CN106632357B - The method of one pot process TTBN - Google Patents
The method of one pot process TTBN Download PDFInfo
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- CN106632357B CN106632357B CN201610888311.5A CN201610888311A CN106632357B CN 106632357 B CN106632357 B CN 106632357B CN 201610888311 A CN201610888311 A CN 201610888311A CN 106632357 B CN106632357 B CN 106632357B
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- ttbn
- tngu
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- methenamine
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- 238000005580 one pot reaction Methods 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 16
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 17
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229960004011 methenamine Drugs 0.000 claims abstract description 15
- 230000007062 hydrolysis Effects 0.000 claims abstract description 12
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 8
- 230000002378 acidificating effect Effects 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 238000005903 acid hydrolysis reaction Methods 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical group 0.000 claims description 2
- 159000000009 barium salts Chemical class 0.000 abstract description 8
- 238000000926 separation method Methods 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 27
- HKTUDNFYVIXYSQ-UHFFFAOYSA-N 1,3,4,6-tetranitro-3a,6a-dihydroimidazo[4,5-d]imidazole-2,5-dione Chemical compound [O-][N+](=O)N1C(=O)N([N+]([O-])=O)C2C1N([N+]([O-])=O)C(=O)N2[N+](=O)[O-] HKTUDNFYVIXYSQ-UHFFFAOYSA-N 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000007787 solid Substances 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- 238000010792 warming Methods 0.000 description 10
- 238000011049 filling Methods 0.000 description 9
- 239000012065 filter cake Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000413 hydrolysate Substances 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- POCJOGNVFHPZNS-ZJUUUORDSA-N (6S,7R)-2-azaspiro[5.5]undecan-7-ol Chemical compound O[C@@H]1CCCC[C@]11CNCCC1 POCJOGNVFHPZNS-ZJUUUORDSA-N 0.000 description 1
- XQJMXPAEFMWDOZ-UHFFFAOYSA-N 3exo-benzoyloxy-tropane Natural products CN1C(C2)CCC1CC2OC(=O)C1=CC=CC=C1 XQJMXPAEFMWDOZ-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- LSOBKXIVGIAUTO-UHFFFAOYSA-N N-(3,6,9-trinitro-1,3,6,9-tetrazabicyclo[3.2.2]nonan-4-yl)nitramide Chemical compound C1N2CN(C(C(N1[N+](=O)[O-])N[N+](=O)[O-])N(C2)[N+](=O)[O-])[N+](=O)[O-] LSOBKXIVGIAUTO-UHFFFAOYSA-N 0.000 description 1
- QQXLDOJGLXJCSE-UHFFFAOYSA-N N-methylnortropinone Natural products C1C(=O)CC2CCC1N2C QQXLDOJGLXJCSE-UHFFFAOYSA-N 0.000 description 1
- BSPUVYFGURDFHE-UHFFFAOYSA-N Nitramine Natural products CC1C(O)CCC2CCCNC12 BSPUVYFGURDFHE-UHFFFAOYSA-N 0.000 description 1
- QIZDQFOVGFDBKW-DHBOJHSNSA-N Pseudotropine Natural products OC1C[C@@H]2[N+](C)[C@H](C1)CC2 QIZDQFOVGFDBKW-DHBOJHSNSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- POCJOGNVFHPZNS-UHFFFAOYSA-N isonitramine Natural products OC1CCCCC11CNCCC1 POCJOGNVFHPZNS-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- CYHOMWAPJJPNMW-JIGDXULJSA-N tropine Chemical compound C1[C@@H](O)C[C@H]2CC[C@@H]1N2C CYHOMWAPJJPNMW-JIGDXULJSA-N 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/08—Bridged systems
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to technical field of chemistry, specifically, are related to a kind of method of one pot process TTBN, are directly reacted with methenamine by TNGU acidic hydrolysis, one-pot synthesis TTBN is specifically included：At room temperature, TNGU is added in the acidic catalyst aqueous solution of a concentration of 2 8M, at 15 40 DEG C after 30 180min of stirring hydrolysis, is directly added into methenamine, 30 90min, one-pot synthesis TTBN are reacted at 30 60 DEG C.This invention simplifies the preparation processes of TTBN, and TNGU is hydrolyzed in acid condition, without separation, need not also prepare the barium salt of TNAE, but directly react one-pot synthesis TTBN with methenamine.
