CN101735146A - Composite method of high-energy insensitive explosive 2,6-diamino-3,5-dinitro pyridine-1-oxide - Google Patents
Composite method of high-energy insensitive explosive 2,6-diamino-3,5-dinitro pyridine-1-oxide Download PDFInfo
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- CN101735146A CN101735146A CN200810195094A CN200810195094A CN101735146A CN 101735146 A CN101735146 A CN 101735146A CN 200810195094 A CN200810195094 A CN 200810195094A CN 200810195094 A CN200810195094 A CN 200810195094A CN 101735146 A CN101735146 A CN 101735146A
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Abstract
The invention relates to a composite method of high-energy insensitive explosive 2,6-diamino-3,5-dinitro pyridine-1-oxide. In the method, 2,6-diamino pyridine is nitrified in a mixed acid or super acid nitrifying system; mixture is poured into trash ice to separate out yellow sediment; solid obtained by filtering is boiled by distilled water, and yellowish-brown solid is obtained by filtering; in acetic acid, or trifluoroacetic acid or organic acid solution, the nitrogen oxidation reaction of the 2,6-diamino-3,5-dinitro pyridine is realized at the temperature of 75-250 DEG C in the presence of peroxy acid and catalyst; and luminous yellow solid is obtained by filtering after reaction ends. The invention has moderate reaction condition, does not need special devices, has abundant raw material resources, low cost, simple technology, safe and reliable production, simple product aftertreatment and small harm on environment and satisfies the basic requirements of industrial scale-up production; in addition, the invention has high total yield of target products, obviously lowers cost and has stronger market competitiveness.
Description
Technical field
The present invention relates to a kind of explosive synthetic technology, particularly a kind of high-energy insensitive explosive 2,6-diamino-3,5-di nitryl pyridine-1-oxide compound (2,6-diamino-3,5-dinitropyridine-1-oxide is abbreviated as: synthetic method DADNPO).
Background technology
TATB (triamino trinitrobenzene) obtains the maximum high energy high temperature powder kind of practical application at present both at home and abroad.Because it has high ability to bear to heat and mechanical effect, thereby enjoy favor in military equipment such as guided missile, rocket, aerospace and special dimensions such as ultra-deep exploration hypocentrum cartridge, civil blast.But, TATB cost height, price expensive (up to 2,000,000 dollars/ton) and high pollution, high toxicity have seriously limited its mass production and application again.Along with domestic and international reinforcement military project, strengthen expanding economy trend, people press for that some costs of exploitation are lower, the high-energy insensitive explosive of superior performance and environmental protection.
Nearest quantum chemistry calculation result has confirmed that many nitropyridines of polyamino and oxynitride thereof are TATB ideal substitutes.Though, external investigator has fuzzy to this compounds and simple report (referring to Hollins R, et al, J Heterocycl Chem, 1996,33:896-904), but its synthetic route and technology have determined that they can only be low-yield (＜50%), many impurity and expensive, are difficult to realize industrialization.
Summary of the invention
The object of the present invention is to provide a kind of total yield height, purity height, can realize industrialized high-energy insensitive explosive 2,6-diamino-3, the synthetic method of 5-di nitryl pyridine-1-oxide compound.
The technical solution that realizes the object of the invention is: a kind of high-energy insensitive explosive 2, and 6-diamino-3, the synthetic method of 5-di nitryl pyridine-1-oxide compound may further comprise the steps:
The first step, 2,6-diamino-3,5-di nitryl pyridine synthetic promptly in nitration mixture or super acid nitrating agent system, realized 2, and 6-diamino-pyridine nitrated when reaction finishes poured mixture into and separates out yellow mercury oxide in the trash ice, and precipitation is with 0.1～10molL
-1Sodium hydroxide solution handle, will filter the gained solid and boil through distilled water, filter the tawny solid;
Second step, 2,6-diamino-3,5-di nitryl pyridine-1-oxide compound synthetic, promptly in acetic acid, trifluoroacetic acid or organic acid solvent, under oxygenant peroxy acid and catalyzer existence condition, (also can not add catalyzer), realize 2,6-diamino-3, the nitrogen oxidizing reaction of 5-di nitryl pyridine, reaction finish to filter glassy yellow solid 2,6-diamino-3,5-di nitryl pyridine-1-oxide compound.
The present invention compared with prior art, its remarkable advantage is: (1) reaction conditions gentleness, do not need that special device, raw material are easy to get, low price, technology is simple, production safety is reliable, product postprocessing is simple, little to environmental hazard, satisfy the basic demand of industry's enlarging production; (2) target product total yield height, cost significantly reduces, and has the stronger market competitiveness.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail.
