CN105968018B - A kind of method of solvent-free catalysis substituted-nitrobenzene hydrogenating reduction - Google Patents
A kind of method of solvent-free catalysis substituted-nitrobenzene hydrogenating reduction Download PDFInfo
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- CN105968018B CN105968018B CN201610563337.2A CN201610563337A CN105968018B CN 105968018 B CN105968018 B CN 105968018B CN 201610563337 A CN201610563337 A CN 201610563337A CN 105968018 B CN105968018 B CN 105968018B
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- LQNUZADURLCDLV-UHFFFAOYSA-N [O-][N+](c1ccccc1)=O Chemical compound [O-][N+](c1ccccc1)=O LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The present invention relates to a kind of method of solvent-free catalysis substituted-nitrobenzene hydrogenating reduction, belong to pesticide chemical product preparation method field；The method of described solvent-free catalysis substituted-nitrobenzene hydrogenating reduction is comprised the following steps：By in raw material substituted-nitrobenzene addition reduction reaction kettle, solvent-free, under Raney Ni is catalysts conditions, 80 DEG C are warming up to steam, it is passed through hydrogen, at 80~90 DEG C, hydrogenation reduction is carried out under the conditions of 2.5~4.0 MPa heat-insulation pressure keepings, after reaction terminates, it is cooled to 65 DEG C, catalyst is recovered by filtration under normal pressure, filtrate is that can obtain the product that nitro is reduced to amino with 0.09MPa, 115~125 DEG C of negative pressure rectifying；Whole process of the present invention uses solvent-free process condition, reduces the discharge of the organic matter of Conventional process；The amino reaction generation carbaryl class accessory substance of methyl alcohol equal solvent and reduction is overcome, product purity is improve；Lower than existing solvent method temperature, energy consumption is smaller, reduces production cost, is conducive to energy-saving and emission-reduction.
Description
Technical field
The invention belongs to pesticide chemical product preparation method field, the solvent-free catalysis of particularly a kind of substituted-nitrobenzene adds
Hydrogen reduction is the method for amino.
Background technology
O-, m-, p-trifluoromethylaniline and substitution trifluoro-methoxyaniline are a kind of weights wide variety of in recent years
The fluorine-containing medicines intermediate wanted, has quite varied application in industries such as medicine, agricultural chemicals and dyestuffs.Can synthesize including anti-inflammatory
Tens of kinds of new Drugs Containing Fluorines such as medicine, tranquilizer, chlorpromazine, diuretics, antineoplastic, with effect is fast, good effect, medicine
The advantages of effect is long, applied widely and toxic and side effect is small；Can be additionally used in production herbicide fluometuron, fluorochloridone.Existing neighbour,
Between, the synthetic method of p-trifluoromethylaniline mainly have ammonification, Dehalogenation reduction, nitro reduction etc. several classes：
(1) ammoniation process.O-, m-, p-chloro benzo trifluoride-99 and Sodamide react in liquefied ammonia and 3-Aminotrifluorotoluene are obtained.It is former
Material is typically prepared by benzotrifluoride chlorination, and chlorizate is 3 kinds of mixtures of isomers of o-, m- and p- chlorobenzotrifluoride, its
In, a, boiling point very low with para-isomer fusing point is identical, thus is difficult to separate.Additionally, ammonification yield only 52%.
(2) Dehalogenation reduction method.With p-chloro benzo trifluoride-99 as raw material, 3- nitro -4- chlorobenzotrifluorides are obtained through mixed acid nitrification,
With methyl alcohol or ethanol as solvent, under 10%Pd-C catalysis, hydrogenating reduction obtains target compound.This method is urged using expensive palladium
Agent, production cost is high, and dehalogenation obtains accessory substance and equipment is corrosive with environment.
(3) nitro reducing process.It is o-, m-, to nitro-trifluoromethyl toluene be raw material reduction prepare o-, m-, p-trifluoromethylaniline,
Mainly include iron powder reducing method, electrochemical reducing and catalytic hydrogenation method.The pollution of the first corrosion and environment to equipment is all
It is extremely serious, Limit exploitation at present；Second energy consumption is big, and technology is immature, it is difficult to industrialized production；And catalytic hydrogenation method is
A kind of rising production technology of cleaning, pollutes small with process environment, is subject to the advantages of product yield high extensively
Concern, but carried out under high pressure more than current hydrogen addition technology, equipment investment is big, and dangerous high, catalyst service life is short, production
High cost, during also often with dehalogenation reaction and cause selectivity it is not high, particularly, course of reaction needs to use methyl alcohol or second
The organic solvents such as alcohol not only pollute environment but also harm producers as reaction medium.
