CN107629003A - A kind of preparation method of the nitropyrazole of 1 methyl 4 - Google Patents
A kind of preparation method of the nitropyrazole of 1 methyl 4 Download PDFInfo
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- CN107629003A CN107629003A CN201710801452.3A CN201710801452A CN107629003A CN 107629003 A CN107629003 A CN 107629003A CN 201710801452 A CN201710801452 A CN 201710801452A CN 107629003 A CN107629003 A CN 107629003A
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- nitropyrazoles
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Abstract
The invention provides a kind of synthetic method of the nitropyrazole of 1 methyl 4, and 1 methylpyrazole, N nitropyrazoles and sulfuric acid solution are mixed and carry out nitration reaction, obtains the nitropyrazole of 1 methyl 4.The preparation method of the present invention is using N nitropyrazoles and sulfuric acid as nitrating agent, 1 methylpyrazole is directly nitrified into the i.e. available nitropyrazole of 1 methyl 4, raw material sources enrich, cost is low, and it is nitrating agent to avoid using nitration mixture, the generation of course of reaction uncontaminated gases nitrogen oxides, does not produce spent acid, and environmental pollution is small；Further, preparation method reaction condition provided by the invention is gentle, it is not necessary to reacts for a long time at high temperature, requires relatively low to consersion unit, be easy to purify, and products therefrom purity is high.
Description
Technical field
The present invention relates to the synthesis field of organic compound, more particularly to a kind of preparation side of 1- methyl -4- nitropyrazoles
Method.
Background technology
1- methyl -4- nitropyrazoles are a kind of typical heterocyclic nitrogen compounds, the structure contain high enthalpy C=C double bonds and
N-N singly-bounds, there is the higher enthalpy of formation, high density and environment amenable feature, there is considerable energy, fried in high energy
There is good prospect in medicine, safe insensitiveness, low sense additive etc. field, are new energetic material 1- methyl -3,4,5- trinitro- pyrroles
The intermediate of azoles etc..
The nitrification of pyrazoles or methylpyrazole is typically using fuming nitric aicd-acetic anhydride or fuming nitric aicd-concentrated sulfuric acid as nitrification
Reagent, the N- nitrifications of pyrazole ring use fuming nitric aicd-acetic anhydride as nitrating agent, the C- of pyrazole ring nitrify use fuming nitric aicd-
The concentrated sulfuric acid is nitrating agent.
In the prior art, the preparation of 1- methyl -4- nitropyrazoles is typically using 1- methylpyrazoles and fuming nitric aicd-concentrated sulfuric acid
Nitrification system is reacted.But nitrating agent fuming nitric aicd-concentrated sulfuric acid that this method uses can produce substantial amounts of oxides of nitrogen gas
And excessive spent acid and cause environmental pollution.
The content of the invention
In view of this, it is an object of the invention to provide a kind of preparation method of 1- methyl -4- nitropyrazoles, this method to close
Simple into technique, it is nitrating agent to avoid using fuming nitric aicd, and environmental pollution is small.
In order to realize foregoing invention purpose, the present invention provides following technical scheme：
A kind of preparation method of 1- methyl -4- nitropyrazoles, comprises the following steps：
1- methylpyrazoles, N- nitropyrazoles and sulfuric acid solution are mixed and carry out nitration reaction, obtains 1- methyl -4- nitro pyrroles
Azoles.
Preferably, the amount ratio of the material of the 1- methylpyrazoles, N- nitropyrazoles and sulfuric acid solution is 1:1~3:7.5~
12.5。
Preferably, the temperature of the nitration reaction is 20~80 DEG C.
Preferably, the temperature of the nitration reaction is 40~60 DEG C.
Preferably, the time of the nitration reaction is 2~8h.
Preferably, the time of the nitration reaction is 4~6h.
Preferably, the mass concentration of the sulfuric acid solution is 40%~98%.
Preferably, the mixing of the 1- methylpyrazoles, N- nitropyrazoles and sulfuric acid solution is specially：
Will 1- methylpyrazoles and sulfuric acid solution mix after be heated to 20~80 DEG C, obtain 1- methylpyrazoles and sulfuric acid solution
Hot mixing liquid；
Divide 8~12 times and N- nitropyrazoles are added into the hot mixing liquid of the 1- methylpyrazoles and sulfuric acid solution.
