CN104262266A - Synthetic method of 1,4-diformyl-2,3,5,6-tetrahydroxypiperazine - Google Patents
Synthetic method of 1,4-diformyl-2,3,5,6-tetrahydroxypiperazine Download PDFInfo
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- CN104262266A CN104262266A CN201410528360.9A CN201410528360A CN104262266A CN 104262266 A CN104262266 A CN 104262266A CN 201410528360 A CN201410528360 A CN 201410528360A CN 104262266 A CN104262266 A CN 104262266A
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- diformyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
- C07D241/04—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
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Abstract
The invention discloses a synthetic method of 1,4-diformyl-2,3,5,6-tetrahydroxypiperazine. The 1,4-diformyl-2,3,5,6-tetrahydroxypiperazine is shown in structural formula in the specification. The synthetic method comprises the following steps: adding glyoxal aqueous solution and formamide in a reaction vessel according to the molar ratio of 1: (0.5-2), stirring and fully mixing; dropwise adding organic alkali in which the molar ratio of water to glyoxal is 100: (6-15), controlling the temperature within 30-60 DEG C and immediately generating white precipitates after the completion of dropwise adding within 5-10 minutes, filtering, washing the precipitates with water and an organic solvent and drying to obtain the 1,4-diformyl,3,5,6-tetrahydroxypiperazine. The synthetic method is used for the preparation of the 1,4-diformyl-2,3,5,6-tetrahydroxypiperazine.
Description
Technical field
The present invention relates to a kind of synthetic method of piperazine compounds, particularly relate to a kind of synthetic method of Isosorbide-5-Nitrae-diformyl-2,3,5,6-tetrahydroxy piperazine.
Background technology
4,10-dinitrobenzene-2,6,8,12-tetra-oxa--4,10-diaza Fourth Ring [5,5,0,0
5.90
3.11] dodecane (TEX) is a kind of typical caged insensitive high energy explosive.Polynuclear plane makes TEX energy high, and high detonation and immunity thereof make it in casting and pressed explosive, have very large using value.TEX can by nitrated the obtaining of Isosorbide-5-Nitrae-diformyl-2,3,5,6-tetrahydroxy piperazine (THDFP).Document [.4,10-dinitrobenzene-2,6,8,12-tetra-oxa--4, the 10-diaza Fourth Ring [5,5,0,0 such as Cui Kejian, Xu Zhibin, Shi Yuhui
5.90
3.11] synthesis [J] of dodecane. Beijing Institute of Technology's journal, 2013, the synthetic method of the THDFP 33 (4): 413-415.] reported is for raw material with 40% glyoxal water solution and methane amide, NaOH makes catalyzer, in glyoxal water solution, first add NaOH solution regulate PH to 9, methane amide solid is added after stirring 10min, be warming up to 50 ~ 60 DEG C again, to occurring white solid, stop heating, be cooled to less than 25 DEG C, stopped reaction after stirring 15min, precipitates and obtain THDFP sterling after 0.1mol/L dilute hydrochloric acid solution is refining.This synthetic method product yield lower (68%), need through complicated polishing purification, product loss is serious, product purity also can only reach 98%, and synthesis cycle long (3 hours), in building-up process, the amount of catalyst n aOH is difficult to control by regulating PH, and the heating of the reaction needed external world just can complete in addition.
Summary of the invention
The technical problem to be solved in the present invention is the defect for prior art, the invention provides that a kind of productive rate is high, purity is high, synthesis cycle is short, the synthetic method of building-up process simple Isosorbide-5-Nitrae-diformyl-2,3,5,6-tetrahydroxy piperazine.
For solving the problems of the technologies described above, the invention provides a kind of synthetic method of Isosorbide-5-Nitrae-diformyl-2,3,5,6-tetrahydroxy piperazine, the structural formula of Isosorbide-5-Nitrae-diformyl-2,3,5,6-tetrahydroxy piperazine is as shown in the formula shown in (1):
Synthetic route of the present invention is as shown in the formula shown in (2):
This synthetic method comprises the following steps: add glyoxal water solution and methane amide in reaction vessel, stirs after making it fully mix, dropwise adds organic bases; control temperature is at 30 ~ 60 DEG C; after within 5 ~ 10 minutes, dropwising, there is white precipitate immediately, filtered while hot; precipitation is through water and organic solvent washing; Isosorbide-5-Nitrae-diformyl-2,3 is obtained after oven dry; 5,6-tetrahydroxy piperazine.
Above-mentioned synthetic method, described organic bases is triethylamine, piperidines or liquid methanol sodium.
Above-mentioned synthetic method, described organic solvent is methyl alcohol, ethanol or acetone.
