CN103113397A - Preparation method of amino borane - Google Patents
Preparation method of amino borane Download PDFInfo
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- CN103113397A CN103113397A CN2013100455498A CN201310045549A CN103113397A CN 103113397 A CN103113397 A CN 103113397A CN 2013100455498 A CN2013100455498 A CN 2013100455498A CN 201310045549 A CN201310045549 A CN 201310045549A CN 103113397 A CN103113397 A CN 103113397A
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Abstract
The invention relates to a preparation method of amino borane. According to the method, through taking ammonium salts and sodium borohydride as raw materials, taking an organic solvent as a reaction medium, and taking ethyl ether as a purification medium, methylamine borane is synthesized through common chemical reaction. The invention provides a method capable of synthesizing amino borane in the air, which provides great convenience for future industrial production and applications. The preparation method disclosed by the invention is simple in reaction method, low in cost and moderate in temperature; an operation of reaction can be performed at room temperature, and obtained products are high in purity and high in yield.
Description
Technical field
The present invention relates to the preparation method of hydrogen energy source carrier, particularly a kind of preparation method of amido borine.
Background technology
Due to long-term a large amount of consumption of the fossil oils such as oil, resource is petered out, and the mankind are more and more higher to the demand of the energy, and a new energy carrier is by strong request.Hydrogen Energy is paid close attention to by people, yet is realized that the application facet of Hydrogen Energy exists several challenges as a kind of efficient, energy cleaning.At first be there is no direct hydrogen resource, the product hydrogen over 90% is by obtaining from fossil oil such as Sweet natural gas, still can follow the discharging of carbonic acid gas simultaneously, environment having been caused pollution; Then be exactly now also not have the Infrastructure of Hydrogen Energy transportation, and to set up a new Hydrogen Energy distribution system be very expensive; At last, along with being gradually improved of fuel cell technology, vehicle-mounted hydrogen storage technology becomes the maximum constraints factor of the application of Hydrogen Energy on automobile, and therefore, a kind of research and development of efficient hydrogen storage material are very important.Methyl ammonia borine has very high Theoretical Mass hydrogen-storage density (17.8%), methyl ammonia borine can be sloughed 3equiv hydrogen by the mode dehydrogenation of hydrolysis, it is the maximum a kind of dehydrogenation mode of dehydrogenation, can also be by the solvolysis dehydrogenation except the hydrolysis dehydrogenation, can slough 2equiv hydrogen at most in organic solvent, the dehydrogenation equation of hydrolysis and solvolysis is as follows:
That research is more at present is ammonia borine (ammonia borane, NH
3BH
3) hydrolysis and solvolysis dehydrogenation, also fewer for the research of methyl ammonia borine, methyl ammonia borine is in the situation that the suitable 3 molecule hydrogen that also can complete hydrolysis produce of catalyzer.Ammonia borine (Aldrich, purity 90% and 97%, 10g price are respectively 1,695.33 yuan and 3,885.57 yuan) and dimethylamino borine ((CH
3)
2NHBH
3, Aldrich, purity is that 97%, 5g price is 200.07 yuan) can buy on market and obtain, methyl ammonia borine can't have been bought from the market, illustrates that the synthetic method that obtains the highly purified methyl ammonia of high yield borine is very important.Methyl ammonia borine also can be used as reductive agent simultaneously except as hydrogen storage material, its reductibility than the ammonia borine a little less than, between ammonia borine and dimethylamino borine, can control that nano particle diameter distributes and composition aspect play certain regulating and controlling effect.
Summary of the invention
The object of the invention is to provides a kind of simple amido borine synthetic method for the problem that exists in background technology.
Concrete technical scheme of the present invention is as follows:
A kind of synthetic method of amido borine is characterized in that: comprise the following steps:
1) ratio that is ammonium salt/sodium borohydride=1:1-1:2 according to mol ratio respectively takes ammonium salt and sodium borohydride, with its mixing, add excessive tetrahydrofuran (THF), be to react 2-24 hours under 10-40oC condition in temperature, obtain reaction mixture, reaction mixture is filtered collect filtrate, the organic solvent in filtrate is removed in evaporation, obtains head product.
