CN109705152A - A kind of method that the boron nitrogen chain cyclization reaction of iodine induction prepares cyclic annular boron hydronitrogen - Google Patents
A kind of method that the boron nitrogen chain cyclization reaction of iodine induction prepares cyclic annular boron hydronitrogen Download PDFInfo
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- CN109705152A CN109705152A CN201910137887.1A CN201910137887A CN109705152A CN 109705152 A CN109705152 A CN 109705152A CN 201910137887 A CN201910137887 A CN 201910137887A CN 109705152 A CN109705152 A CN 109705152A
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Abstract
The invention discloses the methods that a kind of boron nitrogen chain cyclization reaction of iodine induction prepares cyclic annular boron hydronitrogen, belong to the cyclization technical field of boron hydronitrogen.Technical solution of the present invention main points are as follows: under conditions of anhydrous and oxygen-free, by metal boron hydronitrogen M (BxNy‑R,R’Hz) and non-metal oxidant I2The cyclic annular boron hydronitrogen for being made pure is stirred to react in -30~50 DEG C in tetrahydrofuran solution, wherein M=Li, Na or K, x=2 or 3, y=1 or 2, z=8,10 or 12, R, R '=H or CH3.The present invention relatively before method cost is relatively low, and reaction rate is exceedingly fast, and easy to operate, low toxicity is harmless, securely and reliably.
Description
Technical field
The invention belongs to the cyclization technical fields of boron hydronitrogen, and in particular to a kind of boron nitrogen chain link of iodine induction
Change the method that reaction prepares cyclic annular boron hydronitrogen.
Background technique
Cyclization is occurred in organic compound mostly, typically refers to form new carbon in organic compound molecule
The reaction of ring or heterocycle mainly has the several types such as electronics cyclization, [2+2] reaction and cycloaddition reaction, in boron nitrogen hydrogen
In compound, B-N and C-C isoelectronic species each other, the former has stronger polarity, can theoretically show more richer than C-C
Reaction property.Boron hydronitrogen is widely used, but can not show a candle to hydrocarbon for its reactive Quality Research, to boron nitrogen chain
Cyclization research then opposite lack.Therefore finding the simple and direct boron nitrogen chain cyclization reaction method of one kind is highly desirable, at present
Relevant boron nitrogen chain cyclization reaction is mainly reflected in the intermediate product or by-product of some reactions or research, representative to lure
The reaction of lead ring mainly have it is several under it is several:
1, one's early years Keller is when studying dimethylaminoethyl borane anion, find to dimethylamino diborane yin from
When being passed through diborane gas in the ethylene glycol dimethyl ether solution of son, the compound of the chain can cyclization formation four-membered ring shape compound
Dimethylamino diborane.
2,1973, Keller had found HB [N (CH3)2]2When 1:1 reacts in molar ratio with diborane gas, it can produce
Six-membered cyclic compound μ-[(CH with bridge hydrogens3)N2]2B3H7, and under cryogenic, the molar ratio of corresponding reactant is
When 2:1, then a quaternary ring-type boron-nitrogen compound [(CH can be generated3)2NBH2]2。
3, to ring-typeization and conjunction object B3H6N3H6Stability study in find nitrogen atmosphere under in liquefied ammonia by NaC=
CH is added to BH2(BH3)2BH4(DADB) when in, six-membered cyclic compound B is detected during the reaction3H6N3H6Generation,
But yield is considerably less, and yield only has 15%.
In view of the limitation of above cyclization research, it is necessary to design it is a kind of cost is relatively low, synthesis process rate is fast and
The method of easy to operate, safe and reliable cyclization, and more rare boron nitrogen chain compound is mainly studied in the research
Form the cyclization of cyclic compound.
Summary of the invention
The technical problem to be solved by the present invention is to provide one kind, cost is relatively low, easy to operate, safe and reliable and less toxic harmless
Iodine induction the boron nitrogen chain cyclization reaction method for preparing cyclic annular boron hydronitrogen.
