CN102351714A - Method for preparing p-chloroaniline through catalytic hydrogenation of p-chloronitrobenzene - Google Patents
Method for preparing p-chloroaniline through catalytic hydrogenation of p-chloronitrobenzene Download PDFInfo
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- CN102351714A CN102351714A CN2011102358188A CN201110235818A CN102351714A CN 102351714 A CN102351714 A CN 102351714A CN 2011102358188 A CN2011102358188 A CN 2011102358188A CN 201110235818 A CN201110235818 A CN 201110235818A CN 102351714 A CN102351714 A CN 102351714A
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- parachloronitrobenzene
- acid amide
- nickel catalyst
- chlorobenzoic acid
- solvent
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Abstract
The invention belongs to the technical field of organic synthesis and provides a method for performing catalytic hydrogenation on p-chloronitrobenzene with a modified Raney nickel catalyst and preparing p-chloroaniline. The method comprises the following steps: adding p-chloronitrobenzene, the modified Raney nickel catalyst with an additional metal material and a solvent in a high-pressure reaction kettle, wherein the weight ratio of p-chloronitrobenzene to the solvent is 1:2-1:5 and the weight ratio of p-chloronitrobenzene to the catalyst is 1:(0.02-0.06); performing nitrogen replacement, then performing hydrogen replacement, wherein the pressure of hydrogen is 1.0-3.5MPa and the reaction temperature is 60-100 DEG C; and stirring to react for 1-4 hours to obtain the product p-chloroaniline. The method has simple technology, low demand on equipment and low environmental pollution and is easy to realize industrialization; and the reaction conversion rate is 99.9%, the selectivity is not less than 98% and the yield is not less than 95%.
Description
Technical field
The invention belongs to technical field of organic synthesis, propose method through modified skeletal nickel catalyst catalysis parachloronitrobenzene hydrogenation preparing p-Chlorobenzoic acid amide.
Background technology
P-Chlorobenzoic acid amide is the main raw material and the intermediate of Chemicals such as synthetic rubber, chemical reagent, dyestuff, pigment and medicine, agricultural chemicals, photography, medicine etc., and purposes very extensively.
The technology of synthetic p-Chlorobenzoic acid amide mainly contains: metal powder reduction method, sodium sulphite reduction method, electrochemical reducing, CO reduction method, hydrazine hydrate reduction method, photo catalytic reduction method, borohydride reduction method, catalytic hydrogenating reduction method.Wherein the metal powder reduction method is to equipment corrosion, serious wear, and the Operation and Maintenance expense is high; The sodium sulphite reduction method can produce and contain the sulfonic group by product, and the generation meeting of sulfur-containing waste water has certain pollution to environment, is difficult for handling; Electrochemical reducing, CO reduction method require relatively harsher to reaction conditions, unsuitable industrial application of carrying out p-Chlorobenzoic acid amide; Hydrazine Hydrate 80 and hydroborate price are more expensive in hydrazine hydrate reduction method, the borohydride reduction method, and the aftertreatment cost is high; Its shortcoming of photo catalytic reduction method is that photocatalysis efficiency is not ideal enough, and nano powder catalyst is not easily separated, and the sunlight utilization ratio is not high.
The synthetic of p-Chlorobenzoic acid amide mainly is to obtain through its corresponding parachloronitrobenzene of catalyst to catalyzing hydrogenating and reducing at present.Though the p-Chlorobenzoic acid amide synthesis technique has the industrialization maturation process; And get constantly through various countries' chemist and to explore and effort; The p-Chlorobenzoic acid amide synthesis technique is greatly improved; Also produced different processes; But exist always that yield is not high, unstable product quality and to the problems such as havoc of environment, so the research and development of the synthesis technique of p-Chlorobenzoic acid amide and catalyzer remain a focus of chemical engineering industry circle.
The patent of the Zhang Tianyong of University Of Tianjin " photoactivation reduction preparation p-Chlorobenzoic acid amide " has proposed a kind of new method for preparing p-Chlorobenzoic acid amide.This method adopts the above UV-light of 300nm, excites the generation of hydrogenation reaction through adding hole scavenging agent and photocatalyst under the normal temperature.This method is simple, and just the p-Chlorobenzoic acid amide yield is on the low side, can only accomplish about 80%, and reaction is unstable.
Summary of the invention
The objective of the invention is to that the parachloronitrobenzene shortening is prepared the p-Chlorobenzoic acid amide technology and improve, and a kind of improved parachloronitrobenzene shortening that proposes prepares the method for p-Chlorobenzoic acid amide.
