CN112939867A - Preparation method of 4-nitropyrazole - Google Patents
Preparation method of 4-nitropyrazole Download PDFInfo
- Publication number
- CN112939867A CN112939867A CN202110374462.XA CN202110374462A CN112939867A CN 112939867 A CN112939867 A CN 112939867A CN 202110374462 A CN202110374462 A CN 202110374462A CN 112939867 A CN112939867 A CN 112939867A
- Authority
- CN
- China
- Prior art keywords
- nitropyrazole
- temperature
- pyrazole
- feeding
- sulfuric acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- XORHNJQEWQGXCN-UHFFFAOYSA-N 4-nitro-1h-pyrazole Chemical compound [O-][N+](=O)C=1C=NNC=1 XORHNJQEWQGXCN-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 230000000802 nitrating effect Effects 0.000 claims abstract description 12
- TYNVOQYGXDUHRX-UHFFFAOYSA-N 1-nitropyrazole Chemical compound [O-][N+](=O)N1C=CC=N1 TYNVOQYGXDUHRX-UHFFFAOYSA-N 0.000 claims abstract description 11
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- 238000010907 mechanical stirring Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 3
- 239000012295 chemical reaction liquid Substances 0.000 abstract description 4
- 238000006396 nitration reaction Methods 0.000 description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- MZRUFMBFIKGOAL-UHFFFAOYSA-N 5-nitro-1h-pyrazole Chemical compound [O-][N+](=O)C1=CC=NN1 MZRUFMBFIKGOAL-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000003226 pyrazolyl group Chemical group 0.000 description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000012013 faujasite Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- JCZMXVGQBBATMY-UHFFFAOYSA-N nitro acetate Chemical compound CC(=O)O[N+]([O-])=O JCZMXVGQBBATMY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- RSXKSXDNAQPZQD-UHFFFAOYSA-N 1,4-dinitropyrazole Chemical compound [O-][N+](=O)C=1C=NN([N+]([O-])=O)C=1 RSXKSXDNAQPZQD-UHFFFAOYSA-N 0.000 description 1
- YLTPBDJQPIRWTQ-UHFFFAOYSA-N 3,4,5-trinitro-1h-pyrazole Chemical compound [O-][N+](=O)C1=NNC([N+]([O-])=O)=C1[N+]([O-])=O YLTPBDJQPIRWTQ-UHFFFAOYSA-N 0.000 description 1
- VXMCBBMNFIAYQD-UHFFFAOYSA-N 4,5-dinitro-1h-pyrazole Chemical compound [O-][N+](=O)C=1C=NNC=1[N+]([O-])=O VXMCBBMNFIAYQD-UHFFFAOYSA-N 0.000 description 1
- LLNQWPTUJJYTTE-UHFFFAOYSA-N 4-iodopyrazole Chemical compound IC=1C=NNC=1 LLNQWPTUJJYTTE-UHFFFAOYSA-N 0.000 description 1
- RUKDVLFJSMVBLV-UHFFFAOYSA-N 5-iodo-1h-pyrazole Chemical class IC1=CC=NN1 RUKDVLFJSMVBLV-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 150000001543 aryl boronic acids Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- -1 nitrogen heterocyclic compound Chemical class 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000003612 virological effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/16—Halogen atoms or nitro radicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The invention discloses a preparation method of 4-nitropyrazole, which takes pyrazole as raw material, N-nitropyrazole and H2SO4The method for preparing 4-nitropyrazole by using nitrating agent comprises the following steps: 8ml of 98% sulfuric acid is taken in a four-mouth bottle, 0.012mol of pyrazole is dropwise added into concentrated sulfuric acid under the condition of mechanical stirring at the temperature of 20 ℃, after the feeding is finished, the temperature is raised to 60 ℃ in a water bath, 0.024mol of N-nitropyrazole is evenly and sequentially added into 4 parts at the temperature, the temperature rise phenomenon occurs in a reaction system in the feeding process, the feeding is carried out again after the temperature is lowered to the initial temperature, after the feeding is finished, the stirring is kept, the reaction is carried out at the constant temperature of 65 ℃ for 6 hours, the reaction liquid is poured into a container filled with ice blocks while the reaction liquid is hot, the solution is stirred to be lowered to 5 ℃, and white substances.
Description
Technical Field
The invention relates to the field of compound preparation, and particularly relates to a preparation method of 4-nitropyrazole.