The present invention adopts the following technical scheme that solve above-mentioned technical problem, and a kind of boron nitrogen chain cyclization of iodine induction reacts system
The method of standby ring-type boron hydronitrogen, it is characterised in that detailed process are as follows: under conditions of anhydrous and oxygen-free, by metal boron nitrogen hydrogen
Compound M (BxNy-R,R’Hz) and non-metal oxidant I2It is stirred to react in tetrahydrofuran solution in -30~50 DEG C and is made pure
Net cyclic annular boron hydronitrogen, wherein M=Li, Na or K, x=2 or 3, y=1 or 2, z=8,10 or 12, R, R '=H or
CH3。
Preferably, the method that the boron nitrogen chain cyclization reaction of iodine induction prepares cyclic annular boron hydronitrogen, feature
It is specific steps are as follows: in nitrogen glove box, by metal boron hydronitrogen M (BxNy-R,R’Hz) it is packed into schlenk reaction
In bottle, schlenk reaction flask is removed into glove box with after plug seal, by non-metal oxidant I2It is anti-to be packed into another schlenk
It answers in bottle, two schlenk reaction flasks is connected into biexhaust pipe, reaction system N2Displacement three times, and it is being continually fed into N2Condition
Under, it is dissolved respectively with tetrahydrofuran solvent, makes 0.2~2mmol/mL of its solution concentration, by metal boron hydronitrogen M
(BxNy-R,R’Hz) tetrahydrofuran solution be transferred to non-metal oxidant I2Tetrahydrofuran solution in, wherein metal boron nitrogen hydrogen
Compound M (BxNy-R,R’Hz) and non-metal oxidant I2Molar ratio be 100:1~1:20, in -30~50 DEG C stir
Reaction is until metal boron hydronitrogen M (BxNy-R,R’Hz) fully reacting, it is filtered to remove insoluble matter, at filtrate fractional distillation
Reason obtains pure cyclic annular boron hydronitrogen.
Preferably, the reaction temperature of reaction process is room temperature.
Preferably, the metal boron hydronitrogen M (BxNy-R,R’Hz) and non-metal oxidant I2Molar ratio
For 2:1.
The boron nitrogen chain cyclization reaction of iodine induction of the present invention prepares the reaction in the method for cyclic annular boron hydronitrogen
Equation are as follows:
2Na(BH3NH2BH3)+I2→2NB2H7+2NaI+H2。
Compared with the prior art, the invention has the following beneficial effects: the present invention is higher than method reaction efficiency before,
And easy to operate, cost is relatively low, and low toxicity is harmless, securely and reliably.
Detailed description of the invention
Fig. 1 is ring-type boron hydronitrogen aminodiborane NB made from embodiment 12H7In tetrahydrofuran11B liquid
Nuclear-magnetism figure；
Fig. 2 is ring-type boron hydronitrogen aminodiborane NB made from embodiment 12H7In tetrahydrofuran11B{H}
Liquid core magnetic chart.
Specific embodiment
Above content of the invention is described in further details by the following examples, but this should not be interpreted as to this
The range for inventing above-mentioned theme is only limitted to embodiment below, and all technologies realized based on above content of the present invention belong to this hair
Bright range.
Embodiment 1
All operations carry out in a nitrogen atmosphere.In nitrogen glove box, the schlenk to the 25mL equipped with magneton is anti-
Answer addition Na (BH in bottle3NH2BH3) (4mmol, 0.268g), schlenk reaction flask is removed into glove box with after plug seal, it will
I2(2mmol, 0.5076g) is fitted into another schlenk reaction flask, and two schlenk reaction flasks are connected biexhaust pipe, reactant
System uses N2Displacement three times, and it is being continually fed into N2Under conditions of, it is separately added into tetrahydrofuran 6mL, by Na (BH3NH2BH3) tetrahydro
Tetrahydrofuran solution is transferred to I2Tetrahydrofuran solution in, reaction is stirred at room temperature, is filtered to remove insoluble matter, collects filtrate, i.e.,
For cyclic annular boron hydronitrogen aminodiborane NB2H7.Obtained NB2H7It is weighed as 0.32g, calculating yield is 70%, nuclear-magnetism
Its purity is detected close to 100%.
