CN106278926A - Bianry alloy catalyzes and synthesizes the method for 3 amino 4 p-methoxyacetanilides - Google Patents
Bianry alloy catalyzes and synthesizes the method for 3 amino 4 p-methoxyacetanilides Download PDFInfo
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- CN106278926A CN106278926A CN201610629622.XA CN201610629622A CN106278926A CN 106278926 A CN106278926 A CN 106278926A CN 201610629622 A CN201610629622 A CN 201610629622A CN 106278926 A CN106278926 A CN 106278926A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
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Abstract
The present invention relates to a kind of method that Nanometer Copper/silver bianry alloy catalyst to catalyzing hydrogenating 3 nitro 4 p-methoxyacetanilide (NMA) synthesizes 3 amino 4 p-methoxyacetanilides, belong to nano-catalytic field.Reaction of the present invention is carried out in autoclave, under catalyst action, it is provided that hydrogen is hydrogen source.In course of reaction, this catalyst has high activity, high selectivity, and catalyst not easy in inactivation, has good stability in use.
Description
Technical field
The present invention relates to a kind of Nanometer Copper/silver bianry alloy catalyst to catalyzing hydrogenating 3-nitro-4-p-methoxyacetanilide
(NMA) method synthesizing 3-amino-4-methoxyacetanilide, belongs to nano-catalytic field.
Background technology
3-amino-4-methoxyacetanilide is synthesis organic azo-type disperse dyes and the important centre of some drugs
Body, can be used for preparing the intermediate of the dyestuffs such as C.I. Disperse Blue-79, C.I. disperse blue 301 and disperse violet 58, is also disperse dark blue
The coupling component of HGL, can be additionally used in the synthesis of acid stain, reactive dye and pigment simultaneously, occupies critical role in the industry.
China is 3-amino-4-methoxyacetanilide manufacturing country maximum in the world, being in great demand at home and abroad, has good
Market prospect.
It is from chlorobenzene that traditional industry produces synthesis 3-amino-4-methoxyacetanilide route, first passes through nitrification, ether
Changing, reduction, acylated synthesis methacetin, then nitrification, iron powder reducing obtains 3-amino 4-p-methoxyacetanilide.Adopt
With iron powder reducing method reduction intermediate product 3-nitro-4-p-methoxyacetanilide synthetic product 3-amino-4-methoxyl acetophenone
Amine, although its technique is simple, applicable surface is wider, it is not necessary to high pressure equipment, and safety is also compared in operation, but the use of iron powder makes
Producing substantial amounts of iron cement waste residue and acid waste water, serious environment pollution in course of reaction, therefore, this synthesizes 3-amino-4-methoxy
The technique of base acetanilide is urgently improved.
At present, in the commercial production of aromatic amine compound, catalytic hydrogenation method used catalyst be mainly Raney-Ni and Pt,
The rare precious metals such as Pd, Ru and Rh.But, it is amino that commercial Raney-Ni is not only catalyzed nitro hydrogenation, and is catalyzed phenyl ring and adds
Hydrogen, causes having by-product to produce, and reduces major product purity.Along with developing rapidly of nanotechnology, metallic catalyst is being urged
Change the catalytic performance showing excellence in nitro-aromatic selective hydrogenation reaction.But, metallic catalyst existence and stability is poor,
The shortcomings such as easy reunion.And carrier nanometer catalyst is in activation process, nano-noble metal is easily reduced and is prone to be grown to
Large-sized metallic particles, the dispersibility causing active component is low low with catalysis activity.
For the shortcoming of unitary metallic catalyst, it is converted into bianry alloy by nanocrystalline for unitary, high living can be prepared
The metallic catalyst of property.The alloying of metal not only increases the ability of the anti-sintering of granule, changes catalyst simultaneously and lives
The Electronic Performance of property component and geometry.Compared with unitary metallic catalyst, binary alloy nano metallic catalyst exists
Catalysis nitro-aromatic selective hydrogenation reaction demonstrates more excellent catalysis activity and selectivity.Therefore, research Nanometer Copper/silver
Bianry alloy catalysis 3-nitro-4-p-methoxyacetanilide synthetic product 3-amino-4-methoxyacetanilide has important grinding
Study carefully meaning.
Summary of the invention
It is an object of the invention to provide one and utilize Nanometer Copper/silver bianry alloy catalyst to catalyzing hydrogenating 3-nitro-4-
The method of p-methoxyacetanilide synthesis 3-amino-4-methoxyacetanilide.Reaction of the present invention is in autoclave
Carry out, under catalyst action, it is provided that hydrogen is hydrogen source.In course of reaction, this catalyst has high activity, high selectivity, and urges
Agent not easy in inactivation, has good stability in use.