Preferably, purification process is also included after the nitration reaction, is comprised the following steps：
By gained nitration reaction liquid cooled and filtered after nitration reaction, filtrate and the first solid are obtained；
The filtrate is extracted and distilled successively, obtains the second solid；
Recrystallized after first solid and the mixing of the second solid, obtain 1- methyl -4- nitropyrazoles.
Preferably, the chilling temperature is 0~5 DEG C.
Advantageous effects：
The invention provides a kind of preparation method of 1- methyl -4- nitropyrazoles.The preparation method of the present invention is with N- nitros
Pyrazoles and sulfuric acid are nitrating agent, directly nitrify 1- methylpyrazoles and can obtain 1- methyl -4- nitropyrazoles, and raw material comes
Source is enriched, and cost is low, and it is nitrating agent to avoid using nitration mixture, course of reaction uncontaminated gases nitrogen oxides
Generation, do not produce spent acid, environmental pollution is small；Further, preparation method provided by the invention is at a temperature of 20~80 DEG C
Nitration reaction is carried out, reaction condition is gentle, it is not necessary to react for a long time at high temperature, relatively low is required to consersion unit, is easy to carry
It is pure, and products therefrom purity is high.Embodiment result shows, 1- methyl -4- nitro pyrroles are prepared with preparation method provided by the invention
Azoles, the purity of the 1- methyl -4- nitropyrazoles of gained after purification can reach more than 99%, and yield is 50%~75%.
Brief description of the drawings
Fig. 1 is the high-efficient liquid phase chromatogram for the target product that embodiment 1 is prepared；
Fig. 2 is the infrared spectrogram for the target product that embodiment 1 is prepared；
Fig. 3 is the mass spectrogram for the target product that embodiment 1 is prepared；
Fig. 4 is the proton nmr spectra for the target product that embodiment 1 is prepared；
Fig. 5 is the carbon-13 nmr spectra for the target product that embodiment 1 is prepared.
Embodiment
The invention provides a kind of preparation method of 1- methyl -4- nitropyrazoles, comprise the following steps：
1- methylpyrazoles, N- nitropyrazoles and sulfuric acid solution are mixed and carry out nitration reaction, obtains 1- methyl -4- nitro pyrroles
Azoles.
In the present invention, the amount ratio of the material of sulfuric acid is preferred in the 1- methylpyrazoles, N- nitropyrazoles and sulfuric acid solution
For 1:1~3:7.5~12.5, more preferably 1:1.5~2.5:9~11；The mass concentration of the sulfuric acid solution is preferably 40%
~98%, more preferably 75%~90%, most preferably 85~90%.In the present invention, sulfuric acid can be by N- nitropyrazoles not
Substituted nitrogen atom protonates so that the nitro on its adjacent nitrogen-atoms activates and produces nitryl oxonium ion (NO2 +), nitryl oxonium ion
(NO2 +) C- nitration reactions further occur with N- methylpyrazoles.
In the present invention, the temperature of the nitration reaction is preferably 20~80 DEG C, more preferably 40~60 DEG C；The nitrification
The time of reaction is preferably 2~8h, more preferably 4~6h.
In the present invention, the mixing of the 1- methylpyrazoles, N- nitropyrazoles and sulfuric acid solution is preferably specially：
Will 1- methylpyrazoles and sulfuric acid solution mix after be heated to 20~80 DEG C, obtain 1- methylpyrazoles and sulfuric acid solution
Hot mixing liquid；
Divide 8~12 times and N- nitropyrazoles are added into the hot mixing liquid of the 1- methylpyrazoles and sulfuric acid solution.
The present invention is heated to 20~80 DEG C after mixing 1- methylpyrazoles and sulfuric acid solution, obtains 1- methylpyrazoles and sulfuric acid
The hot mixing liquid of solution.1- methylpyrazoles are preferably added drop-wise in sulfuric acid solution by the present invention under agitation, obtain 1- methyl
The mixed liquor of pyrazoles and sulfuric acid solution, the rate of addition are preferably 1~2 drop/sec；The mixing speed is preferably 300~400
Rev/min, more preferably 320~380 revs/min, most preferably 350 revs/min；The present invention is not particularly limited to stirring means, is selected
It is specific such as mechanical agitation with the conventional stirring means in this area.
After obtaining the mixed liquor of 1- methylpyrazoles and sulfuric acid, the present invention preferably adds the mixed liquor of 1- methylpyrazoles and sulfuric acid
Heat obtains the hot mixing liquid of 1- methylpyrazoles and sulfuric acid to 20~80 DEG C.In the present invention, the speed of the heating is preferably 1
~5 DEG C/minute, more preferably 2~3 DEG C/minute；The hot mixing liquid is more preferably heated to 40~60 DEG C.
