CN106316859A - Method for synthesis of 2,4-dichloro-3,5-dinitro trifluorotoluene in micro reactor - Google Patents
Method for synthesis of 2,4-dichloro-3,5-dinitro trifluorotoluene in micro reactor Download PDFInfo
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- CN106316859A CN106316859A CN201510346614.XA CN201510346614A CN106316859A CN 106316859 A CN106316859 A CN 106316859A CN 201510346614 A CN201510346614 A CN 201510346614A CN 106316859 A CN106316859 A CN 106316859A
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Abstract
The invention relates to a method for synthesis of 2,4-dichloro-3,5-dinitro trifluorotoluene in a micro reactor, that is to say, in the micro reactor, a raw material 2,4-dichloro trifluorotoluene and a nitrating agent composed of concentrated sulfuric acid and concentrated nitric acid are introduced in proportion for synthesis of 2,4-dichloro-3,5-dinitro trifluorotoluene. The method is simple, and is good in effect; compared with a traditional method, the method greatly shortens the reaction time (which is reduced from 96 h to about 200 s), improves the production efficiency, and has the 2,4-dichloro-3,5-dinitro trifluorotoluene yield of 40%.
Description
Technical field
The invention belongs to organic fine synthesis field, relate to a kind of microreactor synthesizes 2,4-bis-chloro-3, the method of 5-dinitro-p-trifluorotoluene, i.e. in microreactor, is passed through raw material 2 in proportion, 4-bis-chlorobenzotrifluoride and nitrating agent synthesis 2,4-bis-chloro-3,5-dinitro-p-trifluorotoluene.
Background technology
2,4-bis-chloro-3,5-dinitro-p-trifluorotoluene is a kind of organic intermediate, is commonly used for pesticide and medicine synthesis.At present in domestic literature, yet there are no relevant synthetic technology, foreign literature also rarely has report.Hori Hitoshi et al. is at " Design and Synthesis of New Mitochondiral Cytotoxin N-Thiadiazolyanilines
That Inhibit Tumor Cell Growth " literary composition to be mentioned, 50% concentration oleum mixes as nitrating agent with fuming nitric aicd, with 2,4-bis-chlorobenzotrifluoride stirs reaction 96 hours at 80 DEG C, can synthesize 2,4-bis-chloro-3,5-dinitro-p-trifluorotoluene, productivity about 60%.United States Patent (USP) US4201724 mono-literary composition is mentioned, uses the SO containing 30 ~ 33%3Oleum and 90% nitric acid as nitrating agent, with 2,4-bis-chlorobenzotrifluoride stirs reaction 96 hours at 76 DEG C ± 1 DEG C, 2,4-bis-chloro-3,5-dinitro-p-trifluorotoluene productivity about 79%, Molla M etc. have employed the method in " Synthesis and evaluation of oryzalin analogs against Toxoplasma gondii " literary composition equally
There is presently no and document is mentioned the method synthesizing 2,4-bis-chloro-3,5-dinitro-p-trifluorotoluene in microreactor.
Summary of the invention
The invention belongs to organic fine synthesis field, relate to a kind of microreactor synthesizes 2,4-bis-chloro-3, the method of 5-dinitro-p-trifluorotoluene, i.e. in microreactor, is passed through raw material 2 in proportion, 4-bis-chlorobenzotrifluoride and nitrating agent synthesis 2,4-bis-chloro-3,5-dinitro-p-trifluorotoluene.Method is simple, respond well, compared with traditional method, substantially reduces the response time (being down to about 200s from 96 hours), improves production efficiency.
In microreactor, synthesis 2,4-bis-chloro-3, the method for 5-dinitro-p-trifluorotoluene, is characterized by microreactor, is passed through raw material 2 in proportion, the nitrating agent synthesis 2 that 4-bis-chlorobenzotrifluoride, concentrated sulphuric acid and concentrated nitric acid form, 4-bis-chloro-3,5-dinitro-p-trifluorotoluene.
For reaching object above, the technical scheme that the present invention is usually taken is as follows:
(1)
Sulphuric acid, nitrate mixture nitrating agent the most, sulfonitric mol ratio 3 ~ 8,
(2)
Nitric acid and 2, the mol ratio of 4-bis-chlorobenzotrifluoride is 1.0 ~ 1.3,
(3)
Using two strands of feeding manners, enter in microreactor, reaction temperature controls 100 ~ 180 DEG C, the time of staying 60 ~ 250s in reactor, collecting reactant mixture, separatory removes spent acid, is washed to neutrality, chromatography content, in this method 2,4-bis-chlorobenzotrifluoride conversion ratio is more than 97%, 2,4-bis-chloro-3,5-dinitro-p-trifluorotoluene yield can reach 40%.
The preferred technical scheme of the present invention:
1, sulfuric acid concentration >=98%, concentration of nitric acid 90 ~ 98%, sulfonitric mol ratio is 3 ~ 8, preferably 4 ~ 6；
2, chlorine nitrate benzene mole ratio is 1.0 ~ 1.3, preferably 1.1 ~ 1.2；
3, reaction temperature controls 100 ~ 180 DEG C, preferably 140 ~ 160 DEG C；
4, the time of staying 60 ~ 250s, preferably 120 ~ 150s in reactor.
Beneficial effects of the present invention:
1, in the present invention, the response time only needs about 200s, is significantly shorter than prior art 96 hours；
2, in the present invention, concentrated sulphuric acid is used to substitute oleum as nitrification dehydrant, reduction raw material accumulating and reaction risk；
3, the present invention uses method for continuously synthesizing, react with existing batch tank compared with, easy to operate, safety.
