CN85105850B - Preparation of nitro benzene-oxidized furan and its salt - Google Patents
Preparation of nitro benzene-oxidized furan and its salt Download PDFInfo
- Publication number
- CN85105850B CN85105850B CN85105850A CN85105850A CN85105850B CN 85105850 B CN85105850 B CN 85105850B CN 85105850 A CN85105850 A CN 85105850A CN 85105850 A CN85105850 A CN 85105850A CN 85105850 B CN85105850 B CN 85105850B
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- CN
- China
- Prior art keywords
- salt
- preparation
- nitro benzene
- sodium
- oxidized furan
- Prior art date
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 150000003839 salts Chemical class 0.000 title claims abstract description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 title abstract 14
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 title abstract 3
- 238000000034 method Methods 0.000 claims abstract description 9
- AGUIVNYEYSCPNI-UHFFFAOYSA-N N-methyl-N-picrylnitramine Chemical group [O-][N+](=O)N(C)C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O AGUIVNYEYSCPNI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 7
- 159000000009 barium salts Chemical class 0.000 claims abstract description 4
- -1 that the 4 Chemical compound 0.000 claims abstract 2
- OKEAMBAZBICIFP-UHFFFAOYSA-N 3-oxido-2,1,3-benzoxadiazol-3-ium Chemical compound C1=CC=CC2=[N+]([O-])ON=C21 OKEAMBAZBICIFP-UHFFFAOYSA-N 0.000 claims description 15
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 claims description 8
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- SFAXANKELJNWSA-UHFFFAOYSA-N 2-azido-1,3,5-trinitrobenzene Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=C(N=[N+]=[N-])C([N+]([O-])=O)=C1 SFAXANKELJNWSA-UHFFFAOYSA-N 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 3
- 238000007796 conventional method Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 208000006558 Dental Calculus Diseases 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 2
- 229940045511 barium chloride Drugs 0.000 claims description 2
- 229910001626 barium chloride Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000002798 polar solvent Substances 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 238000000197 pyrolysis Methods 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 7
- 239000002360 explosive Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 abstract 1
- 239000000047 product Substances 0.000 description 7
- HJRJRUMKQCMYDL-UHFFFAOYSA-N 1-chloro-2,4,6-trinitrobenzene Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=C(Cl)C([N+]([O-])=O)=C1 HJRJRUMKQCMYDL-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical class CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- VYZAHLCBVHPDDF-UHFFFAOYSA-N Dinitrochlorobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C([N+]([O-])=O)=C1 VYZAHLCBVHPDDF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004900 laundering Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
The present invention relates to a method for preparing military chemical material. Nitro benzene-oxidized furan is not only violent explosive but also an important explosive intermediate body. Sodium salt, potassium salt, barium salt, etc. of the nitro benzene-oxidized furan can be used as bursters. The existing preparation methods are not suitable for realizing industrial preparation. The present invention provides a novel method for preparing 4, 6-nitro benzene-oxidized furan by using tetryl which is easily obtained as raw material. The present invention also provides a preparation path of salt of the 4, 6-nitro benzene-oxidized furan, namely that the 4, 6-nitro benzene-oxidized furan prepared according to the method is used as an intermediate body, and the intermediate body is used for preparing the salt of the 4, 6-nitro benzene-oxidized furan. The method is simple, the yield is high, and the industrial preparation is easily carried out.
Description
The present invention is a kind of preparation method of military chemical material.
4,6-dinitrobenzene benzo furoxan is a kind of high explosive, and it still is a kind of important explosive intermediate, and its structural formula is (I), and salt such as its sodium, potassium, barium all can be made priming explosive,
Structure is (II), and sylvite detonates functional, detonates easily, and the barium salt sensitivity is low, and is high temperature resistant.
4,6-dinitrobenzene benzo furoxan had multiple preparation method in the past, abroad, and Australian author Spear, Robert J, Norris William P; Rcad Roger W, at Tech Note-Mater.Res, lab(Aust) 1983 MRL-TN-470 have delivered and have described the preparation of 4.6-dinitrobenzene benzo furoxan in the recent period, so far still make raw material with picryl chloride, by azide denitrogenation preparation again, but its preparation condition harshness of picryl chloride, be difficult to obtain: other method is to prepare by nitrated with the benzo furoxan, China author Lu Mingjiu, Liu Hong is in " war industry's journal " fire, change [fascicle 3 12(1982) publish an article, also prepare with this method, but this method long reaction time, yield is lower, and therefore above-mentioned two kinds of methods all are difficult for realizing suitability for industrialized production.
Purpose of the present invention is exactly with facile raw material-tetryl preparation 4,6-dinitrobenzene benzo furoxan, and with this as intermediate, prepare salt such as its sodium, potassium, barium.
4, the preparation method of 6-dinitrobenzene benzo furoxan: sodiumazide and tetryl are reacted in ethanol or other general polar solvents, the consumption of sodiumazide is 1～3 times of theoretical amount, stir down at 15～50 ℃, the thin up after-filtration can obtain faint yellow precipitation, and promptly 2,4,6-trinitro-phenylazide is added to pyrolysis denitrogenation in the acetate (temperature of reaction is about 100 ℃) with it, then cooling, thin up, after the yellow solid of separating out is washed after filtration, can obtain crude product 4,6-dinitrobenzene benzo furoxan, yield can reach more than 80% in tetryl.
Product structure obtains infrared spectra, ultimate analysis, the affirming of organic mass spectrometry and nuclear magnetic resonance spectrum.
