CN106588669B - A method of utilizing microchannel reaction system continuous production of nitrobenzol methyl ether - Google Patents
A method of utilizing microchannel reaction system continuous production of nitrobenzol methyl ether Download PDFInfo
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- CN106588669B CN106588669B CN201710023473.7A CN201710023473A CN106588669B CN 106588669 B CN106588669 B CN 106588669B CN 201710023473 A CN201710023473 A CN 201710023473A CN 106588669 B CN106588669 B CN 106588669B
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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Abstract
The invention discloses a kind of methods using microchannel reaction system continuous production of nitrobenzol methyl ether, include the following steps：The methanol solution of sodium methoxide and nitro-chlorobenzene solid are dissolved in methyl alcohol, is pumped into the reaction system of microchannel, is reacted at 100~140 DEG C, the mixture cooling obtained after reaction collects aftercut and removes solvent, obtains Nitroanisole.Reaction time high conversion rate of the invention, flux is high, and product quality is stablized, and is suitable for industrial production.
Description
Technical field
The invention belongs to the field of chemical synthesis, and in particular to a kind of to utilize microchannel reaction system continuous production of nitrobenzol first
The method of ether.
Background technology
Nitroanisole can be used for producing the dyestuffs such as Fast Blue VB salt, purplish red color base GP, azoic coupling component AS, is situated between into pigment, dyestuff
With medicine important intermediate, as important organic intermediate, in recent years since due to industry such as China's weaving, dyestuff, pharmacy
Development and domestic and international market demand increase, to there is huge market prospects.
Nitro-chlorobenzene catalysis methoxylation, nitrophenol are mainly catalyzed methoxyl group by the production of domestic paranitroanisole
Change, the nitrification of methyl phenyl ethers anisole, the etherificate of nitro-chlorobenzene, phase transfer catalysis process etc..Current most common method is nitro-chlorobenzene catalysis
The etherificate of methoxylation and nitro-chlorobenzene.
Currently, the method for domestic industry metaplasia production Nitroanisole is using nitro-chlorobenzene, methanol and sodium hydroxide as raw material,
10~13h methoxylations are carried out under the pressure of 0.3MPa, then through being evaporated under reduced pressure to paranitroanisole.Reaction need to press
It is carried out in power kettle, the problems such as time is long, and by-product is more, and methanol usage is big, and conversion ratio and yield are low, environmental pollution.
Except in a kettle without catalyst methoxylation method in addition to, Yu Shanxin and Wen Ruiming et al. have invented a kind of simple conjunction
Cheng Fa.When without using catalyst, methanol and sodium hydroxide reaction are raw first at sodium methoxide, and sodium methoxide is reacted with nitro-chlorobenzene again to be generated
Nitroanisole.This method mild condition, it is easy to operate, but in the case of no catalyst, usual reaction rate is slow, takes
It is long, and by-product nitrophenol is more, and environmental pollution is more serious.Kind letter of Yu et al. is not closed using catalyst with simplified method
At, and reaction is heated in the water-bath of (65 scholar 2) DEG C, the study found that the product melting range that reaction obtains after a certain period of time is longer, face
Color is deeper, illustrates that reaction is incomplete, and have by-product generation.Find that by-product is few after replacing NaOH with KOH, obtained product
It is purer.But the features such as reaction process is complicated, and yield is not promoted significantly, poor continuity is not widely popularized.
The Chinese patent CN105503610A of Sinopec Group discloses a kind of using heart-shaped micro- logical
The method of road reactor production Nitroanisole.This method advantage is can be with continuous sample introduction, the shortening reaction time, but this method
In have numerous disadvantages, for example, amplification technique production can not be directly realized by, stopping state can not solve, and heart-shaped microchannel plate should nothing
Method is cleaned, and microchannel material is expensive, and production cost is high, and mostly etc., and this method pertains only to the synthesis of ortho-nitroanisole to wastewater flow rate.
The Chinese patent CN104557557A of Sinopec Group discloses a kind of between nitro-chlorobenzene
The method that position oil prepares Nitroanisole.It does not use water as solvent in this method, successfully solves wastewater problem.But it should
Using meta position oil in method, the reaction of design is high temperature and pressure, improves industrial cost and safety issue.
The Chinese patent CN205653373U of Hubei east Co., Ltd, the China of Zhejiang Co., Ltd of Run Tu research institutes is specially
Sharp CN105399634A, the Chinese patent CN103396318A of Zhejiang Dibang Chemical Co., Ltd. had also been disclosed once to be closed
At the method for Nitroanisole, but all there are the discharge of a large amount of waste water, operating procedure is complicated, and safety is uncontrollable, and equipment is taken up an area
The problems such as area is excessive, and industry expands difficulty, and industrial production is of high cost.
Above in the prior art the yield of product and conversion ratio all between 65~75%.
Invention content
The technical problem to be solved in the present invention is to provide a kind of novel micro passage reaction continuous production of nitrobenzol methyl ethers
Method, to solve waste water of the existing technology, severe reaction conditions, microchannel material, reaction efficiency, industry are amplified and are set
The problems such as standby investment.
