CN101768127A - Preparation method of TAT - Google Patents
Preparation method of TAT Download PDFInfo
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- CN101768127A CN101768127A CN200910263939A CN200910263939A CN101768127A CN 101768127 A CN101768127 A CN 101768127A CN 200910263939 A CN200910263939 A CN 200910263939A CN 200910263939 A CN200910263939 A CN 200910263939A CN 101768127 A CN101768127 A CN 101768127A
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Abstract
The invention relates to a preparation method of TAT, comprising the following steps of: slowly dripping acetic anhydride with 1.5-2.5 times of the mass of HA at 5-10 DEG C by using the HA, ammonium acetate and water as raw materials; reacting for 30-50 minutes to obtain DAPA under stirring; reacting for 2-3 hours by using DAPT and the acetic anhydride as the raw materials and increasing temperature to 100-110 DEG C; and reacting for 1-2 hours by reducing the temperature to 30-35 DEG C to obtain a product TAT, in the presence of water as a catalyst, wherein the water accounts for 5-35 percent of the mass of the acetic anhydride raw material. The invention replaces the catalyst in a Lukasavage process method with the inexpensive water, obviously enhances the yield of the TAT, enables the synthesizing process of the TAT to be easy and reduces the production cost.
Description
Technical field
The present invention relates to a kind of energetic material intermediates preparation, specifically relate to a kind ofly 1,3,5,7-is tetra-acetylated-1,3,5, the preparation method of 7-tetraazacyclododecane octane (TAT).
Background technology
(1,3,5,7-tetra-acetylated-1 for TAT; 3,5,7-tetraazacyclododecane octane) be one of important intermediate of synthetic HMX (octogen); also can be used for suspension agent, stablizer of solution etc., it is nitrated to select suitable nitrating agent that TAT is carried out, and can obtain high yield, highly purified HMX.Since last century the seventies, many R﹠D institutions begin the synthetic method of TAT is studied, and original technology is improved, and have obtained certain achievement, for new vitality has been injected in the utilization of TAT.Up to the present, the preparation of TAT mainly contains following several method:
1,1972, U.S. scientific research personnel with urotropine, diacetyl oxide, water and ammonium acetate 0～20 ℃ of scope internal reaction generate DAPT (1,5-diacetyl-3; 7-endo-methylene group-1; 3,5,7-tetraazacyclododecane octane) solution; in DAPT solution, add diacetyl oxide, sodium-acetate and Acetyl Chloride 98Min. then successively; after becoming ripening reaction, acetone recrystallization is used in underpressure distillation; get white TAT solid, the yield of this technology is about about 89%.
The reaction mechanism of this reaction divided for three steps carried out basically, and the first step is opened the bridge methylene base of DAPT; form 1,3,5-triacetyl-7-methylene radical tetraazacyclododecane octane with the Acetyl Chloride 98Min. that adds; second step, 1,3; 5-triacetyl-7-methylene radical tetraazacyclododecane octane and sodium-acetate reaction generate 1,3; 5-triacetyl-7-acetyl-o-methyl tetraazacyclododecane octane, the 3rd step, 1; 3,5-triacetyl-7-acetyl-o-methyl tetraazacyclododecane octane generates TAT through acetolysis.
2,1976, Siele V.I. separated 1molDAPT with the 10mol acetic anhydride at 110 ℃ of following acyls, and through the 3h reaction, acetone recrystallization is used in underpressure distillation again, can obtain the 74%TAT white solid.
3, calendar year 2001, Lukasavage etc. react with urotropine, diacetyl oxide and water, and after ripe one section reaction, underpressure distillation gets the DAPT solid.DAPT is joined in the acetic anhydride of 2～3 times (mol ratios), stir and be warmed up to 110 ℃ of insulation 2h, cool to 30 ℃ then, behind adding copper and iron (or its oxide compound) the reaction 1.5h, carry out underpressure distillation.Gained faint yellow solid product carries out recrystallization with ebullient acetone, makes product TAT, 165～166 ℃ of fusing points, yield 81%.
More than among several preparation methods, method 1 consumption diacetyl oxide and Acetyl Chloride 98Min. are excessive, if adopt lower temperature (0～10 ℃ or lower), then need to operate under the low temperature refrigerating apparatus of required costliness, if carry out being higher than under the room temperature (as 50 ℃), then quicken undesirable side reaction under the high temperature greatly, reduced the yield of TAT.And the difficult control of reaction process; It is excessive that method 2 consumes diacetyl oxide; Method 3 needs to add solid catalyst, and needs to filter.The existence of these objective factors makes these methods lack application prospect.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of TAT, this method is improved the Lukasavage preparation method, with the water alternative catalysts, to reduce production costs.
TAT preparation method of the present invention improves to obtain on the basis of Lukasavage processing method, its core content is to use green, cheap water to replace the catalyst component in the Lukasavage processing method, and the mol ratio of reactant, reaction times, temperature of reaction etc. are optimized.
