CN107522165A - A kind of preparation method of lithium borohydride tetrahydrofuran solution - Google Patents
A kind of preparation method of lithium borohydride tetrahydrofuran solution Download PDFInfo
- Publication number
- CN107522165A CN107522165A CN201710849428.7A CN201710849428A CN107522165A CN 107522165 A CN107522165 A CN 107522165A CN 201710849428 A CN201710849428 A CN 201710849428A CN 107522165 A CN107522165 A CN 107522165A
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- China
- Prior art keywords
- lithium borohydride
- preparation
- lithium
- tetrahydrofuran solution
- tetrahydrofuran
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
- C01B6/06—Hydrides of aluminium, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony, bismuth or polonium; Monoborane; Diborane; Addition complexes thereof
- C01B6/10—Monoborane; Diborane; Addition complexes thereof
- C01B6/13—Addition complexes of monoborane or diborane, e.g. with phosphine, arsine or hydrazine
- C01B6/15—Metal borohydrides; Addition complexes thereof
- C01B6/19—Preparation from other compounds of boron
- C01B6/21—Preparation of borohydrides of alkali metals, alkaline earth metals, magnesium or beryllium; Addition complexes thereof, e.g. LiBH4.2N2H4, NaB2H7
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N7/00—Analysing materials by measuring the pressure or volume of a gas or vapour
- G01N7/14—Analysing materials by measuring the pressure or volume of a gas or vapour by allowing the material to emit a gas or vapour, e.g. water vapour, and measuring a pressure or volume difference
- G01N7/18—Analysing materials by measuring the pressure or volume of a gas or vapour by allowing the material to emit a gas or vapour, e.g. water vapour, and measuring a pressure or volume difference by allowing the material to react
Abstract
The invention discloses a kind of preparation method of lithium borohydride tetrahydrofuran solution, comprise the following steps：(1) potassium borohydride is added into tetrahydrofuran, is stirred；(2) lithium chloride is added into step (1), temperature is risen to 20 26 DEG C, reacted 18 30 hours；(3) step (2) products therefrom is filtered, filtrate is further distilled, and produces the lithium borohydride tetrahydrofuran solution of required concentration；Lithium borohydride active hydrogen content made from the preparation method is high, and the gentle security of reaction condition is higher, is easy to use, transports and stores.
Description
Technical field
The invention belongs to the preparation method of field of inorganic chemical engineering, more particularly to lithium borohydride tetrahydrofuran solution.
Background technology
Lithium borohydride (LiBH4) be one of most important reducing agent in organic chemistry, belong to hydroboron family into
Member.Reducing agent as hydrogen source and organic group (such as aldehyde, ketone, ester), is mainly used in pharmacy, perfume industry and pesticide industry.With
The fast development of China's economy, the demand of this product is increasingly increased.But the lithium borohydride powder of the solid easy moisture absorption in atmosphere
Decompose and it is inflammable be absolutely unsafe, storage is inconvenient, and aqueous vapor preservation need to completely cut off under the protection of nitrogen, in fume hood operation with
Use.Therefore, this area need badly a kind of convenience, stably, the store method of lithium borohydride that is readily transported.
The content of the invention
Present invention aims at a kind of lithium borohydride tetrahydrofuran solution is provided, solve and asked in actual production security
Topic, course of reaction is gentle, and shipping storage is safe and stable, and lithium borohydride has higher active hydrogen content.
Technical scheme is as follows：
A kind of preparation method of lithium borohydride tetrahydrofuran solution, comprises the following steps：
(1) potassium borohydride is added into tetrahydrofuran, is stirred；
(2) lithium chloride is added into step (1), temperature is risen to 20-26 DEG C, reacts 18-30 hours；
(3) step (2) products therefrom is filtered, filtrate is further distilled, and produces the lithium borohydride tetrahydrochysene of required concentration
Tetrahydrofuran solution.
The mass ratio of the potassium borohydride and lithium chloride is 1.1-1.5:1-2, preferably 1.2:1, the potassium borohydride with
The mass volume ratio of tetrahydrofuran is 1:10-15, preferably 1:11.