Background
At present, 4-nitropyrazole is a typical nitrogen heterocyclic compound, the structure contains high-enthalpy C ═ C double bond and N-N single bond, the compound has the characteristics of high energy, low sensitivity, high density and the like, and is an important intermediate for synthesizing medicines, pesticides and nitropyrazole energetic compounds, 1, 4-dinitropyrazole can be synthesized by the 4-nitropyrazole through N-nitration, 3, 4-dinitropyrazole can be obtained through rearrangement, and 3,4, 5-trinitropyrazole can be obtained through further nitration. More nitropyrazole derivatives can be obtained through other substitution reactions.
Generally, fuming nitric acid-acetic anhydride or fuming nitric acid-concentrated sulfuric acid is used as a nitrating reagent for nitrating pyrazole, fuming nitric acid-acetic anhydride is used as the nitrating reagent for N-nitration of the pyrazole ring, and fuming nitric acid-concentrated sulfuric acid is used as the nitrating reagent for C-nitration of the pyrazole ring.
In the prior art, the preparation of 4-nitropyrazole mainly comprises:
1) n-nitropyrazole was rearranged in concentrated sulfuric acid at 90 ℃ for 24H (Rudolf Hutte, Friedrich Buchele. ber N-Nitro-pyrazole [ J ]. Chemische Berichte,1955,88(10): 1586. minus 1590.) or at room temperature for 20H (Nageswara Rao E, Ravi P, Tewari S P, et al, Experimental and the ecological studiose on the Structure and the viral properties of Nitro pyrazoles [ J ]. Journal of Molecular Structure,2013,1043(Complete 121. minus 131.).
2) 4-nitropyrazole is prepared by taking 4-iodopyrazole as a raw material, faujasite or silicon dioxide as a solid catalyst and fuming nitric acid as a nitrating agent in tetrahydrofuran solution (Ravi P, Tewari S P. Faujasite catalyzed nitration of iodopyrazoles [ J ]. Catalysis Communications,2013,42: 35-39; ravi, P.Experimental and DFT students on the Structure, isolated and Raman spectra properties of dipyridazoles [ J ]. Journal of Molecular Structure,2015.1079,433-447).
3) Pyrazole is taken as a raw material and directly reacts for 6h at 90 ℃ in mixed nitric and sulfuric acid (Kurpet M K, Dbrowska A, Jarossz M M, et al. coupling of C-nitro-NH-azoles with arylboronic acids. A route to N-aryl-C-nitroazoles [ J ]. Beilstein Journal of Organic Chemistry,2013,9(1): 1517-.
The reaction for preparing 4-nitropyrazole by the rearrangement method has the defects of long reaction time, higher reaction temperature and the like, the cost of the raw materials for synthesizing the catalyst method is high, and the direct nitration method fuming nitric acid-concentrated sulfuric acid can generate a large amount of nitrogen oxide gas and excessive waste acid to cause environmental pollution.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of 4-nitropyrazole, which has simple synthesis process, avoids using fuming nitric acid as a nitrating agent and has small environmental pollution.
In order to achieve the purpose, the invention adopts the technical scheme that:
a process for preparing 4-nitropyrazole from N-nitropyrazole and H2SO4The method for preparing 4-nitropyrazole by using nitrating agent comprises the following steps: 8ml of 98% sulfuric acid is taken in a four-mouth bottle, 0.012mol of pyrazole is dropwise added into concentrated sulfuric acid under the condition of mechanical stirring at the temperature of 20 ℃, after the feeding is finished, the temperature is raised to 60 ℃ in a water bath, 0.024mol of N-nitropyrazole is evenly and sequentially added into four parts at the temperature, the temperature rise phenomenon occurs in a reaction system in the feeding process, the feeding is carried out again after the temperature is lowered to the initial temperature, after the feeding is finished, the stirring is kept, the reaction is carried out at the constant temperature of 65 ℃ for 6 hours, the reaction liquid is poured into a container filled with ice blocks while the reaction liquid is hot, the solution is stirred to be lowered to 5 ℃, and white substances.
Further, the rotation speed of the mechanical stirring is 300-400 rpm.
The invention has the following beneficial effects:
the method takes the N-nitropyrazole and the sulfuric acid as the nitrating reagent, directly nitrates the pyrazole to obtain the 4-nitropyrazole, has rich raw material sources and low cost, avoids using mixed acid of nitric acid and sulfuric acid as the nitrating agent, does not generate pollution gas nitrogen oxide in the reaction process, does not generate waste acid, and has little pollution to the environment; furthermore, the preparation method provided by the invention has the advantages that the nitration reaction is carried out at the temperature of 65 ℃, the reaction condition is mild, the long-time reaction at high temperature is not needed, the requirement on reaction equipment is low, the purification is easy, and the purity of the obtained product is high.
