CN108003030A - A kind of pipelineization continuously prepares the method and device of 5- nitro -1,4- dihydros -1,4- endo-methylene groups-naphthalene - Google Patents
A kind of pipelineization continuously prepares the method and device of 5- nitro -1,4- dihydros -1,4- endo-methylene groups-naphthalene Download PDFInfo
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- CN108003030A CN108003030A CN201711099652.5A CN201711099652A CN108003030A CN 108003030 A CN108003030 A CN 108003030A CN 201711099652 A CN201711099652 A CN 201711099652A CN 108003030 A CN108003030 A CN 108003030A
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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 method and device of 5 nitro, 1,4 dihydro, 1,4 endo-methylene group naphthalene is continuously prepared the invention discloses a kind of pipelineization.It would be stored at reservoir I, II 2 amino of reservoir, 6 nitrobenzoyl acid solution, nitrous acid ester solution and continuously inputs into mixer I and mix by metering pump I, metering pump II, enter back into and diazo-reaction is carried out in tubular reactor I, then, cyclopentadiene in reservoir III is inputted to mixer II is interior at the same time by metering pump III with the diazo-reaction liquid in tubular reactor I to be mixed, enter back into tubular reactor II in reaction, reaction solution is entered in receiving tank after reaction, it is post-treated to obtain 5 nitros 1,4 dihydro Isosorbide-5-Nitrae endo-methylene group naphthalenes.Apparatus structure used in the present invention is simple, and its preparation method process safety is good, and easy control of reaction conditions is, it can be achieved that continuous production, and product yield is high, stable quality, industrial only to need a small amount of investment to realize large-scale production.
Description
Technical field
The present invention relates to the preparation method and its device of a kind of compound, and in particular to pipelineization continuously prepare 5- nitros-
The method and device of 1,4- dihydros -1,4- endo-methylene groups-naphthalene.
Background technology
5- nitro -1,4- dihydros -1,4- endo-methylene groups-naphthalene is prepared among the key of wide-spectrum bactericide benzo alkene fluorine bacterium azoles
Body, the relatively simple synthetic method of the intermediate are using 2- amino -6- nitrobenzoic acids as starting material, are given birth to through diazo-reaction
Obtained into diazol, then the heated rear adjacent nitro benzyne that produces with cyclopentadiene generation [4+2] addition reaction.Diazo-reaction is
The mode of operation of batch tank, this method is there are many defects, and such as traditional diazonium to turn to Batch Process mode, and diazol is anti-
The residence time in device is answered to grow, the side reaction occurrence probability such as increase coupling, decomposition；Diazol is unstable, heated to be easily reduced, hydrolyze
Deng, and easily cause security incident.Therefore, diazo-reaction must be strictly controlled reaction temperature（Generally 0 DEG C or so）, but 2-
The salt produced after amino -6- nitrobenzoic acid diazotising have to pass through heating generation adjacent nitro benzyne after with cyclopentadiene occur [4
+ 2] addition reaction can just obtain 5- nitros-Isosorbide-5-Nitrae-dihydro-Isosorbide-5-Nitrae-endo-methylene group-naphthalene, and adjacent nitro benzyne pole in a heated condition
It is unstable.
That has reported at present has following several methods for preparing 5- nitro -1,4- dihydros -1,4- endo-methylene groups-naphthalene：
Method 1：Using 2- amino -6- nitrobenzoic acids as starting material, the cyclopentadiene through diazo-reaction and 18 equivalents reacts
The yield of 18h, 5- nitro-Isosorbide-5-Nitrae-dihydro-Isosorbide-5-Nitrae-endo-methylene group-naphthalene is up to 58%（J.Am.Chem.Soc.1977,36,
3734−3744；WO2011131543）, the method reaction time length, low yield, cyclopentadiene dosage is big, and the more grade of accessory substance lacks
Point, brings difficulty, reaction is as follows to industrialized production：
Method 2：CN101693712 reports a kind of similar method and can be used to prepare 5- nitro -1,4- dihydro -1,4- bridge methylenes
Base-naphthalene, the technique are using ortho-aminobenzoic acid as starting material, and after low temperature diazotising, the diazol prepared is filtered out
Come, be then added in reaction kettle and reacted with cyclopentadiene, the yield of product is up to 75%.To easily it be sent out in the operating process
The diazol of raw explosion, which directly filters out, to be added drop-wise in reaction kettle, dangerous big, is not suitable for industrialized production.
The content of the invention
In view of defect existing in the prior art, it is an object of the invention to provide a kind of pipelineization continuously prepare 5- nitros-
The method and its device of 1,4- dihydros -1,4- endo-methylene groups-naphthalene.