After obtaining hot mixing liquid, the present invention is added in hot mixing liquid for 8~12 times preferably by N- nitropyrazoles point.In the present invention
In, the addition batch of the N- nitropyrazoles is preferably 8~12 times, more preferably 10 times, the N- nitropyrazoles added per batch
Quality be the gross mass of required N- nitropyrazoles and the corresponding ratio for adding batch.In a particular embodiment of the present invention, often
Warming phenomenon occurs after secondary addition N- nitropyrazoles, the present invention preferably adds N- again when temperature is down to initial charge temperature
Nitropyrazole.
After obtaining the mixed liquor of 1- methylpyrazoles, N- nitropyrazoles and sulfuric acid, the present invention is preferably by mixed liquor 20~80
DEG C insulation 2~8h, carry out nitration reaction；The present invention the nitration reaction time since N- nitropyrazoles charging after the completion of calculate.
In the present invention, the equation of the nitration reaction is shown in formula I：
After the completion of nitration reaction, the present invention preferably also includes：Obtained nitration reaction liquid is purified, obtains 1- first
Base -4- nitropyrazole sterlings, the purification preferably include following steps：
By nitration reaction liquid cooled and filtered, filtrate and the first solid are obtained；
The filtrate is extracted and distilled successively, obtains the second solid；
Recrystallized after first solid and second solid are mixed, obtain 1- methyl -4- nitropyrazoles.
Nitration reaction liquid cooled and filtered is obtained filtrate and the first solid by the present invention.In the present invention, the cooling
Temperature is preferably 0~5 DEG C, more preferably 2~4 DEG C；The rate of temperature fall of the cooling is preferably 5~10 DEG C/min, more preferably
7~9 DEG C/min；The present invention is not particularly limited to the method for the cooling, can be cooled to and be required temperature；In this hair
In bright specific embodiment, preferably nitration reaction liquid is mixed with ice cube and cooled down.The present invention is not special to the filtering
It is required that using filter method well known to those skilled in the art, it is specific as filtered.
After being filtrated to get filtrate and the first solid, the filtrate is preferably extracted and distilled successively by the present invention, is obtained
Second solid.In the present invention, the extractant of the extraction is preferably ether, ethanol or ethyl acetate, more preferably ether or
Ethanol；The present invention is not particularly limited to the actual conditions of the extraction, can be by filtrate from this area conventional extraction condition
In 1- methyl -4- nitropyrazoles be extracted into completely in organic phase.
After extraction, the present invention is preferably distilled the organic phase being obtained by extraction, and obtains the second solid.In the present invention
In, the vapo(u)rizing temperature is preferably 35~80 DEG C, more preferably 45~65 DEG C, most preferably 50~60 DEG C, the distillation degree
For organic phase is distilled to stopping distilling when original 1/3rd, pour out liquid naturally dry and obtain the second solid.
In the present invention, main component is sulfuric acid in the raffinate after extraction, and the present invention is preferably concentrated raffinate
Sulfuric acid is reclaimed, the present invention is not particularly limited to the method for concentration, using method for concentration well known to those skilled in the art,
As being concentrated by evaporation.
In the present invention, N- nitropyrazoles take off nitro and are changed into accessory substance pyrazoles after nitration reaction, and pyrazoles is present in extraction
Aqueous phase after taking, pyrazoles can be extracted by benzene and be reclaimed, can be the precursor of other medicines synthesis.The present invention is preferably by caused by
Accessory substance pyrazoles is reclaimed, and the present invention is not particularly limited to the recovery method of pyrazoles, using well known to those skilled in the art time
Receiving method, benzene solvent will be such as added in the aqueous phase after extraction and extracts pyrazoles, evaporation benzene solvent recovery pyrazoles.
After obtaining the first solid and the second solid, the present invention is carried out after preferably mixing first solid and the second solid
Recrystallization, obtains 1- methyl -4- nitropyrazole sterlings.In the present invention, the recrystallization is preferably alcohols solvent with solvent, more
Preferably ethanol.The present invention does not have special limitation to the method for the recrystallization, from the conventional recrystallization method in this area
.
The preparation method provided by the invention to 1- methyl -4- nitropyrazoles is carried out specifically with reference to embodiment
It is bright, but they can not be interpreted as limiting the scope of the present invention.
