CN110467533A - A kind of preparation method of parachloroanilinum hydrochloride - Google Patents
A kind of preparation method of parachloroanilinum hydrochloride Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
- C07C209/365—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst by reduction with preservation of halogen-atoms in compounds containing nitro groups and halogen atoms bound to the same carbon skeleton
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
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Abstract
The present invention provides a kind of preparation method of parachloroanilinum hydrochloride, the preparation method includes: in the presence of the organic solvent of azeotrope with water, using parachloronitrobenzene as starting material, under platinum carbon catalyst catalysis, anti-agent and acid-binding agent is added, it is closed, it is passed through hydrogen, hydrogenation reaction is carried out under high temperature and pressure, is cooled down, catalyst is filtered out, filtrate is collected；Concentrated hydrochloric acid is added into filtrate, in 80-95 DEG C of heat preservation 0.5-2h, continues to lift temperature to boiling, is back to that there is no moisture content to separate by water segregator, filters, it is dry, obtain parachloroanilinum hydrochloride；The preparation method reaction condition is mild controllable, easy to operate, low in cost, and two-step reaction one kettle way is completed, and provides a kind of advanced preparation method for industrialized production.
Description
Technical field
The invention belongs to medicine intermediates to synthesize field, in particular to a kind of preparation method of parachloroanilinum hydrochloride.
Background technique
Parachloroanilinum hydrochloride is important Organic Chemicals and intermediate, medicine, dyestuff, pesticide, rubber chemicals,
The fields such as synthetic resin, fragrance, photography occupy an important position.
Parachloroanilinum is generally restored by parachloronitrobenzene and is made, and reaction equation is as follows:
The restoring method of nitro mainly has iron powder reducing method, sodium sulfide reducing method, hydrazine hydrate reduction method and catalytic hydrogenation also
Former method.The features such as iron powder reducing method has technique relative maturity, and production is relatively easy to control, and side reaction is few is production parachloroanilinum
Main method, but there are iron cement be difficult to recycle, iron powder consumption is big, environmental pollution and equipment seriously corroded, it is difficult to continuous metaplasia
It produces, product separates the shortcomings such as difficulty.Sodium sulfide reducing method prepares the mature production technology of chloro aminobenzen, and big at this stage
Some Enterprises produce a kind of method used in chloro aminobenzen.The method relative to iron reduction method, have reaction condition it is relatively mild,
The features such as by-product sodium thiosulfate of generation can be dissolved in water and product is easily isolated, but three wastes discharge amount is huge, to ring
Guarantor's processing causes certain pressure.Hydrazine hydrate reduction method " three wastes " discharge is less, without dehalogenation side reaction generation, product selectivity height is
The advantages of this method, but hydrazine hydrate is expensive, is more toxic, and greatly limits answering in industrial production
With.Catalytic hydrogenating reduction method has the features such as advanced technique, at low cost, high income, good product purity, small environmental pollution, is mesh
Pre reduction parachloronitrobenzene prepares the development trend of parachloroanilinum.But the catalyst that catalytic hydrogenation method uses at present have it is inorganic
Or noble metal catalyst, porous metal catalyst and the amorphous alloy catalyst etc. of macromolecule carrier load, these catalysis
Prepared by agent catalysis parachloronitrobenzene reduction is easy to happen dechlorination side reaction during parachloroanilinum, not only reduce product quality and
Yield, and generate dechlorinated side product hydrogen chloride severe corrosion equipment, though add anti-agent it is a degree of inhibit it is de-
Chlorine, but increase a series of problems, such as dehalogenation inhibitors separate difficulty with product.