The method that the pipelineization continuously prepares 5- nitros-Isosorbide-5-Nitrae-dihydro-Isosorbide-5-Nitrae-endo-methylene group-naphthalene, it is characterised in that
Preparation method is：Raw material 2- amino -6- nitrobenzoyls acid solution, nitrous acid ester solution, cyclopentadiene are stored in storage respectively
In device I, reservoir II, reservoir III, 2- amino -6- nitrobenzoyls acid solution, nitrous acid ester solution respectively by metering pump I,
Metering pump II is continuously inputted into mixer I, is entered after being mixed in mixer I in tubular reactor I in -10-10 DEG C of progress
Diazo-reaction, the retention time through 1-60s；Then, the cyclopentadiene in reservoir III passes through metering pump III and pipe reaction
Diazo-reaction liquid in device I is inputted to mixer II at the same time, is entered in mixer II after mixing in tubular reactor II
After stopping 1-180s at 1-120 DEG C, reaction solution is entered in receiving tank after reaction, post-treated to obtain 5- nitro -1,
4- dihydros -1,4- endo-methylene groups-naphthalene.
The method that the pipelineization continuously prepares 5- nitros-Isosorbide-5-Nitrae-dihydro-Isosorbide-5-Nitrae-endo-methylene group-naphthalene, it is characterised in that
The ratio between 2- amino -6- nitrobenzoic acids, nitrous acid ester and cyclopentadiene molar flow are 1：1-1.2：1-5.
The method that the pipelineization continuously prepares 5- nitros-Isosorbide-5-Nitrae-dihydro-Isosorbide-5-Nitrae-endo-methylene group-naphthalene, it is characterised in that
The ratio between 2- amino -6- nitrobenzoic acids, nitrous acid ester and cyclopentadiene molar flow are 1：1-5.
The method that the pipelineization continuously prepares 5- nitros-Isosorbide-5-Nitrae-dihydro-Isosorbide-5-Nitrae-endo-methylene group-naphthalene, it is characterised in that
Nitrous acid ester is the molar flow of nitrous acid ester isopentyl ester or nitrite tert-butyl, 2- amino -6- nitrobenzoic acids and nitrous acid ester
The ratio between amount is 1：1-1.2.
The method that the pipelineization continuously prepares 5- nitros-Isosorbide-5-Nitrae-dihydro-Isosorbide-5-Nitrae-endo-methylene group-naphthalene, it is characterised in that
The temperature that diazo-reaction is carried out in tubular reactor I is -5-5 DEG C；It is anti-that diazotising is carried out in tubular reactor II
The temperature answered is 90-120 DEG C.
The method that the pipelineization continuously prepares 5- nitros-Isosorbide-5-Nitrae-dihydro-Isosorbide-5-Nitrae-endo-methylene group-naphthalene, it is characterised in that
Post-processing approach is：Reaction solution first obtains brownish black crude product after vacuum distillation, and organic solvent reflux, mistake are added in the crude product
Filter, organic solvent are concentrated and dried up to 5- nitros-Isosorbide-5-Nitrae-dihydro-Isosorbide-5-Nitrae-endo-methylene group-naphthalene.
The method that the pipelineization continuously prepares 5- nitros-Isosorbide-5-Nitrae-dihydro-Isosorbide-5-Nitrae-endo-methylene group-naphthalene, it is characterised in that
Organic solvent is selected from n-hexane, hexamethylene or petroleum ether.
A kind of pipelineization continuously prepares the device described in 5- nitros-Isosorbide-5-Nitrae-dihydro-Isosorbide-5-Nitrae-endo-methylene group-naphthalene, its
It is characterized in that including tubular reactor I, tubular reactor II, mixer I, mixer II, reservoir I, reservoir II, reservoir
III, metering pump I, metering pump II, metering pump III, receiving tank and vacuum distillation apparatus；The mixer I, tubular reactor I, mix
Clutch II, tubular reactor II and receiving tank pass sequentially through conduit connection, and the reservoir I connects metering pump I's by conduit
Import, the reservoir II by conduit connect metering pump II import, reservoir III by conduit connect metering pump III into
Mouthful, the outlet of metering pump I, the outlet of metering pump II connect mixer I imports, mixer I outlet connecting pipe formula reactors I respectively
Import, the outlet of tubular reactor I is connected the import of mixer II, the outlet of mixer II with the outlet of metering pump III respectively
The import of tubular reactor II is connected, the import of the outlet connection receiving tank of tubular reactor II, the outlet of receiving tank passes through pipe
Road connects after-treatment system, which is equipped with valve port.