The preparation method of TAT of the present invention may further comprise the steps:
With mass ratio is that 1: 0.4～0.6: 0.5～0.8 urotropine (HA), ammonium acetate and water are raw material, control reaction temperature is 5～10 ℃, stir and slowly splash into the diacetyl oxide that accounts for 1.5～2.5 times of HA quality down, add the back and continue stirring reaction 30～50min, reaction solution is warming up to 120 ℃ of underpressure distillation, product of distillation carries out recrystallization with acetone, obtains the DAPA white crystal.
With mass ratio is that 1: 1.9～2.1 DAPT and diacetyl oxide are raw material, is warming up to 100～110 ℃ of reaction 2～3h, is cooled to 30～35 ℃, add and account for the water of diacetyl oxide raw materials quality 5～35% as catalyzer, reaction 1～2h, underpressure distillation, product obtains product TAT with acetone recrystallization.
Studies confirm that,, must as early as possible reacted acetate, diacetyl oxide be separated from solution in order to obtain the DAPT of high yield.The boiling point of diacetyl oxide is than the acetate height, and in vacuum distillation process, acetate is steamed earlier, and wants to steam diacetyl oxide, must further improve temperature.Because DAPT is to thermally labile, the process of elevated temperature has also been impelled the accelerate decomposition of DAPT, has reduced yield.So, before underpressure distillation, add a certain amount of water, make unreacted diacetyl oxide hydrolysis, can reduce the time of underpressure distillation, reduce vacuum distillation temperature, improve the yield of DAPT.
In the acetylation of DAPT, the effect of diacetyl oxide has two, and the first plays the effect of solvent, the DAPT of one of solubilizing reaction thing, and it two is as reaction substrate.Mol ratio according to reaction is calculated, the mol ratio of DAPT and diacetyl oxide be 1: 1 o'clock enough, still such reaction solution is thickness too, be unfavorable for stirring, and the DAPT reaction not exclusively, so need certain excessive acetic anhydride via, the consumption of diacetyl oxide is determining the yield of TAT.Usually, the mass ratio of control DAPT and diacetyl oxide is 1: 1.9～2.1, further increases the consumption of diacetyl oxide, and the yield of TAT does not improve significantly.
According to the reaction mechanism of TAT, DAPT generates intermediate by acetylize---and ester, this ester are in the acidic conditions instability, easily by H
+Attack is converted into methylol, and then accepts a H
+Attack, slough methylol, be converted into secondary amine, secondary amine is an easy acetylizad material, under the condition that diacetyl oxide exists, is easy to and diacetyl oxide generation acetylization reaction, and then is converted into TAT.So, after reaction system is introduced water, promoted intermediate---the hydrolysis of ester, reduced the activation energy in the acetylation, make the acetylization reaction ratio be easier to carry out.
Experiment showed, that when reacting, the yield of TAT has only about 20% if do not add any catalyzer under 110 ℃ condition; If add a certain amount of water, then yield can reach 74%, and is approaching with the productive rate of Lukasavage processing method, and reaction process is operated easily.So the adding of water has influenced the reaction mechanism of this reaction, obviously improved the yield of TAT.Substitute traditional solid catalyst with water, simplified reaction, reduced cost.
Therefore, unusual effect of the present invention is: 1) yield of synthetic DAPT has improved about 10% 2) replaced catalyzer in the Lukasavage processing method with the water of cheapness, technology is simple, and productive rate is constant, has reduced the cost of synthesis technique.
Description of drawings
Fig. 1 is the infrared spectrogram of the TAT for preparing of the embodiment of the invention 1.
Embodiment
Embodiment 1
7g (0.05mol) HA, 3.1g (0.04mol) ammonium acetate and 3.5g (0.2mol) water are joined in the round-bottomed flask, stir into pulpous state, hierarchy of control temperature is at 5～10 ℃, stir down, slowly splash into 15g diacetyl oxide (0.15mol) in 30min, after adding, controlled temperature is below 10 ℃, continue to stir 30min, make to react completely.Reaction solution is warming up to 120 ℃ of following underpressure distillation, in the product that obtains, adds 20mL acetone ebuillition of heated, carry out recrystallization, obtain DAPT white crystal 10.6g, yield 100% (in the HA that adds).
5g (0.024mol) DAPT and 9.6g (0.09mol) diacetyl oxide are joined in the reactor, be warming up to 110C reaction 2h under stirring, be cooled to 30 ℃, add 2mL water reaction 1.5h, underpressure distillation is carried out recrystallization with the faint yellow solid product that obtains with ebullient acetone, makes product TAT5.48g, 166 ℃ of fusing points, yield 80.5%.
The TAT that obtains is carried out structural characterization, and the result is as follows.
1, ultimate analysis: analytical results sees Table 1.
The ultimate analysis of table 1 TAT
By table 1 ultimate analysis as can be known, the percentage composition of its C, N, H element is close, and promptly institute's synthetic product is consistent with the constituent content per-cent of target product, can think the synthetic target product of wanting.