2) head product that the upper step was obtained adds ether to make its dissolving, stirs 1-3 hours under the ice-water bath condition, filters and collects filtrate, and evaporation filtrate is removed ether, obtains white crystals shape solid, and get final product.Preference as this programme:
Described ammonium salt is methylamine hydrochloride, anilinechloride or dimethylamine hydrochloride.
method of the present invention is to adopt ammonium salt, sodium borohydride is raw material, take organic solvent as reaction medium, with ether as the purification medium, by the synthetic amido borine of common chemical reaction, produce a large amount of hydrogen in reaction process, carrying out ventilates processes, through the sodium-chlor of reacted generation because be insoluble to organic solvent, pass through filtering separation, then evaporate organic solvent, obtain the head product of amido borine, in order to improve the purity of product, by ether, head product is purified, again pass through filtering separation, then distill out ether, can obtain so the higher amido borine of purity.By detecting, the purity of the amido borine that the present invention synthesizes can reach 90%, and this method of purification is bright spot of the present invention place just.
The price of amino borane compound is all very high, we with cheap ammonia salt and sodium borohydride as raw material, the methyl ammonia borine that at room temperature reaction obtains and productive rate and the purity of dimethylamino borine and phenylamino borine are all also higher, and purity has reached the purity rubric of a lot of commercially available amino borane compounds.
Beneficial effect of the present invention is presented as:
Declare at customs in prior art in the synthetic of ammonia borine and derivative thereof and all carry out below protection of inert gas, the invention provides and a kind ofly can synthesize the method for amido borine in air, for later industrial production and application provide greatly convenient.Reaction method of the present invention is simple, and is with low cost, and temperature is gentle, at room temperature just can react, and the purity of the product that obtains is higher, and productive rate is also higher.
Description of drawings
In Fig. 1, curve 1 is synthetic methyl ammonia borine
11B NMR collection of illustrative plates, curve 2 are after methyl ammonia borine catalytic hydrolysis
11B NMR collection of illustrative plates;
Synthetic methyl ammonia borine shown in Figure 2
1H NMR collection of illustrative plates, wherein curve 1 solvent is heavy water, curve 2 solvents are deuterochloroform;
Synthetic methyl ammonia borine shown in Figure 3
13C NMR collection of illustrative plates.
Embodiment
In order to understand better content of the present invention, below in conjunction with specific embodiment, content of the present invention is described further, but protection content of the present invention is not limited to following examples.
Embodiment 1
1) take respectively sodium borohydride and the methylamine hydrochloride of 0.15mol, then the mixture of methylamine hydrochloride and sodium borohydride is put in two mouthfuls of round-bottomed flasks of 500mL, putting into magneton then measures the 200mL tetrahydrofuran (THF) and joins round-bottomed flask, temperature of reaction is controlled at 25 ℃, reacted 12 hours, and obtained reaction mixture, the mode with reaction mixture by filtration under diminished pressure obtains filtrate, then at room temperature remove tetrahydrofuran (THF), obtain head product.
2) head product that obtains is dissolved in anhydrous diethyl ether, stirs 1h under ice-water bath, then the mode of filtration under diminished pressure obtains filtrate, and after removing ether, the crystalloid solid that obtains white is methyl ammonia borine.
3) purity detecting
Taking the quality that obtains product is 4.3g, and calculating productive rate is 70%.Then by using RuCl
33H
2O is as its hydrolysis of catalyst, and the test dehydrogenation also detects purity, and concrete operation method is: take 3.2mg RuCl
33H
2O is placed in two mouthfuls of round-bottomed flasks of 100mL, the constant pressure funnel of wherein ining succession flatly, connect flatly in addition gas measurement device, the aqueous solution that 45mg methyl ammonia borine is made into 5mL joins in constant pressure funnel, reaction is carried out under 25 ℃, reaction splashes into from methyl ammonia borine solution and begins to carry out, and 60.9ml hydrogen is emitted in reaction in 2min, is 90% by calculating the purity that can obtain methyl ammonia borine.