High-energy insensitive explosive 2 of the present invention, 6-diamino-3, the molecular formula of 5-di nitryl pyridine-1-oxide compound is C
5H
5N
5O
5, structural formula is:
High-energy insensitive explosive 2 of the present invention, 6-diamino-3, the synthetic route of 5-di nitryl pyridine-1-oxide compound is
May further comprise the steps:
The first step, 2,6-diamino-3,5-di nitryl pyridine synthetic promptly in nitration mixture or super acid nitrating agent system, realized 2, and 6-diamino-pyridine nitrated when reaction finishes poured mixture into and separates out yellow mercury oxide in the trash ice, and precipitation is with 0.1～10molL
-1Sodium hydroxide solution handle, will filter the gained solid and boil through distilled water, filter the tawny solid;
Second step, 2,6-diamino-3,5-di nitryl pyridine-1-oxide compound synthetic, promptly in acetic acid, trifluoroacetic acid or organic acid solvent, under oxygenant peroxy acid and catalyzer existence condition, (also can not add catalyzer), realize 2,6-diamino-3, the nitrogen oxidizing reaction of 5-di nitryl pyridine, reaction finish to filter glassy yellow solid 2,6-diamino-3,5-di nitryl pyridine-1-oxide compound.
The present invention can form intramolecularly, intermolecular hydrogen bonding, thereby increase the stability of molecule owing to have amino, nitro, nitrogen oxygen base in the DADNPO molecule simultaneously, has reduced sensitivity, has improved thermotolerance and crystalline density; The unitary introducing of nitrogen oxide structure has improved oxygen balance, has improved the thoroughness and the exothermicity of oxidizing reaction.So the actual density of DADNPO reaches 1.878g/cm
3, fusing point is greater than 340 ℃, and theoretical explosion velocity is greater than 8000ms
-1, can satisfy and be applicable to the requirement of fields such as nuclear bomb, guided missile, Aeronautics and Astronautics, extraordinary explosion, deep-well exploration and over-all properties heat-resisting to explosive.
High-energy insensitive explosive 2 of the present invention, 6-diamino-3, in the synthetic method of 5-di nitryl pyridine-1-oxide compound, nitration mixture is one of following two kinds mixing solutions: nitric acid 70%～100% and sulfuric acid 80%～98% mixed preparing, perhaps nitrate and sulfuric acid 80%～98% mixed preparing.The concentration unit of all nitration mixture, super acid, nitrating agent etc. is a mass percent.
Super acid is one of following two kinds mixing solutions: nitric acid 70%～100% and oleum 20%～65% mixed preparing, perhaps nitrate and oleum 20%～65% mixed preparing.
Nitrating agent is one of following four kinds of proportionings: nitrating agent is nitric acid 70%～100% and sulfuric acid 80%～98% o'clock, and the ratio of components of reactant is: nitric acid 70%～100%: sulfuric acid 80%～98%: DAP=2～20mol: 0.1～10L: 1mol; When perhaps nitrating agent was nitrosonitric acid and 20%～65% oleum, the ratio of components of reactant was: nitrosonitric acid: oleum 20%～65%: DAP=2～20mol: 0.1～10L: 1mol; Perhaps nitrating agent is nitrate and oleum 20%～65% o'clock, and the ratio of components of reactant is: nitrate: oleum: DAP=2～20mol: 0.1～10L: 1～10mol: 1mol; Perhaps nitrating agent is nitrate and sulfuric acid 80%～98% o'clock, the ratio of components of reactant: nitrate: sulfuric acid 80%～98%: DAP=2～20mol: 0.1～10L: 1mol.Wherein DAP is 2, and 6-diamino-pyridine, nitrate are KNO
3, NaNO
3, NH
4NO
3Or Mg (NO
3)
2
Oxygenant is peroxy acid: RCOOOH, and wherein, R is C
1～C
8Alkyl, CF
3, phenyl, benzyl or aryl.These peroxy acids are synthetic according to a conventional method, and available hydrogen peroxide and other oxygenant and corresponding organic acid reaction make, and with hydrogen peroxide system peroxy acid the time, the concentration of hydrogen peroxide is 10%～100%.Catalyzer is one of following eight kinds: the vitriol oil, acetic anhydride, sodium wolframate, the vitriol oil and sodium pyrosulfate mixed preparing, fumaric acid and fumaric acid anhydride mixed preparing, single peroxy maleic acid and single peroxy maleic acid acid anhydride mixed preparing, toxilic acid and maleic anhydride mixed preparing, the perhaps vitriol oil, acetic anhydride, maleic anhydride and sodium pyrosulfate mixed preparing.
When oxygenant is Peracetic Acid, H
2O
2With the HAc ratio of components be H
2O
2: HAc: DADNPy=6.4ml: 10～200ml: 0.01mol.Wherein DADNPy is 2,6-diamino-3,5-di nitryl pyridine.
When oxygenant is peroxy trifluoroacetic acid, H
2O
2With the TFA ratio of components be H
2O
2: TFA: DADNPy=3ml: 5～100ml: 0.01mol.
When oxygenant is a Peracetic Acid, catalyzer is dense H
2SO
4The time, ratio of components is H
2O
2: HAc: H
2SO
4: DADNPy=2.5ml: 5～100ml: 0.1～10ml: 0.01mol.
