CN102267913B - Synthetic method of 2,3-dimethyl-2,3-dinitrobutane - Google Patents
Synthetic method of 2,3-dimethyl-2,3-dinitrobutane Download PDFInfo
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Abstract
The invention discloses a synthetic method of 2,3-dimethyl-2,3-dinitrobutane. The synthetic method comprises the following steps that 1, acetoxime, water, and catalyst modified titanium silicalite (TS)-1 are added into a reaction container at room temperature; 2, aqueous alkali and hydrogen peroxide are added dropwisely into the reaction system obtained by the previous step at a temperature of 60 to 90 DEG C with stirring; the pH of the reaction system is kept in a range of 8 to 10; and a mol ratio of hydrogen peroxide and acetoxime is in a range of 1 to (3: 1); 3, after dropwiseaddition, the mixture obtained from the step 2 undergoes a reaction at a temperature of 60 to 90 DEG C for 0 to 2 hours; 4, reaction products obtained from the step 3 is cooled to room temperature and then is subjected to a filtration or a centrifugation process thus modified TS-1 is separated from the cooled reaction product and mother liquor is obtained; the modified TS-1 is washed by acetone; washing liquid is collected; and the collected washing liquid is added into the mother liquor; and 5, the mother liquor containing the collected washing liquid is subjected to a distillation process at a temperature less than or equal to 80 DEG C so that acetone in the reaction system is removed; the mother liquor treated by the distillation process is cooled and filtrated; and filter residues are washed by water to form 2,3-dimethyl-2,3-dinitrobutane products. Raw materials adopted by the synthetic method have the advantages of good safety and low cost. 2,3-dimethyl-2,3-dinitrobutane synthesized by the synthetic method has the advantages of less impurities and high product quality.
Description
Technical field
The present invention relates to compou nd synthesis method and technology field, be specifically related to a kind of synthetic method of DMNB.
Background technology
DMNB (DMNB) is a kind of important organic intermediate, and it is of many uses.Have specific function and purposes as the explosive tracer agent as it, International Civil Aviation Organization (ICAO) was in file publishing in 1991, Compulsory Feature is added the detection that tracer agent is convenient to the airport explosive substance in slurry explosives, 2, the 3-dimethyl-2,3-dinitrobutane just can replace nitrotoluene as tracer agent.DMNB is also that synthetic 2-replaces-1,3-dioxy-4,4,5, one of critical materials of 5-tetramethyl-imidazolines material, and this class material has single-minded acquisition performance to NO, and important application is medically being arranged.In addition, one of important source material of the various nitroxyl free radical of main structure body of DMNB or synthetic molecules magnet.Therefore, the DMNB synthetic method tool of efficient, the low consumption of research and development and safety is of great significance.
Seigle L.W. and Hass H.B. (J.Org.Chem.1940,5:100) have reported with 2-nitropropane sodium salt and 2-halogen-2-nitropropane and reacted the method that generates DMNB in alcohol solvents:
X=Cl wherein, Br, I.
Reactant 2-nitropropane sodium salt is first reacted by sodium Metal 99.5 and dehydrated alcohol, then prepares with the reaction of 2-nitropropane; 2-halogen-2-nitropropane can obtain by add halogen in the sodium hydroxide solution of 2-nitropropane.But the yield of this synthetic method only has respectively 9%, 37% and 43%, and the raw material 2-nitropropane that the method will be used is highly toxic substance, poor safety performance.
TsunodaR. etc. (Eur.J.Pharm.1994,262:55) adopted improvement project, first nitropropane mixed with sodium hydroxide solution, then slowly drips bromine under frozen water is cooling, and then adds the ethanol temperature rising reflux and obtain product.This method is more convenient, and yield is higher, can reach 65～92%, but products obtained therefrom is impure many, second-rate, and product fusing point as synthetic in bibliographical information the method only has 129～130 ℃, and will use the highly toxic substances such as 2-nitropropane, bromine equally.
(the Org.Lett.2010 such as Jesse B.M., 12:3522) reported and first used 2-nitropropane and sodium hydride (NaH) reaction Formed negative ion and then with ceric ammonium nitrate (CAN) oxidation preparation generation 2,3-dimethyl-2,3-dinitrobutane, yield are 52%.But the method will be used the raw materials such as hazardous chemical 2-nitropropane, NaH equally, and also will use expensive ceric ammonium nitrate, causes synthetic cost up.
In sum, the synthetic method of the DMNB of prior art is all take the 2-nitropropane as raw material, and uses more hazardous chemical, and safety in production is had larger harm, and impure many, poor product quality.
Summary of the invention
Technical problem to be solved by this invention is the deficiency that overcomes above prior art problem, provide a kind of 2,3-dimethyl-2, the synthetic method of 3-dinitrobutane, the raw materials used safety performance of this synthetic method is good, cost is low, synthetic DMNB is impure less, quality product is high.