Infrared (KBr compressing tablet, Perkin Elmer599B instrument); Measuring data is 3080Cm
-1(in); 1540,1345Cm
-1(by force); 1630,1560,1330Cm
-1(by force).Ultimate analysis: theoretical value C-31.86; H-0.88 N-24.78; Measured value C-32.24.32.30; H-0.92,0.87; N-24.67,24.57, mass spectrum (the FD source K-80GC/MC/DS of Hitachi instrument); Measuring molecular weight is 226, and nuclear-magnetism (deuterated acetone is a solvent PK-250 instrument) is measured data at ambient temperature: δ 9.07ppm(is unimodal), 9.05ppm(is unimodal) integral area ratio is 1: 1.
Embodiment: the ethanol and the 2.5 gram NaN that in 250 ml beakers, add 125 milliliter 95% under the room temperature
3, treat NaN
3Roughly add 5 gram tetryls after the dissolving in batches, add the back and heat up about 2 hours of 25～30 ℃ of reactions, thin up filters, and washs with massive laundering, dry faint yellow product 2,4,6-trinitro-phenylazide 4.0 grams (yield 90.4%).
With make above 2,4,6-trinitro-phenylazide placed the cylinder beaker, adds the pure acetate of 20ml, about 2 hours of 100 ℃ of reactions, till when not having nitrogen and emit, cooling back thin up with a large amount of yellow solids of separating out, obtains 3.3 grams after the washing oven dry after filtration, 4, the thick product of 6-dinitrobenzene benzo furoxan (yield＞90%).Thick product can be made with extra care according to a conventional method with chloroform or acetate.
4, the preparation method of 6-dinitrobenzene benzo furoxan salt: with the tetryl is that raw material is prepared intermediate 4 by above-mentioned condition, 6-dinitrobenzene benzo furoxan, and water with reaction of sodium bicarbonate, can make its sodium salt as medium about 50 ℃ again; As the aqueous solution of this sodium salt and the reactant aqueous solution of saltpetre or vitriolate of tartar can be made its sylvite, this sodium-salt aqueous solution is reacted with bariumchloride or barium nitrate aqueous solution again, can get its barium salt again, be to handle according to a conventional method.
The used basic raw material tetryl of the present invention is cheap Industrial products, raw material is easy to get, and the preparation method is simple, and preparation condition is less demanding, reaction times is shorter, and the yield height, compared with prior art, making the raw material that this product uses at present is picryl chloride, but picryl chloride preparation condition harshness, it by dinitrochlorobenzene about 150 ℃ with oleum and concentrated nitric acid is nitrated makes, generally only be adapted at prepared in laboratory, and the spent acid treatment capacity is big.In addition, the nitrated benzo furoxan of also available nitric-sulfuric acid makes this product, and condition is 0 ℃ feeds in raw material, insulation below 10 ℃ 3 hours, and room temperature was placed 3 days.Find out this long reaction time thus, and yield low (about 33%).Equally from tetryl through intermediate 4,6-dinitrobenzene benzo furoxan preparation 4, salts such as the sodium of 6-dinitrobenzene benzo furoxan, potassium, barium, industrial easy to implement, and cost is low.
Claims (1)
1, preparation 4,6-dinitrobenzene benzo furoxan and and sodium, potassium, the manufacture method of salt such as barium, it is characterized in that: sodiumazide and tetryl are reacted in ethanol or other general polar solvents, and the consumption of sodiumazide is 1～3 times of theoretical amount, and temperature of reaction is 15～50 ℃, make 2,4,6-trinitro-phenylazide, pyrolysis denitrogenation in acetate, temperature of reaction is about 100 ℃, cooling, thin up filters, promptly make 4,6-dinitrobenzene benzo furoxan, water is as medium, about 50 ℃ again, with reaction of sodium bicarbonate, can make its sodium salt, the aqueous solution of this sodium salt and the reactant aqueous solution of saltpetre or vitriolate of tartar can be made its sylvite, this sodium-salt aqueous solution is reacted with bariumchloride or barium nitrate aqueous solution again, can get its barium salt again, be to handle according to a conventional method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85105850A CN85105850B (en) | 1985-08-03 | 1985-08-03 | Preparation of nitro benzene-oxidized furan and its salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85105850A CN85105850B (en) | 1985-08-03 | 1985-08-03 | Preparation of nitro benzene-oxidized furan and its salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85105850A CN85105850A (en) | 1986-01-10 |
| CN85105850B true CN85105850B (en) | 1987-02-18 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85105850A Expired CN85105850B (en) | 1985-08-03 | 1985-08-03 | Preparation of nitro benzene-oxidized furan and its salt |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN85105850B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102952124B (en) * | 2011-08-23 | 2016-08-17 | 北京理工大学 | 3,4-double (1-hydrogen-5-tetrazole radical) furoxans are containing energy ion salt and preparation method thereof |
| CN103450108A (en) * | 2012-06-04 | 2013-12-18 | 南京理工大学 | Polyaminopolynitrobenzofuroxan metal complex and preparation method thereof |
| CN102702131A (en) * | 2012-06-29 | 2012-10-03 | 太仓市新星轻工助剂厂 | Method for synthesizing plasticizer 3-nitro furazan-4-methyl ether |
| CN107501293A (en) * | 2017-10-11 | 2017-12-22 | 中国工程物理研究院化工材料研究所 | Two furazano piperazine nitramine class energetic ion salt and its synthetic method |
-
1985
- 1985-08-03 CN CN85105850A patent/CN85105850B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN85105850A (en) | 1986-01-10 |
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