CN104418752B - Method for synthesizing single nitro-o-xylene employing catalytic nitration in micro-reactor - Google Patents
Method for synthesizing single nitro-o-xylene employing catalytic nitration in micro-reactor Download PDFInfo
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Abstract
The invention discloses a method for synthesizing single nitro-o-xylene employing catalytic nitration in a micro-reactor. The used catalyst is a rare-earth metal salt; the raw materials are o-xylene and nitric acid; and the raw materials are injected into a micro-channel reactor to be nitrified by a high-pressure constant flow pump at ordinary pressure. The method is free of a solvent; and the reinforcing action of the micro-channel reactor on quality and heat transfer processes is well utilized.
Description
Technical field
The invention belongs to organic synthesis field, it is related to the synthesis of single nitro o-Dimethylbenzene, specifically one kind utilizes HNO3Do
Nitrating agent, trifluoromethanesulfonic acid rare earth metal salt makees catalyst, and catalysis o-Dimethylbenzene occurs nitration reaction, in micro passage reaction
The method of the single nitro o-Dimethylbenzene of catalytic nitration synthesis.
Background technology
O-Dimethylbenzene can obtain two kind of one nitration product through nitrification, is 3- nitro o-Dimethylbenzene（3-NOX）With 4- nitro
O-Dimethylbenzene（4-NOX）, wherein 4- nitro o-Dimethylbenzene is new herbicides Pendimethalin and vitamin B2Intermediate, it
Pesticide, medicine and dyestuff also have and is quite widely applied.
Traditionally most nitric-sulfuric acid nitrification process synthesis using o-Dimethylbenzene, before there is nitrification ability in the method, speed
Hurry up, the features such as, but the method regioselectivity is poor, 4- nitro o-Dimethylbenzene only accounts for the 31% ~ 55% of total nitration product, and secondary
Product 3- nitro o-Dimethylbenzene accounts for 55% ~ 69%, and produces substantial amounts of spent acid, pollutes environment；The severe corrosive meeting of nitric-sulfuric acid
Badly damaged equipment, the side reaction such as the polynitration occurring in course of reaction, oxidation also can produce serious potential safety hazard.
Therefore, many research worker have carried out substantial amounts of research work, the main new catalytic including o-Dimethylbenzene nitrification
Agent and the research of nitrating agent.(the Smith K. J.Org.Chem.1998,23 such as Smith: 8448-845）In gentle condition
Under, it is catalyst with H beta-zeolite molecular sieve, nitric acid stoichiometrically and acetic anhydride catalytic nitration o-Dimethylbenzene, total recovery reaches
More than 99%, 4-NOX account for the 44% of total nitration product, and by-product also generates 23% 4- acyl group in addition to generating 32% 3-NOX
O-Dimethylbenzene, in product, the overall selectivity of 4-NOX is not very very high.Olah etc. (Olah G. A. Communications,
1978, 9:690-691) research finds, with perfluorinated sulfonic resin as catalyst, consumption is 10% ~ 25%, and Butylnitrate ester is nitre
Under conditions of agent, obtain 53%, the 3-NOX that optimal yield accounts for total nitration product for 98%, 4-NOX and account for 47%, this product isomer
Ratio is more or less the same with nitric-sulfuric acid system, and perfluorinated sulfonic resin price is costly, and economic serviceability is not high.Jing Dan etc.
(Jing Dan. modern chemical industry. 2010,20 (2), 223-225) investigate P2O5The selectivity of the lower o-Dimethylbenzene nitrification of effect exists
P2O5Mass fraction 4.5%, nitric acid and o-Dimethylbenzene mol ratio 1.15, dehydrating value of sulfuric acid (D.V.S) are 3.16, reaction temperature 20
DEG C, response time 4 h when, in nitration product, 3-NOX and 4-NOX mol ratio reach 0.94, and 1.35 compared with nitric-sulfuric acid significantly reduce,
O-xylene conversion reaches 97.6%；But P2O5Larger to the corrosivity of equipment, be not suitable for large-scale industrial production.
Content of the invention
It is an object of the invention to utilizing HNO3Make nitrating agent, trifluoromethanesulfonic acid rare earth metal salt makees catalyst, catalysis is adjacent
Nitration reaction in dimethylbenzene, the method for the single nitro o-Dimethylbenzene of catalytic nitration synthesis in micro passage reaction there is.