The present invention is achieved through the following technical solutions:
A kind of Nanometer Copper/silver bianry alloy catalyst to catalyzing hydrogenating 3-nitro-4-p-methoxyacetanilide synthesis 3-amino-
The method of 4-p-methoxyacetanilide, is carried out as steps described below:
Step A, in autoclave, add the methanol solution of certain density 3-nitro-4-p-methoxyacetanilide,
Add a certain amount of Nanometer Copper/silver bianry alloy catalyst, install reaction unit, logical N2Empty, then be passed through high-purity
Hydrogen row N2, it is then turned on agitating device.
Step B, step A gained system is heated to reaction temperature；Being passed through certain pressure hydrogen to react, reaction terminates
After, it being cooled to less than 45 DEG C, product is diluted, and uses efficient liquid phase chromatographic analysis result of calculation.
In step A, described 3-nitro-4-p-methoxyacetanilide concentration of methanol solution is 0.05～0.3mol/L.
In step A, the consumption of Nanometer Copper/silver bianry alloy catalyst is every 150mL3-nitro-4-p-methoxyacetanilide
Methanol solution uses 0.1～1.0g.
In step A, described 3-nitro-4-p-methoxyacetanilide methanol solution with the volume ratio of autoclave is
1.5:5, stir speed (S.S.) is 400rpm.
In step B, described Hydrogen Vapor Pressure is 0.4～1.2MPa, and reaction temperature is 80～160 DEG C；Response time is 3h.
In step B, the dilution of described product processes and refers to reacted solution is carried out dilute twice, first uses
Pipet pipettes the reacted solution of 1ml to 25ml volumetric flask, by methanol constant volume, pipettes diluent of 1ml more extremely
25ml volumetric flask, uses methanol constant volume；Reacted solution includes unreacted raw material completely and product.
Nanometer Copper described in such scheme/silver bianry alloy catalyst is with Tween-80, cetyl trimethyl bromine
Change ammonium (CTAB) or citric acid (CA) is to be prepared by wet-chemical reducing process under conditions of organic modifier, concrete preparation
Method is carried out as steps described below:
Step one, presoma and the organic modifier of Cu are dissolved in dehydrated alcohol, ultrasonic whole dissolvings, then heat to
60 DEG C, dropwise dropping NaOH ethanol solution regulates solution ph is 8, obtains mixed liquor A.
Step 2, take hydrazine hydrate and be dissolved in dehydrated alcohol and make hydrazine hydrate weak solution, by described hydrazine hydrate weak solution dropwise
Joining in mixed liquor A, form mixed liquid B, and react, the Nanometer Copper of preparation is cooled to 30 DEG C after terminating by reaction.
Step 3, the presoma of Ag is dissolved in dehydrated alcohol, form mixed liquor C, and C solution is added dropwise over step 2
The product of gained reacts, under magnetic stirring by the Nanometer Copper of preparation/silver bianry alloy cooling after reaction certain time
To room temperature and be stored in ethanol solution, before using, need pretreatment, with dehydrated alcohol repeatedly wash, centrifugation.
In described step one, the presoma of Cu is nitrate trihydrate copper, and the molar concentration of copper nitrate ethanol solution is 0.2mol/
L。
In described step one, in mixed liquor A, organic modifier is cetyl trimethylammonium bromide (CTAB), citric acid
(CA) or tween 80 (Tween-80), its quality is the 10% of nitrate trihydrate copper mass, and the concentration of NaOH ethanol solution is
1.5mol/L。
In described step 2, during preparation hydrazine hydrate weak solution, the volume ratio of hydrazine hydrate and dehydrated alcohol is 3:25.Described water
The mass concentration closing hydrazine is 85%, and hydrazine hydrate alcohol dilute solution is 7:5 with the volume ratio of copper nitrate ethanol solution；Response time is
2h；Reaction temperature is still maintained at 60 DEG C.
In described step 3, the presoma of described Ag is silver nitrate, and the molar concentration of silver nitrate ethanol solution is
0.08mol/L, silver nitrate ethanol solution is 1:2 with the volume ratio of copper nitrate ethanol solution, and described reaction temperature is 30 DEG C, reaction
Time is 1h.