Currently, the biggish manufacturer of parachloroanilinum production capacity is such as: Huludao City's generation star medicine (producing 20000 tons per year), Anhui Aug. 1st
(producing 60000 tons per year) is all made of solventless method catalytic hydrogenation and prepares parachloroanilinum, it may be assumed that by parachloronitrobenzene (fusing point in dissolution kettle
83 DEG C) 85 DEG C are heated to melting, molten state parachloronitrobenzene is added to hydrogen kettle is added by pipeline, catalyst is added and resists de-
Halogen agent, closed plus hydrogen kettle, high temperature and pressure catalytic hydrogenation to hydrogen abstraction reaction finish, 80 DEG C of temperature control or more (parachloroanilinum fusing points 72.5
DEG C) reaction solution is transferred to by separating still by pipeline pump, hydrogenation byproduct water is isolated, remaining crude product material (purity about 90%) is right
Chloroaniline crude product is transferred to rectifying still, and by ten meters high rectifying column rectifying, product parachloroanilinum rectifying part is transmitted by thermo-insulating pipe line
Solid parachloroanilinum is sliced to obtain to slicer cooling, and purity is up to 99.5%, yield 85% or so.Entire production procedure drawback exists
In:
1) inhibit the generation of dechlorination side reaction during catalytic hydrogenation reaction by the addition of anti-agent, dechlorination is secondary anti-
It should look like this:
But still have the generation of part dechlorination object (aniline), cause hydrogenation reaction yield relatively low, crude product product purity is not up to standard
(crude product purity about 90%), in addition, generating also additional by-product with dechlorination object (aniline) with the generation of dechlorination side reaction
The generation of HCl, to adding hydrogen kettle to cause centainly to corrode.
2) it in order to enable the purity of the parachloroanilinum of preparation improves, needs further to purify crude product parachloroanilinum,
The purification of existing crude product parachloroanilinum (purity about 90%) need to be purified by ten meters high rectifying column rectifying and be realized, rectifying column purifying behaviour
Make relatively low complexity, yield, waste of energy, expend working hour, virtually complicates production technology.
It is parachloroanilinum preparation method above, and parachloroanilinum hydrochloride adds hydrochloric acid salt-forming reaction to be made by parachloroanilinum.
Existing industrialized production parachloroanilinum hydrochloride is that parachloroanilinum is added to temperature reaction in a certain amount of concentrated hydrochloric acid, and salt-forming reaction is complete
A large amount of solvents are concentrated out after complete, remaining a small amount of solvent cooling, filters, is dried to obtain product parachloroanilinum hydrochloride.Concentrated hydrochloric acid contains
For water generally 64% or so, parachloroanilinum hydrochloride is highly soluble in water, traditional parachloroanilinum hydrochloride industrialized production work
The later period a small amount of water of residual is concentrated into skill last handling process still has biggish solubility to parachloroanilinum hydrochloride, causes product
Yield (yield is 85% or so) is relatively low.Parachloroanilinum hydrochloric acid salt production process is as follows:
Summary of the invention
For overcome the deficiencies in the prior art, the present invention provides a kind of preparation method of parachloroanilinum hydrochloride, the preparation
Method is suitble to large-scale industrial production.
Specific technical solution of the present invention is as follows:
The one of technical solution of the present invention provides a kind of preparation method of parachloroanilinum hydrochloride, which includes
Following steps:
1) it in the presence of the organic solvent of azeotrope with water, using parachloronitrobenzene as starting material, is catalyzed in platinum carbon catalyst
Under, anti-agent and acid-binding agent is added, it is closed, it is passed through hydrogen, hydrogenation reaction is carried out under high temperature and pressure, cools down, filters out catalyst,
Collect filtrate；
2) concentrated hydrochloric acid is added into filtrate, in 80-95 DEG C of heat preservation 0.5-2h, continues to lift temperature to boiling, is returned by water segregator
It flow to that there is no moisture content to separate, filters, it is dry, obtain parachloroanilinum hydrochloride.
In further improved scheme, the platinum charcoal is 1-1.5% platinum charcoal.
In further improved scheme, the organic solvent of the azeotrope with water is toluene.
In further improved scheme, the anti-agent is dicyandiamide.