The pipelineization continuously prepares the device described in 5- nitros-Isosorbide-5-Nitrae-dihydro-Isosorbide-5-Nitrae-endo-methylene group-naphthalene, its feature
It is that the conduit between reservoir I and metering pump I is equipped with throttle valve I；Set on conduit between reservoir II and metering pump II
There is throttle valve II；The conduit that reservoir III is connected with metering pump III is equipped with throttle valve III.
The pipelineization continuously prepares the device described in 5- nitros-Isosorbide-5-Nitrae-dihydro-Isosorbide-5-Nitrae-endo-methylene group-naphthalene, its feature
It is to carry chuck outside tubular reactor I, tubular reactor II, the tubular reactor I, tubular reactor II are single tube pipeline
Or composed in parallel by two groups or more single tube pipeline.
The pipelineization continuously prepares the device described in 5- nitros-Isosorbide-5-Nitrae-dihydro-Isosorbide-5-Nitrae-endo-methylene group-naphthalene, its feature
It is tubular reactor I, the pipe range of tubular reactor II is 1-20m, pipe diameter 1-20mm.
By using above-mentioned technology, compared with prior art, the beneficial effects of the present invention are：The present invention is by using limit
Fixed pipeline continuous reaction apparatus, it is continuous process to make reaction process, and reaction mass enters after mixer quickly mixes
The tubular reactors of two series connection, make diazol converted in-situ and react immediately with cyclopentadiene after generating, reduce diazonium
Residence time of the salt in reactor, achievees the purpose that to reduce side reaction；By strictly controlling raw material 2- amino -6- nitrobenzoyls
Acid and trichloroacetic acid, cyclopentadiene, the charge proportion of nitrous acid ester, realize the reaction mass ratio in each section pipeline Nei
Keep constant, axially the problems such as local concentration existing in the prior art is uneven is overcome without back-mixing in reactor, it reacts dress
Put structure, easy to operate, post processing is simple, product yield is high, purity is good, suitable industrialized production.
Brief description of the drawings
Fig. 1 is the structure diagram of the present invention.
In figure：1- reservoirs I, 2- reservoir II, 3- reservoirs III, 4- metering pumps I, 5- metering pump II, 6- metering pumps III,
7- mixers I, 8- mixer II, 9- tubular reactors I, 10- tubular reactor II, 11- receiving tanks, 12- throttle valves I, 13- section
Flow valve II, 14- throttle valves III, 15- valve ports.
Embodiment
Illustrate technical scheme, but protection scope of the present invention not limited to this below by way of specific embodiment：
As shown in Figure 1, the pipelineization of the present invention continuously prepares the dress used in 5- nitros-Isosorbide-5-Nitrae-dihydro-Isosorbide-5-Nitrae-endo-methylene group-naphthalene
Put, including：Tubular reactor I 9 and tubular reactor II 10, mixer I 7 and mixer II 8, reservoir I with chuck
1st, reservoir II 2, reservoir III 3, metering pump I 4, metering pump II 5 and metering pump III 6, receiving tank 11 and vacuum distillation dress
Put；Wherein, mixer I 7, tubular reactor I 9, mixer II 8, tubular reactor II 10 and receiving tank 11 pass sequentially through
Conduit connects, and the reservoir I 1 connects the import of metering pump I 4, the reservoir by the conduit equipped with throttle valve I 12
II 2 connect the import of metering pump II 5 by the conduit equipped with throttle valve II 13, and reservoir III 3 passes through equipped with throttle valve III 14
Conduit connection metering pump III 6 import, the outlet of metering pump I 4, the outlet of metering pump II 5 connect respectively mixer I 7 into
Mouth, the import of 7 outlet connecting pipe formula reactor I 9 of mixer I, the outlet of tubular reactor I 9 and the outlet of metering pump III 6
The import of mixer II 8, the import of the outlet connecting pipe formula reactor II 10 of mixer II 8, tubular reactor II are connected respectively
The import of 10 outlet connection receiving tank 11, the outlet of receiving tank 11 connects after-treatment system, the connecting tube by pipeline
Road is equipped with valve port 15.
Tubular reactor I 9, II 10 pipe range of tubular reactor of the present invention is respectively 1 ~ 20m, and pipe diameter is respectively 1 ~
30mm, can make choice as the case may be.
Embodiment 1
Reaction unit structure such as Fig. 1, the tubular reactor I 9 in the present embodiment：Single tube, pipe range 5m, pipe diameter 1mm；Pipe
Formula reactor II 10：Single tube, pipe range 10m, pipe diameter 1mm.
