CN104759215A - Preparation process for lithium aluminum hydride-tetrahydrofuran solution - Google Patents
Preparation process for lithium aluminum hydride-tetrahydrofuran solution Download PDFInfo
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- CN104759215A CN104759215A CN201410829685.0A CN201410829685A CN104759215A CN 104759215 A CN104759215 A CN 104759215A CN 201410829685 A CN201410829685 A CN 201410829685A CN 104759215 A CN104759215 A CN 104759215A
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- tetrahydrofuran solution
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- aluminium hydride
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Abstract
The invention especially relates to a preparation process for a lithium aluminum hydride-tetrahydrofuran solution, which belongs to the field of preparation technology for chemical reagents. The preparation process is characterized by comprising the following steps: material preparation; complexation reaction; drying by distillation; and preparation of the lithium aluminum hydride-tetrahydrofuran solution. The preparation process has the following advantages: a reducing agent with extremely strong reduction capability is synthesized, and rapid development of organic synthesis technology, especially development of the pharmaceutical industry, can be effectively promoted; the lithium aluminum hydride-tetrahydrofuran solution is safe, simple and convenient to use; and finished lithium aluminum hydride-tetrahydrofuran solution products with different concentrations can be blended according to market demands so as to meet demands of different process conditions.
Description
Technical field
The invention belongs to the preparation technology field of fine chemical product, particularly relate to a kind of preparation technology of lithium aluminium hydride reduction-tetrahydrofuran solution.
Background technology
Lithium aluminium hydride reduction is a kind of clad aluminum hydride, and molecular formula is LiAlH
4, molecular weight is 37.95, and this product is the lightweight powder of white porosity, when being long placed in, and the grizzle because of decomposition.Lithium aluminium hydride reduction is abbreviated as LAH, is reducing agent extremely strong in organic synthesis, and especially for the reduction of ester, carboxylic acid and acid amides, its appearance, makes organic synthesis there occurs revolutionary change.Pure lithium aluminium hydride reduction is relatively stable below 120 DEG C and in dry air, but meets water and explosive decomposition.Lithium aluminium hydride reduction dissolves in the ether solvent such as ether, oxolane, proportion 0.917, and under vacuo, 130 DEG C are decomposed into lithium hydride, aluminium and hydrogen.
Lithium aluminium hydride reduction, as extremely strong reducing agent, is widely used in pharmaceuticals industry, pesticide industry, electronics industry, daily chemical industry and the additive as high-energy fuel.Because the application of lithium aluminium hydride reduction expands rapidly, attract the concern of numerous scientist to its synthesis technique, need again one mole or 2.5 moles of tetrahydrofuran solution commodity by this product due to the consideration to its use safety problem in a large number.Because industrialization uses solid hydride aluminium in a large number, lithium is unsafe, and if with solution, then it is foolproof for from workshop, material Cemented filling can being dropped into reactor.
Summary of the invention
The present invention is directed to above-mentioned technical problem, provide the processing technology that one prepares lithium aluminium hydride reduction-tetrahydrofuran solution.
The technical solution adopted in the present invention is: a kind of preparation technology of lithium aluminium hydride reduction-tetrahydrofuran solution, is characterized in that, comprise the steps:
(1) get the raw materials ready
(1) block lithium hydride is pulverized, stand-by;
(2) in ice-water bath, 100-120g alchlor is divided and joins in 250-350ml ether for several times, make alchlor diethyl ether solution;
(2) complex reaction
The lithium hydride pulverized in described step (1) is joined in 550-650ml ether, stir and be warming up to 23-33 DEG C, form the diethyl ether solution of lithium hydride, slowly be added drop-wise in the diethyl ether solution of lithium hydride by alchlor diethyl ether solution obtained in described step (2), time for adding is 6-10 hour, and dropping process is carried out at the temperature of aether backflow, the mol ratio of alchlor and lithium hydride is 1:4-1:6, after dropwising, cross and filter sediment, obtain transparency liquid;
(3) evaporate to dryness
Transparency liquid evaporate to dryness obtained in described step (two) is obtained lithium aluminium hydride reduction powder;
(4) lithium aluminium hydride reduction-tetrahydrofuran solution is prepared
Take 40g lithium aluminium hydride reduction powder to join in the anhydrous tetrahydrofuran solution of the 1000ml in ice-water bath, obtaining one has sedimentary mixed liquor, and cross and filter sediment, obtaining concentration is 1mol/L lithium aluminium hydride reduction-tetrahydrofuran solution.
