CN100457712C - One-step method for synthesizing phenylamine from direct oxidation and amination of bezene - Google Patents
One-step method for synthesizing phenylamine from direct oxidation and amination of bezene Download PDFInfo
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- CN100457712C CN100457712C CNB2005100205055A CN200510020505A CN100457712C CN 100457712 C CN100457712 C CN 100457712C CN B2005100205055 A CNB2005100205055 A CN B2005100205055A CN 200510020505 A CN200510020505 A CN 200510020505A CN 100457712 C CN100457712 C CN 100457712C
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- aniline
- acetic acid
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Abstract
The one-step synthetic method for aniline comprises: in weak acid medium, with soluble vandic salt as catalyst and hydroxylamine hydrochloride as aminating agent, oxidating and aminating directly the benzene to syntheze the aniline in one step. This invention needs mild reaction condition (normal pressure and less than 100Deg), and has high yield and selectivity.
Description
The present invention relates to a kind of method by benzene direct oxidation amination one-step synthesis aniline.
Aniline, molecular formula are C
6H
5NH
2, be commonly called as A Jilin oil, colourless oil liquid, boiling point 457.4K.Aniline is important Organic Chemicals and fine-chemical intermediate, is widely used in urethane, rubber ingredients, dyes pigment, industrial circle such as agricultural chemicals, medicine and special fibre.External aniline is mainly used in each urethane raw diphenylmethanediisocyanate (MDI) of system.
Existing Aniline Production route is that oil of mirbane is carried out reduction under shortening or other conditions, or with phenol, halogeno-benzene and amino displacement and obtain.These method stepss are many, operational condition is harsh, atom utilization is low, additive reagent and by product are many, and are big to environmental hazard, thereby do not meet the needs of sustainable Green Chemistry industrial development.Adopt novel method directly amino to be introduced phenyl ring, can simplify reaction process, polystep reaction is become the synthetic aniline of single step reaction, obviously improve the atom utilization of reaction, important meaning is arranged economizing on resources and eliminating environmental pollution.
1958, Thomas etc. in Canadian Patent No.553988, at first propose by benzene and ammonia a kind of reducible metal (as Fe, Ni, Co, Sn, Sb, Bi and Cu) under the oxide compound effect, gas-phase reaction one-step synthesis aniline in 100-1000 ℃ of temperature range (as reaction I).Afterwards at US-A-2948755, JP-A06/293715, US Patent Nos.3919155 and 3929889 has mentioned similar process among the US Patent No.4031106.These methods all be with ammonia or anhydrous ammonia as aminating agent, catalyzer has been used VI-B family, VIII family metal element compound and a kind of easy reductive metal oxide.Yet these process ubiquity severe reaction conditions (high temperature, high pressure), transformation efficiency or selectivity is lower and the shortcoming that can not get both.As, benzene is at Fe-SiO
2Under the catalyst action, generate aniline in 400 ℃ of aminations, wherein the transformation efficiency of benzene is 0.85%, and the selectivity of aniline is 97.3%.
---reaction II
Add oxygenant in above reaction system, molecular balance can move (as reaction II) to the direction that generates aniline.Canadian Patent No.553988, Cat.Let.54,125-128 (1998), DE 19634110A1, WO 00/69804, WO 99/10311, WO 00/09473, use oxygen or air as oxygenant among the US Patent No.5861536, use therein catalyzer mostly load noble metal component, or use the oxide compound of transition metal or lanthanon or actinide elements to make the catalyst activity component, method for preparing catalyst is more loaded down with trivial details, and reaction process need be carried out under High Temperature High Pressure, and high temperature can cause the side reaction on the thermodynamics and kinetics to take place, and has quickened the decomposition of raw material ammonia, reactor embrittlement owing to newborn nitrogen, make the useful life of reactor obviously shorten, the yield of aniline and/or selectivity are not high.