The technical solution adopted in the present invention comprises the following steps for a kind of synthetic method of DMNB is provided:
(1) at room temperature add acetoxime, aqueous solvent, catalyst modification TS-1 in reaction vessel; The consumption of water is 1～10 times of acetoxime weight, and modification TS-1 consumption is 0.05～0.3 times of acetoxime weight;
(2) be to drip alkaline solution and hydrogen peroxide in the above-mentioned reaction system of 60～90 ℃ to temperature while stirring, guarantee the pH of reaction system 8～10, the middle mol ratio that adds acetoxime of hydrogen peroxide and step (1) is 1～3: 1;
(3) be added dropwise to complete after, react 0～2h (0h represents while dripping reaction, drips also and has just reacted) at 60～90 ℃ of temperature;
(4) be cooled to room temperature, filtration or centrifugation go out modification TS-1 and obtain mother liquor, and modification TS-1 collects washings with washing with acetone; Washings is added in mother liquor;
(5) acetone of mother liquor in not removing reaction system higher than 80 ℃ of temperature backspins steamings of washings will have been added in step (4); Then cooling, filter, wash with water filter residue, obtain the product DMNB.
Also comprise in above-mentioned steps (5) and make the raw material of step (1) with filtering the gained filtered solution with reuse with chloroform extraction recovery acetoxime; The consumption of chloroform is middle 2 times of adding acetoxime weight of step (1).
In above-mentioned steps (1), the preparation method of catalyst modification TS-1 is: in reaction vessel, in every 1L aqueous solvent, add acetone 20mol, TS-1 100g, then drip simultaneously ammoniacal liquor 36mol and hydrogen peroxide 20mol at 65～80 ℃ of temperature, be added dropwise to complete rear insulation reaction 0.5h, then the centrifuging and taking precipitation; Precipitation repeats said process 6～10 times again, gets modification TS-1.
The consumption of water is preferably 2～4 times of acetoxime weight in above-mentioned steps (1), and the consumption of aqueous solvent crosses that I haven't seen you for ages causes product yield low, and the too high productivity that causes of consumption descends, and decomposing hydrogen dioxide solution increases, and energy consumption increases.
The middle modification TS-1 consumption of above-mentioned steps (1) is preferably 0.1～0.15 times of acetoxime weight, and consumption product yield very little is low, and decomposing hydrogen dioxide solution increases, and the too high cost that causes of consumption increases.
Alkaline solution is ammonia soln or alkali hydroxide soln in above-mentioned steps (2), sodium hydroxide more preferably, and the yield of ammonia soln is lower under the identical dioxygen water yield, and other alkali hydroxide soln can cause cost high.
When dripping hydrogen peroxide and alkaline solution in above-mentioned steps (2), the temperature of reaction system is preferably 80～90 ℃, and temperature is too low, and product yield obviously descends, and is too high, and decomposing hydrogen dioxide solution will roll up; It is too low that the pH of reaction system is preferably 9～10, pH, and de-oxime reaction is serious, and product yield descends, and too high catalyzer can dissolve destructing and inactivation.
The mol ratio that adds acetoxime in above-mentioned steps (2) in hydrogen peroxide and step (1) is preferably 2～2.5: 1, and the mol ratio of hydrogen peroxide and acetoxime is too low, and yield is lower, and is too high, can cause acetoxime substantially to transform, weak effect.
It is 80～90 ℃ that temperature of reaction after dripping in above-mentioned steps (3) is preferably, and temperature too low reaction is too slow, and too high decomposing hydrogen dioxide solution side reaction increases; It is 0.5～1h that reaction times is preferably, and the reaction times, too the incomplete hydrogen peroxide utilization ratio of short reaction was low, and oversize effect increases few.
The synthetic method of DMNB provided by the invention, its reaction principle is:
Acetoxime is added in water, then adds catalyst modification TS-1, then drip alkaline solution and hydrogen peroxide under certain temperature, certain pH conditions, reaction formula is:
Taking off oxime or claiming hydrolysis reaction to generate acetone of acetoxime can occur in the time of except the above-mentioned reaction of generation:
Filter or modification TS-1 catalyzer is removed in centrifugation, then vacuum rotary steam removes byproduct acetone, the cooling product of separating out filters, and washing just obtains product.
Compared with prior art, the present invention has following remarkable advantage and beneficial effect:
1. do not use the raw material of the poor safety performance such as 2-nitropropane, sodium hydride, bromine in the synthetic method of DMNB of the present invention, reaction conditions is gentle, good operation safety, and aftertreatment is simple, be easy to suitability for industrialized production, and by-product acetone is recyclable, safety and environmental protection.