In Fig. 1, curve 1 is synthetic methyl ammonia borine
11B NMR collection of illustrative plates, methyl ammonia borine
11B NMR peak value is-18.8ppm in the chemical shift that is take deuterochloroform as solvent, and the solvent in our experiment is common distilled water, can see that peak value is-20.848ppm, can illustrate-BH on scheming
3The existence at peak, curve 2 are after methyl ammonia borine catalytic hydrolysis
11B NMR collection of illustrative plates, chemical shift has for showing-BO
2Existence;
Synthetic methyl ammonia borine shown in Figure 2
1H NMR collection of illustrative plates, wherein curve 1 solvent is heavy water, can see-CH
3With-BH
3The peak ,-NH
2The peak is because the exchange of the hydrogen in amino hydrogen and water is too fast, and the peak can not show, and curve 2 solvents are deuterochloroform, just can see-NH
2The peak, owing to deuterochloroform the inside containing a small amount of water, so the water summit occur at 4.8ppm, therefore-BH
3The peak is not identical quartet, because there is the water peak to be included, has comprised-NH in the compound that binding curve 1 can be determined to synthesize
2The peak ,-CH
3The peak and-BH
3The peak;
Synthetic methyl ammonia borine shown in Figure 3
13C NMR collection of illustrative plates can be seen-CH
3The peak.
Embodiment 2
1) take respectively sodium borohydride and the methylamine hydrochloride of 0.005mol, then the mixture of methylamine hydrochloride and sodium borohydride is put in two mouthfuls of round-bottomed flasks of 100mL, put into magneton, then will measure the 10ml tetrahydrofuran (THF) and join in round-bottomed flask, temperature of reaction is controlled at 25 ℃, and the reaction times is respectively 2h, 4h, 6h and 24h, obtain reaction mixture, mode with reaction mixture by filtration under diminished pressure obtains filtrate, then at room temperature removes tetrahydrofuran (THF), obtains head product.
2) head product that obtains is dissolved in anhydrous diethyl ether, stirs 1h under ice-water bath, then the mode of filtration under diminished pressure obtains filtrate, removes ether, and the crystalloid solid that obtains white is methyl ammonia borine.
3) purity detecting
Taking the amount that obtains the methyl ammonia borine that the reaction times obtains when being respectively 2h, 4h, 6h and 24h is 0.10g, 0.11g and 0.07g, and the 0.15g productive rate is respectively 44.36%, 48.80%, 31.05% and 66.37%.Record according to the described method of embodiment 1 the methyl ammonia borine purity that obtains and be respectively 73.3%, 76.7%, 81.7% and 52.9%.
This explanation is along with the purity of the prolongation product in reaction times increases, reaction times, the oversize purity that can make descended, and this may cause because portion of product decomposes, once report under room temperature in the past, ammonia borine solid can be preserved for a long time, and slowly hydrolysis in solution.
Embodiment 3
1) take respectively sodium borohydride and the dimethylamine hydrochloride of 0.005mol, then the mixture of dimethylamine hydrochloride and sodium borohydride is put in two mouthfuls of round-bottomed flasks of 100mL, put into magneton, then measure the 10ml tetrahydrofuran (THF) and join in round-bottomed flask, temperature of reaction is controlled at 25 ℃, reaction 12h, obtain reaction mixture, mode with reaction mixture by filtration under diminished pressure obtains filtrate, then at room temperature removes tetrahydrofuran (THF), obtains head product.
2) head product that obtains is dissolved in anhydrous diethyl ether, stirs 1h under ice-water bath, then the mode of filtration under diminished pressure obtains filtrate, and after removing ether, the crystalloid solid that obtains white is the dimethylamino borine.
3) purity detecting
The quality that takes product is the dimethylamino borine of 0.15g, and productive rate is 50.76%, and purity is 61.3%.
Method according to embodiment 1 records the dimethylamino borine that obtains 0.15g, and productive rate is 50.76%, and recording according to the described method of embodiment 1 the dimethylamino borine purity that obtains is 61.3%.
Although the synthetic dimethylamino borine of this method does not have commercially available purity high, than commercially available price (Aldrich, purity is that 97%, 5g price is 200.07 yuan), cost is very low, so be also that certain actual application value is arranged.
Embodiment 4
1) take respectively sodium borohydride and the anilinechloride of 0.005mol, then the mixture of general or anilinechloride and sodium borohydride is put in two mouthfuls of round-bottomed flasks of 100mL, put into magneton, then measure the 10ml tetrahydrofuran (THF) and join in round-bottomed flask, temperature of reaction is controlled at 25 ℃, reaction 12h, obtain reaction mixture, mode with reaction mixture by filtration under diminished pressure obtains filtrate, then at room temperature removes tetrahydrofuran (THF), obtains head product.