The technical solution realizing the object of the invention is：
A kind of method of the single nitro o-Dimethylbenzene of catalytic nitration synthesis in microreactor, with trifluoromethanesulfonic acid rare earth metal
As catalyst, with o-Dimethylbenzene, nitric acid is raw material to salt, carries out nitration reaction with normal pressure in micro passage reaction；Concrete step
Suddenly it is：
The first step, by nitric acid and the mixing of trifluoromethanesulfonic acid rare earth metal salt, respectively by this mixed liquor and o-Dimethylbenzene difference
It is delivered to the two entrances of micro passage reaction via the high pressure constant flow pump of energy accurate flow control；
Second step, after two strands of liquid mix in micro passage reaction and contact and react, from the exit of reactor
Exit into collecting tank；
3rd step, after completion of the reaction, uses CH2Cl2Extraction, by solution left standstill, reaction system is divided into liquid-liquid diphase, and lower floor is
The nitration product of o-Dimethylbenzene, upper strata is rare earth metal salt, water, the mixture of nitric acid, separates biphase, lower floor using separatory funnel
Product is scrubbed, neutralization, be dried after obtain single nitro o-Dimethylbenzene；The aqueous phase that upper strata contains rare earth metal salt removes after vacuum distillation
Remove water and nitric acid, then through oven drying, reclaim trifluoromethanesulfonic acid rare earth metal salt.
Wherein, micro passage reaction at least has two entrances, one outlet, is formed by glass processing, glass material
Reactor good corrosion resistance, inlet microchannel size and microchannel size are inconsistent, and intake channel size is larger, so has
Beneficial to improving microring array efficiency, in the microchannel that micro passage reaction is had, it contains thousands of cylindricality hybrid channels, can
So that big droplet distribution uniformly emulsion, enhance mixed effect, be conducive to the carrying out of two phase reaction.
Control o-Dimethylbenzene, the volume flow of nitric acid in the first step, make used molar ratio of material be n（Nitric acid）：n
（O-Dimethylbenzene）=1.0～3.0:1, n (o-Dimethylbenzene）：n([Re(OTf)3）=5～20:1.
In second step, reaction temperature is 20 DEG C～80 DEG C.In second step, the response time is 30s～300s.
The preparation method of catalyst trifluoromethanesulfonic acid rare earth metal salt:
The preparation of trifluoromethanesulfonic acid rare earth metal salt is according to the method for document, golden with excessive group of the lanthanides using trifluoromethanesulfonic acid
Belong to oxide to be heated to reflux in aqueous, almost quantitative complete to react and obtain product.Reaction equation is as follows：
Typical preparation process is as follows：Excessive metal-oxide is added to trifluoromethanesulfonic acid aqueous solution (50%V/V)
In, being heated to reflux to solution is in neutrality, is cooled to room temperature, is filtered to remove unreacted soild oxide, filtrate rotary evaporation,
Obtain pressed powder.
Compared with prior art, its remarkable advantage is the present invention：The present invention is using utilizing trifluoro in micro passage reaction
Methanesulfonic acid rare earth metal salt be catalyzed o-Dimethylbenzene nitrification technique, compared with the prior art, its key technology be to employ with
The different micro passage reaction of conventional reactor, employs trifluoromethanesulfonic acid rare earth metal salt and replaces sulphuric acid as the catalyst to urging
Change o-Dimethylbenzene to be reacted, it is advantageous that：
(1) reaction temperature is lower than the industrial temperature carrying out methylbenzene nitration reaction, due to the ratio table that microreactor is larger
Area, reaction system heat exchange is fast, which reduces the probability accidents caused because of misoperation；
(2) due to not adding sulphuric acid in nitrifying process, use rare earth metal salt catalysis instead, decrease the generation of spent acid,
Ratio greatly improves 4- nitro o-Dimethylbenzene in the product；
(3) micro- reaction can make material quickly mix, and can be completed in a relatively short time reaction, and can obtain near
Higher yield, has saved cost of material；
(4) preparation of trifluoromethanesulfonic acid rare earth metal salt is convenient, moisture-stable, and catalyst non-inactivation can be recycled；
(5) this technique can continuous prodution it is easy to integrated and amplify, have good prospects for commercial application.
