesizing 1,5-diaminonaphthalene by one step with naphthalene |
| CN104829464A (en) * | 2015-05-20 | 2015-08-12 | 湘潭大学 | Method for synthesizing 1,5-diaminonaphthalene with 1-naphthylamine |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5861536A (en) * | 1997-07-31 | 1999-01-19 | Sun Company, Inc. (R&M) | Oxidative ammination of benzene to aniline using molecular oxygen as the terminal oxidant |
| AU8742598A (en) * | 1997-08-21 | 1999-03-16 | Huntsman International Llc | Process for the production of aromatic amines |
-
2004
- 2004-10-30 CN CNB2004100945182A patent/CN100551899C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008009668A1 (en) * | 2006-07-21 | 2008-01-24 | Basf Se | Direct amination of hydrocarbons |
| CN101870656A (en) * | 2010-07-20 | 2010-10-27 | 陈虎魁 | Method for preparing 2,4-dimethylaniline by direct amination of m-xylene |
| CN104447353A (en) * | 2014-12-10 | 2015-03-25 | 河北工业大学 | Method for directly preparing aniline by virtue of reaction between benzene and hydroxylammonium salt |
| CN104447353B (en) * | 2014-12-10 | 2016-06-22 | 河北工业大学 | A kind of benzene and hydroxylamine salt react the method directly preparing aniline |
| CN104829463A (en) * | 2015-05-20 | 2015-08-12 | 湘潭大学 | Environment-friendly synthesis method of 1-naphthylamine |
| CN104829462A (en) * | 2015-05-20 | 2015-08-12 | 湘潭大学 | Method for synthesizing 1,5-diaminonaphthalene by one step with naphthalene |
| CN104829464A (en) * | 2015-05-20 | 2015-08-12 | 湘潭大学 | Method for synthesizing 1,5-diaminonaphthalene with 1-naphthylamine |
| CN104829464B (en) * | 2015-05-20 | 2017-10-13 | 湘潭大学 | The method that 1,5 diaminonaphthalenes are synthesized by 1 naphthylamines |
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| Publication number | Publication date |
|---|---|
| CN100551899C (en) | 2009-10-21 |
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