2. the raw material that uses of the synthetic method of DMNB of the present invention is sodium hydroxide and hydrogen peroxide except acetoxime and catalyst modification TS-1, and raw material is easy to get, and price is low, and production cost is low.
3. use the product DMNB process that the present invention synthesizes to detect, find that the product fusing point is high, impurity is few, quality is high.
Embodiment
Below in conjunction with embodiment, the present invention is further described in detail, but the present invention not only is confined to following examples.
Embodiment 1:
add 73g water in the there-necked flask of the 250mL that thermometer, constant pressure funnel, electric mixing device are housed, then add 29.2g (0.40mol) acetoxime and 2.9g modification TS-1, vigorous stirring 0.5h under electric stirring, then warming-in-water to 85 ℃, drip simultaneously the hydrogen peroxide of 113.3g (1.00mol) 30% and 30% sodium hydroxide under 85～90 ℃, keep the pH of reaction system 9～10, be added dropwise to complete under rear 90 ℃ and be incubated 0.5h, then cool to room temperature, carry out centrifugation with the 3000rpm rotating speed and remove modification TS-1, modification TS-1 washs at twice with 6g acetone, after washing acetone evaporate to dryness, residue is merged in mother liquor, then at 80 ℃, 0.05MPa under that the mother liquor vacuum rotary steam is removed acetone is (quantitative through GC, 0.32mol is arranged), cool to room temperature again, filter, wash with water, get product 2, 3-dimethyl-2, the 3-dinitrobutane.After oven dry under 70 ℃, get product 3.9g (0.022mol), molar yield is 11.2%; Fusing point is 210.2～212.0 ℃.
1H?NMR(400Hz，DMSO-d6)，δ：1.71(s，2H)。
13C?NMR(100MHz，DMSO-d6)，δ：23.02，91.47。
Filtered solution after the filtration DMNB at room temperature extracts at twice with the 58g chloroform, merges, and steams except chloroform, through the GC quantitative analysis, also has the acetoxime of 0.025mol.
Embodiment 2:
The consumption of aqueous solvent changes 146g into, the other the same as in Example 1, and result is: the molar yield 12.5% of DMNB, fusing point are 210.5～212.1 ℃, acetone 0.33mol, acetoxime 0.01mol.
Embodiment 3:
Modification TS-1 consumption changes 4.3g into, the other the same as in Example 1, and result is: the molar yield 11.4% of DMNB, fusing point are 210.2～212.0 ℃, acetone 0.34mol, acetoxime trace.
Embodiment 4:
Replace 30% sodium hydroxide with 30% ammonia, the other the same as in Example 1, result is: the molar yield 5.7% of DMNB, fusing point are 210.3～212.2 ℃, acetone 0.21mol, acetoxime 0.16mol.
Embodiment 5:
Temperature when dripping hydrogen peroxide and alkaline solution changes 75～80 ℃ into, is added dropwise to complete the afterreaction temperature and changes 80 ℃ into, the other the same as in Example 1, result is: the molar yield 8.9% of DMNB, fusing point is 210.2～212.2 ℃, acetone 0.25mol, acetoxime 0.10mol.
Embodiment 6:
The consumption of hydrogen peroxide changes 90.6g (0.8mol) into, the other the same as in Example 1, and result is: the molar yield 8.6% of DMNB, fusing point are 210.1～212.2 ℃, acetone 0.21mol, acetoxime 0.14mol.
In the embodiment of the present invention, each raw material used, unless otherwise indicated, be the commercially available prod; Testing apparatus used or test apparatus are conventional instrument, device in industry.
The above embodiment of the present invention is can not be used for restriction the present invention to explanation of the present invention, and the implication suitable with claims of the present invention and any change in scope all should be thought to be included in the scope of claims.
Claims (8)
1. the synthetic method of a DMNB is characterized in that comprising the following steps:
(1) at room temperature add acetoxime, aqueous solvent, catalyst modification TS-1 in reaction vessel; The consumption of water is 1～10 times of acetoxime weight, and modification TS-1 consumption is 0.05～0.3 times of acetoxime weight;
(2) be to drip alkaline solution and hydrogen peroxide in the above-mentioned reaction system of 60～90 ℃ to temperature while stirring, guarantee the pH of reaction system 8～10, the middle mol ratio that adds acetoxime of hydrogen peroxide and step (1) is 1～3: 1;
(3) be added dropwise to complete after, react 0～2h at 60～90 ℃ of temperature;
(4) be cooled to room temperature, filtration or centrifugation go out modification TS-1 and obtain mother liquor, and modification TS-1 collects washings with washing with acetone; Washings is added in mother liquor;
(5) acetone of mother liquor in not removing reaction system higher than 80 ℃ of temperature backspins steamings of washings will have been added in step (4); Then cooling, filter, wash with water filter residue, obtain the product DMNB;
In above-mentioned steps (1), the preparation method of catalyst modification TS-1 is: in reaction vessel, in every 1L aqueous solvent, add acetone 20mol, TS-1100g, then drip simultaneously ammoniacal liquor 36mol and hydrogen peroxide 20mol at 65～80 ℃ of temperature, be added dropwise to complete rear insulation reaction 0.5h, then the centrifuging and taking precipitation; Precipitation repeats said process 6～10 times again, gets modification TS-1.