The present invention is distinctive be technology is characterized in that
By changing organic modifier type, prepare different structure, the Nanometer Copper/silver bianry alloy of different-shape is urged
Agent, it is achieved the complementation on catalytic performance, cooperation between nano metal, improves the catalysis activity and selectivity of nano metal, it is thus achieved that
Beyond thought catalytic effect, this is a big characteristic of the present invention.
Detailed description of the invention
It is below presently preferred embodiments of the present invention, it is possible to be more fully understood that the present invention, but embodiments of the invention are not limited to
This, data shown in it does not represent the restriction to feature of present invention scope simultaneously.
Embodiment 1
The preparation of catalyst:
In the presence of organic modifier CTAB, with nitrate trihydrate copper, silver nitrate, hydrazine hydrate as raw material, use wet-chemical
Reduction method for preparing nanometer copper/silver bianry alloy catalyst.
1.93g nitrate trihydrate copper and 0.193g CTAB being dissolved in the dehydrated alcohol of 40ml, ultrasonic 30min all dissolves
Form mixed liquor, when mixed liquor is warming up to 60 DEG C, dropwise dropping 1.5mol/L NaOH ethanol solution, regulate mixed liquor pH value
It is 8；The most dropwise dropping hydrazine hydrate alcohol dilute solution (hydrazine hydrate of 6ml 85%/50ml dehydrated alcohol), and in magnetic agitation
Lower reaction 2h, the Nanometer Copper of preparation is cooled to 30 DEG C after terminating by reaction；Weigh 0.27g silver nitrate and be dissolved in 20ml dehydrated alcohol
In, it is added dropwise to silver nitrate ethanol solution be prepared as nanometer copper-silver bianry alloy Cu-after the mixed liquor after cooling carries out reacting 1h
Ag.Finally it is stored in ethanol solution.Need pretreatment before using, with dehydrated alcohol repeatedly wash, centrifugation.
3-nitro-4-p-methoxyacetanilide catalytic hydrogenation reaction:
3-nitro-4-p-methoxyacetanilide the methanol taking certain mass is configured to the reactant liquor addition 500mL of 150mL
Autoclave in, add 0.6g Nanometer Copper/silver bianry alloy catalyst, wherein 3-nitro-4-p-methoxyacetanilide
Concentration is 0.2mol/L；Install reaction unit, be passed through nitrogen purging 10min and empty, then be passed through High Purity Hydrogen row N2, then
Open agitating device, stir speed (S.S.) 400rpm, when reaction temperature rises to 120 DEG C, be passed through 0.8MPa H2Reaction 3h；Reaction knot
Shu Hou, is cooled to less than 45 DEG C, and product is diluted, and uses efficient liquid phase chromatographic analysis and calculates, the results are shown in Table 1.
Embodiment 2
The method using embodiment 1 same prepares Nanometer Copper/silver bianry alloy catalyst, only changes organic modifier respectively
For CA, Tween-80, the process of catalyst to catalyzing hydrogenating 3-nitro-4-p-methoxyacetanilide uses same as in Example 1
Method, i.e. can get different modifying agent and prepares Nanometer Copper/silver bianry alloy catalyst and urge 3-nitro-4-p-methoxyacetanilide
Change the impact of hydrogenation reaction, the results are shown in Table 1.
Table 1 different modifying agent is prepared Nanometer Copper/silver bianry alloy catalyst and is catalyzed 3-nitro-4-p-methoxyacetanilide
The impact of hydrogenation reaction
Embodiment 3
Use the method preparing nano Cu-Ag catalyst that embodiment 1 is same, be catalyzed 3-nitro-4-p-methoxyacetanilide
Hydrogenation, only changes still interior reaction temperature and is respectively 80 DEG C, 100 DEG C, 140 DEG C and 160 DEG C, i.e. can get reaction temperature to 3-nitre
The impact of base-4-p-methoxyacetanilide catalytic hydrogenation reaction, the results are shown in Table 2.
The impact on 3-nitro-4-p-methoxyacetanilide catalytic hydrogenation reaction of table 2 reaction temperature
Embodiment 4
Use the method preparing nano Cu-Ag catalyst that embodiment 1 is same, be catalyzed 3-nitro-4-p-methoxyacetanilide
Hydrogenation, the concentration only changing 3-nitro-4-p-methoxyacetanilide is respectively 0.05mol/L, 0.1mol/L, 0.3mol/L, i.e.
The available material concentration impact on 3-nitro-4-p-methoxyacetanilide catalytic hydrogenation reaction, the results are shown in Table 3.