Below in conjunction with the accompanying drawings the present invention is described in further detail.
Brief description
Fig. 1 is a kind of flow chart of the method for the single nitro o-Dimethylbenzene of catalytic nitration synthesis in microreactor of the present invention.
Fig. 2 is the structural representation of microreactor device of the present invention.
Specific embodiment
The following examples can make those skilled in the art that the present invention is more fully understood.
Embodiment 1
A certain amount of trifluoromethanesulfonic acid rare earth metal salt is dissolved in 95% fuming nitric aicd in room temperature, in 80 DEG C of water bath with thermostatic control bars
Under part, acid is mutually injected micro passage reaction by high pressure constant flow pump and reacted with organic phase solution, controls nitric acid and adjacent two
The mol ratio of toluene is 2:1, o-Dimethylbenzene and trifluoromethanesulfonic acid rare earth metal salt（Y(OTf)3）Mol ratio is 10:1, pass through
After 180s reaction, product flows continually out reactor, and in catcher, room temperature is collected, and uses CH2Cl2Extraction, stratification, warp
After dividing liquid, organic layer is extremely neutral after the washing of alkali cleaning, washing and saturation NaCl solution, then through Mg2SO4It is dried, through by gas phase
Chromatograph detects, it is 66.47%, 4-NOX/3- that reaction conversion ratio reaches 90.1%, 3-NOX ratio for 33.53%, 4-NOX proportion
The ratio 1.98 of NOX.Aqueous phase removes water and nitric acid after vacuum distillation, then through oven drying, reclaims trifluoromethanesulfonic acid rare earth metal
Salt.
Embodiment 2
Process, with embodiment 1, does not change the mol ratio of nitric acid and o-Dimethylbenzene, changes o-Dimethylbenzene and rare earth metal salt
Mol ratio is 20:1, by this charging reaction, through vapor detection, reaction conversion ratio is 83.1%, 3-NOX ratio is 35.49%, 4-
NOX proportion is the ratio 1.82 of 64.51%, 4-NOX/3-NOX.
Embodiment 3
Process, with embodiment 1, only changes the mol ratio of nitric acid and o-Dimethylbenzene, and the mol ratio of nitric acid and o-Dimethylbenzene is
1:1, by this charging reaction, through vapor detection, reaction conversion ratio is 54.3%, 3-NOX ratio is 37.03%, 4-NOX proportion
Ratio 1.70 for 62.97%, 4-NOX/3-NOX.
Embodiment 4
Process, with embodiment 1, only changes the mol ratio of nitric acid and o-Dimethylbenzene, the mol ratio of nitric acid and toluene is 1.5:
1, by this charging reaction, through vapor detection, reaction conversion ratio for 67.6%, 3-NOX ratio for 36.59%, 4-NOX proportion is
The ratio 1.73 of 63.41%, 4-NOX/3-NOX.
Embodiment 5
Process, with embodiment 1, only changes the mol ratio of nitric acid and o-Dimethylbenzene, the mol ratio of nitric acid and toluene is 3:1,
By this charging reaction, through vapor detection, reaction conversion ratio for 92.5%, 3-NOX ratio for 32.69%, 4-NOX proportion is
The ratio 2.05 of 67.31%, 4-NOX/3-NOX.
Embodiment 6
Process, with embodiment 1, only changes reaction temperature, reaction temperature is changed into 20 DEG C, through vapor detection, reaction conversion ratio
It is the ratio 1.95 that 35.25%, 4-NOX proportion is 64.75%, 4-NOX/3-NOX for 61.7%, 3-NOX ratio.
Embodiment 7
Process, with embodiment 1, only changes reaction temperature, reaction temperature is changed into 70 DEG C, through vapor detection, reaction conversion ratio
It is the ratio 1.98 that 33.88%, 4-NOX proportion is 66.12%, 4-NOX/3-NOX for 83.5%, 3-NOX ratio.
Embodiment 8
Process, with embodiment 1, only changes the species of metal salts of trifluoromethane sulphonic acid, uses La (OTf) instead3, through vapor detection,
Reaction conversion ratio reaches the ratio that 89.4%, 3-NOX ratio is that 32.82%, 4-NOX proportion is 67.18%, 4-NOX/3-NOX
2.05.