In further improved scheme, the acid-binding agent is ammonium hydroxide, triethylamine or pyridine.
In further improved scheme, the temperature of the high-temperature and high-pressure hydrogenation reaction is 90-100 DEG C, pressure 1-
1.5MPa。
In further improved scheme, the time of the hydrogenation reaction is 6-7h.
In further improved scheme, the inventory of the catalyst is the 1-3 ‰ of parachloronitrobenzene inventory.
In further improved scheme, the inventory of the anti-agent is the 5-10% to catalyst butt inventory.
The advantages of preparation method of parachloroanilinum hydrochloride provided by the invention, is as follows:
1) parachloroanilinum hydrochloric acid salt production process reaction condition provided by the invention is suitable for that operation and post-processing are relatively simple
Single, this preparation method selects suitable catalyst, anti-agent during catalytic hydrogenation reaction and controls dosage, and strict control is anti-
Temperature, reaction pressure are answered, to efficiently inhibit the generation of dechlorination object.
2) the by-product HCl that micro dechlorination reaction generates in preparation process and the acid-binding agent of addition neutralize, it is entirely avoided
Corrosion to equipment.
3) preparation method provided by the invention can with high-purity, obtain hydrogenation products parachloroanilinum, parachloroanilinum in high yield
Purity is up to 99.6%, and intermediate parachloroanilinum completely dispenses with rectifying column rectifying purifying, does not also have to any post-processing and purifies, directly
It connects and hydrochloric acid progress salt-forming reaction is added.
4) two-step reaction one kettle way complete, salt-forming reaction post-processing reaction solution is directly lifted temperature to 100 DEG C, using toluene with
Water azeotropic takes moisture content in reaction solution out of completely, and target product parachloroanilinum hydrochloride does not dissolve in toluene, hangs in toluene reaction solution
Floating, other impurities are dissolved in toluene, and cooling is filtered to reach the separation of product Yu mother liquor, impurity, and a small amount of toluene washing produces
Product, dry, high-purity obtains target product parachloroanilinum hydrochloride in high yield, and product purity is up to 99.9%, two step total moles
Yield is up to 94% or more, washed to the neutral continuation recovery of mother liquor toluene.
5) reaction condition of the present invention is mild controllable, easy to operate, low in cost, and two-step reaction one kettle way is completed, for industry
Metaplasia production provides a kind of advanced preparation method.
Specific embodiment
1. the purity of parachloroanilinum and the assay of relative substance
1.1 measuring principle
Parachloroanilinum and relative substance (dechlorination object) are measured using reversed-phased high performace liquid chromatographic, use ultraviolet inspection
It surveys device to be detected, the purity of parachloroanilinum and the content of relative substance are quantitative using areas of peak normalization method.
1.2 instrument and equipment
Liquid chromatograph: be infused range of pump flow rates 0.1mL/min-5.0mL/min, its discharge stability is within this range
± 1%；Detector is multi-wavelength ultraviolet spectrometry detector or the spectrophotometric detector with equal performance.
Chromatographic column: a length of 150mm, stainless steel column of the internal diameter for 4.6mm, stationary phase C18ODS, 3 μm of partial size；
Chromatographic work station or integrator；
Tack micro syringe: 25 μ L；
Supersonic generator.
1.3 kit solution
Methanol: chromatographically pure；
Buffered saline solution: 4g/L potassium dihydrogen phosphate, phosphoric acid tune pH ≈ 3；
Water: it is filtered through 0.45 μm of film.
1.4 operation condition of chromatogram
Mobile phase: volume ratio=43:57 of methanol and buffered saline solution；
Wavelength: 235nm；
Flow: 0.6mL/min；
Sample volume: 5 μ L；
Column temperature: 35 DEG C.
The preparation of 1.5 parachloroanilinum sample solutions
25mg parachloroanilinum is weighed in 25mL brown volumetric flask, methanol is added to dissolve and is diluted to scale, is uniformly mixed, in
Oscillation, sufficiently dissolution, spare in ultrasonic generator.