Alfred Hagemeyer and co-worker thereof study under the solid catalyst effect with combinational chemistry in Aplied Catalysis A:General227 (2002) 43-61 and Catalysis Today 81 (2003) 319-328, as the ammonia source, synthesize aniline with volatile salt by benzene direct oxidation amination.Catalyzer Rh/Ni-Mn/K-TiO after preferably
2Effect down in 300bar, 300 ℃ of reactions 2 hours, makes the reaction of benzene generation oxidative amination, and the benzene transformation efficiency is greater than l0%, and the selectivity of aniline is greater than 95%.This catalyzer since load noble metal component, do not have cost advantage on the Preparation of Catalyst, and the catalyst system operational condition is still relatively harsher, aniline yield rate is also not high enough.
N.I.Kuznetsova etc. introduce a kind of oxammonium sulfate that utilizes and make aminating agent in Journal of Molecular Catalysis A:Chemical161 (2000) 1-9, the method for synthetic aniline of direct oxidation amination benzene or toluene or Tolylamine in airtight acetic acid-water or acetic acid-sulfuric acid-water medium.Discovery is at 90 ℃ of reaction 5h, soluble salt shows catalytic activity preferably in acetic acid-water medium, loaded catalyst is better active in acetic acid-sulfuric acid-water medium, the aniline yield rate that obtains higher (maximum reaches 27%), but in acetic acid-sulfuric acid-water medium, have the dissolved problem of catalyzer.Because reaction is to carry out in enclosed system, ammonia that generates in the reaction process and hydrogen can cause the system internal pressure to increase, and is bigger to reactor wear, and hydrogen can not in time be discharged, make reaction be subjected to the restriction of equilibrium problem, aniline yield rate can not be improved, and does not therefore realize commercialization.
Under the catalyst action with two or three in nickel-loaded, molybdenum, vanadium, manganese, zirconium, the cerium among the publication CN 1555921A, with ammoniacal liquor as aminating agent, with hydrogen peroxide as oxygenant, make benzene under relatively mild reaction conditions (normal pressure, be lower than 100 ℃) through oxidative amination one-step synthesis aniline.This catalyzer is cheap and easy to get, and reaction process is simple, but aniline yield rate is not ideal enough.
It is easier to the purpose of this invention is to provide a kind of synthetic method, can make the method for benzene and aminating agent high reactivity and highly selective one-step synthesis aniline under relatively mild reaction conditions (normal pressure, be lower than 100 ℃).
Main points of the present invention are: with the solubility vanadic salts is catalyzer, is aminating agent with the oxammonium hydrochloride, reacts in acetic aid medium, and wherein 1. the mol ratio of benzene and solubility vanadic salts is 22.5: 1-225: 1, be preferably 45: 1-112.5: 1; The mol ratio of benzene and aminating agent is 1: 1-1: 2; The volume ratio of the acetic aid medium aqueous solution and benzene is 7.5: 1-10: 1; Water and acetic acid volume ratio are 1: 2-1: 9; 2. be reflected under the normal pressure and carry out, temperature of reaction is at 50-90 ℃, reaction times 1-5 hour.Optimal reaction temperature 80-90 ℃, optimum reacting time 4-5 hour.
Solubility vanadic salts of the present invention refers to sodium metavanadate, ammonium meta-vanadate.
Concrete reaction process of the present invention is as follows:
Go into constant temperature waters groove with two necks that are connected with spherical condensation tube are bottled, add soluble vanadium salt catalyst and acetic acid-aqueous solution, be stirred to catalyst dissolution, add oxammonium hydrochloride at 30 ℃ of constant temperature.In above-mentioned suspension liquid, add benzene, reactive tank is heated up stopped reaction after constant temperature, the back flow reaction.Reaction system is naturally cooled to room temperature, after the NaOH aqueous solution with 30% is neutralized to pH=6-8, go out organic phase with extracted with diethyl ether, with the chromatograph-mass spectrometer coupling analyser product is carried out qualitative analysis, mark carries out quantitatively aniline in doing with meta-aminotoluene.
Characteristics of the present invention are, are catalyzer with the solubility vanadic salts, under relatively mild reaction conditions (normal pressure, be lower than 100 ℃), make benzene and oxammonium hydrochloride direct reaction one-step synthesis aniline in acetic aid medium.The present invention has overcome prior art energy consumption height, defect of high cost, has higher aniline yield rate (the highest yield can reach 68.44%), and byproduct of reaction is few, and reaction process is easy to operate, and production cost is low.