Preferred technical scheme is: add glyoxal water solution and methane amide in reaction vessel, stirs after making it fully mix, dropwise adds triethylamine, control temperature is at 45 DEG C, after within 8 minutes, dropwising, there is white precipitate immediately, filtered while hot, precipitation is through water and washing with alcohol, Isosorbide-5-Nitrae-diformyl-2,3 is obtained after oven dry, 5,6-tetrahydroxy piperazine; Wherein oxalic dialdehyde is 1:1 with the mol ratio of methane amide, and oxalic dialdehyde is 100:7.5 with the mol ratio of triethylamine.
Advantage of the present invention: the synthetic yield of (1) Isosorbide-5-Nitrae-diformyl-2,3,5,6-of the present invention tetrahydroxy piperazine is 80%, higher than documents reported values (68%); (2) high purity 99.5% of Isosorbide-5-Nitrae-diformyl-2,3,5,6-tetrahydroxy piperazine of the present invention's synthesis, higher than documents report method sintetics purity (98%); (3) of the present invention 1,4-diformyl-2, the synthesising reacting time of 3,5,6-tetrahydroxy piperazine is short, just react completely after adding organic bases, reaction terminates rear filtered while hot, precipitates and can obtain very pure product through water and organic solvent washing, eliminates treating process complicated in document, thus shortening synthesis cycle, synthesis cycle only has 15min; (4) utilize exothermic heat of reaction to be naturally warmed up to temperature of reaction in the building-up process of Isosorbide-5-Nitrae-diformyl-2,3,5,6-tetrahydroxy piperazine of the present invention, eliminate the extraneous heating method of the complexity of bibliographical information; (5) in the building-up process of Isosorbide-5-Nitrae-diformyl-2,3,5,6-tetrahydroxy piperazine of the present invention, the amount of catalyzer alkali does not need to control by measuring PH, but adds by certain ingredient proportion, simplifies operating process.
Embodiment
Below in conjunction with embodiment, the present invention is elaborated:
Embodiment 1
Glyoxal water solution and 45g (1.0mol) methane amide of 145g 40% (1.0mol) is added in three mouthfuls of round-bottomed flasks of 500ml, after stirring makes it fully mix, dropwise add 10ml (0.075mol) triethylamine, control temperature at 45 DEG C, after within 8 minutes, dropwising, there is white precipitate immediately, filtered while hot, precipitates through water and washing with alcohol, obtains white powdery solids 82.5g after oven dry, purity 99.5%, productive rate 80%.
Fusing point: 192 ~ 195 DEG C (literature values 196 DEG C).
Structural Identification:
1HNMR(DMSO-d
6，δ/ppm)：δ8.26(s，2H)，δ6.04(s，2H)，δ5.92(s，2H)，δ5.46(s，2H)，δ4.98(s，2H)。
13CNMR(DMSO-d
6，δ/ppm)，δ：164.4，164.3，79.3，78.9，72.5，72.2。
Ultimate analysis (C
6h
10n
2o
6):
Mass spectrum: MS (m/e) 206 (M
+).
The material that said structure appraising datum proved synthetic method obtains is Isosorbide-5-Nitrae-diformyl-2,3,5,6-tetrahydroxy piperazine really.
Embodiment 2
Glyoxal water solution and 45g (1.0mol) methane amide of 145g 40% (1.0mol) is added in three mouthfuls of round-bottomed flasks of 500ml, after stirring makes it fully mix, dropwise add 12ml (0.09mol) triethylamine, control temperature at 45 DEG C, after within 10 minutes, dropwising, there is white precipitate immediately, filtered while hot, precipitates through water and washing with alcohol, obtains white powdery solids 78.2g after oven dry, purity 99%, productive rate 75.9%.
Embodiment 3
Glyoxal water solution and 45g (1.0mol) methane amide of 145g 40% (1.0mol) is added in three mouthfuls of round-bottomed flasks of 500ml, after stirring makes it fully mix, dropwise add 8ml (0.06mol) triethylamine, control temperature at 45 DEG C, after within 5 minutes, dropwising, there is white precipitate immediately, filtered while hot, precipitates through water and washing with alcohol, obtains white powdery solids 75.2g after oven dry, purity 99.2%, productive rate 73%.
Embodiment 4
Glyoxal water solution and 54g (1.2mol) methane amide of 145g 40% (1.0mol) is added in three mouthfuls of round-bottomed flasks of 500ml, after stirring makes it fully mix, dropwise add 10ml (0.075mol) triethylamine, control temperature at 45 DEG C, after within 8 minutes, dropwising, there is white precipitate immediately, filtered while hot, precipitates through water and washing with alcohol, obtains white powdery solids 82.6g after oven dry, purity 99.4%, productive rate 80.2%.