To solve the above problems, the technical solution adopted by the present invention is as follows：
A kind of method of microchannel reaction system continuous production of nitrobenzol methyl ether, includes the following steps：
(1) methanol solution of sodium methoxide and the dissolving of nitro-chlorobenzene solid are formed into homogeneous phase solution in methyl alcohol；
(2) homogeneous phase solution obtained in step (1) is pumped into the reaction system of microchannel, is reacted at 100~140 DEG C,
The mixture cooling obtained after reaction collects aftercut and removes solvent, obtains Nitroanisole.Preferably, described anti-
The temperature answered is 120~130 DEG C.
The molar ratio of the nitro-chlorobenzene and the sodium methoxide is 1:0.8~2, preferably 1:1.2~1.5；It is described anti-
The time answered is 0.5~30min, preferably 25~30min；The flow velocity of the reaction is 0.06~2mL/min, preferably
0.08~0.6mL/min.
The sodium methoxide is made by the way that sodium hydroxide to be dissolved in methanol, at normal temperatures, sodium hydroxide is dissolved in first
In alcohol, the sodium hydroxide is 1 with the preferred molar ratio of methanol:10, obtain the sodium methoxide of 2.47mol/L.
The size internal diameter of the micro passage reaction is 0.5~5mm, and length is 0.5~40m.
The micro passage reaction is pore passage structure, and the material in the duct is polytetrafluoroethylene (PTFE), the number in the duct
Amount is 5~30, decreases or increases duct quantity as needed, the increase of reacting dose may be implemented, be embodied directly in microchannel
In reactor the reaction of synthesizing nitryl methyl phenyl ethers anisole from laboratory lab scale toward pilot scale and the direct transition of industrialized big examination.
The reaction system can improve reaction process also using one-way back pressure valve to control the pressure in reaction system
In safety while reaction yield is increased to 95% by 85% in conventional microreactor.The nitro-chlorobenzene is selected from
Ortho position or contraposition any one of nitro-chlorobenzene or two kinds.
Due to suitable concentration system in reaction system of the present invention, volume external adding water or other solvents are not needed.The present invention is anti-
Process is answered not use any catalyst.
Compared with prior art, the system of water need not additionally be added by being used during (1) is of the invention, and solvent can be straight in product
It connects to steam again and be recycled；(2) system involved in the present invention is without solid insoluble, no microchannel blockage problem, convenient for direct
It is amplified to industrial production.(3) the micro passage reaction material used in the present invention is readily transported and drops significantly for polytetrafluoroethylene (PTFE)
Low production cost；(4) for the present invention without using catalyst, it is long to overcome reaction time in the prior art, and production cost is high, energy consumption
The shortcomings of height, danger coefficient is high；(5) reaction time shortens in the present invention, and the conversion ratio of reaction improves, high-throughput, the matter of product
Amount is stablized, and continuity height is conducive to continuous uninterrupted amplification production, easy to operate, safe, can effectively overcome traditional anti-
The shortcomings that answering kettle；(6) production of ortho position involved in the present invention and contraposition Nitroanisole, industrially solves equipment investment and asks
Topic；(7) involved reaction is flat top response in the present invention, is suitable for industrial production；(8) product yield of the invention be 88~
96%, yield reaches as high as 95%.
Advantageous effect：Reaction time high conversion rate of the invention, flux is high, and product quality is stablized, and is suitable for industrial production.
Description of the drawings
Fig. 1 reaction process schematic diagrams of the present invention, wherein 1 be injector, 2 be micro passage reaction, 3 be one-way back pressure valve, 4
For sample receiver.
Specific implementation mode
According to following embodiments, the present invention may be better understood.However, as it will be easily appreciated by one skilled in the art that real
It applies content described in example and is merely to illustrate the present invention, without sheet described in detail in claims should will not be limited
Invention.
It is prepared by the methanol solution of sodium methoxide：Under room temperature, sodium hydroxide is dissolved in methanol, sodium hydroxide and Methanol Molar
Than being 1:10, obtain the methanol solution of the sodium methoxide of 2.47mol/L.
The microreactor that the present invention uses is made by oneself by 3D printer, and coil pipe internal diameter is 0.5mm, length 0.5m, duct
Quantity be 8.
Embodiment 1
0.5514g paranitrochlorobenzenes (3.5mmol, 1.0equiv) are weighed, are measured on 1.7ml (4.2mmol, 1.2equiv)
The methanol solution for stating the sodium methoxide of configuration is dissolved with the methanol of 33.3ml, is loaded in syringe until completely dissolved.Reaction solution
It is pumped into the reactor that coil pipe internal diameter is 0.5mm, the flow velocity of microreactor is 0.6mol/min, and reaction controlling is stopped at 105 DEG C
Time 4min.Reaction process (petroleum ether is detected by TLC：Ethyl acetate=50:1 expansion).Water washing, liquid separation, water phase second
Acetoacetic ester extracts three times, merges organic phase, and with saturated common salt water washing, anhydrous sodium sulfate drying can must turn after concentration through analysis
Rate is 89%, yield 75%
Embodiment 2~11 and the reaction step of comparative example D1~D4 are consistent with embodiment 1, different parameters and obtain
Conversion ratio and yield be shown in Table 1.Wherein S1 is paranitrochlorobenzene, and S2 is 2- nitro-chlorobenzenes, and T is the reaction time, and M is nitro-chlorobenzene
With the molar ratio of the sodium methoxide, V is the flow velocity of reaction, and solvent is water in the reaction of subscript b, in the reaction of subscript c, microchannel
There is no counterbalance valve in reaction system.