When oxygenant is a Peracetic Acid, catalyzer is dense H
2SO
4And NaHSO
4The time, ratio of components is H
2O
2: HAc: H
2SO
4: NaHSO
4: DADNPy 2.5ml: 5～100ml: 0.1～10ml: 0.05～1g: 0.01mol.
When oxygenant is a Peracetic Acid, when catalyzer was single peroxy maleic acid and maleic anhydride, ratio of components was H
2O
2: HAc: single peroxy maleic acid/acid anhydride: DADNPy=2.5ml: 5～100ml: 0.05～1g: 0.05～1g: 0.01mol.
When oxygenant is a Peracetic Acid, when catalyzer was fumaric acid and fumaric acid anhydride, ratio of components was H
2O
2: HAc: fumaric acid/acid anhydride: DADNPy.=5ml: 5～100ml: 0.05～1g: 0.05～1g: 0.01mol.
When oxygenant is a Peracetic Acid, catalyzer is dense H
2SO
4, acetic anhydride, maleic anhydride and NaHSO
4The time, ratio of components is H
2O
2: HAc: dense H
2SO
4: acetic anhydride: maleic anhydride: NaHSO
4: DADNPy=2.5ml: 5～100ml: 0.1～10ml: 0.5～50ml: 0.01～1g: 0.01～1g: 0.01mol.
When oxygenant is a Peracetic Acid, catalyzer is Na
2WO
4The time, ratio of components is H
2O
2: HAc: Na
2WO
4: DADNPy=2.5ml: 5～100ml: 0.01～1g: 0.01mol.
One, 2,6-diamino-3,5-di nitryl pyridine synthetic.
Embodiment 1
2,6-diamino-3,5-di nitryl pyridine synthetic, synthetic route is referring to accompanying drawing II.At 100mL agitator is housed, in the there-necked flask of thermometer, adds the dense H of 75mL98%
2SO
4, stir and to add 2.18g 2 down, the 6-diamino-pyridine, treat that solid dissolves fully after, continue to be stirred to mixture temperature to be reduced to below 30 ℃; In 10min, add 0.075molKNO
3(ice-water bath control mixture temperature is below 30 ℃) add KNO
3Process in keep vigorous stirring; After reacting end in three hours mixture is poured in the trash ice, stirred, separate out a large amount of tawny solids, filter, washing; Move into after the vacuum-drying in the flask of 100mL, add 50mL 2molL
-1NaOH, stirred 2 hours, cooling is filtered, washing, drying is boiled the gained solid one hour through distilled water, filters drying, weighing, yield 75%.
Embodiment 2
2,6-diamino-3,5-di nitryl pyridine synthetic, synthetic route is referring to accompanying drawing II.At 100mL agitator is housed, in the there-necked flask of thermometer, adds the H of being fuming of 15ml 65%
2SO
4, stir and to add 2.18g 2 down, the 6-diamino-pyridine, treat that solid dissolves fully after, continue to be stirred to mixture temperature to be reduced to below 20 ℃; In 10min, add 0.04molNaNO
3(ice-water bath control mixture temperature is below 20 ℃) keep vigorous stirring in the process of adding nitrate; After reacting end in three hours mixture is poured in the trash ice, stirred, separate out a large amount of tawny solids, filter, washing; Move into after the vacuum-drying in the flask of 100ml, add 50ml2molL
-1NaOH, stirred 2 hours, cooling is filtered, washing, drying is boiled the gained solid one hour through distilled water, filters drying, yield 90%.
Embodiment 3
2,6-diamino-3,5-di nitryl pyridine synthetic, synthetic route is referring to accompanying drawing II.At 5L agitator is housed, in the there-necked flask of thermometer, adds the oleum of 2400ml20%, stir and add 300g2 down, the 6-diamino-pyridine, treat that solid dissolves fully after, continue to be stirred to mixture temperature to be reduced to below 30 ℃; In 15min, add the 240ml HNO of being fuming
3(ice-water bath control mixture temperature is below 30 ℃) add the HNO of being fuming
3Process in keep vigorous stirring; After reacting end in three hours mixture is poured in the trash ice, stirred, separate out a large amount of tawny solids, filter, washing; Move into 5000ml2molL after the vacuum-drying
-1NaOH solution in, stirred 2 hours, cooling is filtered, washing, drying is boiled the gained solid one hour through distilled water, filters drying, yield 93%.
Embodiment 4
2,6-diamino-3,5-di nitryl pyridine synthetic, synthetic route is referring to accompanying drawing II.At 100ml agitator is housed, in the there-necked flask of thermometer, adds the 50ml vitriol oil, stir and add 3g2 down, the 6-diamino-pyridine, treat that solid dissolves fully after, continue to be stirred to mixture temperature to be reduced to below 40 ℃; In 15min, add the 2.4ml HNO of being fuming
3(ice-water bath control mixture temperature is below 40 ℃) add the HNO of being fuming
3Process in keep vigorous stirring; After reacting end in three hours mixture is poured in the trash ice, stirred, separate out a large amount of tawny solids, filter, washing.Move into 50ml2molL after the vacuum-drying
-1NaOH solution in, stirred 2 hours, cooling is filtered, washing, drying is boiled the gained solid one hour through distilled water, filters drying, weighing, yield 80%.