Embodiment 9
Process, with embodiment 1, only changes the species of metal salts of trifluoromethane sulphonic acid, uses Pr (OTf) instead3, through vapor detection,
Reaction conversion ratio reaches the ratio that 88.6%, 3-NOX ratio is that 33.32%, 4-NOX proportion is 66.68%, 4-NOX/3-NOX
2.00.
Embodiment 10
Process, with embodiment 1, only changes the species of metal salts of trifluoromethane sulphonic acid, uses Nd (OTf) instead3, through vapor detection,
Reaction conversion ratio reaches the ratio that 90.4%, 3-NOX ratio is that 32.64%, 4-NOX proportion is 67.36%, 4-NOX/3-NOX
2.06.
Embodiment 11
Process, with embodiment 1, only changes the species of metal salts of trifluoromethane sulphonic acid, uses Sm (OTf) instead3, through vapor detection,
Reaction conversion ratio reaches the ratio that 87.6%, 3-NOX ratio is that 33.96%, 4-NOX proportion is 66.04%, 4-NOX/3-NOX
1.94.
Embodiment 12
Process, with embodiment 1, only changes the species of metal salts of trifluoromethane sulphonic acid, uses Eu (OTf) instead3, through vapor detection,
Reaction conversion ratio reaches the ratio that 89.4%, 3-NOX ratio is that 34.19%, 4-NOX proportion is 65.81%, 4-NOX/3-NOX
1.92.
Embodiment 13
Process, with embodiment 1, only changes the species of metal salts of trifluoromethane sulphonic acid, uses Gd (OTf) instead3, through vapor detection,
Reaction conversion ratio reaches the ratio that 87.1%, 3-NOX ratio is that 34.04%, 4-NOX proportion is 65.96%, 4-NOX/3-NOX
1.94.
Embodiment 14
Process, with embodiment 1, only changes the species of metal salts of trifluoromethane sulphonic acid, uses Tb (OTf) instead3, through vapor detection,
Reaction conversion ratio reaches the ratio that 90.4%, 3-NOX ratio is that 33.13%, 4-NOX proportion is 66.87%, 4-NOX/3-NOX
2.02.
Embodiment 15
Process, with embodiment 1, only changes the species of metal salts of trifluoromethane sulphonic acid, uses Dy (OTf) instead3, through vapor detection,
Reaction conversion ratio reaches the ratio that 88.4%, 3-NOX ratio is that 32.31%, 4-NOX proportion is 67.69%, 4-NOX/3-NOX
2.10.
Embodiment 16
Process, with embodiment 1, only changes the species of metal salts of trifluoromethane sulphonic acid, uses Ho (OTf) instead3, through vapor detection,
Reaction conversion ratio reaches the ratio that 90.9%, 3-NOX ratio is that 33.86%, 4-NOX proportion is 66.14%, 4-NOX/3-NOX
1.95.
Embodiment 17
Process, with embodiment 1, only changes the species of metal salts of trifluoromethane sulphonic acid, uses Er (OTf) instead3, through vapor detection,
Reaction conversion ratio reaches the ratio that 87.9%, 3-NOX ratio is that 32.45%, 4-NOX proportion is 67.55%, 4-NOX/3-NOX
2.08.
Embodiment 18
Process, with embodiment 1, only changes the species of metal salts of trifluoromethane sulphonic acid, uses Tm (OTf) instead3, through vapor detection,
Reaction conversion ratio reaches the ratio that 89.2%, 3-NOX ratio is that 31.90%, 4-NOX proportion is 68.10%, 4-NOX/3-NOX
2.13.
Embodiment 19
Process, with embodiment 1, only changes the species of metal salts of trifluoromethane sulphonic acid, uses Yb (OTf) instead3, through vapor detection,
Reaction conversion ratio reaches the ratio that 86.4%, 3-NOX ratio is that 33.17%, 4-NOX proportion is 66.83%, 4-NOX/3-NOX
2.01.