Description
Technical field
The invention belongs to technical field of chemistry, specifically, are related to a kind of method of one pot process TTBN.
Background technology
Existing pass N- (four azabicyclo [3.2.2] nonane -4- bases of 3,6,9- trinitro-s -1,3,6,9-) nitramine (N- (3,6,
9-trinitro-1,3,6,9-tetraazabicyclo [3,2,2] nonan-4-yl) nitramide, abbreviation TTBN) synthesis
Method is seldom, and unique method is：By tetranitro glycoluril (TNGU) in NaHCO3After being hydrolyzed in aqueous solution, it is added into aqueous solution
Ba(OH)2Acetum makes the pH value of reaction solution control in 4-5, and white barium salt precipitation is precipitated, barium salt solid is obtained by filtration.It will
Methenamine is dissolved in 10% hydrochloric acid, and barium salt is added at 10 DEG C or less and stirs 5min, is warming up to 50 DEG C, is first precipitated after solid again
Dissolving, it is cooling that solid is precipitated, product TTBN is obtained by filtration.The shortcomings that preparation method：(1) complex process, agents useful for same are more；
(2) during preparing the barium salt of four nitramino ethane (TNAE), pH value needs to adjust to faintly acid from alkalescent, and TNAE pairs
PH value is very sensitive, is extremely unstable between 3-8 in pH value, so causing raw material TNAE losses larger；(3) product yield
It is low, purity is low.
Invention content
It is an object of the invention to be directed to after TNGU basic hydrolysises in the prior art, TNAE is prepared by adjusting pH value
Barium salt, then react the technological deficiency for preparing TTBN with the methenamine being dissolved in advance in acid solution, a kind of operation letter be provided
The high TTBN synthetic methods of list, high income, purity.
The embodiment provides a kind of method of one pot process TTBN, by TNGU acidic hydrolysis directly with black Lip river
Tropine reacts, and one-pot synthesis TTBN is specifically included：At room temperature, TNGU is added to the acidic catalyst water of a concentration of 2-8M
In solution, at 15-40 DEG C after stirring hydrolysis 30-180min, it is directly added into methenamine, reacts 30-90min at 30-60 DEG C,
One-pot synthesis TTBN.
Further, which is hydrochloric acid, hydrobromic acid or sulfuric acid.
Further, the molar ratio of the methenamine and TNGU of addition is 0.8:1-1.5:1, TNGU and acidic catalyst rub
You are than being 1:5-1:20.
Compared with prior art the beneficial effects of the invention are as follows：
(1) present invention is when TNGU is hydrolyzed, with HCl, HBr or H2SO4Acidic aqueous solution replaces NaHCO3Or the alkalinity of NaOH
Hydrolysis, reduces the step of basic hydrolysis is acidified again so that hydrolysate TNAE divides during removing from from alkalescent to faintly acid
From process, improve the stability of TNAE, make TNAE yields improve, to make TTBN yields improve；
(2) by one pot of progress of synthetic reaction of the hydrolysis of TNGU and TTBN, separation TNAE is both eliminated, middle is reduced
The loss of product is managed, and makes to reduce using plurality of raw materials such as barium hydroxide, acetic acid, sodium bicarbonates.
(3) synthesis step is short, at low cost, high income, and purity is high.
Specific implementation mode
The present invention is described in detail below, but it should explanation, these embodiments are not the limit to the present invention
System, those of ordinary skill in the art according in function, method or structure made by these embodiments equivalent transformation or replace
Generation, all belong to the scope of protection of the present invention within.