Embodiment 5
2,6-diamino-3,5-di nitryl pyridine synthetic, synthetic route is referring to accompanying drawing II.At 5L agitator is housed, in the there-necked flask of thermometer, adds the 2000ml vitriol oil, stir and add 109g2 down, the 6-diamino-pyridine, treat that solid dissolves fully after, continue to be stirred to mixture temperature to be reduced to below 15 ℃; In 15min, add the 90ml HNO of being fuming
3(ice-water bath control mixture temperature is below 15 ℃) add the HNO of being fuming
3Process in keep vigorous stirring; After reacting end in three hours mixture is poured in the trash ice, stirred, separate out a large amount of tawny solids, filter, washing; Move into 500ml2molL after the vacuum-drying
-1NaOH solution in, stirred 2 hours, cooling is filtered, washing, drying is boiled the gained solid one hour through distilled water, filters drying, yield 90%.
Embodiment 6
2,6-diamino-3,5-di nitryl pyridine synthetic, synthetic route is referring to accompanying drawing II.At 2L agitator is housed, in the there-necked flask of thermometer, adds the oleum of 800ml20%, stir and add 109g2 down, the 6-diamino-pyridine, treat that solid dissolves fully after, continue to be stirred to mixture temperature to be reduced to below 20 ℃; In 15min, add the 95ml HNO of being fuming
3(ice-water bath control mixture temperature is below 20 ℃) add the HNO of being fuming
3Process in keep vigorous stirring; After reacting end in three hours mixture is poured in the trash ice, stirred, separate out a large amount of tawny solids, filter, washing; Move into 500ml2molL after the vacuum-drying
-1NaOH solution in, stirred 2 hours, cooling is filtered, washing, drying is boiled the gained solid one hour through distilled water, filters drying, yield 95%.
Embodiment 7
2,6-diamino-3,5-di nitryl pyridine synthetic, synthetic route is referring to accompanying drawing II.At 10ml agitator is housed, in the there-necked flask of thermometer, adds 3ml95% sulfuric acid, stir and add 0.11g2 down, the 6-diamino-pyridine, treat that solid dissolves fully after, continue to be stirred to mixture temperature to be reduced to below 27 ℃; In 1min, add the 0.1ml HNO of being fuming
3(ice-water bath control mixture temperature is below 27 ℃) add the HNO of being fuming
3Process in keep vigorous stirring; After reacting end in three hours mixture is poured in the trash ice, stirred, separate out a large amount of tawny solids, filter, washing; Move into 5ml2molL after the vacuum-drying
-1NaOH solution in, stirred 2 hours, cooling is filtered, washing, drying is boiled the gained solid one hour through distilled water, filters drying, yield 75%.
Embodiment 8
2,6-diamino-3,5-di nitryl pyridine synthetic, synthetic route is referring to accompanying drawing II.At 100ml agitator is housed, in the there-necked flask of thermometer, adds the 35ml vitriol oil, stir and add 1.1g2 down, the 6-diamino-pyridine, treat that solid dissolves fully after, continue to be stirred to mixture temperature to be reduced to below 16 ℃; In 5min, add the 0.9ml HNO of being fuming
3(ice-water bath control mixture temperature is below 16 ℃) add the HNO of being fuming
3Process in keep vigorous stirring; After reacting end in three hours mixture is poured in the trash ice, stirred, separate out a large amount of tawny solids, filter, washing; Move into 10ml2molL after the vacuum-drying
-1NaOH solution in, stirred 2 hours, cooling is filtered, washing, drying is boiled the gained solid one hour through distilled water, filters drying, yield 67%.
Embodiment 9
2,6-diamino-3,5-di nitryl pyridine synthetic, synthetic route is referring to accompanying drawing II.At 100ml agitator is housed, in the there-necked flask of thermometer, adds 45ml90% sulfuric acid, stir and add 0.11g2 down, the 6-diamino-pyridine, treat that solid dissolves fully after, continue to be stirred to mixture temperature to be reduced to below 30 ℃; In 1min, add 1.5ml89%HNO
3(ice-water bath control mixture temperature is below 30 ℃) add the HNO of being fuming
3Process in keep vigorous stirring; After reacting end in three hours mixture is poured in the trash ice, stirred, separate out a large amount of tawny solids, filter, washing; Move into 50ml2molL after the vacuum-drying
-1NaOH solution in, stirred 2 hours, cooling is filtered, washing, drying is boiled the gained solid one hour through distilled water, filters drying, yield 65%.