The reaction temperature is preferably 24 DEG C, and the reaction time is 24 hours.
The active hydrogen content in lithium borohydride is measured by the following method, lithium borohydride tetrahydrofuran solution is entered
Row distillation, steams tetrahydrofuran, and lithium borohydride solid is made, can react according to lithium borohydride with water, thus can according to sample and
Gas volume is released to calculate the active hydrogen content of sample after water reaction.
LiBH4+2H2O→LiBO2+4H2↑
Calculation formula：
V in formula1：Sample do not reacted with water before in system gas cumulative volume ml
V2:Sample and the volume of gas ml in system after water reaction
Pt:The atmospheric pressure Pa of environment during measure
PWater：The saturated vapor pressure Pa of water during measure under environment temperature
T0:Temperature 273K under standard state
Tt:Survey temperature (273+ room temperatures) K of timing hierarchy
V3：The volume ml of sample
W：The weight g of sample
22400：Constant, volume of any gas of 1 gram molecule in standard state
21.78：The molecular weight of lithium borohydride
4：Contained hydrogen atom among lithium borohydride
The assay method comprises the steps of：
(1) the conical flask correct amount of a dried and clean is taken, sample is weighed and is put into conical flask, capping plug is tight, is designated as W；
(2) mixed liquor of water and dioxane is added in constant pressure funnel；
(3) constant pressure funnel and the conical flask equipped with sample and gas constant pressure capacity tester are connected to become closed system,
The volume number of the graded tube in gas constant pressure capacity tester is write down, is designated as V1；
(4) conical flask equipped with sample is placed in ice-water bath；
(5) water in constant pressure funnel and dioxane mixed liquor are added on the sample of conical flask；
(6) sample stands 15 minutes in ice-water bath after completion of the reaction with water, then stands 30 minutes at normal temperatures, record
The volume number of graded tube in lower gas constant pressure capacity tester, is designated as V2；
(7) it is that lithium aluminium hydride reduction reacts the gas released with water by the volume that the volume of graded tube after reaction is subtracted before reaction
Volume.
Step (2) reclaimed water：The volume ratio of dioxane is 5:5.
The beneficial effects of the invention are as follows：Lithium borohydride tetrahydrofuran solution reaction condition prepared by the present invention is gentle, yield
Up to more than 98%, security is more preferable, is easy to store, transport and use, the active hydrogen content of obtained lithium borohydride is higher, can
Up to 99%.
Embodiment
Embodiment 1
A kind of preparation method of lithium borohydride tetrahydrofuran solution, comprises the following steps：
(1) 55g potassium borohydrides are added into 650mL tetrahydrofurans, are stirred；
(2) 47g lithium chlorides are added into step (1), temperature is risen to 24 DEG C, reacted 8 hours；
(3) step (2) products therefrom is filtered, filtrate is further distilled, and produces the lithium borohydride tetrahydrochysene of required concentration
Tetrahydrofuran solution.
Embodiment 2-8
Step is shown in Table 1 with embodiment 1, reactant dosage and reaction condition.
Embodiment 9
The assay method of the active hydrogen content of lithium borohydride in lithium borohydride tetrahydrofuran made from embodiment 1-8：
(1) lithium borohydride tetrahydrofuran solution made from embodiment 1-8 is distilled, removes tetrahydrofuran, obtain boron
Lithium hydride solid；
(2) the conical flask correct amount of a dried and clean is taken, sample is weighed and is put into conical flask, capping plug is tight, is designated as W；
(3) by water and the mixed liquor (water of dioxane：The volume ratio of dioxane is 5:5) it is added in constant pressure funnel；
(4) constant pressure funnel and the conical flask equipped with sample and gas constant pressure capacity tester are connected to become closed system,
The volume number of the graded tube in gas constant pressure capacity tester is write down, is designated as V1；
(5) conical flask equipped with sample is placed in ice-water bath；
(6) water in constant pressure funnel and dioxane mixed liquor are added on the sample of conical flask；
(7) sample stands 15 minutes in ice-water bath after completion of the reaction with water, then stands 30 minutes at normal temperatures, record
The volume number of graded tube in lower gas constant pressure capacity tester, is designated as V2；
(8) it is that lithium borohydride reacts the gas released with water by the volume that the volume of graded tube after reaction is subtracted before reaction
Volume.