2, Infrared spectroscopy: infrared spectrogram such as Fig. 1.
As seen from Figure 1 :-CH
2-characteristic peak: 2937cm
-1Carbonyl characteristic peak: 1662cm
-1, 1635cm
-1C-N characteristic peak: 1298cm
-1, 1263cm
-1
Can judge that according to above-mentioned characterization result the product that reaction finally obtains is TAT.
Embodiment 2
9.5g (0.068mol) HA, 5g (0.065mol) ammonium acetate and 6mL (0.343mol) water (5～10 ℃ of water temperatures) are joined in the 50mL round-bottomed flask, stir into pulpous state, hierarchy of control temperature is at 5～10 ℃, stir and in 50min, slowly splash into 18g diacetyl oxide (0.18mol) down, after adding, controlled temperature continues to stir 40min below 10 ℃, makes to react completely.Reaction solution is warming up to 120 ℃ of underpressure distillation, adds 40mL acetone in the product of distillation, behind the ebuillition of heated, carry out recrystallization, obtain DAPA white crystal 14.38g, yield 100% (in the HA that adds).
8gDAPT and 16.7g diacetyl oxide are joined in the 100mL reactor, be warming up to 100 ℃ of reaction 2h under stirring, be cooled to 30 ℃, add 4mL water reaction 1.5h, underpressure distillation, gained faint yellow solid product ebullient acetone recrystallization, make product TAT8.55g, 165 ℃ of fusing points, yield 79.8%.
Embodiment 3
22g (0.157mol) HA, 9.5g (0.123mol) ammonium acetate and 11mL (0.628mol) water (5～10 ℃ of water temperatures) are joined in the 50mL round-bottomed flask, stir into pulpous state, hierarchy of control temperature is at 5～10 ℃, stir and in 30min, slowly splash into 50g diacetyl oxide (0.5mol) down, after adding, controlled temperature continues to stir 35min below 10 ℃, makes to react completely.Reaction solution is warming up to 120 ℃ of underpressure distillation, adds 30mL acetone in the product, carry out recrystallization behind the ebuillition of heated, get DAPA white crystal 33.14g, yield 100% (in the HA that adds).
10gDAPT and 19.2g diacetyl oxide are joined in the 100mL reactor, be warming up to 110 ℃ of reaction 2h under stirring, be cooled to 30 ℃, add 3mL water reaction 1.5h, underpressure distillation, gained faint yellow solid product ebullient acetone recrystallization makes product TAT10.85g, 166 ℃ of fusing points, yield 81.0%.
Claims (3)
1.TAT the preparation method, may further comprise the steps:
1) be that 1: 0.4～0.6: 0.5～0.8 HA, ammonium acetate and water are raw material with mass ratio, control reaction temperature is 5～10 ℃, stirs down and slowly splashes into the diacetyl oxide that accounts for 1.5～2.5 times of HA quality, and stirring reaction 30～50min obtains DAPA;
2) be that 1: 1.9～2.1 DAPT and diacetyl oxide are raw material with mass ratio,, be cooled to 30～35 ℃ in 100～110 ℃ of reaction 2～3h, add account for diacetyl oxide raw materials quality 5～35% water as catalyzer, reaction 1～2h obtains TAT.
2. the preparation method of TAT according to claim 1 is characterized in that the DAPA reaction solution that reaction is obtained is warming up to 120 ℃ of underpressure distillation, and product of distillation carries out recrystallization with acetone and obtains the DAPA crystal.
3. the preparation method of TAT according to claim 1 is characterized in that product of distillation is with acetone recrystallization with the underpressure distillation of TAT reaction solution.
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| CN200910263939A CN101768127A (en) | 2009-12-25 | 2009-12-25 | Preparation method of TAT |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103351351A (en) * | 2013-07-01 | 2013-10-16 | 太仓市恒益医药化工原料厂 | Preparation process for TAT |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103351351A (en) * | 2013-07-01 | 2013-10-16 | 太仓市恒益医药化工原料厂 | Preparation process for TAT |
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Inventor after: Li Yongxiang Inventor after: Chen Lizhen Inventor after: Wang Jianlong Inventor after: Cao Duanlin Inventor after: Li Quanliang Inventor after: Xu Chunyan Inventor before: Wang Jianlong Inventor before: Chen Lizhen Inventor before: Cao Duanlin Inventor before: Li Yongxiang Inventor before: Li Quanliang Inventor before: Xu Chunyan |
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Free format text: CORRECT: INVENTOR; FROM: WANG JIANLONG CHEN LIZHEN CAO DUANLIN LI YONGXIANG LI QUANLIANG XU CHUNYANTO: LI YONGXIANG CHEN LIZHEN WANG JIANLONG CAO DUANLIN LI QUANLIANG XU CHUNYAN |
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Open date: 20100707 |