Drawings
FIG. 1 is a schematic diagram of a synthesis scheme for preparing a target product in example 1 of the present invention;
FIG. 2 is an infrared spectrum of a target product prepared in example 1 of the present invention;
FIG. 3 is a NMR spectrum of a target product obtained in example 1 of the present invention;
FIG. 4 is a NMR carbon spectrum of a target product prepared in example 1 of the present invention;
FIG. 5 is a high performance liquid chromatography of the target product prepared in example 1 of the present invention;
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
The embodiment of the invention provides a preparation method of 4-nitropyrazole, which takes pyrazole as raw material, N-nitropyrazole and H2SO4The synthetic route of the 4-nitropyrazole prepared by the nitrating agent is shown in figure 1; the method specifically comprises the following steps: adding 98% sulfuric acid 8ml into a four-mouth bottle, dropwise adding pyrazole 0.012mol into concentrated sulfuric acid under the condition of mechanical stirring at the temperature of 20 ℃, heating to 60 ℃ in a water bath after feeding, uniformly adding N-nitropyrazole 0.024mol into four parts in sequence at the temperature, wherein the reaction system has a temperature rise phenomenon in the feeding process, feeding again after the temperature is reduced to the initial temperature, stirring after feeding, reacting at the constant temperature of 65 ℃ for 6 hours, pouring the reaction solution into a container filled with ice blocks while the solution is hot, stirring to reduce the temperature of the solution to 5 ℃, separating out white solid, recrystallizing with diethyl ether/hexane, and obtaining the yield65.3 percent, the melting point of the product is measured by an X-4B micro melting point instrument, the melting point of the product is 163-164 ℃ (the literature value is 163-165 ℃), and the product is primarily judged to be 4-nitropyrazole with the purity of 99.4 percent.
Table 1 results of elemental analysis of the objective product in example 1
The target product was subjected to elemental analysis and test, and the results are shown in Table 1, from which the found values and calculated values were substantially matched, and further determined to be 4-nitropyrazole.
TABLE 1 elemental analysis results of the target products
FIG. 2 is an infrared spectrum of the target product prepared in example 1, with the following data:
IR(KBr,v cm-1)3308cm-1an absorption peak is positioned at the peak position of N-H; at 3258cm-1And 3129cm-1An absorption peak is formed, which indicates the existence of a pyrazole ring; at 1561cm-1、1369cm-1Has strong absorption peak, and is proved to have C-NO2Is present.
FIG. 3 is a NMR spectrum of a target product obtained in example 1 of the present invention;
the solvent used for the test was deuterated dimethyl sulfoxide (DMSO-d 6). Chemical shifts of 8.808ppm and 8.292ppm should indicate hydrogen attached to the carbon at the 3,5 position and chemical shifts of 13.924ppm should indicate hydrogen attached to the nitrogen at the 1 position.
FIG. 4 is a NMR carbon spectrum of a target product prepared in example 1 of the present invention;
the solvent used for the test was deuterated dimethyl sulfoxide (DMSO-d 6). The 129.83ppm should represent the chemical shift of the same carbon at the 3,5 positions and the 135.84ppm should represent the chemical shift of the carbon at the 4 position.
FIG. 5 is a high performance liquid chromatography of the target product prepared in example 1 of the present invention;
chromatographic conditions are as follows: preparing solution containing target substance with chromatographic methanol at flow rate of 1.0 mL/min and water ratio of 80:20-1The ultraviolet absorption wavelength is 254nm, and the sample injection amount is 20 mu L. As shown in FIG. 5, the retention time of the target product was about 5.28min, and the purity of the product was 99.4% by area normalization.
In summary, the molecular structure of the measured target product is consistent with the molecular structure of 4-nitropyrazole, that is, the target product obtained in the embodiment 1 of the present invention is 4-nitropyrazole, and the purity of the product is 99.4%.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the present application may be combined with each other arbitrarily without conflict.
Claims (3)
1. A preparation method of 4-nitropyrazole is characterized in that: using pyrazole as raw material, N-nitropyrazole and H2SO44-nitropyrazole is prepared for the nitrating agent.
2. The process for the preparation of 4-nitropyrazole of claim 1 wherein: the method comprises the following steps: adding 0.012mol of pyrazole into concentrated sulfuric acid in a four-mouth bottle at the temperature of 20 ℃ under the condition of mechanical stirring by taking 8ml of 98% sulfuric acid, heating the mixture to 60 ℃ in a water bath after the charging is finished, adding 0.024mol of N-nitropyrazole into the mixture in turn at the temperature of 4 parts on average, wherein the reaction system has a temperature rise phenomenon in the charging process, charging the mixture again after the temperature is reduced to the initial temperature, keeping stirring after the charging is finished, reacting at the constant temperature of 65 ℃ for 6 hours, pouring the reaction solution into a container filled with ice blocks while the solution is hot, stirring the solution to reduce the temperature to 5 ℃, and separating out white substances.