Table 3 3-nitro-4-p-methoxyacetanilide concentration is to 3-nitro-4-p-methoxyacetanilide catalytic hydrogenation reaction
Impact
Embodiment 5
Use the method preparing nano Cu-Ag catalyst that embodiment 1 is same, be catalyzed 3-nitro-4-p-methoxyacetanilide
Hydrogenation, only changes Hydrogen Vapor Pressure and is respectively 0.4MPa and 1.2MPa, i.e. can get Hydrogen Vapor Pressure to 3-nitro-4-methoxyl group acetyl
The impact of aniline catalytic hydrogenation reaction, the results are shown in Table 4.
The impact on 3-nitro-4-p-methoxyacetanilide catalytic hydrogenation reaction of table 4 Hydrogen Vapor Pressure
Embodiment 6
Use the method preparing nano Cu-Ag catalyst that embodiment 1 is same, be catalyzed 3-nitro-4-p-methoxyacetanilide
Hydrogenation, only changes catalyst amount and is respectively 0.1g, 0.2g and 1.0g, i.e. can get catalyst amount to 3-nitro-4-methoxy
The impact of base acetanilide catalytic hydrogenation reaction, the results are shown in Table 5.
The impact on 3-nitro-4-p-methoxyacetanilide catalytic hydrogenation reaction of table 5 catalyst amount
Embodiment 7
Use the method preparing nano Cu-Ag catalyst that embodiment 1 is same, be catalyzed 3-nitro-4-p-methoxyacetanilide
Hydrogenation, by catalyst and catalytic hydrogenation product centrifugation, with absolute ethanol washing, is dried, and uses the 2nd time, the 3rd time, and the 4th
Secondary, the 5th, catalyst recycling performance in 3-nitro-4-p-methoxyacetanilide catalytic hydrogenation reaction, result can be obtained
It is shown in Table 6,
The impact on 3-nitro-4-p-methoxyacetanilide catalytic hydrogenation reaction of the table 6 catalyst access times
Claims (9)
1. the method that bianry alloy catalyzes and synthesizes 3-amino-4-methoxyacetanilide, it is characterised in that enter in accordance with the following steps
OK:
Step A, in autoclave, add the methanol solution of certain density 3-nitro-4-p-methoxyacetanilide, then add
Enter a certain amount of Nanometer Copper/silver bianry alloy catalyst, install reaction unit, logical N2Empty, then be passed through High Purity Hydrogen row
N2, it is then turned on agitating device；
Step B, step A gained system is heated to reaction temperature；It is passed through certain pressure hydrogen to react, after reaction terminates,
Being cooled to less than 45 DEG C, product is diluted, and uses efficient liquid phase chromatographic analysis result of calculation.
2. the method that bianry alloy as claimed in claim 1 catalyzes and synthesizes 3-amino-4-methoxyacetanilide, its feature exists
In: in step A, described 3-nitro-4-p-methoxyacetanilide concentration of methanol solution is 0.05～0.3mol/L；Nanometer Copper/silver
The consumption of bianry alloy catalyst is that every 150mL3-nitro-4-p-methoxyacetanilide methanol solution uses 0.1～1.0g；Institute
3-nitro-4-p-methoxyacetanilide the methanol solution stated is 1.5:5 with the volume ratio of autoclave, and stir speed (S.S.) is
400rpm。
3. the method that bianry alloy as claimed in claim 2 catalyzes and synthesizes 3-amino-4-methoxyacetanilide, its feature exists
In: described 3-nitro-4-p-methoxyacetanilide concentration of methanol solution is 0.1mol/L, Nanometer Copper/silver bianry alloy catalyst
Consumption be every 150mL3-nitro-4-p-methoxyacetanilide methanol solution use 0.6g.
4. the method that bianry alloy as claimed in claim 1 catalyzes and synthesizes 3-amino-4-methoxyacetanilide, its feature exists
In: in step B, described Hydrogen Vapor Pressure is 0.4～1.2MPa, and reaction temperature is 80～160 DEG C；Response time is 3h；Described
The dilution of product process and refer to reacted solution is carried out dilute twice, after first pipetting 1ml reaction with pipet
Solution to 25ml volumetric flask, by methanol constant volume, pipette diluent of 1ml the most again to 25ml volumetric flask, use methanol constant volume；
Reacted solution includes unreacted raw material completely and product.