Embodiment 20
Process, with embodiment 1, only changes the species of metal salts of trifluoromethane sulphonic acid, uses Lu (OTf) instead3, through vapor detection,
Reaction conversion ratio reaches the ratio that 87.8%, 3-NOX ratio is that 32.86%, 4-NOX proportion is 67.14%, 4-NOX/3-NOX
2.04.
After the circulation of trifluoromethanesulfonic acid rare earth metal salt, catalytic performance compares
Repeat the process of embodiment 1, the aqueous phase containing nitric acid and slaine after point liquid removes water and nitre after vacuum distillation
Acid, then after being vacuum dried, regeneration, again plus nitric acid, prepare solution rear feeding secondary response more in molar ratio.
| Sequence number | Conversion ratio | 4-NOX/3-NOX |
| 1 | 90.2% | 1.99 |
| 2 | 89.3% | 2.01 |
| 3 | 88.8% | 1.97 |
| 4 | 88.4% | 1.97 |
| 5 | 88.2% | 1.98 |
Claims (5)
1. a kind of method of the single nitro o-Dimethylbenzene of catalytic nitration synthesis in microreactor it is characterised in that：With fluoroform sulphur
As catalyst, with o-Dimethylbenzene, nitric acid is raw material to acid rare earth slaine, carries out nitrification with normal pressure anti-in micro passage reaction
Should；Concretely comprise the following steps：
The first step, by nitric acid and the mixing of trifluoromethanesulfonic acid rare earth metal salt, respectively by this mixed liquor and o-Dimethylbenzene respectively via
The high pressure constant flow pump of energy accurate flow control is delivered to the two entrances of micro passage reaction；
Second step, after two strands of liquid mix in micro passage reaction and contact and react, flows out from the exit of reactor
Enter collecting tank；
3rd step, after completion of the reaction, uses CH2Cl2Extraction, by solution left standstill, reaction system is divided into liquid-liquid diphase, and lower floor is adjacent two
The nitration product of toluene, upper strata is rare earth metal salt, water, the mixture of nitric acid, separates biphase, lower floor's product using separatory funnel
Scrubbed, neutralization, be dried after obtain single nitro o-Dimethylbenzene；The aqueous phase that upper strata contains rare earth metal salt removes water after vacuum distillation
And nitric acid, then through oven drying, reclaim trifluoromethanesulfonic acid rare earth metal salt.
2. synthesize the method for single nitro o-Dimethylbenzene according to claim 1 it is characterised in that：Micro passage reaction is at least gathered around
There are two entrances, one outlet, formed by glass processing, the reactor good corrosion resistance of glass material, inlet microchannel size
Inconsistent with microchannel size, intake channel size is larger, is so conducive to improving microring array efficiency, in microchannel reaction
In the microchannel that device is had, it contains thousands of cylindricality hybrid channels, can make big droplet distribution uniformly emulsion, by force
Change mixed effect, be conducive to the carrying out of two phase reaction.
3. synthesize the method for single nitro o-Dimethylbenzene according to claim 1 it is characterised in that：Control adjacent diformazan in the first step
Benzene, the volume flow of nitric acid, make used molar ratio of material be n（Nitric acid）：n（O-Dimethylbenzene）=1.0～3.0:1, n (adjacent two
Toluene）：n([Re(OTf)3）=5～20:1.
4. synthesize the method for single nitro o-Dimethylbenzene according to claim 1 it is characterised in that：In second step, reaction temperature is
20 DEG C～80 DEG C.
5. synthesize the method for single nitro o-Dimethylbenzene according to claim 1 it is characterised in that：In second step, the response time is
30s～300s.
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| CN106748795A (en) * | 2016-11-18 | 2017-05-31 | 天津市安凯特科技发展有限公司 | A kind of Safe production method of ketone musk |
| CN111362803A (en) * | 2018-12-25 | 2020-07-03 | 南京大学淮安高新技术研究院 | Microchannel reaction process for continuously synthesizing 1-nitro mesitylene |
| CN112851516A (en) * | 2019-11-27 | 2021-05-28 | 西华大学 | Method for nitrifying o-xylene by using microchannel reactor |
| CN117603097A (en) * | 2023-11-29 | 2024-02-27 | 安徽泽升科技股份有限公司 | Method for rapidly preparing 2-bromo-5-nitrobenzenesulfonyl chloride |
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