The inventive method mainly is that the skeleton nickel hydrogenation catalyst has been carried out handling modification in earlier stage, thereby has avoided in reaction, adding organism as the dechlorination suppressor factor.Reduce subsequent treatment process, reduced cost.Under the prerequisite that parachloronitrobenzene 99.9% transforms, the selectivity of p-Chlorobenzoic acid amide >=98%.
Main technical schemes of the present invention is: prepare the method for p-Chlorobenzoic acid amide, main method step through modified skeletal nickel catalyst shortening parachloronitrobenzene: in autoclave, add parachloronitrobenzene, added the modified skeletal nickel catalyst and the solvent of metallics; The mass ratio of parachloronitrobenzene and solvent is: 1:2～1:5; The mass ratio of parachloronitrobenzene and catalyzer is 1:0.02～0.06; With using hydrogen exchange behind the nitrogen replacement, hydrogen pressure is at 1.0MPa～3.5 MPa; Temperature of reaction is 60 ℃～100 ℃; Stirring reaction 1～4 hour obtains the product p-Chlorobenzoic acid amide.
Usually, the catalyst modification thing that the inventive method can supply be selected for use is a metal-salt, and for reaction, preferably metal-salt in one or more following thing groups is like Zn (NO
3)
2, CuSO
4, (NH
4)
6Mo
7O
24, Fe
2(SO
4)
3, Al
2(SO4)
3, Cr (NO
3)
3, preferred again Zn (NO
3)
2, CuSO
4, (NH
4)
6Mo
7O
24, Cr (NO
3)
39H
2Among the O one or more, preferred again (NH
4)
6Mo
7O
24, Cr (NO
3)
39H
2A kind of among the O, preferred again (NH
4)
6Mo
7O
24
Parachloronitrobenzene with the mass ratio that has added the skeletal nickel catalyst behind the modified material is: 1:2.5～1:3, preferred mass ratio is: 1:0.02～0.06.
The solvent that can supply select for use is water, methyl alcohol, ethanol, n-propyl alcohol, again particular methanol, ethanol, preferred alcohol again.
The mass ratio of parachloronitrobenzene and solvent is: 1:2～1:5.Preferred mass ratio is: 1:2.5～1:3.
Temperature of reaction is preferably 60 ℃～100 ℃, preferred 70 ℃～85 ℃.If temperature of reaction is low, parachloronitrobenzene is not easy to be dissolved in the solvent, and speed of reaction is just slow, and temperature surpasses 85 ℃, and solvent evaporates into gas easily in a large number, has increased reactant concn, is unfavorable for reacting carrying out equably.
Reaction times is preferably 1～4 hour, preferred 1～2 hour.
The reactive hydrogen atmospheric pressure is preferably 1.0MPa～3.5 MPa, preferred 1.5MPa～2.5 MPa.
The inventive method technology is simple, equipment requirements is low, and environmental pollution is little, is prone to industrialization; Reaction conversion ratio 99.9%, selectivity >=98%, yield >=95%.
Embodiment
Below in conjunction with embodiment, the inventive method is described in detail.
Embodiment 1
With parachloronitrobenzene 50g, dehydrated alcohol 200mL, catalyzer 3g.Add in the autoclave, behind the logical nitrogen replacement 5 times with hydrogen exchange 5 times, reservation hydrogen partial pressure 2.5 MPa.At 70 ℃ of stirring reaction 3h, the p-Chlorobenzoic acid amide yield is 93.9%..
Embodiment 2
With parachloronitrobenzene 50g, dehydrated alcohol 200mL, catalyzer 1g.Add in the autoclave, behind the logical nitrogen replacement 5 times with hydrogen exchange 5 times, reservation hydrogen partial pressure 1.5 MPa.At 80 ℃ of stirring reaction 3h, the p-Chlorobenzoic acid amide yield is 92.2%.
Embodiment 3
With parachloronitrobenzene 50g, dehydrated alcohol 200mL, catalyzer 2g.Add in the autoclave, behind the logical nitrogen replacement 5 times with hydrogen exchange 5 times, reservation hydrogen partial pressure 2.0 MPa.At 80 ℃ of stirring reaction 2h, the p-Chlorobenzoic acid amide yield is 96.9%.
Embodiment 4
With parachloronitrobenzene 50g, dehydrated alcohol 200mL, catalyzer 2g.Add in the autoclave, behind the logical nitrogen replacement 5 times with hydrogen exchange 5 times, reservation hydrogen partial pressure 2.0 MPa.At 80 ℃ of stirring reaction 3h, the p-Chlorobenzoic acid amide yield is 96.1%.