Catalytic hydrogenation method：With benzotrifluoride as raw material, it is o-, m-, right to be respectively obtained through mixed acid nitrification, washing, vacuum distillation
Trifluoromethyl nitrobenzene, then under Pd/C catalysis, absolute ethyl alcohol is solvent, and atmospheric hydrogenation reduction obtains target compound (king
It is gorgeous brave, Yang Dongpeng, Zhang Hongpeng, Zhou Liming, the small flat nitrifications of Gong and normal pressure catalytic hydrogenation method are by trifluoro between trifluoromethylbenzene preparation
Methylaniline Speciality Petrochemicals .2003, Isosorbide-5-Nitrae 0-43).
Noble metal catalyst is applied to halogenated nitrobenzene selective hydrogenation and has been seen in substantial amounts of document report, in crowd
In many homogeneous and multi-phase selective catalytic reactions, palladium series catalyst is closed because of its catalysis activity higher and selectivity
Note.In order to reduce the hydrogenolysis of C-X keys, generally palladium catalyst is modified, such as by forming the phase between alloy, metal and carrier
Interaction and addition particular matter (such as accelerator and polymerization inhibitor) mode improve the selectivity of product.
There is the report of loaded noble metal catalyst in recent years, with ethanol as solvent, TiO2 loads Pd-Fe makees catalyst,
M-nitryl benzotrifluoride atmospheric hydrogenation prepares 3-Aminotrifluorotoluene (Liu Changchun Liu Changchun：TiO2 load Pd-Fe catalyst is normal
The research chemical reagent of pressure hydrogenation m-nitryl benzotrifluoride, 2008,30 (5), 375-37).
The substitute purpose of noble metal catalyst is that, in order to reduce production cost, document report lacquer original nickel makees catalyst, nothing
Water-ethanol is solvent, under 45 DEG C of normal pressures by m-nitryl benzotrifluoride hydro-reduction be 3-Aminotrifluorotoluene (Luo Xinxiang, Wen Rui
The synthesis synthesis chemistry .2005 of bright 3-Aminotrifluorotoluenes, 13 (5), 510-512) the method can realize atmospheric hydrogenation, and
Yield is higher；But catalyst preparation inconvenience, is reacted with zinc powder, Nickel dichloride hexahydrate, reacts very exothermic, while hydrogen is released,
There is safety problem, post processing needs a large amount of glacial acetic acid activation, and largely distills water washing.
But, above-mentioned catalytic hydrogenating reduction have the shortcomings that it is following one or more：1st, it is both needed to use organic solvent
Methyl alcohol, ethanol cause a certain degree of harm as reaction medium to surrounding environment, personnel；2nd, methyl alcohol equal solvent and reduction
Amino reaction generation carbaryl class accessory substance, influences product purity；3rd, reaction need to be carried out under the conditions of 105~120 DEG C, temperature compared with
Height, energy consumption is larger.
Therefore, it is necessary to the o-, m-, p-trifluoromethylaniline of existing synthesis and the side of substitution trifluoro-methoxyaniline
Method is improved, reducing energy consumption, improves yield.
The content of the invention
Not enough present in background technology in order to overcome, the solvent-free catalysis the invention provides a kind of substituted-nitrobenzene adds
Hydrogen reduction is the method for amino, there is provided an inter-species nitrotrimethylolmethane methyl fluoride benzene, adjacent nitro trifluoromethylbenzene, to nitro trifluoromethyl
Benzene, the solvent-free catalytic hydrogenating reduction to the substituted-nitrobenzene containing trifluoromethyl or trifluoromethoxy such as p-nitro-trifluoromethyl
Be the new method of amino, with substituted-nitrobenzene as raw material, Raney Ni be catalyst, condition of no solvent under hydrogenating reduction obtain target
Compound.