Embodiment 1:
Constant temperature waters groove temperature is controlled at 30 ℃, in two neck bottles, adds 0.032g (2 * 10 successively
-4Mol) NaVO
32H
2O and 15mL acid medium (1.5mL water and 13.5mL acetic acid), constant temperature is stirred to catalyst dissolution, adds 1.56g (0.0225mol) NH
2OHHCl and 2mL (0.0225mol) benzene rises to 80 ℃ with waters groove temperature, and constant temperature, stirring, back flow reaction be after about 5 hours, stopped reaction.After reaction system naturally cooled to room temperature, the NaOH solution with 30% was neutralized to pH=6-8, goes out organic phase with the 5mL extracted with diethyl ether, carries out qualitative analysis with the chromatograph-mass spectrometer coupling analyser, carries out quantitative analysis with meta-aminotoluene as interior mark.The molar yield of aniline is 24.06%.
Embodiment 2-10:
With 0.032g (2 * 10
-4Mol) NaVO
32H
2O is a catalyzer, and 15mL acetic acid-aqueous solution is made medium, with the benzene of 1: 1 mol ratio (2mL, 0.0225mol) and oxammonium hydrochloride (1.56g, 0.0225mol) charging experimentize according to embodiment 1 described step, and reaction conditions and reaction result are listed in the table 1.
Table 1
| The embodiment sequence number | Acid medium (V H2O/V HOAc) | Temperature of reaction (℃) | Reaction times (h) | Aniline molar yield (with respect to benzene) |
| 2 | 0∶15 | 90 | 5 | 31.11 |
| 3 | 1∶9 | 90 | 1 | 11.11 |
| 4 | 1∶9 | 60 | 3 | 1.67 |
| 5 | 1∶9 | 80 | 4 | 59.20 |
| 6 | 1∶2 | 70 | 5 | 32.93 |
| 7 | 1∶2 | 90 | 2 | 19.11 |
| 8 | 2∶1 | 90 | 3 | 15.75 |
| 9 | 9∶1 | 90 | 4 | 7.16 |
| 10 | 9∶1 | 50 | 5 | 1.58 |
Embodiment 11:
Constant temperature waters groove temperature is controlled at 30 ℃, in two neck bottles, adds 0.023g (2 * 10 successively
-4Mol) NH
4VO
3With 15mL acid medium (1.5mL water adds 13.5mL acetic acid), constant temperature is stirred to catalyst dissolution, adds 1.56g (0.0225mol) NH
2OHHCl and 2mL (0.0225mol) benzene rises to 80 ℃ with waters groove temperature, and constant temperature, stirring, back flow reaction be after about 4 hours, stopped reaction.After reaction system naturally cooled to room temperature, the NaOH solution with 30% was neutralized to pH=6-8, goes out organic phase with the 5mL extracted with diethyl ether, carries out qualitative analysis with the chromatograph-mass spectrometer coupling analyser, carries out quantitative analysis with meta-aminotoluene as interior mark.The molar yield of aniline is 19.60%.
Embodiment 12-14:
With 0.032g (2 * 10
-4Mol) NaVO
32H
2O is a catalyzer, 15mL acetic acid-aqueous solution (V
H2O/ V
HOAc=1: 2) make medium, with the charging of 2mL (0.0225mol) benzene, experimentize according to embodiment 1 described step, reaction conditions and reaction result are listed in the table 2.
Table 2
| The embodiment sequence number | NH 2OH·HCl(g) | Temperature of reaction (℃) | Reaction times (h) | Aniline molar yield (with respect to benzene) |
| 12 | 1.56(0.0225mol) | 90 | 5 | 30.22 |
| 13 | 2.34(0.0338mol) | 90 | 5 | 38.22 |
| 14 | 3.12(0.0450mol) | 90 | 5 | 41.04 |
Embodiment 15-18:
With 1.56g (0.0225mol) NH
2OHHCl is an aminating agent, 15mL acetic acid-aqueous solution (V
H2O/ V
HOAc=1: 2) make medium, with the charging of 2mL (0.0225mol) benzene, experimentize according to embodiment 1 described step, reaction conditions and reaction result are listed in the table 3.