The molar flow ratio of cyclopentadiene, isoamyl nitrite and 2- amino -6- nitrobenzoic acids is 2: 1:1；
Pre-configured 2- amino -6- nitrobenzoyl acid solutions：2- amino -6- nitrobenzoic acids（1.82Kg 10mol）, diethylene glycol
Dimethyl ether 9.5Kg.
Pre-configured nitrous acid ester solution：Isoamyl nitrite（1.17Kg 10mol）, trichloroacetic acid（1.62Kg 10mol）.
The good cyclopentadiene of pre-preparation：Cyclopentadiene（1.32Kg 20mol）.
Tubular reactor I 9 is cooled to 10 DEG C and is kept the temperature, 2- amino -6- nitrobenzoyls acid solution, nitrous acid ester is molten
Liquid is stored in reservoir I 1 and reservoir II 2 respectively, and cyclopentadiene is stored in reservoir III 3,2- amino -6- nitrobenzenes
Formic acid solution, nitrous acid ester solution are continuously inputted into mixer I 7 and mixed by metering pump I 4, metering pump II 5 respectively
Close, while make 2- amino -6- nitrobenzoyls acid solution and nitrous acid different by throttle valve I 12 and II 13 coutroi velocity of throttle valve
The molar flow ratio of pentyl ester is 1:1.2, enter tubular reactor I 9 after being mixed in mixer I 7, in tubular reactor I 9
Interior to carry out diazo-reaction in 10 DEG C, the retention time through 1s, then, the cyclopentadiene in reservoir III 3 pass through metering pump III
6 input to mixer II 8 at the same time with the diazo-reaction liquid in tubular reactor I 9, are controlled by adjusting throttle valve III 14
It is 2 that flow velocity processed, which makes into the cyclopentadiene of mixer II 8 and the molar flow of 2- amino -6- nitrobenzoyl acid solutions,:1, mixed
Enter tubular reactor II 10 after mixing in clutch II 8, after stopping 1s at 90 DEG C in tubular reactor II 10, directly
Enter in receiving tank 11, then, reaction solution is exported into discharge from receiving tank 11, then be evaporated under reduced pressure, recycling is organic molten
Agent diethylene glycol dimethyl ether, obtains brownish black residue, adds n-hexane thereto（3000ml）Flow back, filter, filtrate
Concentration, it is dry, obtain 5- nitros-Isosorbide-5-Nitrae-dihydro-Isosorbide-5-Nitrae-endo-methylene group-naphthalene 0.73Kg, yield 39%, GC contents 91.7%.[GC
Method：Rich 9,790 II type gas chromatograph of power；Chromatographic column：SE-54；Injector：330℃；Detector：340℃；Column temperature：250℃].
Embodiment 2
Reaction unit structure such as Fig. 1, tubular reactor I 9：Single tube, pipe range 5m, pipe diameter 3mm, tubular reactor II
10：Single tube, pipe range 20m, pipe diameter 3mm.
The molar flow ratio of cyclopentadiene and 2- amino -6- nitrobenzoic acids is 5:1, it is anti-in tubular reactor I 9
It is 5 DEG C, retention time 60s to answer temperature, and the residence time in tubular reactor II 10 is 10s,
Other operations finally obtain 5- nitros-Isosorbide-5-Nitrae-dihydro-Isosorbide-5-Nitrae-endo-methylene group-naphthalene 1.06Kg with embodiment 1, yield 57%,
GC contents 92.4%.Vapor detection condition is the same as embodiment 1.
Embodiment 3
Reaction unit structure such as Fig. 1, tubular reactor I 9：Single tube, pipe range 5m, pipe diameter 3mm, tubular reactor II
10：Single tube, pipe range 1m, pipe diameter 6mm.
The molar flow ratio of cyclopentadiene and 2- amino -6- nitrobenzoic acids is 5:1, the reaction in tubular reactor I9
Temperature is -10 DEG C, retention time 60s, and the reaction temperature in tubular reactor II 10 is 120 DEG C, residence time 180s.
Other operations finally obtain 5- nitros-Isosorbide-5-Nitrae-dihydro-Isosorbide-5-Nitrae-endo-methylene group-naphthalene 0.89Kg, yield with embodiment 1
48%, GC content 95.3%.Vapor detection condition is the same as embodiment 1.
Embodiment 4
Reaction unit structure such as Fig. 1, tubular reactor I 9：Single tube, pipe range 20m, pipe diameter 20mm, tubular reactor II
10：Single tube, pipe range 1m, pipe diameter 6mm.
The molar flow ratio of cyclopentadiene and 2- amino -6- nitrobenzoic acids is 5:1, it is anti-in tubular reactor I 9
It is 0 DEG C, retention time 30s to answer temperature, and the reaction temperature in tubular reactor II 10 is 100 DEG C, residence time 180s.