In order to achieve the above object, the present invention proposes following technical scheme：
The method of described solvent-free catalysis substituted-nitrobenzene hydrogenating reduction is comprised the following steps：By raw material substituted-nitrobenzene
In adding reduction reaction kettle, solvent-free, under Raney Ni is catalysts conditions, 80 DEG C are warming up to steam, hydrogen are passed through, 80
~90 DEG C, hydrogenation reduction is carried out under the conditions of 2.5~4.0MPa heat-insulation pressure keepings, after reaction terminates, be cooled to 65 DEG C, under normal pressure
Catalyst is recovered by filtration, filtrate is that can obtain the product that nitro is reduced to amino with 0.09MPa, 115~125 DEG C of negative pressure rectifying,
Reaction equation is as follows：
Further, nitro trifluoromethylbenzene, adjacent nitro trifluoromethylbenzene between described substituted-nitrobenzene is, to nitro trifluoro
Methylbenzene, to any one in p-nitro-trifluoromethyl.
Further, described raw material is with the mass ratio of catalyst：1：0.001~0.002.
Further, whole process uses condition of no solvent, and displaced air before hydrogenation is first used<1MPa nitrogen continuously blows
Sweep 3 times, then carry out hydrogenation reaction, purge gas are discharged by blow-down pipe.
Further, replacing hydrogen after hydrogenation：With<Continuously purging 3 times of 1MPa nitrogen, then carry out postprocessing working procedures, lead to
Cross blow-down pipe discharge purge gas.
Beneficial effects of the present invention：
1st, whole process of the present invention uses solvent-free process condition, reduces the row of the organic matter of Conventional process
Put, to environment and the comparatively safe reliability of operating personnel；
2nd, the amino reaction generation carbaryl class accessory substance of methyl alcohol equal solvent and reduction is overcome, product purity is improve；
3rd, reaction need to be carried out under the conditions of 80~90 DEG C, and lower than existing solvent method temperature, energy consumption is small, and reduction is produced into
This, is conducive to energy-saving and emission-reduction.
Specific embodiment
Below in conjunction with embodiments of the invention, the technical scheme in the embodiment of the present invention is clearly and completely retouched
State, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments, based on the present invention
In embodiment, this area control all other implementation for being obtained under the premise of creative work is not made of technical staff
Example, belongs to the scope of protection of the invention.
Embodiment 1
First with nitrogen (<1MPa) continuous purging 5000L reduction reactions kettle 3 times, purge gas are discharged by blow-down pipe.In nothing
Under solvent condition, by 2000kg m-nitryl benzotrifluorides addition reactor, 2kg raney nickel catalysts are added, heated up with steam
To 80 DEG C, hydrogen is passed through, hydrogenation reduction is carried out 6 hours under the conditions of heat-insulation pressure keeping (80~90 DEG C, 2.5~4.0MPa).
Reaction terminate after, with nitrogen (<1MPa) continuous purging 3 times, 65 DEG C, natural filtration reclaims catalyst, and filtrate uses negative pressure rectifying
(0.09MPa, 115~125 DEG C) 120 hours, you can obtain 3-Aminotrifluorotoluene (120 ± 2 DEG C) 1600kg, o-trifluoromethyl
Aniline (118 ± 2 DEG C) 20kg, p-trifluoromethylaniline (123 ± 2 DEG C) 60kg, rectification residue is by there is qualification processed in units.
Embodiment 2
First with nitrogen (<1MPa) continuous purging 5000L reduction reactions kettle 3 times, purge gas are discharged by blow-down pipe.In nothing
Under solvent condition, by 2001kg m-nitryl benzotrifluorides addition reactor, 4kg raney nickel catalysts are added, heated up with steam
To 80 DEG C, hydrogen is passed through, hydrogenation reduction is carried out 6 hours under the conditions of heat-insulation pressure keeping (80~90 DEG C, 2.5~4.0MPa).
Reaction terminate after, with nitrogen (<1MPa) continuous purging 3 times, 65 DEG C, natural filtration reclaims catalyst, and filtrate uses negative pressure rectifying
(0.09MPa, 120~125 DEG C) 120 hours, you can obtain 3-Aminotrifluorotoluene (120 ± 2 DEG C) 1610kg, o-trifluoromethyl
Aniline (118 ± 2 DEG C) 20kg, p-trifluoromethylaniline (123 ± 2 DEG C) 50kg, rectification residue is by there is qualification processed in units.