2. the synthetic method of DMNB according to claim 1 is characterized in that: in above-mentioned steps (1), the consumption of water is 2～4 times of acetoxime weight.
3. the synthetic method of DMNB according to claim 1 is characterized in that: in above-mentioned steps (1), modification TS-1 consumption is 0.1～0.15 times of acetoxime weight.
4. the synthetic method of DMNB according to claim 1, it is characterized in that: in above-mentioned steps (2), alkaline solution is ammonia soln or alkali hydroxide soln.
5. the synthetic method of DMNB according to claim 4, it is characterized in that: in above-mentioned steps (2), alkaline solution is sodium hydroxide.
6. the synthetic method of DMNB according to claim 1, it is characterized in that: when dripping hydrogen peroxide and alkaline solution in above-mentioned steps (2), the temperature of reaction system is 80～90 ℃, guarantees that the pH of reaction system is 9～10.
7. the synthetic method of DMNB according to claim 1, it is characterized in that: in above-mentioned steps (2), hydrogen peroxide is 2～2.5: 1 with the middle mol ratio that adds acetoxime of step (1).
8. the synthetic method of DMNB according to claim 1, it is characterized in that: the temperature of reaction after dripping in above-mentioned steps (3) is 80～90 ℃, and the reaction times is 0.5～1h.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110146239 CN102267913B (en) | 2011-05-20 | 2011-05-20 | Synthetic method of 2,3-dimethyl-2,3-dinitrobutane |
| PCT/CN2011/079347 WO2012159390A1 (en) | 2011-05-20 | 2011-09-05 | Method for preparing 2,3-dimethyl-2,3-dinitrobutane |
| US13/823,831 US8692036B2 (en) | 2011-05-20 | 2011-09-05 | Method for preparing 2,3-dimethyl-2,3-dinitrobutane |
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| CN 201110146239 CN102267913B (en) | 2011-05-20 | 2011-05-20 | Synthetic method of 2,3-dimethyl-2,3-dinitrobutane |
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| CN102267913B true CN102267913B (en) | 2013-06-12 |
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| CN105732393B (en) * | 2016-04-05 | 2018-01-02 | 宁波四明化工有限公司 | A kind of synthetic method of 2 nitropropane |
| CN106045859A (en) * | 2016-07-01 | 2016-10-26 | 定州旭阳科技有限公司 | Method for preparing 2-nitropropane |
| CN106631809B (en) * | 2016-10-10 | 2019-02-22 | 南京工业大学 | A kind of oxime oxidation prepares the green synthesis method of nitroparaffins |
| CN108178731A (en) * | 2018-01-19 | 2018-06-19 | 广州印田新材料有限公司 | One kettle way prepares the green synthesis method of AMP-95 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0638362A1 (en) * | 1993-08-11 | 1995-02-15 | Mitsubishi Gas Chemical Company, Inc. | Titanosilicate catalyst particle |
| CN1743314A (en) * | 2004-09-03 | 2006-03-08 | 首都医科大学 | 2-substituted-4,4,5,5-tetramethyl-1-oxyimidazoline, and its synthesis and use |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0638362A1 (en) * | 1993-08-11 | 1995-02-15 | Mitsubishi Gas Chemical Company, Inc. | Titanosilicate catalyst particle |
| CN1743314A (en) * | 2004-09-03 | 2006-03-08 | 首都医科大学 | 2-substituted-4,4,5,5-tetramethyl-1-oxyimidazoline, and its synthesis and use |
Non-Patent Citations (4)
| Title |
|---|
| A NEW SYNTHESIS OF DINITROPARAFFINS;L.W.SEIGLE;《Journal of Organic Chemistry》;19401231;第5卷;第100-105页 * |
| Efficient Synthesis of a Peculiar Vicinal Diamine Semiochemical from Streptomyces natalensis;Jesse B. Morin;《ORGANIC LETTERS》;20100715;第12卷(第15期);第3522-3524页 * |
| Jesse B. Morin.Efficient Synthesis of a Peculiar Vicinal Diamine Semiochemical from Streptomyces natalensis.《ORGANIC LETTERS》.2010,第12卷(第15期),3522-3524. |
| L.W.SEIGLE.A NEW SYNTHESIS OF DINITROPARAFFINS.《Journal of Organic Chemistry》.1940,第5卷100-105. |
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