Other operations finally obtain 5- nitros-Isosorbide-5-Nitrae-dihydro-Isosorbide-5-Nitrae-endo-methylene group-naphthalene 0.95Kg, yield with embodiment 1
51%, GC content 95.2%.Vapor detection condition is the same as embodiment 1.
Embodiment 5
Reaction unit structure such as Fig. 1, tubular reactor I 9：Single tube, pipe range 20m, pipe diameter 6mm, tubular reactor II
10：Single tube, pipe range 2m, pipe diameter 6mm.
The molar flow ratio of cyclopentadiene and 2- amino -6- nitrobenzoic acids is 5:1, it is anti-in tubular reactor I 9
It is 0 DEG C, retention time 40s to answer temperature, and the reaction temperature in tubular reactor II 10 is 100 DEG C, residence time 100s.
Other operations finally obtain 5- nitros-Isosorbide-5-Nitrae-dihydro-Isosorbide-5-Nitrae-endo-methylene group-naphthalene 1.10Kg, yield with embodiment 1
59%, GC content 95.0%.Vapor detection condition is the same as embodiment 1.
Embodiment 6
Reaction unit structure such as Fig. 1, tubular reactor I 9：Single tube, pipe range 5m, pipe diameter 20mm, tubular reactor II
10：Single tube, pipe range 10m, pipe diameter 6mm.
The molar flow ratio of isoamyl nitrite and 2- amino -6- nitrobenzoic acids is 1.1:1, cyclopentadiene and 2- ammonia
The molar flow ratio of base -6- nitrobenzoic acids is 4:1, the reaction temperature in tubular reactor I 9 is 0 DEG C, and retention time is
30s, the reaction temperature in tubular reactor II 10 are 120 DEG C, residence time 100s.
Other operations finally obtain 5- nitros-Isosorbide-5-Nitrae-dihydro-Isosorbide-5-Nitrae-endo-methylene group-naphthalene 1.40Kg, yield with embodiment 1
75%, GC content 95.7%.Vapor detection condition is the same as embodiment 1.
Embodiment 7
Reaction unit structure such as Fig. 1, tubular reactor I 9：Single tube, pipe range 5m, pipe diameter 20mm, tubular reactor II
10：Single tube, pipe range 10m, pipe diameter 20mm.
The molar flow ratio of isoamyl nitrite and 2- amino -6- nitrobenzoic acids is 1.1:1, cyclopentadiene and 2- ammonia
The molar flow ratio of base -6- nitrobenzoic acids is 5:1, the reaction temperature in tubular reactor I 9 is 0 DEG C, and retention time is
30s, the reaction temperature in tubular reactor II 10 are 120 DEG C, residence time 100s.
Other operations finally obtain 5- nitros-Isosorbide-5-Nitrae-dihydro-Isosorbide-5-Nitrae-endo-methylene group-naphthalene 1.27Kg, yield with embodiment 1
68%, GC content 96.1%.Vapor detection condition is the same as embodiment 1.
Embodiment 8
Reaction unit structure such as Fig. 1, tubular reactor I 9：Single tube, pipe range 5m, pipe diameter 10mm, tubular reactor II
10：Single tube, pipe range 6m, pipe diameter 6mm.
The molar flow ratio of isoamyl nitrite and 2- amino -6- nitrobenzoic acids is 1.1:1, cyclopentadiene and 2- ammonia
The molar flow ratio of base -6- nitrobenzoic acids is 5:1, the reaction temperature in tubular reactor I 9 is 0 DEG C, and retention time is
30s, the reaction temperature in tubular reactor II 10 are 120 DEG C, residence time 100s.
Other operations finally obtain 5- nitros-Isosorbide-5-Nitrae-dihydro-Isosorbide-5-Nitrae-endo-methylene group-naphthalene 1.53Kg, yield with embodiment 1
82%, GC content 94.3%.Vapor detection condition is the same as embodiment 1.
Embodiment 9
Reaction unit structure such as Fig. 1, tubular reactor I 9：Single tube, pipe range 5m, pipe diameter 10mm, tubular reactor II
10：Single tube, pipe range 6m, pipe diameter 6mm.
The molar flow ratio of isoamyl nitrite and 2- amino -6- nitrobenzoic acids is 1.1:1, cyclopentadiene and 2- ammonia
The molar flow ratio of base -6- nitrobenzoic acids is 4:1, the reaction temperature in tubular reactor I 9 is -5 DEG C, and retention time is
30s, the reaction temperature in tubular reactor II 10 are 120 DEG C, residence time 100s.