Embodiment 3
First with nitrogen (<1MPa) continuous purging 5000L reduction reactions kettle 3 times, purge gas are discharged by blow-down pipe.Will
2002kg m-nitryl benzotrifluorides are added in reactor, add 2.5kg raney nickel catalysts, and 80 DEG C are warming up to steam, are passed through
Hydrogen, hydrogenation reduction is carried out 6 hours under the conditions of heat-insulation pressure keeping (80~90 DEG C, 2.5~4.0MPa).After reaction terminates,
With nitrogen (<1MPa) continuous purging 3 times, 65 DEG C, natural filtration reclaims catalyst, filtrate with negative pressure rectifying (0.09MPa, 115~
125 DEG C) 120 hours, you can obtain 3-Aminotrifluorotoluene (120 ± 2 DEG C) 1620kg, o-trifluoromethyl aniline (118 ± 2 DEG C)
20kg, p-trifluoromethylaniline (123 ± 2 DEG C) 40kg, rectification residue is by there is qualification processed in units.
Embodiment 4
First with nitrogen (<1MPa) continuous purging 5000L reduction reactions kettle 3 times, purge gas are discharged by blow-down pipe.In nothing
Under solvent condition, by 2000kg m-nitryl benzotrifluorides addition reactor, 3kg raney nickel catalysts are added, heated up with steam
To 80 DEG C, hydrogen is passed through, hydrogenation reduction is carried out 6 hours under the conditions of heat-insulation pressure keeping (80~90 DEG C, 2.5~4.0MPa).
Reaction terminate after, with nitrogen (<1MPa) continuous purging 3 times, 65 DEG C, natural filtration reclaims catalyst, and filtrate uses negative pressure rectifying
(0.09MPa, 115~125 DEG C) 120 hours, you can obtain 3-Aminotrifluorotoluene (120 ± 2 DEG C) 1605kg, o-trifluoromethyl
Aniline (118 ± 2 DEG C) 20kg, p-trifluoromethylaniline (123 ± 2 DEG C) 45kg, rectification residue is by there is qualification processed in units.
Embodiment 5
First with nitrogen (<1MPa) continuous purging 5000L reduction reactions kettle 3 times, purge gas are discharged by blow-down pipe.In nothing
Under solvent condition, by 2000kg m-nitryl benzotrifluorides addition reactor, 3.5kg raney nickel catalysts are added, use steam liter
Temperature is passed through hydrogen to 80 DEG C, and it is small to carry out hydrogenation reduction 6 under the conditions of heat-insulation pressure keeping (80~90 DEG C, 2.5~4.0MPa)
When.Reaction terminate after, with nitrogen (<1MPa) continuous purging 3 times, 65 DEG C, natural filtration reclaims catalyst, and filtrate uses negative pressure rectifying
(0.09MPa, 115~125 DEG C) 120 hours, you can obtain 3-Aminotrifluorotoluene (120 ± 2 DEG C) 1615kg, o-trifluoromethyl
Aniline (118 ± 2 DEG C) 20kg, p-trifluoromethylaniline (123 ± 2 DEG C) 50kg, rectification residue is by there is qualification processed in units.
Embodiment 6
First with nitrogen (<1MPa) continuous purging 5000L reduction reactions kettle 3 times, purge gas are discharged by blow-down pipe.In nothing
Under solvent condition, by 2000kg adjacent nitros benzotrifluoride addition reactor, 2kg raney nickel catalysts are added, heated up with steam
To 80 DEG C, hydrogen is passed through, hydrogenation reduction is carried out 6 hours under the conditions of heat-insulation pressure keeping (80~90 DEG C, 2.5~4.0MPa).
Reaction terminate after, with nitrogen (<1MPa) continuous purging 3 times, 65 DEG C, natural filtration reclaims catalyst, and filtrate uses negative pressure rectifying
(0.09MPa, 115~125 DEG C) 120 hours, you can obtain 3-Aminotrifluorotoluene (120 ± 2 DEG C) 20kg, o-trifluoromethyl benzene
Amine (118 ± 2 DEG C) 1600kg, p-trifluoromethylaniline (123 ± 2 DEG C) 50kg, rectification residue is by there is qualification processed in units.
Embodiment 7
First with nitrogen (<1MPa) continuous purging 5000L reduction reactions kettle 3 times, purge gas are discharged by blow-down pipe.In nothing
Under solvent condition, by 2000kg in nitro-trifluoromethyl toluene addition reactor, addition 2kg raney nickel catalysts are heated up with steam
To 80 DEG C, hydrogen is passed through, hydrogenation reduction is carried out 6 hours under the conditions of heat-insulation pressure keeping (80~90 DEG C, 2.5~4.0MPa).