Embodiment 5
With parachloronitrobenzene 50g, dehydrated alcohol 200mL, catalyzer 2g.Add in the autoclave, behind the logical nitrogen replacement 5 times with hydrogen exchange 5 times, reservation hydrogen partial pressure 2.5 MPa.At 80 ℃ of stirring reaction 2h, the p-Chlorobenzoic acid amide yield is 97.5%.
Embodiment 6
With parachloronitrobenzene 50g, dehydrated alcohol 200mL, catalyzer 2g.Add in the autoclave, behind the logical nitrogen replacement 5 times with hydrogen exchange 5 times, reservation hydrogen partial pressure 2.5 MPa.At 80 ℃ of stirring reaction 3h, the p-Chlorobenzoic acid amide yield is 97.1%.
Embodiment 7
With parachloronitrobenzene 50g, dehydrated alcohol 200mL, catalyzer 3g.Add in the autoclave, behind the logical nitrogen replacement 5 times with hydrogen exchange 5 times, reservation hydrogen partial pressure 1.5 MPa.At 80 ℃ of stirring reaction 2h, the p-Chlorobenzoic acid amide yield is 95.9%.
Embodiment 8
With parachloronitrobenzene 50g, dehydrated alcohol 200mL, catalyzer 3g.Add in the autoclave, behind the logical nitrogen replacement 5 times with hydrogen exchange 5 times, reservation hydrogen partial pressure 2.0 MPa.At 80 ℃ of stirring reaction 2h, the p-Chlorobenzoic acid amide yield is 98.5%.
Embodiment 9
With parachloronitrobenzene 50g, dehydrated alcohol 200mL, catalyzer 3g.Add in the autoclave, behind the logical nitrogen replacement 5 times with hydrogen exchange 5 times, reservation hydrogen partial pressure 2.5 MPa.At 80 ℃ of stirring reaction 2h, the p-Chlorobenzoic acid amide yield is 97.6%.
Embodiment 10
With parachloronitrobenzene 50g, dehydrated alcohol 200mL, catalyzer 3g.Add in the autoclave, behind the logical nitrogen replacement 5 times with hydrogen exchange 5 times, reservation hydrogen partial pressure 2.0 MPa.At 80 ℃ of stirring reaction 3h, the p-Chlorobenzoic acid amide yield is 97.0%.
Embodiment 11
With parachloronitrobenzene 60g, dehydrated alcohol 200mL, catalyzer 3g.Add in the autoclave, behind the logical nitrogen replacement 5 times with hydrogen exchange 5 times, reservation hydrogen partial pressure 2.0 MPa.At 80 ℃ of stirring reaction 2h, the p-Chlorobenzoic acid amide yield is 96.2%.
Embodiment 12
With parachloronitrobenzene 70g, dehydrated alcohol 200mL, catalyzer 3g.Add in the autoclave, behind the logical nitrogen replacement 5 times with hydrogen exchange 5 times, reservation hydrogen partial pressure 2.0 MPa.At 80 ℃ of stirring reaction 2h, the p-Chlorobenzoic acid amide yield is 95.7%.
The present invention is not limited to the technology described in the embodiment, and its description is illustrative, is not limitation.
Claims (11)
1. a parachloronitrobenzene shortening prepares the method for p-Chlorobenzoic acid amide; Be the method for preparing p-Chlorobenzoic acid amide through modified skeletal nickel catalyst shortening parachloronitrobenzene, it is characterized in that method steps is following: in autoclave, add parachloronitrobenzene, added the modified skeletal nickel catalyst and the solvent of metallics; The mass ratio of parachloronitrobenzene and solvent is: 1:2～1:5; The mass ratio of parachloronitrobenzene and catalyzer is 1:0.02～0.06; With using hydrogen exchange behind the nitrogen replacement, hydrogen pressure is at 1.0MPa～3.5 MPa; Temperature of reaction is 60 ℃～100 ℃; Stirring reaction 1～4 hour obtains the product p-Chlorobenzoic acid amide.
2. method according to claim 1 is characterized in that metallics that the skeletal nickel catalyst modification is added is selected from one or more in the following thing group: Zn (NO
3)
2, CuSO
4, (NH
4)
6Mo
7O
24, Fe
2(SO
4)
3, Al
2(SO4)
3, Cr (NO
3)
3
3. method according to claim 2 is characterized in that the metallics that the skeletal nickel catalyst modification is added is selected from Zn (NO
3)
2, CuSO
4, (NH
4)
6Mo
7O
24, Cr (NO
3)
39H
2Among the O one or more.