2) head product that obtains is dissolved in anhydrous diethyl ether, stirs 1h under ice-water bath, then the mode of filtration under diminished pressure obtains filtrate, and after removing ether, the crystalloid solid that obtains white is the aniline borine.
3) purity detecting
The quality that takes product is the aniline borine of 0.18g, and productive rate is 34.28%, and purity is 66.1%.
Method according to embodiment 1 records the phenylamino borine that obtains 0.18g, and productive rate is 34.28%, and recording according to the described method of embodiment 1 the aniline borine purity that obtains is 66.1%.
The phenylamino borine does not also have commercially available, so our method synthesizing amino boranes compound is very significant.
Embodiment 5
1) take respectively sodium borohydride and the methylamine hydrochloride of 0.005mol, then the mixture of methylamine hydrochloride and sodium borohydride is put in two mouthfuls of round-bottomed flasks of 100mL, put into magneton, then measure the 10ml tetrahydrofuran (THF) and join in round-bottomed flask, temperature of reaction is controlled at respectively 10 ℃, reaction 12h, obtain reaction mixture, mode with reaction mixture by filtration under diminished pressure obtains filtrate, then at room temperature removes tetrahydrofuran (THF), obtains head product.
2) head product that obtains is dissolved in anhydrous diethyl ether, stirs 1h under ice-water bath, then the mode of filtration under diminished pressure obtains filtrate, and after removing ether, the crystalloid solid that obtains white is methyl ammonia borine.
3) purity detecting
The quality that takes product is 0.066g, and productive rate is respectively 29.33%, and recording methyl ammonia borine purity according to the described method of embodiment 1 is 86.5%.
Embodiment 6
1) take respectively sodium borohydride and the methylamine hydrochloride of 0.005mol, then the mixture of methylamine hydrochloride and sodium borohydride is put in two mouthfuls of round-bottomed flasks of 100mL, put into magneton, then measure the 10ml tetrahydrofuran (THF) and join in round-bottomed flask, temperature of reaction is controlled at respectively 40 ℃, reaction 12h, obtain reaction mixture, mode with reaction mixture by filtration under diminished pressure obtains filtrate, then at room temperature removes tetrahydrofuran (THF), obtains head product.
2) head product that obtains is dissolved in anhydrous diethyl ether, stirs 1h under ice-water bath, then the mode of filtration under diminished pressure obtains filtrate, and after removing ether, the crystalloid solid that obtains white is methyl ammonia borine.
3) purity detecting
The quality that takes product is 0.12g, and productive rate is respectively 54.66%, and recording methyl ammonia borine purity according to the described method of embodiment 1 is 70.6%.
The presentation of results high temperature of embodiment 5 and embodiment 6 is conducive to the carrying out that react, but the product that obtains also can decompose on a small quantity, and under low temperature, productive rate is very low, is optimum temps so temperature is 25 ℃.
Embodiment 7
1) be that sodium borohydride/methylamine hydrochloride=2:1 and sodium borohydride/methylamine hydrochloride=1:2 take sodium borohydride and methylamine hydrochloride by the mol ratio of sodium borohydride and methylamine hydrochloride respectively, namely take 0.01mol sodium borohydride and 0.005mol methylamine hydrochloride; 0.005mol sodium borohydride and 0.01mol methylamine hydrochloride, then the mixture of methylamine hydrochloride and sodium borohydride is put in two mouthfuls of round-bottomed flasks of 100mL, put into magneton, then measure the 10ml tetrahydrofuran (THF) and join in round-bottomed flask, temperature of reaction is controlled at 25 ℃, reaction 12h, obtain reaction mixture, mode with reaction mixture by filtration under diminished pressure obtains filtrate, then at room temperature removes tetrahydrofuran (THF), obtains head product.
2) head product that obtains is dissolved in anhydrous diethyl ether, stirs 1h under ice-water bath, then the mode of filtration under diminished pressure obtains filtrate, and after removing ether, the crystalloid solid that obtains white is methyl ammonia borine.
3) purity detecting
Be that the quality that takes product under 2:1 and 1:2 condition is 0.11g and 0.064g in the mol ratio of sodium borohydride and methylamine hydrochloride, productive rate is respectively 49.73% and 28.53%, records methyl ammonia borine purity according to the described method of embodiment 1 and is respectively 81.7% and 78.6%.The amount that this explanation increases a reactant can the augmenting response product productive rate and purity, can waste raw material on the contrary, so the mol ratio of best raw material is 1:1.
