CN102241634A - Preparation method of 2-nitro-4,5-dicyan-1H-imidazole - Google Patents
Preparation method of 2-nitro-4,5-dicyan-1H-imidazole Download PDFInfo
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- CN102241634A CN102241634A CN2011101282336A CN201110128233A CN102241634A CN 102241634 A CN102241634 A CN 102241634A CN 2011101282336 A CN2011101282336 A CN 2011101282336A CN 201110128233 A CN201110128233 A CN 201110128233A CN 102241634 A CN102241634 A CN 102241634A
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Abstract
The invention discloses a preparation method of 2-nitro-4,5-dicyan-1H-imidazole. The structural formula of the 2-nitro-4,5-dicyan-1H-imidazole is shown as (I). 2-amino-4,5-dicyan-1H-imidazole is taken as a raw material of which the structural formula is shown as (II). The method comprises the following steps of: adding 2-amino-4,5-dicyan-1H-imidazole into a sodium nitrite aqueous solution at the temperature between 15 DEG C below zero and 0 DEG C; dropwise adding an acid solution; raising the temperature to 35-60 DEG C; reacting until no air bubble is produced; lowering the temperature of a reaction liquid to room temperature; extracting with ethyl acetate; drying with anhydrous magnesium sulfate; evaporating sodium nitrite serving as an eluent; and performing column chromatography to obtain 2-nitro-4,5-dicyan-1H-imidazole, wherein the molar ratio of the sodium nitrite to the 2-amino-4,5-dicyan-1H-imidazole is 5:1-15:1. The method is used for preparing 2-nitro-4,5-dicyan-1H-imidazole.
Description
Technical field
The present invention relates to a kind of 2-nitro-4, the preparation method of 5-dicyano-1H-imidazoles belongs to the field of chemical synthesis.
Background technology
The glyoxaline compound that nitro replaces has the characteristics to static, friction and bump insensitiveness and Heat stability is good, is the novel good insensitive explosive of a class.In recent years, both at home and abroad to 1,4-dinitrobenzene imidazoles, 2,4-dinitrobenzene imidazoles and 1-methyl-2,4,5-trinitro-imidazoles is studied, and finds that it can be used as energetic material and uses.Nitroimidazole compound still is the important intermediate during medicine synthesizes.2-nitro-4, the molecular structure of 5-dicyano-1H-imidazoles is to introduce nitro and cyano group on imidazole ring, make this compound have advantages such as low sense, high Enthalpies of Formation and Heat stability is good, can be used as novel contain can ion salt acid constituents and ligands for metal complexes such as novel combustioncatalysts lead, copper, be with a wide range of applications in the energetic material field.
" Stereoselective synthesis of dithymidine phosphorothioates using d-xylose derived chiralauxiliaries ", Tetrahedron, 2001,57:1677-1687 one literary composition discloses a kind of 2-nitro-4, the preparation method of 5-dicyano-1H-imidazoles, its preparation route is:
This method at ambient temperature, (5-dicyano-1H-imidazoles mixes with 30mL water for 1.33g, 2-amino-4 10mmol), and the concentrated hydrochloric acid that adds 7.5mL makes material dissolution.Ice-water bath cooling reaction solution, in above-mentioned solution, drip (0 ℃ was stirred 10 minutes, leached solid, got 2-diazonium-4 for 1g, the 14mmol) aqueous solution of Sodium Nitrite, the 5-dicyano imidazole, and its structural formula is shown in (III).Under the room temperature condition, in the reaction flask of compound III, drip the sodium nitrite in aqueous solution of equimolar amount, with thin-layer chromatography monitoring reaction process, after reaction finishes, through ethyl acetate extraction, drying, rapid column chromatography is purified and is obtained product 2-nitro-4,5-dicyano-1H-imidazoles, and the two-step reaction total recovery is 80%.But this method steps is more, and reaction yield is lower.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiencies in the prior art and defective, provides the less reaction yield again of a kind of not only step higher 2-nitro-4, the preparation method of 5-dicyano-1H-imidazoles.