3. The process for the preparation of 4-nitropyrazole of claim 2 wherein: the rotation speed of the mechanical stirring is 300-400 rpm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110374462.XA CN112939867A (en) | 2021-04-07 | 2021-04-07 | Preparation method of 4-nitropyrazole |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110374462.XA CN112939867A (en) | 2021-04-07 | 2021-04-07 | Preparation method of 4-nitropyrazole |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112939867A true CN112939867A (en) | 2021-06-11 |
Family
ID=76230501
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110374462.XA Pending CN112939867A (en) | 2021-04-07 | 2021-04-07 | Preparation method of 4-nitropyrazole |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112939867A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115825299A (en) * | 2022-11-24 | 2023-03-21 | 中北大学 | Purity analysis method of 1-methyl-3, 4, 5-trinitropyrazole |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107629003A (en) * | 2017-09-07 | 2018-01-26 | 中北大学 | A kind of preparation method of the nitropyrazole of 1 methyl 4 |
| CN108610291A (en) * | 2018-06-11 | 2018-10-02 | 中北大学 | A kind of preparation method of 3,4- binitropyrazoles |
| CN113072450A (en) * | 2021-04-07 | 2021-07-06 | 中北大学 | Preparation method of m-nitrochlorobenzene |
-
2021
- 2021-04-07 CN CN202110374462.XA patent/CN112939867A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107629003A (en) * | 2017-09-07 | 2018-01-26 | 中北大学 | A kind of preparation method of the nitropyrazole of 1 methyl 4 |
| CN108610291A (en) * | 2018-06-11 | 2018-10-02 | 中北大学 | A kind of preparation method of 3,4- binitropyrazoles |
| CN113072450A (en) * | 2021-04-07 | 2021-07-06 | 中北大学 | Preparation method of m-nitrochlorobenzene |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115825299A (en) * | 2022-11-24 | 2023-03-21 | 中北大学 | Purity analysis method of 1-methyl-3, 4, 5-trinitropyrazole |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2602968C (en) | Crystals of morphinan derivative and process for producing the same | |
| CN107629003A (en) | A kind of preparation method of the nitropyrazole of 1 methyl 4 | |
| CN112939867A (en) | Preparation method of 4-nitropyrazole | |
| CN113717082B (en) | Hydrazide material with photodegradation function and preparation method and application thereof | |
| CN109516986B (en) | 2,4,4,8, 8-pentanitro-2-azaadamantane and synthetic method thereof | |
| CN110922369B (en) | Trifluoromethyl substituted dihydrofuran amine compound and preparation method and application thereof | |
| JPH03106855A (en) | Preparation of aromatic amine | |
| CN115490698B (en) | 6-nitro-2-oxa-6-azaadamantane-4, 8-diol dinitrate and preparation method thereof | |
| CN110724080B (en) | Synthetic method of aryl selenium cyanogen compound | |
| CN113072450A (en) | Preparation method of m-nitrochlorobenzene | |
| Dong et al. | Vilsmeier-Haack Reaction of α-Oxo Ketene Dithioacetals to α-Chlorovinyl/Ethynyl Ketene Dithioacetals | |
| CN115043788A (en) | Trifluoromethyl oxazole-2-ketone compound and preparation method and application thereof | |
| CN111440198A (en) | 1,10 a-dihydro-2H-pyridine [1,2-d ] [1,4] sulfur nitrogen compound and preparation method thereof | |
| CN113582843A (en) | Preparation method of 5-chloro-2-fluoro-3-hydroxybenzoic acid ethyl ester | |
| Ji et al. | Base-promoted direct synthesis of sulfinates from N-sulfonylhydrazones under metal-free conditions | |
| CN114907279B (en) | Synthesis method of N-oxybenzene propyl triazole | |
| CN112062731A (en) | Synthesis method of 1-phenyl-5-mercapto tetrazole | |
| CN113061113A (en) | Preparation method of 4-nitroimidazole | |
| CN110776472B (en) | Preparation method of tetrahydrophenazine derivative | |
| CN113087629A (en) | Preparation method of 1, 5-dichloro-2, 4-dinitrobenzene | |
| CN113149844B (en) | Novel synthesis process of 2,4,6-trinitrobenzoic acid | |
| Gierczyk et al. | 15N NMR and FTIR studies of 2, 4-dinitroanilines and their salts | |
| CN115772105B (en) | Synthesis method of 4-nitroanisole | |
| CN111116613B (en) | Polysubstituted benzimidazole thiazole and derivative and synthesis method thereof | |
| CN111285846B (en) | 2- (2-indolyl) -acetate derivative and synthesis method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210611 |