Table 3
| The embodiment sequence number | NaVO 3·2H 2O(g) | Temperature of reaction (℃) | Reaction times (h) | Aniline molar yield (with respect to benzene) |
| 15 | 0.016g(1×10 -4mol) | 80 | 4 | 45.34％ |
| 16 | 0.048g(3×10 -4mol) | 80 | 4 | 56.88％ |
| 17 | 0.080g(5×10 -4mol) | 80 | 4 | 68.44％ |
| 18 | 0.160g(1×10 -3mol) | 80 | 4 | 17.08％ |
Embodiment 19:
Constant temperature waters groove temperature is controlled at 30 ℃, in two neck bottles, adds 0.032g (2 * 10 successively
-4Mol) NaVO
32H
2O and 20mL acetic aid medium (V
H2O/ V
HOAc=1: 3), constant temperature is stirred to catalyst dissolution, adds 1.56g (0.0225mol) NH
2OHHCl and 2mL (0.0225mol) benzene rises to 80 ℃ with waters groove temperature, and constant temperature, stirring, back flow reaction be after about 4 hours, stopped reaction.After reaction system naturally cooled to room temperature, the NaOH solution with 30% was neutralized to pH=6-8, goes out organic phase with the 5mL extracted with diethyl ether, carries out qualitative analysis with the chromatograph-mass spectrometer coupling analyser, carries out quantitative analysis with meta-aminotoluene as interior mark.The molar yield of aniline is 45.92%.
Claims (5)
1. the method by benzene direct oxidation amination one-step synthesis aniline is characterized in that 1. the solubility vanadic salts is a catalyzer, and oxammonium hydrochloride is an aminating agent, and aqueous acetic acid is a medium, and wherein the mol ratio of benzene and catalyzer is 22.5: 1-225: 1; The mol ratio of benzene and aminating agent is 1: 1-1: 2; The volume ratio of aqueous acetic acid and benzene is 7.5: 1-10: 1; The volume ratio of water and acetic acid is 1: 2-1: 9; 2. be reflected under the normal pressure and carry out, temperature of reaction is 50-90 ℃, and the reaction times is 1-5 hour.
2. by the described method of claim 1, it is characterized in that used solubility vanadic salts is sodium metavanadate, ammonium meta-vanadate.
3. by the described method of claim 1, the mol ratio that it is characterized in that benzene and catalyzer is 45: 1-112.5: 1.
4. by the described method of claim 1, it is characterized in that temperature of reaction is 80-90 ℃.
5. by the described method of claim 1, it is characterized in that the reaction times is 4-5 hour.
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| 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 |
| CN104829462B (en) * | 2015-05-20 | 2017-07-14 | 湘潭大学 | By the method for the diaminonaphthalene of naphthalene one-step synthesis 1,5 |
| CN104829463B (en) * | 2015-05-20 | 2017-07-18 | 湘潭大学 | A kind of green synthesis method of 1 naphthylamines |
| CN104829464B (en) * | 2015-05-20 | 2017-10-13 | 湘潭大学 | The method that 1,5 diaminonaphthalenes are synthesized by 1 naphthylamines |
| CN106278904B (en) * | 2016-08-08 | 2018-03-27 | 河北工业大学 | The method that cyclohexylamine is prepared by benzene one kettle way |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1555921A (en) * | 2004-01-09 | 2004-12-22 | 四川大学 | Preparation method of catalyst for direct oxidation amination one step synthesizing aniline from benzene |
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| CN1555921A (en) * | 2004-01-09 | 2004-12-22 | 四川大学 | Preparation method of catalyst for direct oxidation amination one step synthesizing aniline from benzene |
Non-Patent Citations (2)
| Title |
|---|
| amination of benzene and toluene with hydroxyamine inthepresence of transition metal redox catalysts. N.I.Kuznetsova et. al.Journal of molecular catalysis A,Vol.161 . 2000 |
| amination of benzene and toluene with hydroxyamine inthepresence of transition metal redox catalysts. N.I.Kuznetsova et. al.Journal of molecular catalysis A,Vol.161 . 2000 * |
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