Embodiment 1
1.4g (0.012mol) N- nitropyrazoles are taken respectively, and 1g (0.012mol) 1- methylpyrazoles are standby, by 8mL 98%
The concentrated sulfuric acid add equipped with mechanical agitation, thermometer, charging hopper 100mL four-hole bottles in, at 20 DEG C with charging hopper to
1- methylpyrazoles are added dropwise in the concentrated sulfuric acid, charging completes warming-in-water to 60 DEG C, point 10 addition N- nitropyrazoles at a temperature of this,
Each addition is 0.0012mol, and charging is completed, and is kept stirring for isothermal reaction 6h, after the completion of reaction, is while hot poured into reaction solution
Stirred in beaker equipped with ice cube, there is the tiny crystalline solid of white to separate out, ice cube melts entirely, filters, obtains white solid I and filtrate；
Filtrate is extracted with ether, merges solvent, and vacuum rotary steam removes solvent, white solid II obtained, by white solid I and white solid
II is recrystallized after merging with ethanol, obtains target product.The purity of product is 99%, and product fusing point is：90~93 DEG C；Receive
Rate is 72.53%.
Elementary analysis result of the table 1 to target product in embodiment 1
From the elementary analysis of table 1, gained target product N, C, H constituent content and 1- methyl -4- nitropyrazoles are managed
It is basically identical by being worth.
Fig. 1 is the high-efficient liquid phase chromatogram of test gained target product purity
Chromatographic condition：Solution containing object is prepared using chromatogram methanol, using water and methanol as mobile phase, water and methanol
Volume ratio is 45：55 be mobile phase, UV absorption wavelength 237nm, flow velocity 1mLmin-1, the μ L of sample size 10.Test result
As shown in Figure 1, the retention time of 1- methyl -4- nitropyrazoles is 4.37min, and calculating product purity with area normalization method is
99.1%.
Fig. 2 is the infrared spectrogram for the target product that embodiment 1 is prepared, and the data obtained is：
IR(KBr,v cm-1):3112 (pyrazole ring C-H), 2980 (methyl C-H), 1535,1331 (C-NO2).Can by Fig. 2
Know nitro, methyl, pyrazole ring in measured target product structure be present.
Fig. 3 is the mass spectrogram for the target product that embodiment 1 is prepared, and molecular ion peak is 127 in Fig. 3, with 1- methyl-
4- nitropyrazoles molecular weight 127.10 is close.
Fig. 4 is the hydrogen nuclear magnetic resonance spectrogram for the target product that embodiment 1 is prepared, and the data obtained is as follows：
1H NMR(Acetone-d6)δ：8.55(1H),8.05(1H),3.99(3H).From above-mentioned data, measured target
Product is with the presence of 3 kinds of hydrogen atoms.
Fig. 5 is gained target product carbon-13 nmr spectra figure, and the data obtained is as follows：
13C NMR(Acetone-d6):39.34(t,CH3), 135.59 (t, C3), 130.09 (t, C5), 135.05 (t,
C4).From above-mentioned data, measured target product is with the presence of 4 kinds of carbon atoms.
In summary, the molecular structure for surveying target product is consistent with 1- methyl -4- nitropyrazole molecular structures, i.e. this hair
Gained target product is 1- methyl -4- nitropyrazoles in bright embodiment 1, and the purity of product is 99.1%.
Embodiment 2
4.1g (0.036mol) N- nitropyrazoles are taken respectively, and 1g (0.012mol) 1- methylpyrazoles are standby, by 6mL 98%
The concentrated sulfuric acid add equipped with mechanical agitation, thermometer, charging hopper 100mL four-hole bottle in, use constant pressure addition at 20 DEG C
1- methylpyrazoles are added dropwise into the concentrated sulfuric acid for funnel, and charging completes warming-in-water to 80 DEG C, point 12 addition N- nitre at a temperature of this
Base pyrazoles, 0.003mol is added every time, after the completion of charging, isothermal reaction 4h, while hot pours into reaction solution equipped with ice at 20 DEG C
Stirred in the beaker of block, there is the tiny crystalline solid of white to separate out, after ice cube melts entirely, filtered, obtain white solid I；Filtrate ether
Extraction, merges solvent, and vacuum rotary steam removes solvent, obtains white solid II；Used after white solid I is merged with white solid II
Ethanol carries out recrystallizing to obtain target product.