When solvent is water known to result in comparative example D1~D3, reaction yield substantially reduces；By comparative example D4 it is found that micro-
There is no counterbalance valve reaction yield to substantially reduce in pathway reaction system.
The method that table 1 utilizes microchannel reaction system continuous production of nitrobenzol methyl ether
Claims (3)
1. a kind of method using microchannel reaction system continuous production of nitrobenzol methyl ether, which is characterized in that include the following steps：
（1）The methanol solution of sodium methoxide and the dissolving of nitro-chlorobenzene solid are formed into homogeneous phase solution in methyl alcohol；
（2）By step（1）In obtained homogeneous phase solution be pumped into the reaction system of microchannel, react 30min at 120 ~ 130 DEG C,
The mixture cooling obtained after reaction collects aftercut and removes solvent, obtains Nitroanisole；The nitro-chlorobenzene
Molar ratio with the sodium methoxide is 1:The flow velocity of 1.2 ~ 1.5 reactions is 0.08mL/min；The microchannel reaction system
Include injector, micro passage reaction, one-way back pressure valve and the sample receiver being sequentially connected in series by pipeline；By described
One-way back pressure valve controls the back pressure of the microchannel reaction system in 7 ~ 15 bar；The micro passage reaction is tied for duct
The material of structure, the duct is polytetrafluoroethylene (PTFE), and the quantity in the duct is 5 ~ 30；In the size of the micro passage reaction
Diameter is 0.5~5mm, and length is 0.5~40m.
2. according to the method described in claim 1, it is characterized in that, the methanol solution of the sodium methoxide pass through sodium hydroxide is molten
Solution is made in methanol.
3. according to the method described in claim 1, it is characterized in that, the nitro-chlorobenzene is in ortho position or contraposition nitro-chlorobenzene
It is any one or two kinds of.
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| CN110003052A (en) * | 2019-05-17 | 2019-07-12 | 常州工程职业技术学院 | A method of using micro passage reaction synthesizing o-hydroxy formonitrile HCN |
| WO2021119717A1 (en) * | 2019-12-19 | 2021-06-24 | Commonwealth Scientific And Industrial Research Organisation | Preparation of halogenated alkoxyethane |
Citations (6)
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|---|---|---|---|---|
| EP1437355A1 (en) * | 2003-01-07 | 2004-07-14 | Bayer Chemicals AG | Copper carbene complexes and the use thereof |
| WO2008136770A1 (en) * | 2007-05-02 | 2008-11-13 | Agency For Science, Technology And Research | Poly-n-heterocyclic carbene transition metal complexes and n-heterocyclic carbene transition metal complexes for carbon-sulfur and carbon-oxygen coupling reactions |
| CN102276483A (en) * | 2011-06-30 | 2011-12-14 | 辽宁世星药化有限公司 | Production method of oamino pheylmethyl ether |
| CN105399634A (en) * | 2015-11-23 | 2016-03-16 | 浙江闰土研究院有限公司 | Clean production method of paranitroanisole |
| CN105503610A (en) * | 2014-09-23 | 2016-04-20 | 中国石油化工股份有限公司 | Method for preparing o-nitro anisole by using micro-channel reaction apparatus |
| CN106279664A (en) * | 2016-08-22 | 2017-01-04 | 江苏擎宇化工科技有限公司 | A kind of method using micro passage reaction to produce alcoxylates |
-
2017
- 2017-01-13 CN CN201710023473.7A patent/CN106588669B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1437355A1 (en) * | 2003-01-07 | 2004-07-14 | Bayer Chemicals AG | Copper carbene complexes and the use thereof |
| WO2008136770A1 (en) * | 2007-05-02 | 2008-11-13 | Agency For Science, Technology And Research | Poly-n-heterocyclic carbene transition metal complexes and n-heterocyclic carbene transition metal complexes for carbon-sulfur and carbon-oxygen coupling reactions |
| CN102276483A (en) * | 2011-06-30 | 2011-12-14 | 辽宁世星药化有限公司 | Production method of oamino pheylmethyl ether |
| CN105503610A (en) * | 2014-09-23 | 2016-04-20 | 中国石油化工股份有限公司 | Method for preparing o-nitro anisole by using micro-channel reaction apparatus |
| CN105399634A (en) * | 2015-11-23 | 2016-03-16 | 浙江闰土研究院有限公司 | Clean production method of paranitroanisole |
| CN106279664A (en) * | 2016-08-22 | 2017-01-04 | 江苏擎宇化工科技有限公司 | A kind of method using micro passage reaction to produce alcoxylates |
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| 微反应器在合成化学中的应用;何伟;《应用化学》;20131231;第30卷(第12期);第1375-1385 * |
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