CN108358166A - A kind of preparation of lithium aluminium hydride reduction tetrahydrofuran solution and detection method - Google Patents
A kind of preparation of lithium aluminium hydride reduction tetrahydrofuran solution and detection method Download PDFInfo
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- CN108358166A CN108358166A CN201810140469.3A CN201810140469A CN108358166A CN 108358166 A CN108358166 A CN 108358166A CN 201810140469 A CN201810140469 A CN 201810140469A CN 108358166 A CN108358166 A CN 108358166A
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- aluminium hydride
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- 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
- C01B6/24—Hydrides containing at least two metals; Addition complexes thereof
- C01B6/243—Hydrides containing at least two metals; Addition complexes thereof containing only hydrogen, aluminium and alkali metals, e.g. Li(AlH4)
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- 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
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Abstract
The invention discloses a kind of preparation methods of lithium aluminium hydride reduction tetrahydrofuran solution, include the following steps：It is (1) accurate that weigh lithium hydride spare；(2) it is accurate weigh alchlor be dissolved into it is for use in ether；(3) ether is added in there-necked flask, then the lithium hydride is added, after stirring evenly, the aluminum trichloride solution is slowly added drop-wise in there-necked flask, it is reacted after initiator is added, controlling reaction temperature, (4) are precipitated 5 hours after completion of the reaction, then supernatant is poured out, solution, which is carried out distillation decompression, makes it become lithium aluminium hydride reduction solid powder；(5) then by lithium aluminium hydride reduction solid powder be dissolved into tetrahydrofuran lithium aluminium hydride reduction tetrahydrofuran solution；A kind of method measuring lithium aluminium hydride reduction content in lithium aluminium hydride reduction tetrahydrofuran solution is also disclosed, utilizes lithium aluminium hydride reduction active hydrogen content made from preparation method disclosed in the present application high, the mild safety higher of reaction condition is easy to use, transports and stores.
Description
Technical field
The invention belongs to field of inorganic chemical engineering, the more particularly to preparation method of lithium aluminium hydride reduction tetrahydrofuran solution.
Background technology
Lithium aluminium hydride reduction, Chinese nickname：Lithium Aluminium Hydride, molecular formula：LiALH4, molecular weight：37.9543 No. CAS：16853-
85-3, lithium aluminium hydride reduction (Lithium Aluminum Hydride) is a complex hydride, and white or pale white crystals body are
Very important reducing agent in organic synthesis, especially for the reduction of fat, carboxylic acid and amide.Pure lithium aluminium hydride reduction is white brilliant
Solid is filled, is stablized relatively in 120 DEG C or less and dry air, but meets water, that is, explosive decomposition, fusing point is 140 DEG C, insoluble
In hydro carbons, it is dissolved in the molten fiber of ether, tetrahydrofuran, dimethyl, is slightly soluble in n-butyl ether, insoluble or pole common vetch is dissolved in hydro carbons and two and dislikes
Alkane, density are relative density (water=1) 0.92, and chemical stability is preferable, is stabilized in dry air under room temperature, but easily
It is acted on by moisture, meets water and vigorous reaction, risk markings occur for alcohol：10 (dangerous when wets), main application are used as polymerization
Catalyst, reducing agent, jet fuel are also used for synthetic drug.
Many reducing organic compounds can be dissolvable in water ether by lithium aluminium hydride reduction, in the organic solvents such as tetrahydrofuran；It can
Aldehyde, ketone acid, acid anhydrides, ester, quinone, acyl chlorides etc. are reduced to alcohol, nitrile is reduced to primary amine, halogenated hydrocarbon is reduced to hydrocarbon；But usually not
Carbon-to-carbon double bond can be made to hydrogenate.
Due to solid lithium aluminium hydride reduction powder in air the easy moisture absorption decompose and it is inflammable be absolutely unsafe, storage inconvenience etc.
Factor, there is an urgent need for a kind of preparation of lithium aluminium hydride reduction and storage technologies, and the lithium aluminium hydride reduction obtained to preparation is made certain performance and examined
It surveys.