Embodiment 10
2,6-diamino-3,5-di nitryl pyridine synthetic, synthetic route is referring to accompanying drawing II.At 50ml agitator is housed, in the there-necked flask of thermometer, adds the oleum of 30ml65%, stir and add 1.1g2 down, the 6-diamino-pyridine, treat that solid dissolves fully after, continue to be stirred to mixture temperature to be reduced to below 33 ℃; In 5min, add 2gNH
4NO
3(ice-water bath control mixture temperature is below 33 ℃) add NH
4NO
3Process in keep vigorous stirring; After reacting end in three hours mixture is poured in the trash ice, stirred, separate out a large amount of tawny solids, filter, washing; Move into 50ml2molL after the vacuum-drying
-1NaOH solution in, stirred 2 hours, cooling is filtered, washing, drying is boiled the gained solid one hour through distilled water, filters drying, yield 92%.
Embodiment 11
2,6-diamino-3,5-di nitryl pyridine synthetic, synthetic route is referring to accompanying drawing II.At 50ml agitator is housed, in the there-necked flask of thermometer, adds the 25ml vitriol oil and 0.1gP
2O
5, stir and to add 1.1g2 down, the 6-diamino-pyridine, treat that solid dissolves fully after, continue to be stirred to mixture temperature to be reduced to below 34 ℃; In 5min, add 1.6gNH
4NO
3(ice-water bath control mixture temperature is below 34 ℃) add NH
4NO
3Process in keep vigorous stirring; After reacting end in three hours mixture is poured in the trash ice, stirred, separate out a large amount of tawny solids, filter, washing; Move into 50ml2molL after the vacuum-drying
-1NaOH solution in, stirred 2 hours, cooling is filtered, washing, drying is boiled the gained solid one hour through distilled water, filters drying, yield 94%.
Embodiment 12
2,6-diamino-3,5-di nitryl pyridine synthetic, synthetic route is referring to accompanying drawing II.At 2L agitator is housed, in the there-necked flask of thermometer, adds the 1000ml vitriol oil, stir and add 109g2 down, the 6-diamino-pyridine, treat that solid dissolves fully after, continue to be stirred to mixture temperature to be reduced to below 25 ℃; In 15min, add 170gNaNO
3(ice-water bath control mixture temperature is below 30 ℃) add NaNO
3Process in keep vigorous stirring; After reacting end in three hours mixture is poured in the trash ice, stirred, separate out a large amount of tawny solids, filter, washing; Move into 1000ml2molL after the vacuum-drying
-1NaOH solution in, stirred 2 hours, cooling is filtered, washing, drying is boiled the gained solid one hour through distilled water, filters drying, yield 92%.
Embodiment 13
2,6-diamino-3,5-di nitryl pyridine synthetic, synthetic route is referring to accompanying drawing II.At 5L agitator is housed, in the there-necked flask of thermometer, adds 3000ml80% sulfuric acid, stir and add 109g2 down, the 6-diamino-pyridine, treat that solid dissolves fully after, continue to be stirred to mixture temperature to be reduced to below 10 ℃; In 15min, add 202gKNO
3(ice-water bath control mixture temperature is below 30 ℃) add KNO
3Process in keep vigorous stirring; After reacting end in three hours mixture is poured in the trash ice, stirred, separate out a large amount of tawny solids, filter, washing; Move into 2000ml2molL after the vacuum-drying
-1NaOH solution in, stirred 2 hours, cooling is filtered, washing, drying is boiled the gained solid one hour through distilled water, filters drying, yield 63%.
Embodiment 14
2,6-diamino-3,5-di nitryl pyridine synthetic, synthetic route is referring to accompanying drawing II.At 5L agitator is housed, in the there-necked flask of thermometer, adds 4000ml95% sulfuric acid, stir and add 109g2 down, the 6-diamino-pyridine, treat that solid dissolves fully after, continue to be stirred to mixture temperature to be reduced to below 5 ℃; In 15min, add the 90ml HNO of being fuming
3(ice-water bath control mixture temperature is below 5 ℃) add the HNO of being fuming
3Process in keep vigorous stirring; After reacting end in three hours mixture is poured in the trash ice, stirred, separate out a large amount of tawny solids, filter, washing; Move into 500ml2molL after the vacuum-drying
-1NaOH solution in, stirred 2 hours, cooling is filtered, washing, drying is boiled the gained solid one hour through distilled water, filters drying, yield 87%.
Embodiment 15
2,6-diamino-3,5-di nitryl pyridine synthetic, synthetic route is referring to accompanying drawing II.At 10L agitator is housed, in the there-necked flask of thermometer, adds 5000ml90% sulfuric acid, stir and add 109g2 down, the 6-diamino-pyridine, treat that solid dissolves fully after, continue to be stirred to mixture temperature to be reduced to below 0 ℃; In 15min, add 125ml86%HNO
3(ice-water bath control mixture temperature is below 0 ℃) adds HNO
3Process in keep vigorous stirring; After reacting end in three hours mixture is poured in the trash ice, stirred, separate out a large amount of tawny solids, filter, washing; Move into 5000ml2molL after the vacuum-drying
-1NaOH solution in, stirred 2 hours, cooling is filtered, washing, drying is boiled the gained solid one hour through distilled water, filters drying, yield 77%.