Embodiment 8
1) take respectively sodium borohydride and the methylamine hydrochloride of 0.005mol, then the mixture of methylamine hydrochloride and sodium borohydride is put in two mouthfuls of round-bottomed flasks of 100mL, put into magneton, then measure the 10ml tetrahydrofuran (THF) and join in round-bottomed flask, temperature of reaction is controlled at 25 ℃, reaction 12h, obtain reaction mixture, mode with reaction mixture by filtration under diminished pressure obtains filtrate, then at room temperature removes tetrahydrofuran (THF), obtains head product.
2) head product that obtains is dissolved in anhydrous diethyl ether, stirs 3h under ice-water bath, then the mode of filtration under diminished pressure obtains filtrate, and after removing ether, the crystalloid solid that obtains white is methyl ammonia borine.
3) to take the quality of product be 0.053g to purity detecting, and productive rate is 23.34%, and recording methyl ammonia borine purity according to the described method of embodiment 1 is 82.46%.When this explanation is purified, churning time is long can not increase productive rate, and can lose time, and is the best when churning time is 1h.
Claims (2)
1. the synthetic method of an amido borine is characterized in that: comprise the following steps:
1) ratio that is ammonium salt/sodium borohydride=1:1-1:2 according to mol ratio respectively takes ammonium salt and sodium borohydride, and it is mixed, and adds excessive tetrahydrofuran (THF), is 10-40 in temperature
oReacted 2-24 hours under the C condition, obtain reaction mixture, reaction mixture is filtered collect filtrate, remove the organic solvent in filtrate, obtain head product;
2) head product that the upper step was obtained adds ether to make its dissolving, stirs 1-3 hours under the ice-water bath condition, filters and collects filtrate, and evaporation filtrate is removed ether, obtains white crystals shape solid, and get final product.
2. the synthetic method of amido borine as claimed in claim 1, it is characterized in that: described ammonium salt is methylamine hydrochloride or dimethylamine hydrochloride or anilinechloride.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103569967A (en) * | 2013-11-18 | 2014-02-12 | 复旦大学 | Preparation method of ammonia borane (NH3BH3) |
| CN108586266A (en) * | 2018-06-07 | 2018-09-28 | 东莞市乐远化工科技有限公司 | A kind of dimethyamine borane synthesis technology |
| CN109879294A (en) * | 2019-02-25 | 2019-06-14 | 河南师范大学 | It is a kind of using B, N, Cl element as the preparation method of new polymers (NH2BHCl) x of skeleton |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56158792A (en) * | 1980-05-13 | 1981-12-07 | Yasuo Kikukawa | Preparation of amineborane |
| CN101481384A (en) * | 2008-01-07 | 2009-07-15 | 上海浩洲化工有限公司 | Method for refining dimethylamine borane |
| CN102718786A (en) * | 2012-06-21 | 2012-10-10 | 上海申宇医药化工有限公司 | Dimethylamine borane preparation method |
-
2013
- 2013-02-05 CN CN2013100455498A patent/CN103113397A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56158792A (en) * | 1980-05-13 | 1981-12-07 | Yasuo Kikukawa | Preparation of amineborane |
| CN101481384A (en) * | 2008-01-07 | 2009-07-15 | 上海浩洲化工有限公司 | Method for refining dimethylamine borane |
| CN102718786A (en) * | 2012-06-21 | 2012-10-10 | 上海申宇医药化工有限公司 | Dimethylamine borane preparation method |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103569967A (en) * | 2013-11-18 | 2014-02-12 | 复旦大学 | Preparation method of ammonia borane (NH3BH3) |
| CN103569967B (en) * | 2013-11-18 | 2015-10-28 | 复旦大学 | A kind of preparation method of ammonia borine |
| CN108586266A (en) * | 2018-06-07 | 2018-09-28 | 东莞市乐远化工科技有限公司 | A kind of dimethyamine borane synthesis technology |
| CN108586266B (en) * | 2018-06-07 | 2021-04-20 | 东莞市乐远化工科技有限公司 | Synthesis process of dimethylamine borane |
| CN109879294A (en) * | 2019-02-25 | 2019-06-14 | 河南师范大学 | It is a kind of using B, N, Cl element as the preparation method of new polymers (NH2BHCl) x of skeleton |
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Application publication date: 20130522 |