1.6 determination step
Open chromatograph.After instrument operations conditional stability, 5 μ L sample solutions note is drawn respectively with micro syringe
Enter in sampling valve, distribute and finish to the last one group, carries out result treatment with chromatographic work station or integrator.
1.7 results calculate
The mass fraction of parachloroanilinum and the content of organic impurities are with wiMeter is calculated by formula (1):
In formula:
AiThe peak area of parachloroanilinum and relative substance in-sample solution；
∑AiThe sum of parachloroanilinum and the peak area of relative substance in-sample solution.
Calculated result remains into after decimal point 2.If result is less than 0.01%, then retain 1 effective digital.
2. the measurement (gas chromatography) of parachloroanilinum hydrochloric acid purity salt
2.1 measuring principle
Using gas chromatography, the purity of parachloroanilinum hydrochloride is acquired with face normalization method.
2.2 instrument cartridge devices
A) gas chromatograph；Fid detector；
B) chromatographic column: OV-1701 (30m × 0.25mm × 0.5mm)；
C) data processing: chromatographic work station or integrator；
D) micro syringe: 10 μ L syringes.
2.3 reagent
Methanol: it analyzes pure (AR)
2.4 chromatographic condition
A) hydrogen: 0.1MPa；
B) air: 0.1MPa；
C) nitrogen: 0.05MPa；
D) vaporizing chamber: 250 DEG C；
F) column temperature: 200 DEG C；
G) sample volume: 0.6 μ L；
The preparation of 2.5 sample solutions
Parachloroanilinum hydrochloride sample 0.5g is weighed, methanol is added, is uniformly mixed, it is spare after completely dissolution.
2.6 analytical procedure
Chromatograph is opened, after instrument operations conditional stability, with micro syringe into 0.6 μ L of sample solution, to most
The latter group, which distributes, to be finished, and carries out result treatment with chromatographic work station or integrator.
2.7 purity results calculate
Parachloroanilinum hydrochloric acid purity salt is with wtMeter is calculated by formula (2):
In formula: AtThe peak area numerical value of component t；
∑AtThe sum of peak area numerical value of each component；
Calculated result remains into 2 significant digits.
3. the measurement (titration) of parachloroanilinum hydrochloride content
3.1 instrument and equipment
A) assay balance: sensibility reciprocal 0.001g；
B) buret 50mL；
C) beaker 500mL.
3.2 reagent
A) hydrochloric acid: analysis is pure；
B) it 0.1N sodium nitrite standard solution: provides to prepare by GB/T601:
C) it potassium iodide starch test paper or test solution: provides to execute by GB/T601.
3.3 determination step
0.7g~0.8g is weighed (to be accurately placed in a beaker to 0.0001g) sample, add 20mL hydrochloric acid (1:1) again plus 100mL
Aquae destillata is completely dissolved sample, and 10mL (10%) potassium bromide solution is added, and uses the sodium nitrite mark of 0.3mol/L at normal temperature
Quasi- standardization of solution uses potassium iodide starch test paper or test solution at normal temperature, and moment is presented haloing blue, tries after 3 minutes, still occur again
Circle repeatedly blue is terminal；
3.4 calculated result
Parachloroanilinum hydrochloride content is calculated in terms of X by formula (3):
In formula: X-parachloroanilinum hydrochloride content；
V0-blank consumption sodium nitrite volume, mL；
V-sample consumption sodium nitrite standard solution volume, mL；
C-sodium nitrite standard solution molar concentration, mol/L；
M-sample quality, g；
0.1642-with 1mol sodium nitrite standard solution C (HCL)=0.3000mol, it is comparable in grams to chlorine
Anilinechloride quality.