Block lithium hydride is crushed to below 100 orders in (1) by described step.
Described step is carried out in (2) under the condition of ice-water bath.
In described step (two), the more excellent temperature forming the diethyl ether solution of lithium hydride is 28 DEG C.
In described step (three), the evaporate to dryness of transparency liquid carries out under the state of decompression.
In described step (), the optimum consumption of alchlor is 110g, and the optimum consumption of ether is 300ml.
In described step (two), the optimum consumption of lithium hydride is 31g, and the optimum consumption of ether is 600ml.
Beneficial effect of the present invention is:
1, advantage of the present invention is to have synthesized the extremely strong reducing agent of reducing power, effectively can promote the fast development of organic synthesis technique, especially the development of pharmaceutical industry.
2, the use safety, easy of lithium aluminium hydride reduction-tetrahydrofuran solution.
3, this product according to the demand in market, can mix the finished product of various variable concentrations, to meet the demand of different technology conditions.
Detailed description of the invention
Embodiment 1-12
One, each raw material is weighed according to the consumption in table 1;
The dosage of each raw material in table 1 embodiment 1-12
Two, lithium aluminium hydride reduction-tetrahydrofuran solution is prepared in accordance with the following steps:
(1) get the raw materials ready
1, block lithium hydride is crushed to below 100 orders in ball mill, stand-by;
2, in ice-water bath, divide several to join in ether alchlor, make alchlor diethyl ether solution;
(2) complex reaction
In the there-necked flask of 1000ml, stirring, constant pressure funnel and straight type condenser are installed, add ether, add lithium hydride, start and stir and be warmed up to 28 DEG C with electric jacket, alchlor diethyl ether solution is slowly added drop-wise to from constant pressure funnel in the diethyl ether solution of lithium hydride, the about 6-10 hour of time for adding, dropping process is carried out at the temperature of aether backflow, after dropwising, cross and filter sediment, obtain a colourless transparent liquid or micro-yellow transparent liquid.
(3) evaporate to dryness
Distill out water white ether and reclaim, then evaporated under reduced pressure obtains lithium aluminium hydride reduction powder.
(4) lithium aluminium hydride reduction-tetrahydrofuran solution is prepared
Take 40g lithium aluminium hydride reduction powder, join 1000ml in ice-water bath except in the tetrahydrofuran solution anhydrated, obtaining one has sedimentary mixed liquor, removes sediment after filtration, obtains the colourless transparent liquid that concentration is 1mol/L.
Three, experimental result
Weigh the quality of embodiment 1-12 gained lithium aluminium hydride reduction powder and measure Product Activity hydrogen content in lithium aluminium hydride reduction powder, concrete outcome is in table 2.
The quality of table 2 lithium aluminium hydride reduction powder and Product Activity hydrogen content detail list
| Embodiment | Product weight (g) | Product Activity hydrogen content (%) | Outward appearance |
| 1 | 32.85 | 76.27 | Yellowish |
| 2 | 32.85 | 76.27 | Yellowish |
| 3 | 32.23 | 78.63 | Yellowish |
| 4 | 31.76 | 84.81 | Micro-Huang |
| 5 | 30.9 | 93.69 | Micro-Huang |
| 6 | 29.8 | 97.89 | White |
| 7 | 30.21 | 97.91 | White |
| 8 | 31.09 | 97.68 | White |
| 9 | 32.15 | 97.57 | White |
| 10 | 32.15 | 97.57 | White |
| 11 | 27.09 | 97.89 | White |
| 12 | 32.5 | 97.89 | White |
In table 2, Product Activity hydrogen content is tested as follows:
(1), requirement
The molecular formula of lithium aluminium hydride reduction: LiAlH
4, molecular weight: 37.95
1, appearance requirement: white or pale powder or particle.