5. the method that bianry alloy as claimed in claim 4 catalyzes and synthesizes 3-amino-4-methoxyacetanilide, its feature exists
In: reaction temperature is 140 DEG C, and described Hydrogen Vapor Pressure is 0.8MPa.
6. the method that bianry alloy as claimed in claim 1 catalyzes and synthesizes 3-amino-4-methoxyacetanilide, its feature exists
In: described Nanometer Copper/silver bianry alloy catalyst is with Tween-80, cetyl trimethylammonium bromide (CTAB) or Fructus Citri Limoniae
Acid (CA) is to be prepared by wet-chemical reducing process under conditions of organic modifier, and concrete preparation method is as steps described below
Carry out:
Step one, presoma and the organic modifier of Cu are dissolved in dehydrated alcohol, ultrasonic whole dissolvings, then heat to 60
DEG C, dropwise dropping NaOH ethanol solution regulates solution ph is 8, obtains mixed liquor A；
Step 2, take hydrazine hydrate and be dissolved in dehydrated alcohol and make hydrazine hydrate weak solution, described hydrazine hydrate weak solution is added dropwise over
In mixed liquor A, forming mixed liquid B, and react, the Nanometer Copper of preparation is cooled to 30 DEG C after terminating by reaction；
Step 3, the presoma of Ag is dissolved in dehydrated alcohol, form mixed liquor C, and C solution is added dropwise over step 2 gained
Product in react, under magnetic stirring reaction certain time after the Nanometer Copper of preparation/silver bianry alloy is cooled to room
Temperature is also stored in ethanol solution, needs pretreatment before using, with dehydrated alcohol repeatedly wash, centrifugation.
7. the method that bianry alloy as claimed in claim 6 catalyzes and synthesizes 3-amino-4-methoxyacetanilide, its feature exists
In: in described step one, the presoma of Cu is nitrate trihydrate copper, and the molar concentration of copper nitrate ethanol solution is 0.2mol/L；Mixed
Closing organic modifier in liquid A is cetyl trimethylammonium bromide, and its quality is the 10% of nitrate trihydrate copper mass, NaOH ethanol
The concentration of solution is 1.5mol/L.
8. the method that bianry alloy as claimed in claim 6 catalyzes and synthesizes 3-amino-4-methoxyacetanilide, its feature exists
In: in described step 2, during preparation hydrazine hydrate weak solution, the volume ratio of hydrazine hydrate and dehydrated alcohol is 3:25.Described hydrazine hydrate
Mass concentration be 85%, the volume ratio of hydrazine hydrate alcohol dilute solution and copper nitrate ethanol solution is 7:5；Response time is 2h；
Reaction temperature is still maintained at 60 DEG C.
9. the method that bianry alloy as claimed in claim 6 catalyzes and synthesizes 3-amino-4-methoxyacetanilide, its feature exists
In: in described step 3, the presoma of described Ag is silver nitrate, and the molar concentration of silver nitrate ethanol solution is 0.08mol/L, nitre
Acid silver ethanol solution is 1:2 with the volume ratio of copper nitrate ethanol solution, and described reaction temperature is 30 DEG C, and the response time is 1h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107746380A (en) * | 2017-11-06 | 2018-03-02 | 宁夏中盛新科技有限公司 | A kind of industrialized preparing process of the acetyl-anisidine of 2 amino 4 |
| CN110252383A (en) * | 2019-05-17 | 2019-09-20 | 江苏大学 | A kind of Cu@Ru/MCM-41 nanocatalyst and its preparation method and application |
| CN113578346A (en) * | 2021-08-13 | 2021-11-02 | 江苏大学 | Copper/silver alloy nano catalyst and preparation method and application thereof |
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| CN101565383A (en) * | 2009-05-08 | 2009-10-28 | 江苏大学 | Method for synthesizing 3-amino-4-methacetin by catalytic hydrogenation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107746380A (en) * | 2017-11-06 | 2018-03-02 | 宁夏中盛新科技有限公司 | A kind of industrialized preparing process of the acetyl-anisidine of 2 amino 4 |
| CN107746380B (en) * | 2017-11-06 | 2020-04-07 | 宁夏中盛新科技有限公司 | Industrial production method of 2-amino-4-acetamino anisole |
| CN110252383A (en) * | 2019-05-17 | 2019-09-20 | 江苏大学 | A kind of Cu@Ru/MCM-41 nanocatalyst and its preparation method and application |
| CN113578346A (en) * | 2021-08-13 | 2021-11-02 | 江苏大学 | Copper/silver alloy nano catalyst and preparation method and application thereof |
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