Invention content
The present invention proposes lithium aluminium hydride reduction tetrahydrofuran solution, the invention solution of lithium aluminium hydride reduction tetrahydrofuran according to customer demand
The safety that the client that determined applies in actual production, timeliness in reaction process, the safety etc. during shipping storage are asked
Topic and product quality are guaranteed.
Present invention aims at provide a kind of preparation method of lithium aluminium hydride reduction tetrahydrofuran solution comprising following steps：
It is (1) accurate that weigh lithium hydride 32g spare；
(2) it is accurate weigh alchlor be dissolved into it is for use in ether；
(3) ether is added in there-necked flask, the lithium hydride is then added, after stirring evenly, by the alchlor
Solution is slowly added drop-wise in there-necked flask, is reacted after initiator is added, and controlling reaction temperature is 30-38 DEG C,
(4) it is precipitated after completion of the reaction 5 hours by the small the reaction times of 3-4.5, then pours out supernatant, solution is carried out
Distillation decompression makes it become lithium aluminium hydride reduction solid powder；
(5) and then by the lithium aluminium hydride reduction solid powder be dissolved into tetrahydrofuran, lithium aluminium hydride reduction tetrahydrofuran
Solution.
The dosage of the alchlor is 112-133g, and total dosage of the ether is 800g.
Further, the alchlor dosage is 112g, and the reaction time is 3.5 hours, the hydrogenation obtained at this time
Aluminium lithium product content highest.
The key point of the present invention will will be added initiator and reacted after being lithium hydride and alchlor mixing, secondly anti-
Temperature should be controlled, secondly in reactant dosage, alchlor is in shortage to reacting advantageous, in alchlor compared to theory
Dosage in shortage 15% or so is best, the obtained lithium aluminium hydride reduction product content highest.
A method of lithium aluminium hydride reduction content in lithium aluminium hydride reduction tetrahydrofuran solution is measured, is specifically included：
1) conical flask, the correct amount in a ten thousandth assay balance for taking a clean dried；
2) it takes sample to be put into conical flask, seals, and correct amount obtains example weight W；
3) mixed liquor of water and dioxane is added in constant pressure funnel；
4) constant pressure funnel is connected to become closed system with the conical flask and gas constant pressure capacity tester that sample is housed, it will
The level of barostat and graded tube is opposite, and the volume number of the graded tube under accurate recording in gas constant pressure capacity tester is denoted as
V1；
5) conical flask equipped with sample is placed in ice-water bath；
6) by constant pressure funnel water and dioxane mixed liquor be added on the sample of conical flask, and pay attention to see calibration pipe
SEA LEVEL VARIATION；
7) sample stands 15 minutes in ice-water bath after completion of the reaction with water, then stands 30 minutes at normal temperatures, perseverance
For the water level of depressor and graded tube to flat, the volume number scale for accurately writing down the graded tube in gas constant pressure capacity tester is V2；
8) volume of graded tube after reaction is subtracted to the volume V before reaction2-V1As lithium aluminium hydride reduction reacts releasing with water
Hydrogen volume；
9) it calculates
In formula：V1The sample not total volume ml with the gas in water reacting precursor system；
V2The total volume ml of gas after sample is reacted with water in system；
PtThe atmospheric pressure Pa of environment when measuring；
PWaterThe saturated vapor pressure Pa of water when measuring under environment temperature；
ToTemperature 273K under standard state；
TtSystem temperature (273+ room temperatures) K when measuring；
PoGas pressure 1013.2472Pa under standard state；
The weight g of W- samples；
22400- constants；
37.95- lithium aluminium hydride reduction molecular weight；
4- lithium aluminium hydride reductions hydrogen ion contained in.
Lithium aluminium hydride reduction solid content concrete numerical value is obtained to see (table one)
Description of the drawings
In the accompanying drawings：
Fig. 1 is the flow chart of the preparation method of lithium aluminium hydride reduction tetrahydrofuran solution.
Fig. 2 is the flow chart for measuring the method for lithium aluminium hydride reduction content in lithium aluminium hydride reduction tetrahydrofuran solution.