2, this product should meet following rank and requirement (defining the level with minimum hydrogen desorption capacity)
а) special superfine product hydrogen desorption capacity (in active hydrogen content) >=98%
ь) primes hydrogen desorption capacity (in active hydrogen content) >=96%
с) seconds hydrogen desorption capacity (in active hydrogen content) >=95%
(2), test method
1. the inspection of outward appearance: under natural daylight, observe with eye.
2, lithium aluminium hydride reduction assay: the mensuration of lithium aluminium hydride reduction content measures by GB4370-84.
3, the detection of hydrogen desorption capacity
3.1 measuring principle
Lithium aluminium hydride reduction can react releasing hydrogen gas with water, and the gas volume of releasing after therefore can reacting with water per sample carrys out the active hydrogen content of calculation sample.
LiAlH
4+4H
2O→LiOH+Al(OH)
3+4H
2
3.2 computing formula
In formula: V
1---sample not with the cumulative volume ml of the gas in water reacting precursor system;
V
2---the cumulative volume ml of the gas after sample and water react in system;
P
t---the atmospheric pressure pa of environment during mensuration;
P
water---water saturation vapour pressure pa during mensuration under environment temperature;
T
o---the temperature 273K under standard state;
T
t---system temperature (273+ room temperature) K during mensuration;
P
o---the gas pressure 1013.2472pa under-standard state;
The weight g of W---sample;
22400----constant;
38----lithium aluminium hydride reduction molecular weight
3.3 tester
Baking oven, ten thousand/assay balance, stainless steel sample spoon, 100ml conical flask, atmospheric pressure meter, gas pressure vessel analyzer (precision 0.1) constant pressure funnel.
3.4 operating procedure
A) conical flask correct amount (being accurate to ten thousand/) in ten thousand/assay balance of a dried and clean is got;
B) sample getting 0.3g is put in conical flask, adds capping plug tight, and correct amount (being accurate to ten thousand/);
C) mixed liquor (water: dioxane=4:6) of water and dioxane is joined in constant pressure funnel;
D) constant pressure funnel and the conical flask and gas pressure vessel analyzer that sample is housed are connected to become closed system;
E) by the water level of barostat and graded tube to flat, accurately write down the ml number in each graded tube;
F) conical flask that sample is housed is placed in ice-water bath;
G) water in constant pressure funnel and dioxane mixed liquor are added on the sample of conical flask, and note observing graded tube SEA LEVEL VARIATION;
H) sample and water after completion of the reaction with ice-water bath in leave standstill 15 minutes, then at room temperature leave standstill 30 minutes;
I) by the water level of barostat and graded tube to flat, accurately write down the ml number in each graded tube;
J) volume of graded tube after reaction is deducted the volume before reaction and be lithium aluminium hydride reduction and water reacts the hydrogen volume of releasing.
Above 12 embodiments of the present invention have been described in detail, but described content being only preferred embodiment of the present invention, can not being considered to for limiting practical range of the present invention.All equalizations done according to the present patent application scope change and improve, and all should still belong within patent covering scope of the present invention.
Claims (7)
1. a preparation technology for lithium aluminium hydride reduction-tetrahydrofuran solution, is characterized in that, comprises the steps:
(1) get the raw materials ready
(1) block lithium hydride is pulverized, stand-by;
(2) under cryogenic, 100-120g alchlor is divided and joins in 250-350ml ether for several times, make alchlor diethyl ether solution;
(2) complex reaction
The lithium hydride pulverized in described step (1) is joined in 550-650ml ether, stir and be warming up to 23-33 DEG C, form the diethyl ether solution of lithium hydride, slowly be added drop-wise in the diethyl ether solution of lithium hydride by alchlor diethyl ether solution obtained in described step (2), time for adding is 6-10 hour, and dropping process is carried out at the temperature of aether backflow, the mol ratio of alchlor and lithium hydride is 1:4-1:6, after dropwising, cross and filter sediment, obtain transparency liquid;
(3) evaporate to dryness
Transparency liquid evaporate to dryness obtained in described step (two) is obtained lithium aluminium hydride reduction powder;
(4) lithium aluminium hydride reduction-tetrahydrofuran solution is prepared
Take 40g lithium aluminium hydride reduction powder to add in the anhydrous tetrahydrofuran solution of 1000ml, obtaining one has sedimentary mixed liquor, and cross and filter sediment, obtaining concentration is 1mol/L lithium aluminium hydride reduction-tetrahydrofuran solution.