Embodiment 2
All operations carry out in a nitrogen atmosphere.In nitrogen glove box, the schlenk to the 25mL equipped with magneton is anti-
Answer addition Na (BH in bottle3-N(CH3)H-BH3) (4mmol, 0.324g), schlenk reaction flask is removed into hand with after plug seal
Casing, by I2(2mmol, 0.5076g) is fitted into another schlenk reaction flask, and two schlenk reaction flask connections are double
Pipe, reaction system N2Displacement three times, and it is being continually fed into N2Under conditions of, it is separately added into tetrahydrofuran 6mL, by Na (BH3-N
(CH3)H-BH3) tetrahydrofuran solution be transferred to I2Tetrahydrofuran solution in, be stirred to react at room temperature, cross filter out
Insoluble matter is removed, filtrate, as ring-type boron hydronitrogen monomethyl aminodiborane μ-MeNHB are collected2H5.Obtained μ-
MeNHB2H5It is weighed as 0.34g, calculating yield is 66%, and nuclear-magnetism detects its purity close to 93%.
Embodiment 3
All operations carry out in a nitrogen atmosphere.In nitrogen glove box, the schlenk to the 25mL equipped with magneton is anti-
Answer addition Na [BH in bottle3N(CH3)2BH3] (4mmol, 0.38g), schlenk reaction flask is removed into gloves with after plug seal
Case, by I2(2mmol, 0.5076g) is fitted into another schlenk reaction flask, and two schlenk reaction flasks are connected biexhaust pipe,
Reaction system N2Displacement three times, and it is being continually fed into N2Under conditions of, it is separately added into tetrahydrofuran 6mL, by Na [BH3N(CH3)2BH3] tetrahydrofuran solution be transferred to I2Tetrahydrofuran solution in, reaction is stirred at room temperature, is filtered to remove insoluble matter, receive
Collect filtrate, as ring-type boron hydronitrogen dimethylamino diborane μ-Me2NB2H5.Obtained μ-Me2NB2H5It is weighed as
0.29g, calculating yield is 63%, and nuclear-magnetism detects its purity close to 100%.
Embodiment 4
All operations carry out in a nitrogen atmosphere.In nitrogen glove box, the schlenk to the 25mL equipped with magneton is anti-
Answer addition Na (BH in bottle3NH2BH3NH2BH3) (4mmol, 0.388g), schlenk reaction flask is removed into gloves with after plug seal
Case, by I2(2mmol, 0.5076g) is fitted into another schlenk reaction flask, and two schlenk reaction flasks are connected biexhaust pipe,
Reaction system N2Displacement three times, and it is being continually fed into N2Under conditions of, it is separately added into tetrahydrofuran 6mL, by Na (BH3N(CH3)2BH3) tetrahydrofuran solution be transferred to I2Tetrahydrofuran solution in, reaction is stirred at room temperature progresss, and the reaction is by iodine
Induction can first generate six-membered cyclic boron hydronitrogen (N2B3H11, contain a bridge hydrogens), this can be monitored under cryogenic
Compound, but the compound is unstable at room temperature, it can the cracking cyclic annular boron hydronitrogen amino for being transformed into quaternary
Diborane NB2H7, after reaction, it is filtered to remove insoluble matter, collects filtrate, pure amino second boron can be obtained after fractional distillation
Alkane NB2H7.Obtained NB2H7It is weighed as 0.38g, calculating yield is 71%, and nuclear-magnetism detects its purity close to 100%.
Embodiment above describes basic principles and main features of the invention and advantage, the technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe originals of the invention
Reason, under the range for not departing from the principle of the invention, various changes and improvements may be made to the invention, these changes and improvements are each fallen within
In the scope of protection of the invention.