The structure of the target product is characterized using the method for testing in embodiment 1, gained test result is with implementing
Example 1 is similar, it was demonstrated that gained target product is 1- methyl -4- nitropyrazoles in embodiment 2, and the purity of product is 99.1%, product
Fusing point is：89~92 DEG C；Yield is 69.52%.
Embodiment 3
2.7g (0.024mol) N- nitropyrazoles are taken respectively, and 1g (0.012mol) 1- methylpyrazoles are standby, by 8mL 98%
The concentrated sulfuric acid add equipped with mechanical agitation, thermometer, the 100mL four-hole bottles of charging hopper, use constant pressure funnel at 20 DEG C
1- methylpyrazoles are added dropwise into the concentrated sulfuric acid, charging completes warming-in-water to 35 DEG C, point 10 addition N- nitro pyrroles at a temperature of this
Azoles, adds 0.0024mol, isothermal reaction 6h every time, pours into the beaker equipped with ice cube reaction solution stir while hot, has white thin
Small crystalline solid separates out, and after ice cube melts entirely, filters, obtains white solid I and filtrate；Filtrate is extracted with ether, merges solvent, decompression
Revolving removes solvent, obtains white solid II, and obtaining target with ethyl alcohol recrystallization after white solid I and white solid II is merged produces
Thing.
The structure of the target product is characterized using the method for testing in embodiment 1, gained test result is with implementing
Example 1 is similar, it was demonstrated that gained target product is 1- methyl -4- nitropyrazoles in embodiment 3, and the purity of product is 99.2%, product
Fusing point is：90~91 DEG C；Yield is 74.01%.
Embodiment 4
2.7g (0.024mol) N- nitropyrazoles are taken respectively, and 1g (0.012mol) 1- methylpyrazoles are standby, by 8mL 60%
The concentrated sulfuric acid add equipped with mechanical agitation, thermometer, the 100mL four-hole bottles of charging hopper, use constant pressure funnel at 20 DEG C
1- methylpyrazoles are added dropwise into the concentrated sulfuric acid, charging completes warming-in-water to 30 DEG C, point 8 addition N- nitro pyrroles at a temperature of this
Azoles, adds 0.003mol, isothermal reaction 4h every time, pours into the beaker equipped with ice cube reaction solution stir while hot, has white thin
Small crystalline solid separates out, and after ice cube melts entirely, filters to obtain white solid I and filtrate；Gained filtrate is extracted with ether, merges solvent,
Vacuum rotary steam removes solvent, obtains white solid II, and mesh is obtained with ethyl alcohol recrystallization after white solid I and white solid II is merged
Mark product.
The structure of the target product is characterized using the method for testing of embodiment 1, gained test result and embodiment 1
It is similar, it was demonstrated that gained target product is 1- methyl -4- nitropyrazoles in embodiment 4, and the purity of product is 99.1%, product fusing point
For：90~92 DEG C；Yield is 53.81%.
Embodiment 5
4.1g (0.036mol) N- nitropyrazoles are taken respectively, and 1g (0.012mol) 1- methylpyrazoles are standby, by 8mL 40%
The concentrated sulfuric acid add equipped with mechanical agitation, thermometer, the 100mL four-hole bottles of charging hopper, use constant pressure funnel at 20 DEG C
1- methylpyrazoles are added dropwise into the concentrated sulfuric acid, charging completes warming-in-water to 50 DEG C, point 12 addition N- nitro pyrroles at a temperature of this
Azoles, each addition are 0.003mol, isothermal reaction 3h, pour into the beaker equipped with ice cube reaction solution stir while hot, have white
The tiny crystalline solid of color separates out, and after ice cube melts entirely, filters to obtain white solid I and filtrate；Gained filtrate is extracted with ether, is merged molten
Agent, vacuum rotary steam remove solvent, obtain white solid II, and ethyl alcohol recrystallization is used after white solid I and white solid II is merged
Obtain target product.
The structure of the target product is characterized using the method for testing in embodiment 1, gained test result is with implementing
Example 1 is similar, it was demonstrated that gained target product is 1- methyl -4- nitropyrazoles in embodiment 5, and the purity of product is 99.1%, product
Fusing point is：89~92 DEG C；Yield is 51.26%.