Preparation route of the present invention is:
In order to solve the problems of the technologies described above, 2-nitro-4 of the present invention, the preparation method of 5-dicyano-1H-imidazoles, its structural formula is shown in (I), and the present invention is with 2-amino-4, and 5-dicyano-1H-imidazoles is a raw material, and its structural formula comprises that step is as follows shown in (II):
In temperature is under-15 ℃~0 ℃, with 2-amino-4,5-dicyano-1H-imidazoles joins in the sodium nitrite in aqueous solution, after dripping acid solution, be warming up to 35 ℃~60 ℃ of temperature, reaction is reduced to room temperature with reacting liquid temperature till do not have bubble and produce, with ethyl acetate extraction 6 times, each 50mL, behind the anhydrous magnesium sulfate drying extraction liquid, steam ethyl acetate and get crude product, with the ethyl acetate eluent, get product 2-nitro-4 through column chromatography, 5-dicyano-1H-imidazoles, wherein Sodium Nitrite and 2-amino-4, the mol ratio of 5-dicyano-1H-imidazoles is 5: 1~15: 1.
2-nitro-4, the described acid solution of preparation method of 5-dicyano-1H-imidazoles is the aqueous solution of sulfuric acid, hydrochloric acid, nitric acid and acetic acid.Monoprotic acid (example hydrochloric acid, nitric acid and acetic acid) and 2-amino-4, the mol ratio of 5-dicyano-1H-imidazoles is 2: 1~2.5: 1.Diprotic acid (as sulfuric acid) and 2-amino-4, the mol ratio of 5-dicyano-1H-imidazoles is 1: 1~1.25: 1.The concentration of acid is 1%~20% (quality).
A kind of preferred 2-nitro-4, the preparation method of 5-dicyano-1H-imidazoles, comprise that step is as follows: under temperature is-10 ℃, with 2.058g, 15mmol 2-amino-4,5-dicyano-1H-imidazoles joins and contains 10.455g, in the 24mL aqueous solution of 150mmol Sodium Nitrite, drip 12.045g, behind the hydrochloric acid soln of 33mmol 10% (quality), be warming up to 40 ℃ of temperature, reaction is reduced to room temperature with reacting liquid temperature till do not have bubble and produce, with ethyl acetate extraction 6 times, each 50mL, behind the anhydrous magnesium sulfate drying extraction liquid, steam ethyl acetate and get crude product, with the ethyl acetate eluent, get product 2-nitro-4 through column chromatography, 5-dicyano-1H-imidazoles.
Advantage of the present invention:
2-nitro-4 of the present invention, preparation method's step of 5-dicyano-1H-imidazoles is less, be a step only, and the disclosed preparation method of documents is two steps; Preparation method's provided by the invention yield is higher, and it can reach 90.5%, and the disclosed preparation method's of documents overall yield of reaction 80%.
Embodiment:
Below in conjunction with embodiment the present invention is described in further detail.
Below be the embodiment that the contriver provides, need to prove that these embodiment are more excellent examples, be mainly used in and understand the present invention, but the invention is not restricted to these embodiment.
Embodiment 1:
In the 100mL round-bottomed flask, add 10.455g, the Sodium Nitrite of 150mmol and 24mL water, stir settled solution, cryosel is bathed the cooling reaction solution to temperature-10 ℃, adds 2.058g in flask, the 2-amino-4 of 15mmol, 5-dicyano-1H-imidazoles, drip 12.045g, the hydrochloric acid soln of 33mmol 10% (quality) is after dropwising, make reacting liquid temperature be warming up to 40 ℃ of temperature, have bubble to produce in the reaction process, reaction is reduced to room temperature with reacting liquid temperature till do not have bubble and produce, with ethyl acetate extraction 6 times, each 50mL behind the anhydrous magnesium sulfate drying extraction liquid, steams ethyl acetate and gets crude product, with the ethyl acetate is eluent, get product 2-nitro-4 through column chromatography, 5-dicyano-1H-imidazoles, yield 90.5%.