Reaction terminate after, with nitrogen (<1MPa) continuous purging 3 times, 65 DEG C, natural filtration reclaims catalyst, and filtrate uses negative pressure rectifying
(0.09MPa, 115~125 DEG C) 120 hours, you can obtain 3-Aminotrifluorotoluene (120 ± 2 DEG C) 21kg, o-trifluoromethyl benzene
Amine (118 ± 2 DEG C) 35kg, p-trifluoromethylaniline (123 ± 2 DEG C) 1602kg, rectification residue is by there is qualification processed in units.
Embodiment 8
First with nitrogen (<1MPa) continuous purging 5000L reduction reactions kettle 3 times, purge gas are discharged by blow-down pipe.In nothing
Under solvent condition, by 2000kg in nitro trifluoromethoxy benzaldehyde addition reactor, addition 2kg raney nickel catalysts use steam liter
Temperature is passed through hydrogen to 80 DEG C, and it is small to carry out hydrogenation reduction 6 under the conditions of heat-insulation pressure keeping (80~90 DEG C, 2.5~4.0MPa)
When.Reaction terminate after, with nitrogen (<1MPa) continuous purging 3 times, 65 DEG C, natural filtration reclaims catalyst, and filtrate uses negative pressure rectifying
(20mmHg, 82~85 DEG C) 120 hours, you can obtain to trifluoro-methoxyaniline (83 ± 2 DEG C) 1605kg, rectification residue is by having
Qualification processed in units.
Invention whole process uses solvent-free process condition, reduces the organic matter of Conventional process
Discharge, to environment and the comparatively safe reliability of operating personnel；Overcome the amino reaction generation carbaryl of methyl alcohol equal solvent and reduction
Class accessory substance, improves product purity；Reaction need to be carried out under the conditions of 80~90 DEG C, energy consumption lower than existing solvent method temperature
It is small, production cost is reduced, be conducive to energy-saving and emission-reduction.
Finally illustrate, preferred embodiment above is merely illustrative of the technical solution of the present invention and unrestricted, although logical
Cross above preferred embodiment to be described in detail the present invention, it is to be understood by those skilled in the art that can be
Various changes are made to it in form and in details, without departing from claims of the present invention limited range.
Claims (1)
1. it is a kind of it is solvent-free catalysis substituted-nitrobenzene hydrogenating reduction method, it is characterised in that concretely comprise the following steps：First use<1MPa
Nitrogen continuously purge 5000L reduction reactions kettle 3 times, by blow-down pipe discharge purge gas, by nitro fluoroform between 2002kg
Benzene is added in reactor, adds 2 .5kg raney nickel catalysts, and 80 DEG C are warming up to steam, hydrogen is passed through, in 80~90 DEG C, 2
.5~4 carry out hydrogenation reduction 6 hours under the conditions of the heat-insulation pressure keeping of .0MPa, after reaction terminates, use<The nitrogen of 1MPa connects
Continuous purging 3 times, 65 DEG C, natural filtration reclaims catalyst, filtrate in 0 .09MPa, negative pressure rectifying 120 under the conditions of 115~125 DEG C
Hour, you can obtain the 3-Aminotrifluorotoluene 1620kg that temperature is 120 ± 2 DEG C, the o-trifluoromethyl that temperature is 118 ± 2 DEG C
Aniline 20kg, temperature are 123 ± 2 DEG C of p-trifluoromethylaniline 40kg, and rectification residue is by there is qualification processed in units.
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| CN201610563337.2A CN105968018B (en) | 2016-07-15 | 2016-07-15 | A kind of method of solvent-free catalysis substituted-nitrobenzene hydrogenating reduction |
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| CN201610563337.2A CN105968018B (en) | 2016-07-15 | 2016-07-15 | A kind of method of solvent-free catalysis substituted-nitrobenzene hydrogenating reduction |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1220256A (en) * | 1997-10-07 | 1999-06-23 | 江苏淮河化工总厂 | Process for reduction of methylaniline from nitro-toluene |
| CN103787896A (en) * | 2014-03-10 | 2014-05-14 | 江苏大华化学工业有限公司 | Synthetic method of inter-trifluoromethyl phenylamine |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1220256A (en) * | 1997-10-07 | 1999-06-23 | 江苏淮河化工总厂 | Process for reduction of methylaniline from nitro-toluene |
| CN103787896A (en) * | 2014-03-10 | 2014-05-14 | 江苏大华化学工业有限公司 | Synthetic method of inter-trifluoromethyl phenylamine |
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