Preparation method of the invention is using N- nitropyrazoles and sulfuric acid as nitrating agent as seen from the above embodiment, directly by 1-
Methylpyrazole, which is nitrified, can obtain 1- methyl -4- nitropyrazoles.The preparation method raw material sources of the present invention enrich, cost
It is low, and it is nitrating agent to avoid using nitration mixture, the generation of course of reaction uncontaminated gases nitrogen oxides, to ring
Border pollution is small；And preparation method reaction condition provided by the invention is gentle, it is not necessary to reacts for a long time at high temperature, to reaction
Equipment requirement is relatively low, and products therefrom purity, up to 99%, yield is 50%~75%.
The present invention described above is only the preferred embodiment of the present invention, it is noted that for the common of the art
For technical staff, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these are improved and profit
Decorations also should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of 1- methyl -4- nitropyrazoles, comprises the following steps：
1- methylpyrazoles, N- nitropyrazoles and sulfuric acid solution are mixed and carry out nitration reaction, obtains 1- methyl -4- nitropyrazoles.
2. preparation method according to claim 1, it is characterised in that the 1- methylpyrazoles, N- nitropyrazoles and sulfuric acid
The amount ratio of the material of sulfuric acid is 1 in solution:1~3:7.5~12.5.
3. preparation method according to claim 1, it is characterised in that the temperature of the nitration reaction is 20~80 DEG C.
4. preparation method according to claim 3, it is characterised in that the temperature of the nitration reaction is 40~60 DEG C.
5. according to the preparation method described in claim 1,3 or 4, it is characterised in that the time of the nitration reaction is 2~8h.
6. preparation method according to claim 5, it is characterised in that the time of the nitration reaction is 4~6h.
7. preparation method according to claim 1 or 2, it is characterised in that the mass concentration of the sulfuric acid solution is 40%
~98%.
8. preparation method according to claim 1, it is characterised in that the 1- methylpyrazoles, N- nitropyrazoles and sulfuric acid
The mixing of solution is specially：
20~80 DEG C are heated to after 1- methylpyrazoles and sulfuric acid solution are mixed, the heat for obtaining 1- methylpyrazoles and sulfuric acid solution is mixed
Close liquid；
8~12 batches are divided to add N- nitropyrazoles into the hot mixing liquid of the 1- methylpyrazoles and sulfuric acid solution.
9. preparation method according to claim 1, it is characterised in that also include after the nitration reaction：By nitration reaction
Liquid purifies, the 1- methyl -4- nitropyrazoles purified；The purification comprises the following steps：
By nitration reaction liquid cooled and filtered, filtrate and the first solid are obtained；
The filtrate is extracted and distilled successively, obtains the second solid；
Recrystallized after first solid and second solid are mixed, obtain 1- methyl -4- nitropyrazoles.
10. preparation method according to claim 9, it is characterised in that the temperature of the cooling is 0~5 DEG C.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112939867A (en) * | 2021-04-07 | 2021-06-11 | 中北大学 | Preparation method of 4-nitropyrazole |
| CN113061113A (en) * | 2021-04-07 | 2021-07-02 | 中北大学 | Preparation method of 4-nitroimidazole |
| CN113072450A (en) * | 2021-04-07 | 2021-07-06 | 中北大学 | Preparation method of m-nitrochlorobenzene |
| CN115448866A (en) * | 2022-10-13 | 2022-12-09 | 中北大学 | Preparation method of 1-methyl-2, 3,4, 5-tetranitropyrrole |
| CN115825299A (en) * | 2022-11-24 | 2023-03-21 | 中北大学 | Purity analysis method of 1-methyl-3, 4, 5-trinitropyrazole |
-
2017
- 2017-09-07 CN CN201710801452.3A patent/CN107629003B/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112939867A (en) * | 2021-04-07 | 2021-06-11 | 中北大学 | Preparation method of 4-nitropyrazole |
| CN113061113A (en) * | 2021-04-07 | 2021-07-02 | 中北大学 | Preparation method of 4-nitroimidazole |
| CN113072450A (en) * | 2021-04-07 | 2021-07-06 | 中北大学 | Preparation method of m-nitrochlorobenzene |
| CN115448866A (en) * | 2022-10-13 | 2022-12-09 | 中北大学 | Preparation method of 1-methyl-2, 3,4, 5-tetranitropyrrole |
| CN115448866B (en) * | 2022-10-13 | 2023-11-21 | 中北大学 | Preparation method of 1-methyl-2, 3,4, 5-tetranitropyrrole |
| CN115825299A (en) * | 2022-11-24 | 2023-03-21 | 中北大学 | Purity analysis method of 1-methyl-3, 4, 5-trinitropyrazole |
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| CN107629003B (en) | 2020-03-31 |
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