Embodiment 5
Glyoxal water solution and 90g (2.0mol) methane amide of 145g 40% (1.0mol) is added in three mouthfuls of round-bottomed flasks of 500ml, after stirring makes it fully mix, dropwise add 10ml (0.075mol) triethylamine, control temperature at 45 DEG C, after within 8 minutes, dropwising, there is white precipitate immediately, filtered while hot, precipitates through water and washing with alcohol, obtains white powdery solids 83g after oven dry, purity 99.3%, productive rate 80.5%.
Embodiment 6
Glyoxal water solution and 45g (1.0mol) methane amide of 174g 40% (1.2mol) is added in three mouthfuls of round-bottomed flasks of 500ml, after stirring makes it fully mix, dropwise add 10ml (0.075mol) triethylamine, control temperature at 45 DEG C, after within 8 minutes, dropwising, there is white precipitate immediately, filtered while hot, precipitates through water and washing with alcohol, obtains white powdery solids 82g after oven dry, purity 99.5%, productive rate 79.6%.
Embodiment 7
Glyoxal water solution and 45g (1.0mol) methane amide of 290g 40% (2.0mol) is added in three mouthfuls of round-bottomed flasks of 500ml, after stirring makes it fully mix, dropwise add 10ml (0.075mol) triethylamine, control temperature at 45 DEG C, after within 8 minutes, dropwising, there is white precipitate immediately, filtered while hot, precipitates through water and washing with alcohol, obtains white powdery solids 82.5g after oven dry, purity 99.4%, productive rate 80%.
Embodiment 8
Glyoxal water solution and 45g (1.0mol) methane amide of 145g 40% (1.0mol) is added in three mouthfuls of round-bottomed flasks of 500ml, after stirring makes it fully mix, dropwise add 10ml (0.075mol) triethylamine, control temperature at 60 DEG C, after within 8 minutes, dropwising, there is white precipitate immediately, filtered while hot, precipitates through water and washing with alcohol, obtains white powdery solids 78g after oven dry, purity 99%, productive rate 75.7%.
Embodiment 9
Glyoxal water solution and 45g (1.0mol) methane amide of 145g 40% (1.0mol) is added in three mouthfuls of round-bottomed flasks of 500ml, after stirring makes it fully mix, dropwise add 10ml (0.075mol) triethylamine, control temperature at 30 DEG C, after within 8 minutes, dropwising, there is white precipitate immediately, filtered while hot, precipitates through water and washing with alcohol, obtains white powdery solids 75g after oven dry, purity 99.2%, productive rate 72.8%.
Embodiment 10
Glyoxal water solution and 45g (1.0mol) methane amide of 145g 40% (1.0mol) is added in three mouthfuls of round-bottomed flasks of 500ml, after stirring makes it fully mix, dropwise add 10ml (0.1mol) piperidines, at 45 DEG C, after within 5 minutes, dropwising, there is white precipitate immediately in control temperature, precipitation is through water and washing with alcohol, white powdery solids 58g is obtained, purity 96.8%, productive rate 56.3% after oven dry.
Embodiment 11
Glyoxal water solution and 45g (1.0mol) methane amide of 145g 40% (1.0mol) is added in three mouthfuls of round-bottomed flasks of 500ml, after stirring makes it fully mix, dropwise add 12ml (0.12mol) piperidines, at 45 DEG C, after within 8 minutes, dropwising, there is white precipitate immediately in control temperature, precipitation is through water and washing with alcohol, white powdery solids 73g is obtained, purity 98.5%, productive rate 71.2% after oven dry.
Embodiment 12
Glyoxal water solution and 45g (1.0mol) methane amide of 145g 40% (1.0mol) is added in three mouthfuls of round-bottomed flasks of 500ml, after stirring makes it fully mix, dropwise add 15ml (0.15mol) piperidines, control temperature at 45 DEG C, after within 10 minutes, dropwising, there is white precipitate immediately, filtered while hot, precipitates through water and washing with alcohol, obtains white powdery solids 65g after oven dry, purity 97.5%, productive rate 63%.
Embodiment 13
Glyoxal water solution and 45g (1.0mol) methane amide of 145g 40% (1.0mol) is added in three mouthfuls of round-bottomed flasks of 500ml, after stirring makes it fully mix, dropwise add 10ml (0.075mol) liquid methanol sodium, control temperature at 45 DEG C, after within 5 minutes, dropwising, there is white precipitate immediately, filtered while hot, precipitates through water and washing with alcohol, obtains white powdery solids 62g after oven dry, purity 98.3%, productive rate 60.2%.
Embodiment 14
Glyoxal water solution and 45g (1.0mol) methane amide of 145g 40% (1.0mol) is added in three mouthfuls of round-bottomed flasks of 500ml, after stirring makes it fully mix, dropwise add 16ml (0.12mol) liquid methanol sodium, control temperature at 45 DEG C, after within 8 minutes, dropwising, there is white precipitate immediately, filtered while hot, precipitates through water and washing with alcohol, obtains white powdery solids 72g after oven dry, purity 98.5%, productive rate 70%.