The preparation method of 1 parachloroanilinum hydrochloride of embodiment
Into 1L autoclave be added toluene 400mL, parachloronitrobenzene 200g, 1% platinum charcoal wet product 0.6g (butt amount 0.2g,
Wet product water content 66.7%), dicyandiamide 0.02g, ammonium hydroxide 0.8g, enclosed high pressure kettle vacuumizes 10 minutes, and it is empty to be passed through nitrogen displacement
Gas three times, continues to be passed through hydrogen displacement nitrogen three times, and control is passed through Hydrogen Vapor Pressure 1.0MPa, and reaction solution is lifted temperature to 90-100 DEG C
Hydrogen is no longer inhaled to reaction solution within hydrogenation reaction 6 hours, reaction solution is cooled to 60 DEG C hereinafter, nitrogen replacing hydrogen, filters out catalyst
(wait apply) collects filtrate to 1L reaction flask, 2g activity carbon decoloring is added, concentrated hydrochloric acid 212g is added in filtrate, by reaction solution temperature raising
To 90 DEG C insulation reaction 1 hour, continue to lift temperature to 100 DEG C, by water segregator reflux, toluene band water to there is no moisture content to separate,
A large amount of white solids suspend, and reaction solution is cooled to room temperature, filter, and a small amount of toluene washing, 80 DEG C of filter cake are dried under reduced pressure 4 hours,
Obtain white crystals parachloroanilinum hydrochloride 196g, weight yield 98%, molar yield 94%, purity 99.92%, content
99.81%.
The preparation method of 2 parachloroanilinum hydrochloride of embodiment
It is (butt amount 20g, wet that toluene 40L, parachloronitrobenzene 20kg, 1% platinum charcoal wet product 60g are added into 100L autoclave
Product water content 66.7%), dicyandiamide 2g, ammonium hydroxide 80g, enclosed high pressure kettle vacuumizes 10 minutes, is passed through nitrogen displaced air three
It is secondary, continue to be passed through hydrogen displacement nitrogen three times, control is passed through Hydrogen Vapor Pressure 1.0MPa, and reaction solution is lifted temperature to 90-100 DEG C plus hydrogen
Reaction no longer inhales hydrogen to reaction solution in 6 hours, and reaction solution is cooled to 60 DEG C hereinafter, nitrogen replacing hydrogen, nitrogen filters pressing, which filters out, urges
Agent collects filtrate to 100L enamel reaction still, 200g activity carbon decoloring is added, filtrate is added concentrated hydrochloric acid 21.2kg, will react
Liquid lifts temperature to 90 DEG C of insulation reactions 1 hour, continues to lift temperature to 100 DEG C, by water segregator reflux, toluene band water to there is no moisture content
It separates, a large amount of white solids suspend, and reaction solution are cooled to room temperature, centrifugation removal mother liquor, a small amount of toluene elution, 80 DEG C of filter cake subtract
It press dry dry 4 hours, obtains white crystals parachloroanilinum hydrochloride 19.8kg, weight yield 99%, molar yield 95%, purity
99.91%, content 99.85%.
The preparation method of 3 parachloroanilinum hydrochloride of embodiment
Toluene 800L, parachloronitrobenzene 400kg, 1% platinum charcoal wet product 1.2kg (butt amount are added into 2000L autoclave
0.4kg, wet product water content 66.7%), dicyandiamide 40g, ammonium hydroxide 1.6kg, enclosed high pressure kettle vacuumizes 10 minutes, is passed through nitrogen
Displaced air three times, continues to be passed through hydrogen displacement nitrogen three times, and control is passed through Hydrogen Vapor Pressure 1.0MPa, and reaction solution is lifted temperature to
90-100 DEG C is no longer inhaled hydrogen to reaction solution in hydrogenation reaction 6 hours, and reaction solution is cooled to 60 DEG C hereinafter, nitrogen replacing hydrogen, nitrogen
Air pressure filters out catalyst (wait apply), collects filtrate to 100L enamel reaction still, 4kg activity carbon decoloring is added, filtrate is added
Reaction solution is lifted temperature to 90 DEG C of insulation reactions 1 hour, continues to lift temperature to 100 DEG C by concentrated hydrochloric acid 424kg, passes through water segregator reflux, first
To there is no moisture content to separate, a large amount of white solids suspend benzene band water, reaction solution are cooled to room temperature, centrifugation removes mother liquor, on a small quantity
Toluene elutes filter cake, and 80 DEG C of filter cake are dried under reduced pressure 4 hours, obtain white crystals parachloroanilinum hydrochloride 400kg, weight yield
100%, molar yield 96%, purity 99.94%, content 99.89%.