Active hydrogen content is calculated according to below equation, concrete numerical value is shown in Table 1.
The lithium borohydride reaction condition of table 1 contrasts
From examples it can be seen that when the dosage deficiency of lithium chloride, the yield of lithium borohydride is higher, and purity compared with
It is good, and active hydrogen content also reaches more than 99%, the dosage of tetrahydrofuran influences on the yield and active hydrogen content of lithium borohydride
Also larger, dosage is too small, is unfavorable for fully reacting, and dosage is excessive to will also result in the problem of waste reclaims high energy consumption with product.
Claims (4)
1. a kind of preparation method of lithium borohydride tetrahydrofuran solution, it is characterised in that comprise the following steps：
(1) potassium borohydride is added into tetrahydrofuran, is stirred；
(2) lithium chloride is added into step (1), temperature is risen to 20-26 DEG C, reacts 18-30 hours；
(3) step (2) products therefrom is filtered, filtrate is further distilled, and produces the lithium borohydride tetrahydrofuran of required concentration
Solution.
2. preparation method as claimed in claim 1, it is characterised in that the mass ratio of the potassium borohydride and lithium chloride is 1.1-
1.5:1-2, preferably 1.2:1.
3. preparation method as claimed in claim 1, it is characterised in that the mass volume ratio of the potassium borohydride and tetrahydrofuran
For 1:10-15, preferably 1:11.
4. preparation method as claimed in claim 1, it is characterised in that the reaction temperature is preferably 24 DEG C, and the reaction time is
24 hours.
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| CN201710849428.7A CN107522165A (en) | 2017-09-20 | 2017-09-20 | A kind of preparation method of lithium borohydride tetrahydrofuran solution |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108285130A (en) * | 2018-02-11 | 2018-07-17 | 庄英俊 | A kind of preparation method and detection method of lithium borohydride |
| CN112607706A (en) * | 2020-12-04 | 2021-04-06 | 中核建中核燃料元件有限公司 | Method for reducing activity of high-activity lithium hydride powder |
| CN114853774A (en) * | 2022-06-24 | 2022-08-05 | 盐城迪赛诺制药有限公司 | Preparation method of darunavir key intermediate |
| CN115072663A (en) * | 2022-07-13 | 2022-09-20 | 山东国邦药业有限公司 | Preparation method of lithium borohydride and zinc borohydride |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1302441A2 (en) * | 2001-10-10 | 2003-04-16 | Rohm And Haas Company | An improved method for making lithium borohydride |
| CN101074092A (en) * | 2006-05-19 | 2007-11-21 | 罗门哈斯公司 | Preparation of borohydride salts |
| CN102219187A (en) * | 2010-04-15 | 2011-10-19 | 中国科学院大连化学物理研究所 | Preparation method for calcium borohydride hydrogen-storage material |
-
2017
- 2017-09-20 CN CN201710849428.7A patent/CN107522165A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1302441A2 (en) * | 2001-10-10 | 2003-04-16 | Rohm And Haas Company | An improved method for making lithium borohydride |
| CN101074092A (en) * | 2006-05-19 | 2007-11-21 | 罗门哈斯公司 | Preparation of borohydride salts |
| CN102219187A (en) * | 2010-04-15 | 2011-10-19 | 中国科学院大连化学物理研究所 | Preparation method for calcium borohydride hydrogen-storage material |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108285130A (en) * | 2018-02-11 | 2018-07-17 | 庄英俊 | A kind of preparation method and detection method of lithium borohydride |
| CN112607706A (en) * | 2020-12-04 | 2021-04-06 | 中核建中核燃料元件有限公司 | Method for reducing activity of high-activity lithium hydride powder |
| CN114853774A (en) * | 2022-06-24 | 2022-08-05 | 盐城迪赛诺制药有限公司 | Preparation method of darunavir key intermediate |
| CN115072663A (en) * | 2022-07-13 | 2022-09-20 | 山东国邦药业有限公司 | Preparation method of lithium borohydride and zinc borohydride |
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