Structure is identified:
IR(KBr,cm
-1):3474,3384,3303,2250,1689,1550,1458,1424,1397,1310,1263,1145,850,719,698,675,648,595,527。
15N?NMR(DMSO-d
6,50MHz,δ):263.31,268.61,360.73。
13C?NMR(DMSO-d
6,125MHz,δ):114.18(2C),119.23(2C),156.82(1C)。
Above-mentioned appraising datum confirms material that preparation method of the present invention obtains 2-nitro-4 really, 5-dicyano-1H-imidazoles.
Embodiment 2:
In the 500mL round-bottomed flask, add 5.228g, the Sodium Nitrite of 75mmol and 12mL water, stir settled solution, cryosel is bathed the cooling reaction solution to temperature-15 ℃, adds 2.058g in flask, the 2-amino-4 of 15mmol, 5-dicyano-1H-imidazoles, drip 189.000g, the salpeter solution of 30mmol 1% (quality) is after dropwising, make reacting liquid temperature be warming up to 35 ℃ of temperature, have bubble to produce in the reaction process, reaction is reduced to room temperature with reacting liquid temperature till do not have bubble and produce, with ethyl acetate extraction 6 times, each 50mL behind the anhydrous magnesium sulfate drying extraction liquid, steams ethyl acetate and gets crude product, with the ethyl acetate is eluent, get product 2-nitro-4 through column chromatography, 5-dicyano-1H-imidazoles, yield 86.9%.
Embodiment 3:
In the 250mL round-bottomed flask, add 15.683g, the Sodium Nitrite of 225mmol and 36mL water, stir settled solution, cryosel is bathed the cooling reaction solution to temperature-5 ℃, adds 2.058g in flask, the 2-amino-4 of 15mmol, 5-dicyano-1H-imidazoles, drip 42.000g, the acetum of 35mmol 5% (quality) is after dropwising, make reacting liquid temperature be warming up to 45 ℃ of temperature, have bubble to produce in the reaction process, reaction is reduced to room temperature with reacting liquid temperature till do not have bubble and produce, with ethyl acetate extraction 6 times, each 50mL behind the anhydrous magnesium sulfate drying extraction liquid, steams ethyl acetate and gets crude product, with the ethyl acetate is eluent, get product 2-nitro-4 through column chromatography, 5-dicyano-1H-imidazoles, yield 90.2%.
Embodiment 4:
In the 50mL round-bottomed flask, add 10.455g, the Sodium Nitrite of 150mmol and 24mL water, stir settled solution, ice-water bath cooling reaction solution adds 2.058g, the 2-amino-4 of 15mmol to 0 ℃ of temperature in flask, 5-dicyano-1H-imidazoles, Dropwise 5 .840g, the hydrochloric acid soln of 32mmol 20% (quality) is after dropwising, make reacting liquid temperature be warming up to 50 ℃ of temperature, have bubble to produce in the reaction process, reaction is reduced to room temperature with reacting liquid temperature till do not have bubble and produce, with ethyl acetate extraction 6 times, each 50mL behind the anhydrous magnesium sulfate drying extraction liquid, steams ethyl acetate and gets crude product, with the ethyl acetate is eluent, get product 2-nitro-4 through column chromatography, 5-dicyano-1H-imidazoles, yield 88.7%.
Embodiment 5:
In the 100mL round-bottomed flask, add 12.546g, the Sodium Nitrite of 180mmol and 29mL water, stir settled solution, cryosel is bathed the cooling reaction solution to temperature-8 ℃, adds 2.058g in flask, the 2-amino-4 of 15mmol, 5-dicyano-1H-imidazoles, drip 9.125g, the hydrochloric acid soln of 37.5mmol 15% (quality) is after dropwising, make reacting liquid temperature be warming up to 60 ℃ of temperature, have bubble to produce in the reaction process, reaction is reduced to room temperature with reacting liquid temperature till do not have bubble and produce, with ethyl acetate extraction 6 times, each 50mL behind the anhydrous magnesium sulfate drying extraction liquid, steams ethyl acetate and gets crude product, with the ethyl acetate is eluent, get product 2-nitro-4 through column chromatography, 5-dicyano-1H-imidazoles, yield 90.0%.