Accompanying drawing explanation
Fig. 1 is microreactor feeding manner schematic diagram in embodiment of the present invention method.
Detailed description of the invention
Be described in further detail technical scheme below in conjunction with the accompanying drawings with embodiment, protection scope of the present invention is not limited to following detailed description of the invention.
Following example use two strands of feeding manners, enter as shown in Figure 1 in microreactor, and reaction temperature controls 100 ~ 180 DEG C, the time of staying 60 ~ 250s in reactor, collects reactant mixture, and separatory removes spent acid, is washed to neutrality, chromatography content.
Embodiment 1
95% nitric acid-98% sulphuric acid of mol ratio 1:4,2,4-bis-chlorobenzotrifluoride mol ratios are 1.05, and two strands enter microchannel reaction, time of staying 120s, reaction temperature 140 DEG C.2,4-bis-chlorobenzotrifluoride conversion ratios 97.2%, 2,4-bis-chloro-3,5-dinitro-p-trifluorotoluene productivity 22.6%.
Embodiment 2
95% nitric acid-98% sulphuric acid of mol ratio 1:5,2,4-bis-chlorobenzotrifluoride mol ratios are 1.05, and two strands enter microchannel reaction, time of staying 120s, reaction temperature 150 DEG C.2,4-bis-chlorobenzotrifluoride conversion ratios 97.7%, 2,4-bis-chloro-3,5-dinitro-p-trifluorotoluene productivity 30.8%.
Embodiment 3
95% nitric acid-98% sulphuric acid of mol ratio 1:6,2,4-bis-chlorobenzotrifluoride mol ratios are 1.05, and two strands enter microchannel reaction, time of staying 150s, reaction temperature 160 DEG C.2,4-bis-chlorobenzotrifluoride conversion ratios 98.1%, 2,4-bis-chloro-3,5-dinitro-p-trifluorotoluene productivity 40.7%.
Above-described embodiment, the response time only needs about 200s, easy and simple to handle, respond well.
Claims (7)
1. synthesis 2 in a microreactor, 4-bis-chloro-3, the method for 5-dinitro-p-trifluorotoluene, employing 2,4-bis-chlorobenzotrifluoride and nitrating agent synthesis 2,4-bis-chloro-3,5-dinitro-p-trifluorotoluene, it is characterised in that including:
(1) sulphuric acid, nitrate mixture are as nitrating agent, sulfonitric mol ratio 3 ~ 8,
(2) nitric acid and 2, the mol ratio of 4-bis-chlorobenzotrifluoride is 1.0 ~ 1.3,
(3) using two strands of feeding manners, enter in microreactor, reaction temperature controls 100 ~ 180 DEG C, the time of staying 60 ~ 250s in reactor, collects reactant mixture, and separatory removes spent acid, is washed to neutrality.
Method the most according to claim 1, it is characterised in that described sulfuric acid concentration >=98%, concentration of nitric acid 90 ~ 98%.
Method the most according to claim 1, it is characterised in that sulfonitric mol ratio is 4 ~ 6.
The most according to claim 1, method, it is characterised in that nitric acid and 2, the mol ratio of 4-bis-chlorobenzotrifluoride is 1.1 ~ 1.2.
Method the most according to claim 1, it is characterised in that reaction temperature controls at 140 ~ 160 DEG C.
Method the most according to claim 1, it is characterised in that the time of staying 120 ~ 150s in reactor.
Method the most according to claim 1, it is characterised in that 2,4-bis-chlorobenzotrifluoride conversion ratios are more than 97%, and 2,4-bis-chloro-3,5-dinitro-p-trifluorotoluene yield can reach 40%.
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| CN201510346614.XA CN106316859A (en) | 2015-06-23 | 2015-06-23 | Method for synthesis of 2,4-dichloro-3,5-dinitro trifluorotoluene in micro reactor |
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| CN201510346614.XA CN106316859A (en) | 2015-06-23 | 2015-06-23 | Method for synthesis of 2,4-dichloro-3,5-dinitro trifluorotoluene in micro reactor |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN112358401A (en) * | 2020-11-22 | 2021-02-12 | 江苏永创医药科技股份有限公司 | Preparation method of 2, 4-dichloro-3, 5-dinitrobenzotrifluoride |
| CN114957107A (en) * | 2022-06-14 | 2022-08-30 | 华东理工大学 | Method for continuously synthesizing 2, 6-diamino-3, 5-dinitropyridine by micro-channel |
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| CN101544568A (en) * | 2008-03-28 | 2009-09-30 | 中国科学院大连化学物理研究所 | Dinitrochlorobenzene synthesis method and microreactor |
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| CN104478731A (en) * | 2014-12-31 | 2015-04-01 | 浙江永太科技股份有限公司 | Method for synthesizing 2, 4-dichloro-3-fluoronitrobenzene by means of micro-channel reactors |
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2015
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| US3726930A (en) * | 1970-10-29 | 1973-04-10 | United States Borax Chem | Preparation of 3,5-dinitrobenzotrifluoride compounds |
| US4201724A (en) * | 1975-02-20 | 1980-05-06 | United States Borax & Chemical Corp. | N3 -(Cycloalkyl)alkyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine compounds |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN112358401A (en) * | 2020-11-22 | 2021-02-12 | 江苏永创医药科技股份有限公司 | Preparation method of 2, 4-dichloro-3, 5-dinitrobenzotrifluoride |
| CN114957107A (en) * | 2022-06-14 | 2022-08-30 | 华东理工大学 | Method for continuously synthesizing 2, 6-diamino-3, 5-dinitropyridine by micro-channel |
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