Other operations finally obtain 5- nitros-Isosorbide-5-Nitrae-dihydro-Isosorbide-5-Nitrae-endo-methylene group-naphthalene 1.30Kg, yield with embodiment 1
70%, GC content 95.7%.Vapor detection condition is the same as embodiment 1.
Embodiment 10
Reaction unit structure such as Fig. 1, tubular reactor I 9：Single tube, pipe range 5m, pipe diameter 10mm, tubular reactor II
10：Single tube, pipe range 6m, pipe diameter 20mm.
The molar flow ratio of isoamyl nitrite and 2- amino -6- nitrobenzoic acids is 1.1:1, cyclopentadiene and 2- ammonia
The molar flow ratio of base -6- nitrobenzoic acids is 5:1, the reaction temperature in tubular reactor I (9) is 0 DEG C, and retention time is
30s, the reaction temperature in tubular reactor II 10 are 120 DEG C, residence time 180s.
Other operations finally obtain 5- nitros-Isosorbide-5-Nitrae-dihydro-Isosorbide-5-Nitrae-endo-methylene group-naphthalene 1.29Kg, yield with embodiment 1
69%, GC content 94.8%.Vapor detection condition is the same as embodiment 1.
Embodiment 11
Reaction unit structure such as Fig. 1, tubular reactor I 9：Single tube, pipe range 5m, pipe diameter 10mm, tubular reactor II
10：Single tube, pipe range 6m, pipe diameter 6mm.
The molar flow ratio of isoamyl nitrite and 2- amino -6- nitrobenzoic acids is 1.1:1, cyclopentadiene and 2- ammonia
The molar flow ratio of base -6- nitrobenzoic acids is 5:1, the reaction temperature in tubular reactor I 9 is 0 DEG C, and retention time is
30s, the reaction temperature in tubular reactor II 10 are 120 DEG C, residence time 80s.
Other operations finally obtain 5- nitros-Isosorbide-5-Nitrae-dihydro-Isosorbide-5-Nitrae-endo-methylene group-naphthalene 1.44Kg, yield with embodiment 1
77%, GC content 94.8%.Vapor detection condition is the same as embodiment 1.
5- nitro -1,4- dihydros -1,4- endo-methylene groups-naphthalene1H-NMR data are as follows：
1HNMR(CDCI3,400MHz)δ7.7(dd,1H,J=0.7,8.4Hz),7.45(dt,1H,J=7.3,0.7Hz;),7.07
(dd,1H,J=7.3,8.4Hz),6.9-6.86( m,2H),4.86(bs,1H),4.02( bs,1H),2.38(dt,1H,J=
7.7,1.5Hz); 2.3(dt,1H,J=7.4,1.5Hz).
Embodiment 12
Reaction unit structure such as Fig. 1, tubular reactor I 9：Single tube, pipe range 5m, pipe diameter 20mm, tubular reactor II
10：Single tube, pipe range 10m, pipe diameter 6mm.
The molar flow ratio of nitrite tert-butyl and 2- amino -6- nitrobenzoic acids is 1.2:1, cyclopentadiene and 2- ammonia
The molar flow ratio of base -6- nitrobenzoic acids is 4:1, the reaction temperature in tubular reactor I 9 is 0 DEG C, and retention time is
30s, the reaction temperature in tubular reactor II 10 are 120 DEG C, residence time 100s.
Other operations finally obtain 5- nitros-Isosorbide-5-Nitrae-dihydro-Isosorbide-5-Nitrae-endo-methylene group-naphthalene 1.40Kg, yield with embodiment 1
70%, GC content 95.5%.Vapor detection condition is the same as embodiment 1.
5- nitro -1,4- dihydros -1,4- endo-methylene groups-naphthalene1H-NMR data are as follows：
1HNMR(CDCI3,400MHz)δ7.7(dd,1H,J=0.7,8.4Hz),7.45(dt,1H,J=7.3,0.7Hz;),7.07
(dd,1H,J=7.3,8.4Hz),6.9-6.86( m,2H),4.86(bs,1H),4.02( bs,1H),2.38(dt,1H,J=
7.7,1.5Hz); 2.3(dt,1H,J=7.4,1.5Hz)。
Claims (10)
1. a kind of method that pipelineization continuously prepares 5- nitros-Isosorbide-5-Nitrae-dihydro-Isosorbide-5-Nitrae-endo-methylene group-naphthalene, it is characterised in that prepare
Method is：Raw material 2- amino -6- nitrobenzoyls acid solution, nitrous acid ester solution, cyclopentadiene are stored in reservoir I respectively
（1）, reservoir II（2）, reservoir III（3）In, 2- amino -6- nitrobenzoyls acid solution, nitrous acid ester solution pass through meter respectively
Amount pump I（4）, metering pump II（5）It is continuous to input to mixer I（7）In, in mixer I（7）Enter tubular reactor after middle mixing
I（9）It is interior to carry out diazo-reaction, the retention time through 1-60s in -10-10 DEG C；Then, reservoir III（3）In cyclopentadiene
Pass through metering pump III（6）With tubular reactor I（9）In diazo-reaction liquid input at the same time to mixer II（8）It is interior, mixing
Device II（8）Enter tubular reactor II after interior mixing（10）In stop 1-180s at 1-120 DEG C after, reaction solution after reaction
Enter receiving tank（11）In, it is post-treated to obtain 5- nitros-Isosorbide-5-Nitrae-dihydro-Isosorbide-5-Nitrae-endo-methylene group-naphthalene.