Embodiment 6:
In the 100mL round-bottomed flask, add 10.455g, the Sodium Nitrite of 150mmol and 24mL water, stir settled solution, cryosel is bathed the cooling reaction solution to temperature-4 ℃, adds 2.058g in flask, the 2-amino-4 of 15mmol, 5-dicyano-1H-imidazoles, drip 32.340g, the sulphuric acid soln of 16.5mmol 5% (quality) is after dropwising, make reacting liquid temperature be warming up to 50 ℃ of temperature, have bubble to produce in the reaction process, reaction is reduced to room temperature with reacting liquid temperature till do not have bubble and produce, with ethyl acetate extraction 6 times, each 50mL behind the anhydrous magnesium sulfate drying extraction liquid, steams ethyl acetate and gets crude product, with the ethyl acetate is eluent, get product 2-nitro-4 through column chromatography, 5-dicyano-1H-imidazoles, yield 89.1%.
Embodiment 7:
In the 250mL round-bottomed flask, add 6.970g, the Sodium Nitrite of 100mmol and 16mL water, stir settled solution, cryosel is bathed the cooling reaction solution to temperature-2 ℃, adds 2.058g in flask, the 2-amino-4 of 15mmol, 5-dicyano-1H-imidazoles, drip 73.500g, the sulphuric acid soln of 15mmol 2% (quality) is after dropwising, make reacting liquid temperature be warming up to 55 ℃ of temperature, have bubble to produce in the reaction process, reaction is reduced to room temperature with reacting liquid temperature till do not have bubble and produce, with ethyl acetate extraction 6 times, each 50mL behind the anhydrous magnesium sulfate drying extraction liquid, steams ethyl acetate and gets crude product, with the ethyl acetate is eluent, get product 2-nitro-4 through column chromatography, 5-dicyano-1H-imidazoles, yield 88.6%.
Embodiment 8:
In the 250mL round-bottomed flask, add 10.455g, the Sodium Nitrite of 150mmol and 24mL water, stir settled solution, cryosel is bathed the cooling reaction solution to temperature-6 ℃, adds 2.058g in flask, the 2-amino-4 of 15mmol, 5-dicyano-1H-imidazoles, drip 12.250g, the sulphuric acid soln of 18.75mmol 15% (quality) is after dropwising, make reacting liquid temperature be warming up to 40 ℃ of temperature, have bubble to produce in the reaction process, reaction is reduced to room temperature with reacting liquid temperature till do not have bubble and produce, with ethyl acetate extraction 6 times, each 50mL behind the anhydrous magnesium sulfate drying extraction liquid, steams ethyl acetate and gets crude product, with the ethyl acetate is eluent, get product 2-nitro-4 through column chromatography, 5-dicyano-1H-imidazoles, yield 89.8%.
Claims (5)
1. 2-nitro-4, the preparation method of 5-dicyano-1H-imidazoles, its structural formula is shown in (I), and the present invention is with 2-amino-4, and 5-dicyano-1H-imidazoles is a raw material, and its structural formula comprises that step is as follows shown in (II):
In temperature is-15 ℃~0 ℃, with 2-amino-4,5-dicyano-1H-imidazoles joins in the sodium nitrite in aqueous solution, after dripping acid solution, be warming up to 35 ℃~60 ℃ of temperature, reaction is reduced to room temperature with reacting liquid temperature till do not have bubble and produce, with ethyl acetate extraction 6 times, each 50mL, behind the anhydrous magnesium sulfate drying extraction liquid, steam ethyl acetate and get crude product, ethyl acetate is an eluent, get 2-nitro-4 through column chromatography, 5-dicyano-1H-imidazoles, wherein Sodium Nitrite and 2-amino-4, the mol ratio of 5-dicyano-1H-imidazoles is 5: 1~15: 1.
2. 2-nitro-4 as claimed in claim 1, the preparation method of 5-dicyano-1H-imidazoles is characterized in that: acid solution is the aqueous solution of sulfuric acid, hydrochloric acid, nitric acid or acetic acid.