Specific implementation mode
Embodiment 1
A kind of preparation method of lithium borohydride tetrahydrofuran solution, includes the following steps：
(2) it is accurate weigh 133g alchlors be dissolved into it is for use in ether；
(3) ether is added in there-necked flask, 32g lithium hydrides is then added, it is after stirring evenly, the alchlor is molten
It is 800g that liquid, which is slowly added drop-wise to ether dosage total in there-necked flask, is reacted after initiator is added, and reaction speed is controlled,
(4) it is precipitated after completion of the reaction 5 hours by 4.5 small the reaction times, then pours out supernatant, solution is steamed
Evaporating decompression makes it become lithium aluminium hydride reduction solid powder；
(5) and then by the lithium aluminium hydride reduction solid powder be dissolved into tetrahydrofuran in proportion, lithium aluminium hydride reduction four
Hydrogen tetrahydrofuran solution.
Embodiment 2-8
Step is shown in Table 1 with embodiment 1, wherein reactant dosage and reaction condition.
Embodiment 9
The method for measuring lithium aluminium hydride reduction content in lithium aluminium hydride reduction tetrahydrofuran made from embodiment 1-8：
1) conical flask, the correct amount in a ten thousandth assay balance for taking a clean dried；
2) it takes sample to be put into conical flask, seals, and correct amount obtains example weight W；
3) mixed liquor of water and dioxane is added in constant pressure funnel；
4) constant pressure funnel is connected to become closed system with the conical flask and gas constant pressure capacity tester that sample is housed, it will
The level of barostat and graded tube is opposite, and the volume number of the graded tube under accurate recording in gas constant pressure capacity tester is denoted as
V1；
5) conical flask equipped with sample is placed in ice-water bath；
6) by constant pressure funnel water and dioxane mixed liquor be added on the sample of conical flask, and pay attention to see calibration pipe
SEA LEVEL VARIATION；
7) sample stands 15 minutes in ice-water bath after completion of the reaction with water, then stands 30 minutes at normal temperatures, perseverance
For the water level of depressor and graded tube to flat, the volume number scale for accurately writing down the graded tube in gas constant pressure capacity tester is V2；
8) volume of graded tube after reaction is subtracted to the volume V before reaction2-V1As lithium aluminium hydride reduction reacts releasing with water
Hydrogen volume；
9) it calculates
In formula：V1The sample not total volume ml with the gas in water reacting precursor system；
V2The total volume ml of gas after sample is reacted with water in system；
PtThe atmospheric pressure Pa of environment when measuring；
PWaterThe saturated vapor pressure Pa of water when measuring under environment temperature；
ToTemperature 273K under standard state；
TtSystem temperature (273+ room temperatures) K when measuring；
PoGas pressure 1013.2472Pa under standard state；
The weight g of W- samples；
22400- constants；
37.95- lithium aluminium hydride reduction molecular weight；
4- lithium aluminium hydride reductions hydrogen ion contained in.
1 lithium aluminium hydride reduction solid reaction conditions correlation of table
The key point of the present invention will will be added initiator and reacted after being lithium hydride and alchlor mixing, secondly anti-
Temperature should be controlled, secondly in reactant dosage, alchlor is in shortage to reacting advantageous, in alchlor compared to theory
Dosage in shortage 15% or so is best, the obtained lithium aluminium hydride reduction product content highest.
Claims (5)
1. a kind of preparation method of lithium aluminium hydride reduction tetrahydrofuran solution comprising following steps：
It is (1) accurate that weigh lithium hydride 32g spare；
(2) it is accurate weigh alchlor be dissolved into it is for use in ether；
(3) ether is added in there-necked flask, the lithium hydride is then added, after stirring evenly, by the aluminum trichloride solution
It being slowly added drop-wise in there-necked flask, is reacted after initiator is added, controlling reaction temperature is 30-38 DEG C,
(4) it is precipitated after completion of the reaction 5 hours by the small the reaction times of 3-4.5, then pours out supernatant, solution is distilled
Decompression makes it become lithium aluminium hydride reduction solid powder；
(5) and then by the lithium aluminium hydride reduction solid powder be dissolved into tetrahydrofuran, lithium aluminium hydride reduction tetrahydrofuran solution；
The dosage of the alchlor is 112-133g, and total dosage of the ether is 800g.