2. the method that pipelineization according to claim 1 continuously prepares 5- nitros-Isosorbide-5-Nitrae-dihydro-Isosorbide-5-Nitrae-endo-methylene group-naphthalene,
It is characterized in that the ratio between 2- amino -6- nitrobenzoic acids, nitrous acid ester and cyclopentadiene molar flow are 1：1-5.
3. the method that pipelineization according to claim 1 continuously prepares 5- nitros-Isosorbide-5-Nitrae-dihydro-Isosorbide-5-Nitrae-endo-methylene group-naphthalene,
It is characterized in that nitrous acid ester is nitrous acid ester isopentyl ester or nitrite tert-butyl, 2- amino -6- nitrobenzoic acids and nitrous acid
The ratio between molar flow of ester is 1：1-1.2.
4. the method that pipelineization according to claim 1 continuously prepares 5- nitros-Isosorbide-5-Nitrae-dihydro-Isosorbide-5-Nitrae-endo-methylene group-naphthalene,
It is it is characterized in that described in tubular reactor I（9）The interior temperature for carrying out diazo-reaction is -5-5 DEG C；In tubular reactor II
（10）The interior temperature for carrying out diazo-reaction is 90-120 DEG C.
5. the method that pipelineization according to claim 1 continuously prepares 5- nitros-Isosorbide-5-Nitrae-dihydro-Isosorbide-5-Nitrae-endo-methylene group-naphthalene,
It is characterized in that post-processing approach is：Reaction solution first obtains brownish black crude product after vacuum distillation, is added in the crude product organic
Solvent refluxing, filtering, organic solvent are concentrated and dried up to 5- nitros-Isosorbide-5-Nitrae-dihydro-Isosorbide-5-Nitrae-endo-methylene group-naphthalene.
6. the method that pipelineization according to claim 5 continuously prepares 5- nitros-Isosorbide-5-Nitrae-dihydro-Isosorbide-5-Nitrae-endo-methylene group-naphthalene,
It is characterized in that organic solvent is selected from n-hexane, hexamethylene or petroleum ether.
7. a kind of pipelineization continuously prepares the device described in 5- nitros-Isosorbide-5-Nitrae-dihydro-Isosorbide-5-Nitrae-endo-methylene group-naphthalene, it is characterised in that
Including tubular reactor I（9）, tubular reactor II（10）, mixer I（7）, mixer II（8）, reservoir I（1）, reservoir
Ⅱ（2）, reservoir III（3）, metering pump I（4）, metering pump II（5）, metering pump III（6）, receiving tank（11）And vacuum distillation dress
Put；The mixer I（7）, tubular reactor I（9）, mixer II（8）, tubular reactor II（10）And receiving tank（11）According to
It is secondary to be connected by conduit, the reservoir I（1）Metering pump I is connected by conduit（4）Import, the reservoir II（2）Pass through
Conduit connects metering pump II（5）Import, reservoir III（3）Metering pump III is connected by conduit（6）Import, metering pump I（4）
Outlet, metering pump II（5）Outlet connect mixer I respectively（7）Import, mixer I（7）Outlet connecting pipe formula reactor I
（9）Import, tubular reactor I（9）Outlet and metering pump III（6）Outlet connect mixer II respectively（8）Import,
Mixer II（8）Outlet connecting pipe formula reactor II（10）Import, tubular reactor II（10）Outlet connection receiving tank
（11）Import, receiving tank（11 ）Outlet after-treatment system is connected by pipeline, which is equipped with valve port
（15）.
8. pipelineization according to claim 7 is continuously prepared described in 5- nitro -1,4- dihydros -1,4- endo-methylene groups-naphthalene
Device, it is characterised in that reservoir I（1）With metering pump I（4）Between conduit be equipped with throttle valve I（12）；Reservoir II（2）
With metering pump II（5）Between conduit be equipped with throttle valve II（13）；Reservoir III（3）With metering pump III（6）The conduit of connection
It is equipped with throttle valve III（14）.