2. the preparation technology of a kind of lithium aluminium hydride reduction-tetrahydrofuran solution according to claim 1, is characterized in that, block lithium hydride is crushed to below 100 orders in (1) by described step.
3. the preparation technology of a kind of lithium aluminium hydride reduction-tetrahydrofuran solution according to claim 1, is characterized in that, described step is carried out in (2) under the condition of ice-water bath.
4. the preparation technology of a kind of lithium aluminium hydride reduction-tetrahydrofuran solution according to claim 1, is characterized in that, in described step (two), the more excellent temperature forming the diethyl ether solution of lithium hydride is 28 DEG C.
5. the preparation technology of a kind of lithium aluminium hydride reduction-tetrahydrofuran solution according to claim 1, is characterized in that, in described step (three), the evaporate to dryness of transparency liquid carries out under the state of decompression.
6. the preparation technology of a kind of lithium aluminium hydride reduction-tetrahydrofuran solution according to claim 1, is characterized in that, in described step (), the optimum consumption of alchlor is 110g, and the optimum consumption of ether is 300ml.
7. the preparation technology of a kind of lithium aluminium hydride reduction-tetrahydrofuran solution according to claim 6, is characterized in that, in described step (two), the optimum consumption of lithium hydride is 31g, and the optimum consumption of ether is 600ml.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105033242A (en) * | 2015-07-23 | 2015-11-11 | 中北大学 | Method for preparing porous aluminum powder with specific surface area activity |
| CN106180693A (en) * | 2016-08-31 | 2016-12-07 | 山西润潞碧水环保科技股份有限公司 | A kind of preparation method of the black aluminum of porous spherical |
| CN108358753A (en) * | 2018-02-11 | 2018-08-03 | 庄英俊 | A kind of preparation of three tertiary butyoxies aluminium lithium and detection method |
| CN108358166A (en) * | 2018-02-11 | 2018-08-03 | 庄英俊 | A kind of preparation of lithium aluminium hydride reduction tetrahydrofuran solution and detection method |
| CN108946665A (en) * | 2017-05-24 | 2018-12-07 | 庄英俊 | A kind of preparation method and detection method of deuterate aluminium lithium |
| CN108947771A (en) * | 2017-05-24 | 2018-12-07 | 庄英俊 | A kind of preparation method of three tertiary butyoxies aluminium lithium-tetrahydrofuran solution |
| 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 |
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| GB707851A (en) * | 1951-11-09 | 1954-04-21 | Hans Heinrich Huette G M B H | Process for the preparation of lithium aluminium hydride and lithium gallium hydride |
| CN101300192A (en) * | 2005-09-01 | 2008-11-05 | 凯密特尔有限责任公司 | Solutions of lithium aluminium hydride |
| CN102659080A (en) * | 2012-05-21 | 2012-09-12 | 天津市北斗星精细化工有限公司 | Novel method for preparing lithium aluminum hydride |
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2014
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| GB707851A (en) * | 1951-11-09 | 1954-04-21 | Hans Heinrich Huette G M B H | Process for the preparation of lithium aluminium hydride and lithium gallium hydride |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105033242A (en) * | 2015-07-23 | 2015-11-11 | 中北大学 | Method for preparing porous aluminum powder with specific surface area activity |
| CN106180693A (en) * | 2016-08-31 | 2016-12-07 | 山西润潞碧水环保科技股份有限公司 | A kind of preparation method of the black aluminum of porous spherical |
| CN108946665A (en) * | 2017-05-24 | 2018-12-07 | 庄英俊 | A kind of preparation method and detection method of deuterate aluminium lithium |
| CN108947771A (en) * | 2017-05-24 | 2018-12-07 | 庄英俊 | A kind of preparation method of three tertiary butyoxies aluminium lithium-tetrahydrofuran solution |
| CN108358753A (en) * | 2018-02-11 | 2018-08-03 | 庄英俊 | A kind of preparation of three tertiary butyoxies aluminium lithium and detection method |
| CN108358166A (en) * | 2018-02-11 | 2018-08-03 | 庄英俊 | A kind of preparation of lithium aluminium hydride reduction tetrahydrofuran solution and detection method |
| 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 |
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