Embodiment 16
2,6-diamino-3,5-di nitryl pyridine synthetic, synthetic route is referring to accompanying drawing II.At 10L agitator is housed, in the there-necked flask of thermometer, adds 4500ml85% sulfuric acid, stir and add 109g2 down, the 6-diamino-pyridine, treat that solid dissolves fully after, continue to be stirred to mixture temperature to be reduced to below 35 ℃; In 15min, add 245gKNO
3(ice-water bath control mixture temperature is below 35 ℃) add KNO
3Process in keep vigorous stirring; After reacting end in three hours mixture is poured in the trash ice, stirred, separate out a large amount of tawny solids, filter, washing; Move into 5000ml2molL after the vacuum-drying
-1NaOH solution in, stirred 2 hours, cooling is filtered, washing, drying is boiled the gained solid one hour through distilled water, filters drying, yield 85%.
Two, 2,6-diamino-3,5-di nitryl pyridine-1-oxide compound synthetic.
Embodiment 1
2,6-diamino-3,5-di nitryl pyridine-1-oxide compound synthetic, synthetic route is referring to accompanying drawing II.In 96mlHAc, slowly add 2.5g2,6-diamino-3, the 5-di nitryl pyridine is stirred to mixture and becomes uniform state; In 10min, slowly splash into the H of 12.8ml30%
2O
2Solution, be warming up to 80 ℃ the insulation 3 hours, filter the glassy yellow solid; Use 1molL
-1KCO
3The solution washing solid, washing again gets 2.16g solid, yield 80% after the vacuum-drying.
Embodiment 2
2,6-diamino-3,5-di nitryl pyridine-1-oxide compound synthetic, synthetic route is referring to accompanying drawing II.In 20mTFA, slowly add 2.5g2,6-diamino-3, the 5-di nitryl pyridine is stirred to mixture and becomes uniform state; In 10min, slowly splash into the H of 12ml30%
2O
2Solution, be warming up to 90 ℃ the insulation 3 hours, filter the glassy yellow solid; Use 1molL
-1KCO
3The solution washing solid, washing again gets 2.27g solid, yield 84% after the vacuum-drying.
Embodiment 3
2,6-diamino-3,5-di nitryl pyridine-1-oxide compound synthetic, synthetic route is referring to accompanying drawing II.In 20mlHAc, slowly add 2.5g2,6-diamino-3, the 5-di nitryl pyridine is stirred to mixture and becomes uniform state; In 10min, slowly splash into the H of 6ml30%
2O
2Solution stirs the mixture into uniform state, adds the 0.4ml vitriol oil, is warming up to 95 ℃ of insulations 3 hours, filter the glassy yellow solid; Use 1molL
-1KCO
3The solution washing solid, again the washing, use after the vacuum-drying the 2.28g solid, yield 84.5%.
Embodiment 4
2,6-diamino-3,5-di nitryl pyridine-1-oxide compound synthetic, synthetic route is referring to accompanying drawing II.In 8mlHAc, slowly add 2.5g2,6-diamino-3, the 5-di nitryl pyridine is stirred to mixture and becomes uniform state; In 10min, slowly splash into the H of 5ml30%
2O
2Solution stirs the mixture into uniform state, adds the 0.4ml vitriol oil successively, the 0.1g sodium pyrosulfate, be warming up to 85 ℃ the insulation 3 hours, filter the glassy yellow solid; Use 1molL
-1KCO
3The solution washing solid, washing again, vacuum-drying gets the 2.24g solid, yield 83%.
Embodiment 5
2,6-diamino-3,5-di nitryl pyridine-1-oxide compound synthetic, synthetic route is referring to accompanying drawing II.In 8mlHAc, slowly add 2.5g2,6-diamino-3, the 5-di nitryl pyridine is stirred to mixture and becomes uniform state; In 10min, slowly splash into the H of 5ml30%
2O
2Solution stirs the mixture into uniform state, adds the single peroxy maleic acid/acid anhydride of 0.2/0.12g successively, is warming up to 95 ℃ of insulations 3 hours, filter the glassy yellow solid; Use 1molL
-1KCO
3The solution washing solid, washing again, vacuum-drying gets the 2.29g solid, yield 85%.
Embodiment 6
2,6-diamino-3,5-di nitryl pyridine-1-oxide compound synthetic, synthetic route is referring to accompanying drawing II.In 1600mlHAc, slowly add 500g2,6-diamino-3, the 5-di nitryl pyridine is stirred to mixture and becomes uniform state; In 10min, slowly splash into the H of 1000ml30%
2O
2Solution stirs the mixture into uniform state, adds 3.6/2.4g fumaric acid/acid anhydride successively, be warming up to 75 ℃ the insulation 3 hours, filter the glassy yellow solid; Use 1molL
-1KCO
3The solution washing solid, washing again, vacuum-drying gets the 442g solid, yield 82%.