Experimental example investigates the influence that each reaction condition reacts each step
The condition of investigation changes with the project of investigation, and the preparation method is the same as that of Example 1 for remaining.
1. investigating influence of the hydrogenation solvent to reaction, 1 the results are shown in Table.
Influence result of the 1.1 hydrogenation solvents to reaction
The yield of parachloroanilinum hydrochloride is molar yield in table.
As can be seen from the above table, it is reacted using toluene, tetrahydrofuran and ethyl acetate as reaction dissolvent, reaction dissolvent
It is insoluble to parachloroanilinum hydrochloride, and the water in reaction system is taken out of by azeotropic, but when selection tetrahydrofuran and acetic acid second
When ester, the reaction time is long, and reacts not exclusively, reduces reaction yield, it is therefore preferable that toluene is reaction dissolvent.
2. investigating influence of the catalyst for hydrogenation to reaction, it the results are shown in Table 2.
Influence result of 2 catalyst for hydrogenation of table to reaction
As can be seen from the above table, starting material left can be reduced using palladium charcoal, promotes reaction more complete, when platinum in platinum charcoal
Content is more than after 1.5%, unobvious to the facilitation of reaction, and reduces the purity of parachloroanilinum, improves dechlorination object
It generates, when platinum content is lower than 0.5% in platinum charcoal, starting material left amount is more, it is therefore preferable that 1-1.5% platinum charcoal is catalyst, it is more excellent
Selecting 1% platinum charcoal is catalyst.
3. investigating influence of the anti-agent of hydrogenation reaction to reaction, it the results are shown in Table 3.
Influence result of the anti-agent of 3 hydrogenation reaction of table to reaction
As can be seen from the above table, when anti-agent selects dicyandiamide or Thiodiglycol, starting material left amount is low, reaction
Completely, but when Thiodiglycol is anti-agent, anti-dehalogenation effect is unobvious, and the amount of dehalogenation object reaches 3.3%, therefore, excellent
Selecting dicyandiamide is anti-agent.
4. investigating influence of the hydrogenation reaction temperature to reaction, it the results are shown in Table 4.
Influence result of the 4 hydrogenation reaction temperature of table to reaction
As can be seen from the table, when reaction temperature is 90-120 DEG C, material surplus is low, fully reacting, but works as temperature
More than 100 DEG C, the purity of parachloroanilinum is reduced, and the amount of dechlorination object increases, therefore, preferred 90-100 DEG C of hydrogenation reaction temperature.
5. investigating influence of the hydrogenation reaction pressure to reaction, it the results are shown in Table 5.
Influence result of the 5 hydrogenation reaction pressure of table to reaction
As can be seen from the above table, when reaction pressure is 1-3MPa, reaction mass surplus is few, reacts more complete,
But when reaction pressure is greater than 1.5MPa, the purity of parachloroanilinum is reduced, and the amount of dechlorination object increases, therefore, hydrogenation reaction pressure
It is preferred that 1-1.5MPa, more preferably 1MPa.
6. investigating influence of the hydrogenation reaction time to reaction, it the results are shown in Table 6.
6. influence result of the hydrogenation reaction time to reaction
As can be seen from the above table, when reacted between be 6-8h when, reaction mass surplus is low, react it is more complete, when
When reaction time is more than 7h, the purity of parachloroanilinum is reduced, and the amount of dechlorination object increases, and therefore, the reaction time is preferably 6-7h, more
Preferably 6h.