Embodiment 15
Glyoxal water solution and 45g (1.0mol) methane amide of 145g 40% (1.0mol) is added in three mouthfuls of round-bottomed flasks of 500ml, after stirring makes it fully mix, dropwise add 20ml (0.15mol) liquid methanol sodium, control temperature at 45 DEG C, after within 10 minutes, dropwising, there is white precipitate immediately, filtered while hot, precipitates through water and washing with alcohol, obtains white powdery solids 68g after oven dry, purity 97.5%, productive rate 66%.
Embodiment 16
Glyoxal water solution and 45g (1.0mol) methane amide of 145g 40% (1.0mol) is added in three mouthfuls of round-bottomed flasks of 500ml, after stirring makes it fully mix, dropwise add 10ml (0.075mol) triethylamine, control temperature at 45 DEG C, after within 8 minutes, dropwising, there is white precipitate immediately, filtered while hot, precipitates through water and methanol wash, obtains white powdery solids 82.5g after oven dry, purity 99.4%, productive rate 80%.
Embodiment 17
Glyoxal water solution and 45g (1.0mol) methane amide of 145g 40% (1.0mol) is added in three mouthfuls of round-bottomed flasks of 500ml, after stirring makes it fully mix, dropwise add 10ml (0.075mol) triethylamine, control temperature at 45 DEG C, after within 8 minutes, dropwising, there is white precipitate immediately, filtered while hot, precipitates through water and washing with acetone, obtains white powdery solids 82.3g after oven dry, purity 99.5%, productive rate 79.8%.
Claims (4)
1. the synthetic method of Isosorbide-5-Nitrae-diformyl-2,3,5,6-tetrahydroxy piperazine, the structural formula of Isosorbide-5-Nitrae-diformyl-2,3,5,6-tetrahydroxy piperazine is as shown in the formula shown in (1):
With glyoxal water solution and methane amide for raw material, comprise the following steps: in reaction vessel, add glyoxal water solution and methane amide, stir after making it fully mix, dropwise add organic bases, control temperature at 30 ~ 60 DEG C, after within 5 ~ 10 minutes, dropwising, there is white precipitate immediately, filtered while hot, precipitates through water and organic solvent washing, obtains 1 after oven dry, 4-diformyl-2,3,5,6-tetrahydroxy piperazine; Wherein oxalic dialdehyde is 1:0.5 ~ 2 with the mol ratio of methane amide, and oxalic dialdehyde is 100:6 ~ 15 with the mol ratio of organic bases.
2. the synthetic method of Isosorbide-5-Nitrae-diformyl-2,3,5,6-tetrahydroxy piperazine according to claim 1, described organic bases is triethylamine, piperidines or liquid methanol sodium.
3. the synthetic method of Isosorbide-5-Nitrae-diformyl-2,3,5,6-tetrahydroxy piperazine according to claim 1, described organic solvent is methyl alcohol, ethanol or acetone.
4. Isosorbide-5-Nitrae-diformyl-2,3 according to claim 1, the synthetic method of 5,6-tetrahydroxy piperazine, comprises the following steps: add glyoxal water solution and methane amide in reaction vessel, stirring dropwise adds triethylamine after making it fully mix, and control temperature is at 45 DEG C, after within 8 minutes, dropwising, there is white precipitate immediately, filtered while hot, precipitation, through water and washing with alcohol, obtains Isosorbide-5-Nitrae-diformyl-2 after oven dry, 3,5,6-tetrahydroxy piperazine; Wherein oxalic dialdehyde is 1:1 with the mol ratio of methane amide, and oxalic dialdehyde is 100:7.5 with the mol ratio of triethylamine.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3365454A (en) * | 1964-08-06 | 1968-01-23 | Ici Ltd | 1, 4-diformyl-2, 3, 5, 6-tetrahydroxypiperazine and derivatives and preparation thereof |
| CN1699367A (en) * | 2004-05-19 | 2005-11-23 | 拉斐尔军备发展局有限公司 | Process for synthesis of dinitrotetraoxadiazaisowurzitane (dtiw) |
-
2014
- 2014-10-09 CN CN201410528360.9A patent/CN104262266A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3365454A (en) * | 1964-08-06 | 1968-01-23 | Ici Ltd | 1, 4-diformyl-2, 3, 5, 6-tetrahydroxypiperazine and derivatives and preparation thereof |
| CN1699367A (en) * | 2004-05-19 | 2005-11-23 | 拉斐尔军备发展局有限公司 | Process for synthesis of dinitrotetraoxadiazaisowurzitane (dtiw) |
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Application publication date: 20150107 |