Embodiment 7
2,6-diamino-3,5-di nitryl pyridine-1-oxide compound synthetic, synthetic route is referring to accompanying drawing II.In 80mlHAc, slowly add 25g2,6-diamino-3, the 5-di nitryl pyridine is stirred to mixture and becomes uniform state; In 10min, slowly splash into the H of 50ml30%
2O
2Solution stirs the mixture into uniform state, adds the 2ml vitriol oil successively, the 15ml aceticanhydride, the 0.6g maleic anhydride, the 0.5g sodium pyrosulfate, be warming up to 75 ℃ the insulation 3 hours, filter the glassy yellow solid; Use 1molL
-1KCO
3The solution washing solid, washing again, vacuum-drying gets the 23.1g solid, yield 85.6%.
Embodiment 8
2,6-diamino-3,5-di nitryl pyridine-1-oxide compound synthetic, synthetic route is referring to accompanying drawing II.In 800mlHAc, slowly add 250g2,6-diamino-3, the 5-di nitryl pyridine is stirred to mixture and becomes uniform state; In 10min, slowly splash into the H of 500ml30%
2O
2Solution stirs the mixture into uniform state, adds the 2g sodium wolframate successively, be warming up to 105 ℃ the insulation 3 hours, filter the glassy yellow solid; Use 1molL
-1KCO
3The solution washing solid, washing again gets 238g solid, yield 88% after the vacuum-drying.
Claims (13)
1. high-energy insensitive explosive 2,6-diamino-3, the synthetic method of 5-di nitryl pyridine-1-oxide compound, its synthetic route is:
2. high-energy insensitive explosive 2 according to claim 1,6-diamino-3, the synthetic method of 5-di nitryl pyridine-1-oxide compound is characterized in that may further comprise the steps:
The first step, 2,6-diamino-3,5-di nitryl pyridine synthetic promptly in nitration mixture or super acid nitrating agent system, realized 2, and 6-diamino-pyridine nitrated when reaction finishes poured mixture into and separates out yellow mercury oxide in the trash ice, and precipitation is with 0.1～10molL
-1Sodium hydroxide solution handle, will filter the gained solid and boil through distilled water, filter the tawny solid;
Second step, 2,6-diamino-3,5-di nitryl pyridine-1-oxide compound synthetic, promptly in acetic acid, trifluoroacetic acid or organic acid solvent, under oxygenant peroxy acid and catalyzer existence condition, (also can not add catalyzer), realize 2,6-diamino-3, the nitrogen oxidizing reaction of 5-di nitryl pyridine, reaction finish to filter glassy yellow solid 2,6-diamino-3,5-di nitryl pyridine-1-oxide compound.
3. high-energy insensitive explosive 2 according to claim 2,6-diamino-3, the synthetic method of 5-di nitryl pyridine-1-oxide compound, it is characterized in that: in the first step, nitrated temperature is-30～100 ℃, and the nitration reaction time is 0.1～100 hour, and boiling time is 0.1～100 hour; In second step, oxidizing reaction temperature is 75～250 ℃, and oxidation time is 0.1～100 hour.
4. high-energy insensitive explosive 2 according to claim 2,6-diamino-3, the synthetic method of 5-di nitryl pyridine-1-oxide compound, it is characterized in that: nitration mixture is one of following two kinds mixing solutions: nitric acid 70%～100% and sulfuric acid 80%～98% mixed preparing, perhaps nitrate and sulfuric acid 80%～98% mixed preparing; Super acid is one of following two kinds mixing solutions: nitric acid 70%～100% and oleum 20%～65% mixed preparing, perhaps nitrate and oleum 20%～65% mixed preparing.
5. high-energy insensitive explosive 2 according to claim 2,6-diamino-3, the synthetic method of 5-di nitryl pyridine-1-oxide compound is characterized in that: nitrating agent is one of following four kinds of proportionings, and wherein DAP is 2, and 6-diamino-pyridine, nitrate are KNO
3, NaNO
3, NH
4NO
3Or Mg (NO
3)
2:
Nitrating agent is nitric acid 70%～100% and sulfuric acid 80%～98% o'clock, and the ratio of components of reactant is: nitric acid 70%～100%: sulfuric acid 80%～98%: DAP=2～20mol: 0.1～10L: 1mol;
When perhaps nitrating agent was nitrosonitric acid and 20%～65% oleum, the ratio of components of reactant was: nitrosonitric acid: oleum 20%～65%: DAP=2～20mol: 0.1～10L: 1mol;
Perhaps nitrating agent is nitrate and oleum 20%～65% o'clock, and the ratio of components of reactant is: nitrate: oleum: DAP=2～20mol: 0.1～10L: 1～10mol: 1mol;
Perhaps nitrating agent is nitrate and sulfuric acid 80%～98% o'clock, the ratio of components of reactant: nitrate: sulfuric acid 80%～98%: DAP=2～20mol: 0.1～10L: 1mol;
6. high-energy insensitive explosive 2 according to claim 2,6-diamino-3, the synthetic method of 5-di nitryl pyridine-1-oxide compound is characterized in that: oxygenant is peroxy acid: RCOOOH, wherein, R is C
1～C
8Alkyl, CF
3, phenyl, benzyl or aryl; Catalyzer is one of following eight kinds: the vitriol oil, acetic anhydride, sodium wolframate, the vitriol oil and sodium pyrosulfate mixed preparing, fumaric acid and fumaric acid anhydride mixed preparing, single peroxy maleic acid and single peroxy maleic acid acid anhydride mixed preparing, toxilic acid and maleic anhydride mixed preparing, the perhaps vitriol oil, acetic anhydride, maleic anhydride and sodium pyrosulfate mixed preparing.