7. investigating influence of the catalysis inventory to reaction, it the results are shown in Table 7.
Influence result of the 7 catalyst inventory of table to reaction
As can be seen from the above table, as the 1.0-4.0 ‰ that catalyst inventory (backbone base inventory) is parachloronitrobenzene
When, starting material left amount is low, reacts more complete, but when catalyst inventory is more than 3 ‰, and the purity of parachloroanilinum reduces, and takes off
The amount of chlorine object increases, and therefore, the inventory of catalyst is preferably the 1.0-3.0 ‰ of parachloronitrobenzene inventory, more preferably
1.0‰。
8. investigating influence of the anti-agent to reaction, it the results are shown in Table 8.
Influence result of the anti-agent inventory of table 8 to reaction
As can be seen from the above table, when anti-agent inventory is the 1.0-10% of catalyst butt inventory, raw material
Surplus is low, reacts more complete, but when anti-agent inventory is lower than 5%, the purity of parachloroanilinum is reduced, dechlorination object
Amount increases, and therefore, the inventory of anti-agent is preferably the 5-10% of catalyst butt inventory, more preferably 10%.
Claims (9)
1. a kind of preparation method of parachloroanilinum hydrochloride, which is characterized in that the preparation method includes the following steps:
1) in the presence of the organic solvent of azeotrope with water, using parachloronitrobenzene as starting material, under platinum carbon catalyst catalysis, add
Enter anti-agent and acid-binding agent, it is closed, it is passed through hydrogen, hydrogenation reaction is carried out under high temperature and pressure, cools down, filters out catalyst, is collected
Filtrate；
2) concentrated hydrochloric acid is added into filtrate, in 80-95 DEG C of heat preservation 0.5-2h, continues to lift temperature to boiling, is back to by water segregator
There is no moisture content to separate, and filters, dry, obtains parachloroanilinum hydrochloride.
2. preparation method as described in claim 1, which is characterized in that the platinum charcoal is 1-1.5% platinum charcoal.
3. preparation method as described in claim 1, which is characterized in that the organic solvent of the azeotrope with water is toluene.
4. preparation method as described in claim 1, which is characterized in that the anti-agent is dicyandiamide.
5. preparation method as described in claim 1, which is characterized in that the acid-binding agent is ammonium hydroxide, triethylamine or pyridine.
6. preparation method as described in claim 1, which is characterized in that the temperature of the high-temperature and high-pressure hydrogenation reaction is 90-100
DEG C, pressure 1-1.5MPa.
7. preparation method as described in claim 1, which is characterized in that the time of the hydrogenation reaction is 6-7h.
8. preparation method as described in claim 1, which is characterized in that the inventory of the catalyst feeds intake for parachloronitrobenzene
The 1-3 ‰ of amount.
9. preparation method as described in claim 1, which is characterized in that the inventory of the anti-agent is to catalyst butt
The 5-10% of inventory.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112108182A (en) * | 2020-03-16 | 2020-12-22 | 厦门大学 | Cyanimide compound-Pt-based nanocrystalline catalyst and preparation method and application thereof |
| CN113045547A (en) * | 2019-12-27 | 2021-06-29 | 武汉先路医药科技股份有限公司 | Preparation method of azelastine hydrochloride |
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| CN113045547B (en) * | 2019-12-27 | 2023-03-28 | 武汉先路医药科技股份有限公司 | Preparation method of azelastine hydrochloride |
| CN112108182A (en) * | 2020-03-16 | 2020-12-22 | 厦门大学 | Cyanimide compound-Pt-based nanocrystalline catalyst and preparation method and application thereof |
| CN112108182B (en) * | 2020-03-16 | 2021-07-23 | 厦门大学 | Cyanimide compound-Pt-based nanocrystalline catalyst and preparation method and application thereof |
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