3. 2-nitro-4 as claimed in claim 1, the preparation method of 5-dicyano-1H-imidazoles is characterized in that: hydrochloric acid, nitric acid or acetic acid and 2-amino-4, the mol ratio of 5-dicyano-1H-imidazoles is 2: 1~2.5: 1; Sulfuric acid and 2-amino-4, the mol ratio of 5-dicyano-1H-imidazoles is 1: 1~1.25: 1.
4. 2-nitro-4 as claimed in claim 1, the preparation method of 5-dicyano-1H-imidazoles is characterized in that: the concentration of acid is 1%~20% (quality).
5. 2-nitro-4 as claimed in claim 1, the preparation method of 5-dicyano-1H-imidazoles, comprise that step is as follows: under temperature is-10 ℃, with 2.058g, 15mmol 2-amino-4,5-dicyano-1H-imidazoles joins and contains 10.455g, in the 24mL aqueous solution of 150mmol Sodium Nitrite, drip 12.045g, behind the hydrochloric acid soln of 33mmol 10% (quality), be warming up to 40 ℃ of temperature, reaction is reduced to room temperature with reacting liquid temperature till do not have bubble and produce, with ethyl acetate extraction 6 times, each 50mL, behind the anhydrous magnesium sulfate drying extraction liquid, steam ethyl acetate and get crude product, ethyl acetate is an eluent, get 2-nitro-4 through column chromatography, 5-dicyano-1H-imidazoles.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102952077A (en) * | 2011-08-23 | 2013-03-06 | 北京理工大学 | Preparation method and performance calculation for 2-(dinitromethyl)-3-nitro-1,3-diazacyclo-pent-1-ene ionic salt containing energy |
CN115385860A (en) * | 2022-07-20 | 2022-11-25 | 西安近代化学研究所 | Method for synthesizing 2-cyano-5-aryl-1H-imidazole compound |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3287468A (en) * | 1964-11-17 | 1966-11-22 | Hoffmann La Roche | 2-nitroimidazoles and process |
JP2001122861A (en) * | 1999-10-21 | 2001-05-08 | Mitsubishi Chemicals Corp | Production of 2-nitroimidazole and extraction thereof |
CN1461749A (en) * | 2002-05-28 | 2003-12-17 | 上海依福瑞实业有限公司 | Preparation method of 2-nitroimidazole |
CN101747281A (en) * | 2009-12-25 | 2010-06-23 | 武汉嘉特利佰联创科技有限公司 | Method for preparing 2-nitroimidazole |
-
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3287468A (en) * | 1964-11-17 | 1966-11-22 | Hoffmann La Roche | 2-nitroimidazoles and process |
JP2001122861A (en) * | 1999-10-21 | 2001-05-08 | Mitsubishi Chemicals Corp | Production of 2-nitroimidazole and extraction thereof |
CN1461749A (en) * | 2002-05-28 | 2003-12-17 | 上海依福瑞实业有限公司 | Preparation method of 2-nitroimidazole |
CN101747281A (en) * | 2009-12-25 | 2010-06-23 | 武汉嘉特利佰联创科技有限公司 | Method for preparing 2-nitroimidazole |
Non-Patent Citations (1)
Title |
---|
吴义杰等: "2-硝基咪唑的制备", 《中国医药工业杂志》, vol. 25, no. 4, 31 December 1994 (1994-12-31), pages 181 - 184 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102952077A (en) * | 2011-08-23 | 2013-03-06 | 北京理工大学 | Preparation method and performance calculation for 2-(dinitromethyl)-3-nitro-1,3-diazacyclo-pent-1-ene ionic salt containing energy |
CN115385860A (en) * | 2022-07-20 | 2022-11-25 | 西安近代化学研究所 | Method for synthesizing 2-cyano-5-aryl-1H-imidazole compound |
CN115385860B (en) * | 2022-07-20 | 2024-05-10 | 西安近代化学研究所 | Method for synthesizing 2-cyano-5-aryl-1H-imidazole compound |
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