7. according to claim 2 or 6 described high-energy insensitive explosives 2,6-diamino-3, the synthetic method of 5-di nitryl pyridine-1-oxide compound is characterized in that: when oxygenant is Peracetic Acid, H
2O
2With the HAc ratio of components be H
2O
2: HAc: DADNPy=6.4ml: 10～200ml: 0.01mol; When perhaps oxygenant is peroxy trifluoroacetic acid, H
2O
2With the TFA ratio of components be H
2O
2: TFA: DADNPy=3ml: 5～100ml: 0.01mol, wherein DADNPy is 2,6-diamino-3,5-di nitryl pyridine.
8. according to claim 2 or 6 described high-energy insensitive explosives 2,6-diamino-3, the synthetic method of 5-di nitryl pyridine-1-oxide compound is characterized in that: oxygenant is a Peracetic Acid, catalyzer is dense H
2SO
4The time, ratio of components is H
2O
2: HAc: H
2SO
4: DADNPy=2.5ml: 5～100ml: 0.1～10ml: 0.01mol, wherein DADNPy is 2,6-diamino-3,5-di nitryl pyridine.
9. according to claim 2 or 6 described high-energy insensitive explosives 2,6-diamino-3, the synthetic method of 5-di nitryl pyridine-1-oxide compound is characterized in that: oxygenant is a Peracetic Acid, catalyzer is dense H
2SO
4And NaHSO
4The time, ratio of components is H
2O
2: HAc: H
2SO
4: NaHSO
4: DADNPy 2.5ml: 5～100ml: 0.1～10ml: 0.05～1g: 0.01mol, wherein DADNPy is 2,6-diamino-3,5-di nitryl pyridine.
10. according to claim 2 or 6 described high-energy insensitive explosives 2,6-diamino-3, the synthetic method of 5-di nitryl pyridine-1-oxide compound is characterized in that oxygenant is a Peracetic Acid, when catalyzer was single peroxy maleic acid and maleic anhydride, ratio of components was H
2O
2: HAc: single peroxy maleic acid/acid anhydride: DADNPy=2.5ml: 5～100ml: 0.05～1g: 0.05～1g: 0.01mol, wherein DADNPy is 2,6-diamino-3,5-di nitryl pyridine.
11. according to claim 2 or 6 described high-energy insensitive explosives 2,6-diamino-3, the synthetic method of 5-di nitryl pyridine-1-oxide compound is characterized in that oxygenant is a Peracetic Acid, when catalyzer was fumaric acid and fumaric acid anhydride, ratio of components was H
2O
2: HAc: fumaric acid/acid anhydride: DADNPy.=5ml: 5～100ml: 0.05～1g: 0.05～1g: 0.01mol, wherein DADNPy is 2,6-diamino-3,5-di nitryl pyridine.
12. according to claim 2 or 6 described high-energy insensitive explosives 2,6-diamino-3, the synthetic method of 5-di nitryl pyridine-1-oxide compound is characterized in that oxygenant is a Peracetic Acid, catalyzer is dense H
2SO
4, acetic anhydride, maleic anhydride and NaHSO
4The time, ratio of components is H
2O
2: HAc: dense H
2SO
4: acetic anhydride: maleic anhydride: NaHSO
4: DADNPy=2.5ml; 5～100ml: 0.1～10ml: 0.5～50ml: 0.01～1g: 0.01～1g: 0.01mol, wherein DADNPy is 2,6-diamino-3,5-di nitryl pyridine.
13. according to claim 2 or 6 described high-energy insensitive explosives 2,6-diamino-3, the synthetic method of 5-di nitryl pyridine-1-oxide compound is characterized in that oxygenant is a Peracetic Acid, catalyzer is Na
2WO
4The time, ratio of components is H
2O
2: HAc: Na
2WO
4: DADNPy=2.5ml: 5～100ml: 0.01～1g: 0.01mol, wherein DADNPy is 2,6-diamino-3,5-di nitryl pyridine.
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| CN108586169B (en) * | 2018-05-09 | 2020-04-28 | 中国工程物理研究院化工材料研究所 | 2,4, 6-triamino-5-nitropyrimidine-1, 3-dioxide and hydrogen peroxide self-assembled crystal and preparation method thereof |
| CN109369518A (en) * | 2018-11-27 | 2019-02-22 | 浙江工业大学上虞研究院有限公司 | A kind of superfine molecular sieves base microchannel plate should prepare the nitration method of 2,6- diamino -3,5- di nitryl pyridine |
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