A kind of method of one pot process TTBN is present embodiments provided, it is directly anti-with methenamine by TNGU acidic hydrolysis
It answers, one-pot synthesis TTBN, i.e.,
At room temperature, TNGU is added to HCl, HBr or the H for filling 2-8M2SO4In the three-necked flask of aqueous solution, in 15-
At 40 DEG C, it is sufficiently stirred hydrolysis 30-180min, the methenamine of 0.8-1.5 times of TNGU (molal quantity), stirring and dissolving is added
Afterwards, it is warming up to 30-60 DEG C, 30-90min is reacted, filters after reaction, filter cake is washed with water to neutrality, dichloromethane washing two
It is secondary, it is dried to obtain white solid, 73% or more yield.This process simplify the preparation processes of TTBN, by TNGU in acid condition
Lower hydrolysis need not also prepare the barium salt of TNAE, but directly react one-pot synthesis TTBN with methenamine without separation.
In the present embodiment, the molar ratio of the methenamine and TNGU of addition is 0.8:1-1.5:1, TNGU and acidic catalyst
The molar ratio of agent is 1:5-1:20.
Specific embodiment：
Embodiment 1
At room temperature, 3.2g TNGU are added in the three-necked flask of HCl/water solution for the 2M for filling 30mL, are stirred
After 60min, 2.1g methenamines are added, after stirring and dissolving, is warming up to 40 DEG C, reacts 90min, filter after reaction, filter cake
It is washed with water to neutrality, dichloromethane washes twice, and is dried to obtain white solid, yield 73%, purity 98%.
Embodiment 2
At room temperature, 3.2g TNGU are added in the three-necked flask of HCl/water solution for the 3M for filling 30mL, are stirred
After 120min, 1.1g methenamines are added, after stirring and dissolving, is warming up to 60 DEG C, reacts 30min, filter after reaction, filter cake
It is washed with water to neutrality, dichloromethane washes twice, and is dried to obtain white solid, yield 76%, purity 98%.
Embodiment 3
At room temperature, 3.2g TNGU are added in the three-necked flask of HBr aqueous solutions for the 4M for filling 30mL, are heated to
30 DEG C, after stirring 40min, 1.5g methenamines are added, after stirring and dissolving, is warming up to 35 DEG C, reacts 90min, after reaction
Filtering, filter cake are washed with water to neutrality, and dichloromethane washes twice, and is dried to obtain white solid, yield 82%, purity 98%.
Embodiment 4
At room temperature, 3.2g TNGU are added to the H2SO for the 5M for filling 30mL4In the three-necked flask of aqueous solution, stirring
1.4g methenamines are added in 120min, after stirring and dissolving, are warming up to 40 DEG C, react 50min, filter after reaction, filter cake is used
It is washed to neutrality, dichloromethane washes twice, and is dried to obtain white solid, yield 77%, purity 98%.
Embodiment 5
At room temperature, 3.2g TNGU are added in the three-necked flask of HCl/water solution for the 6M for filling 30mL, are stirred
1.2g methenamines are added in 180min, after stirring and dissolving, are warming up to 50 DEG C, react 60min, filter after reaction, filter cake is used
It is washed to neutrality, dichloromethane washes twice, and is dried to obtain white solid, yield 73%, purity 98%.
Embodiment 6
At room temperature, 3.2g TNGU are added to the H2SO for the 3M for filling 20mL4In the three-necked flask of aqueous solution, 40
After DEG C stirring 30min, 1.5g methenamines are added, stirring and dissolving is warming up to 60 DEG C, reacts 30min, filters after reaction,
Filter cake is washed with water to neutrality, and dichloromethane washes twice, and is dried to obtain white solid, yield 79%, purity 98.5%.
Embodiment 7
At room temperature, 3.2g TNGU are added in the three-necked flask of HCl/water solution for the 3.5M for filling 30mL, 30
After DEG C stirring 60min, 1.5g methenamines are added, stirring and dissolving is warming up to 40 DEG C, reacts 50min, filters after reaction,
Filter cake is washed with water to neutrality, and dichloromethane washes twice, and is dried to obtain white solid, yield 86%, purity 99%.