2. the preparation method of lithium aluminium hydride reduction tetrahydrofuran solution as described in claim 1, wherein the alchlor dosage is
112g。
3. the preparation method of lithium aluminium hydride reduction tetrahydrofuran solution as described in claim 1, wherein the reaction time is 3.5 small
When.
4. a kind of method measuring lithium aluminium hydride reduction content in lithium aluminium hydride reduction tetrahydrofuran solution described in claim 1-3, packet
Include following steps：
1) conical flask, the correct amount in a ten thousandth assay balance for taking a clean dried；
2) it takes sample to be put into conical flask, seals, and correct amount obtains example weight W；
3) mixed liquor of water and dioxane is added in constant pressure funnel；
4) constant pressure funnel is connected to become closed system with the conical flask and gas constant pressure capacity tester that sample is housed, by constant pressure
The level of device and graded tube is opposite, and the volume number of the graded tube under accurate recording in gas constant pressure capacity tester is denoted as V1；
5) conical flask equipped with sample is placed in ice-water bath；
6) by constant pressure funnel water and dioxane mixed liquor be added on the sample of conical flask, and pay attention to see calibration pipe water level
Variation；
7) sample stands 15 minutes in ice-water bath after completion of the reaction with water, then 30 minutes is stood at normal temperatures, barostat
For water level with graded tube to flat, the volume number scale for accurately writing down the graded tube in gas constant pressure capacity tester is V2；
8) volume of graded tube after reaction is subtracted to the volume V before reaction2-V1As lithium aluminium hydride reduction reacts the hydrogen released with water
Volume；
9) it calculates
In formula：V1The sample not total volume ml with the gas in water reacting precursor system；
V2The total volume ml of gas after sample is reacted with water in system；
PtThe atmospheric pressure Pa of environment when measuring；
PWaterThe saturated vapor pressure Pa of water when measuring under environment temperature；
ToTemperature 273K under standard state；
TtSystem temperature (273+ room temperatures) K when measuring；
PoGas pressure 1013.2472Pa under standard state；
The weight g of W- samples；
22400- constants；
37.95- lithium aluminium hydride reduction molecular weight；
4- lithium aluminium hydride reductions hydrogen ion contained in.
5. method as claimed in claim 4, the wherein volume ratio of water described in step 3) and the dioxane are 5:5.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810140469.3A CN108358166A (en) | 2018-02-11 | 2018-02-11 | A kind of preparation of lithium aluminium hydride reduction tetrahydrofuran solution and detection method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115650264A (en) * | 2022-11-28 | 2023-01-31 | 研峰科技(北京)有限公司 | Method for efficiently recovering lithium chloride from lithium aluminum hydride preparation process |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104759215A (en) * | 2014-12-26 | 2015-07-08 | 车荣睿 | Preparation process for lithium aluminum hydride-tetrahydrofuran solution |
-
2018
- 2018-02-11 CN CN201810140469.3A patent/CN108358166A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104759215A (en) * | 2014-12-26 | 2015-07-08 | 车荣睿 | Preparation process for lithium aluminum hydride-tetrahydrofuran solution |
Non-Patent Citations (1)
| Title |
|---|
| 张允什 等: "对氢化铝锂合成反应中诱导期的初步研究", 《无机盐工业》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115650264A (en) * | 2022-11-28 | 2023-01-31 | 研峰科技(北京)有限公司 | Method for efficiently recovering lithium chloride from lithium aluminum hydride preparation process |
| CN115650264B (en) * | 2022-11-28 | 2023-03-21 | 研峰科技(北京)有限公司 | Method for efficiently recovering lithium chloride from lithium aluminum hydride preparation process |
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Application publication date: 20180803 |
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