9. pipelineization according to claim 7 is continuously prepared described in 5- nitro -1,4- dihydros -1,4- endo-methylene groups-naphthalene
Device, it is characterised in that tubular reactor I（9）, tubular reactor II（10）Carry chuck, the tubular reactor I outside（9）、
Tubular reactor II（10）Composed in parallel for single tube pipeline or by two groups or more single tube pipeline.
10. pipelineization according to claim 7 is continuously prepared described in 5- nitro -1,4- dihydros -1,4- endo-methylene groups-naphthalene
Device, it is characterised in that tubular reactor I（9）, tubular reactor II（10）Pipe range be 1-20m, pipe diameter 1-20mm.
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| CN201711099652.5A CN108003030B (en) | 2017-11-09 | 2017-11-09 | Method and device for continuously preparing 5-nitro-1, 4-dihydro-1, 4-methano-naphthalene in pipelining manner |
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| CN201711099652.5A CN108003030B (en) | 2017-11-09 | 2017-11-09 | Method and device for continuously preparing 5-nitro-1, 4-dihydro-1, 4-methano-naphthalene in pipelining manner |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112300033A (en) * | 2020-11-03 | 2021-02-02 | 刘继明 | Device and method for fully and continuously synthesizing 2-nitro-4-methylsulfonylbenzoic acid from 4-methylsulfonyltoluene |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101693712A (en) * | 2009-10-13 | 2010-04-14 | 上海立科化学科技有限公司 | Method for synthesizing Varenicline intermediate 2, 3, 4, 5-tetralin-1, 5-methylene-hydrogen-benzoazepine |
| WO2011131543A1 (en) * | 2010-04-20 | 2011-10-27 | Syngenta Participations Ag | Process for the preparation of pyrazole carboxylic acid amides |
| CN104744295A (en) * | 2015-03-23 | 2015-07-01 | 浙江工业大学 | Method and device for preparing ethylphenylhydrazine hydrochloride by pipelines |
| CN106588745A (en) * | 2016-12-02 | 2017-04-26 | 杭州百昂锐地科技有限公司 | Intermediate of benzovindiflupyr and preparation method and application thereof |
-
2017
- 2017-11-09 CN CN201711099652.5A patent/CN108003030B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101693712A (en) * | 2009-10-13 | 2010-04-14 | 上海立科化学科技有限公司 | Method for synthesizing Varenicline intermediate 2, 3, 4, 5-tetralin-1, 5-methylene-hydrogen-benzoazepine |
| WO2011131543A1 (en) * | 2010-04-20 | 2011-10-27 | Syngenta Participations Ag | Process for the preparation of pyrazole carboxylic acid amides |
| CN102858750A (en) * | 2010-04-20 | 2013-01-02 | 先正达参股股份有限公司 | Process for the preparation of pyrazole carboxylic acid amides |
| CN104744295A (en) * | 2015-03-23 | 2015-07-01 | 浙江工业大学 | Method and device for preparing ethylphenylhydrazine hydrochloride by pipelines |
| CN106588745A (en) * | 2016-12-02 | 2017-04-26 | 杭州百昂锐地科技有限公司 | Intermediate of benzovindiflupyr and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| D.GRAVEL ETAL: "Photochemistry of the o-nitrobenzyl system in solution: effects of O•••H distance and geometrical constraint on the hydrogen transfer mechanism in the excited state", 《CANADIAN JOURNAL OF CHEMISTRY》 * |
| MARK W. GALLEY ETAL: "Effects of a Remote Double Bond or Cyclopropane Ring on Electrophilic Aromatic Substitution", 《JOURNAL OF ORGANIC CHEMISTRY》 * |
| ROBERT A. SNOW ETAL: "Demonstration and analysis of bridging regioselectivity operative during di-π-methane photorearrangement of ortho-substituted benzonorbornadienes and anti-7,8-benzotricyclo[4.2.2.02,5]deca-3,7,9-trienes", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112300033A (en) * | 2020-11-03 | 2021-02-02 | 刘继明 | Device and method for fully and continuously synthesizing 2-nitro-4-methylsulfonylbenzoic acid from 4-methylsulfonyltoluene |
| CN112300033B (en) * | 2020-11-03 | 2023-10-13 | 湖北丰杯生物科技有限公司 | Device and method for fully continuously synthesizing 2-nitro-4-methylsulfonyl benzoic acid from 4-methylsulfonyl toluene |
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