Embodiment 8
At room temperature, 3.2g TNGU are added in the three-necked flask of HCl/water solution for the 8M for filling 30mL, are stirred
After 120min, 1.5g methenamines are added, after stirring and dissolving, is warming up to 60 DEG C, reacts 40min, filter after reaction, filter cake
It is washed with water to neutrality, dichloromethane washes twice, and is dried to obtain white solid, yield 76%, purity 98%.
The present invention has the advantages that：
(1) by one pot of progress of synthetic reaction of the hydrolysis of TNGU and TTBN, synthesis technology is simple.(2) when TNGU is hydrolyzed,
It replaces alkaline aqueous solution to hydrolyze with acidic aqueous solution, reduces the step of basic hydrolysis is acidified again so that hydrolysate TNAE exempts from
Decomposition during going from alkalescent to faintly acid improves the stability of TNAE, so that TNAE yields is improved, to make TTBN yields
It improves；(3) intermediate link for preparing TNAE barium salts is eliminated, is reduced a variety of using barium hydroxide, acetic acid and sodium bicarbonate etc.
Raw material has saved the cost of raw material.
It should be added that the present invention in implementation phase, also attempts to use other alternative solution synthesis TTBN, and
It tests respectively, including：Scheme 1) it is directly reacted in acid condition with TNAE and can also synthesize TTBN；Scheme 2) by TNGU alkali
Property hydrolysis after be acidified, being directly added into methenamine without separation also can one pot process TTBN.By verification, above two is closed
At the method for TTBN, there are wretched insufficiencies：Intermediate regulations pH value can make TNAE decomposeds, so cause product TTBN yields low,
Complex process, it is of high cost.In addition, scheme 2) in due to will produce a large amount of salt in acidization, influence reaction and be effectively performed.
The series of detailed descriptions listed above only for the present invention feasible embodiment specifically
Bright, they are all without departing from equivalent implementations made by technical spirit of the present invention not to limit the scope of the invention
Or change should all be included in the protection scope of the present invention.
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie
In the case of without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended power
Profit requires rather than above description limits, it is intended that all by what is fallen within the meaning and scope of the equivalent requirements of the claims
Variation is included within the present invention.
Claims (3)
1. a kind of method of one pot process TTBN, which is characterized in that directly reacted with methenamine by TNGU acidic hydrolysis, one
Pot synthesis TTBN, specifically includes：At room temperature, TNGU is added in the acidic catalyst aqueous solution of a concentration of 2-8M, in 15-
After 40 DEG C of stirring hydrolysis 30-180min, it is directly added into methenamine, 30-90min, one-pot synthesis are reacted at 30-60 DEG C
TTBN。
2. the method for one pot process TTBN according to claim 1, which is characterized in that the acidic catalyst is salt
Acid, hydrobromic acid or sulfuric acid.
3. the method for one pot process TTBN according to claim 2, which is characterized in that the methenamine of addition with
The molar ratio of the TNGU is 0.8:1-1.5:The molar ratio of 1, the TNGU and the acidic catalyst is 1:5-1:20.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103087069A (en) * | 2013-01-28 | 2013-05-08 | 南京理工大学 | Synthesis method of 3,7-binitro-1,3,5,7-tetraazabicyclo[3.3.1]nonane |
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| US9695177B2 (en) * | 2014-09-29 | 2017-07-04 | The United States Of America As Represented By The Secretary Of The Army | Preparation of tetranitroglycoluril |
| US9512127B2 (en) * | 2014-09-29 | 2016-12-06 | The United States Of America As Represented By The Secretary Of The Army | Process for the production of speherical tetranitroglycouril |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103087069A (en) * | 2013-01-28 | 2013-05-08 | 南京理工大学 | Synthesis method of 3,7-binitro-1,3,5,7-tetraazabicyclo[3.3.1]nonane |
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