4. method according to claim 3 is characterized in that the metallics that the skeletal nickel catalyst modification is added is selected from (NH
4)
6Mo
7O
24, Cr (NO
3)
39H
2A kind of among the O.
5. method according to claim 4 is characterized in that the metallics that the skeletal nickel catalyst modification is added is (NH
4)
6Mo
7O
24
6. method according to claim 1 is characterized in that described solvent is one or more of water, methyl alcohol, ethanol, n-propyl alcohol.
7. method according to claim 6 is characterized in that described solvent is methyl alcohol, ethanol.
8. method according to claim 7 is characterized in that described solvent is an ethanol.
9. the method for narrating according to claim 1 is characterized in that the mass ratio 1:2.5～1:3 of parachloronitrobenzene and solvent.
10. method according to claim 1 is characterized in that the mass ratio 1:0.04～1:0.06 of parachloronitrobenzene and catalyzer.
11. want 1 described method according to right, it is characterized in that the reactive hydrogen atmospheric pressure is 1.5MPa～2.5 MPa, temperature of reaction is 70 ℃～85 ℃, the reaction times is 1～2 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102358188A CN102351714A (en) | 2011-08-17 | 2011-08-17 | Method for preparing p-chloroaniline through catalytic hydrogenation of p-chloronitrobenzene |
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|---|---|---|---|
| CN2011102358188A CN102351714A (en) | 2011-08-17 | 2011-08-17 | Method for preparing p-chloroaniline through catalytic hydrogenation of p-chloronitrobenzene |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104356001A (en) * | 2014-11-07 | 2015-02-18 | 南京理工大学 | Method for preparing amines by reducing nitrocompounds with thiocarbamide |
| CN105413693A (en) * | 2015-12-09 | 2016-03-23 | 山东师范大学 | Parachloronitrobenzene hydrogenation reduction catalyst capable of being magnetically recycled and preparation method |
| CN105622432A (en) * | 2014-11-07 | 2016-06-01 | 中国科学院烟台海岸带研究所 | Method for preparing p-chloroaniline through catalytic hydrogenation of p-chloronitrobenzene |
| CN105884635A (en) * | 2016-05-18 | 2016-08-24 | 大连理工大学 | Method for preparing 1-amino-anthraquinone by taking ammonium molybdate as catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101260044A (en) * | 2008-04-15 | 2008-09-10 | 中国科学院长春应用化学研究所 | Method for preparing arylamines compounds by arene nitro compound catalysis hydrogenation in H2O-CO2 system |
| WO2010094946A1 (en) * | 2009-02-18 | 2010-08-26 | Reaxa Limited | Microencapsulated catalyst |
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2011
- 2011-08-17 CN CN2011102358188A patent/CN102351714A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101260044A (en) * | 2008-04-15 | 2008-09-10 | 中国科学院长春应用化学研究所 | Method for preparing arylamines compounds by arene nitro compound catalysis hydrogenation in H2O-CO2 system |
| WO2010094946A1 (en) * | 2009-02-18 | 2010-08-26 | Reaxa Limited | Microencapsulated catalyst |
Non-Patent Citations (2)
| Title |
|---|
| HAO LIU等: "Synthesis of Nickel Nanoparticles Supported on Boehmite for Selective Hydrogenation of p-Nitrophenol and p-Chloronitrobenzene", 《CATALYSIS LETTERS》 * |
| 陈丹等: "兰尼镍催化加氢制备邻氯苯胺", 《染料工业》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104356001A (en) * | 2014-11-07 | 2015-02-18 | 南京理工大学 | Method for preparing amines by reducing nitrocompounds with thiocarbamide |
| CN105622432A (en) * | 2014-11-07 | 2016-06-01 | 中国科学院烟台海岸带研究所 | Method for preparing p-chloroaniline through catalytic hydrogenation of p-chloronitrobenzene |
| CN105413693A (en) * | 2015-12-09 | 2016-03-23 | 山东师范大学 | Parachloronitrobenzene hydrogenation reduction catalyst capable of being magnetically recycled and preparation method |
| CN105413693B (en) * | 2015-12-09 | 2018-02-02 | 山东师范大学 | It is a kind of can magnetic force recovery parachloronitrobenzene hydrogenating reduction catalyst and preparation method |
| CN105884635A (en) * | 2016-05-18 | 2016-08-24 | 大连理工大学 | Method for preparing 1-amino-anthraquinone by taking ammonium molybdate as catalyst |
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