Claims (4)
1. a kind of method that the boron nitrogen chain cyclization reaction of iodine induction prepares cyclic annular boron hydronitrogen, it is characterised in that detailed process
Are as follows: under conditions of anhydrous and oxygen-free, by metal boron hydronitrogen M (BxNy-R,R’Hz) and non-metal oxidant I2In tetrahydro furan
It mutters and is stirred to react the cyclic annular boron hydronitrogen for being made pure in -30~50 DEG C in solution, wherein M=Li, Na or K, x=2 or 3,
Y=1 or 2, z=8,10 or 12, R, R '=H or CH3。
2. the method that the boron nitrogen chain cyclization reaction of iodine induction according to claim 1 prepares cyclic annular boron hydronitrogen,
It is characterized in that specific steps are as follows: in nitrogen glove box, by metal boron hydronitrogen M (BxNy-R,R’Hz) it is packed into schlenk
In reaction flask, schlenk reaction flask is removed into glove box with after plug seal, by non-metal oxidant I2It is packed into another
In schlenk reaction flask, two schlenk reaction flasks are connected into biexhaust pipe, reaction system N2Displacement three times, and persistently leading to
Enter N2Under conditions of, it is dissolved respectively with tetrahydrofuran solvent, makes 0.2~2 mmol/mL of its solution concentration, by metal boron nitrogen hydrogen
Compound M (BxNy-R,R’Hz) tetrahydrofuran solution be transferred to non-metal oxidant I2Tetrahydrofuran solution in, wherein gold
Belong to boron hydronitrogen M (BxNy-R,R’Hz) and non-metal oxidant I2Molar ratio be 100:1~1:20, in -30~
50 DEG C are stirred to react until metal boron hydronitrogen M (BxNy-R,R’Hz) fully reacting, it is filtered to remove insoluble matter, by filtrate
Fractional distillation handles to obtain pure cyclic annular boron hydronitrogen.
3. the method that the boron nitrogen chain cyclization reaction of iodine induction according to claim 1 or 2 prepares cyclic annular boron hydronitrogen,
It is characterized by: the reaction temperature of reaction process is room temperature.
4. the method that the boron nitrogen chain cyclization reaction of iodine induction according to claim 1 or 2 prepares cyclic annular boron hydronitrogen,
It is characterized by: the metal boron hydronitrogen M (BxNy-R,R’Hz) and non-metal oxidant I2Molar ratio be 2:
1。
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112062135A (en) * | 2020-08-10 | 2020-12-11 | 河南师范大学 | Method for synthesizing chain boron-nitrogen-hydrogen compound |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2782236A (en) * | 1953-10-15 | 1957-02-19 | Callery Chemical Co | Production of aminodiboranes |
| US20100168404A1 (en) * | 2007-04-13 | 2010-07-01 | The Board Of Trustees Of The University Of Illinoi | Metal Complex Compositions and Methods for Making Metal-Containing Films |
| CN108483397A (en) * | 2018-04-13 | 2018-09-04 | 河南师范大学 | The method of one pot synthesis synthesis of cyclic boron hydronitrogen aminodiborane |
| CN108622857A (en) * | 2018-04-13 | 2018-10-09 | 河南师范大学 | The preparation method of cyclic annular boron hydronitrogen aminodiborane |
-
2019
- 2019-02-25 CN CN201910137887.1A patent/CN109705152A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2782236A (en) * | 1953-10-15 | 1957-02-19 | Callery Chemical Co | Production of aminodiboranes |
| US20100168404A1 (en) * | 2007-04-13 | 2010-07-01 | The Board Of Trustees Of The University Of Illinoi | Metal Complex Compositions and Methods for Making Metal-Containing Films |
| CN108483397A (en) * | 2018-04-13 | 2018-09-04 | 河南师范大学 | The method of one pot synthesis synthesis of cyclic boron hydronitrogen aminodiborane |
| CN108622857A (en) * | 2018-04-13 | 2018-10-09 | 河南师范大学 | The preparation method of cyclic annular boron hydronitrogen aminodiborane |
Non-Patent Citations (4)
| Title |
|---|
| GEORGE R. WHITTELL ET AL.: "Reactions of Amine– and Phosphane–Borane Adducts with Frustrated Lewis Pair CombinationsofGroup 14Triflates and Sterically Hindered Nitrogen", 《EUROPEAN JOURNAL OF INORGANIC CHEMISTRY》 * |
| SCOTT R. DALY ET AL.: "Synthesis, Characterization, and Structures of Divalent Europium and Ytterbium N,N-Dimethylaminodiboranates", 《INORGANIC CHEMISTRY》 * |
| 李慧珍等: "氨硼烷: 一种高性能化学储氢材料", 《科学通报》 * |
| 王瑞瑞: "N-取代硼氮丁烷类似物的合成、机构和性质", 《工程科技1辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112062135A (en) * | 2020-08-10 | 2020-12-11 | 河南师范大学 | Method for synthesizing chain boron-nitrogen-hydrogen compound |
| CN112062135B (en) * | 2020-08-10 | 2023-09-15 | 河南师范大学 | Synthesis method of chain boron nitrogen hydrogen compound |
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