CN106565573B - The preparation method of two (dimethylamino) telluriums - Google Patents
The preparation method of two (dimethylamino) telluriums Download PDFInfo
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- CN106565573B CN106565573B CN201610846720.9A CN201610846720A CN106565573B CN 106565573 B CN106565573 B CN 106565573B CN 201610846720 A CN201610846720 A CN 201610846720A CN 106565573 B CN106565573 B CN 106565573B
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- C07C395/00—Compounds containing tellurium
Abstract
The preparation method of two (dimethylamino) telluriums, step are as follows: under an inert atmosphere, dimethylamine and alkane solvent are added into reaction vessel, it stirs evenly, and reaction vessel is placed between -20 ~ -80 DEG C, the hexane solution of n-BuLi is added dropwise into reaction vessel, is stirred to react after dripping 16 hours；Solid telluric chloride is added in above-mentioned reaction system, keeps the temperature of reaction system between -80 DEG C to -40 DEG C, after adding telluric chloride, reaction system is stirred to react 8 ~ 24 hours under conditions of inert gas shielding；After reaction, normal pressure removes reaction dissolvent, after equal solvent completely removes, Decompression Sublimation, and the compound of as two (dimethylamino) telluriums.The present invention improves synthesis technology, and operation is simple, and equipment is common.Single hydrocarbon solvent n-hexane is used simultaneously, is reduced costs and is reacted toxicity, while improving yield, be more conducive to the production of scale.
Description
Technical field
The present invention relates to the synthetic methods of metal organic complex in chemical field, are specifically exactly raw for semiconductor
The synthetic method of the metallic tellurium of long raw material amino compound coordination.
Background technique
In Semiconductor industry, tellurium is mainly used to make semi-conductor thermoelectric material.Novel thermocouple containing tellurium can be used
To generate electricity and refrigeration.It mixes the semiconductors such as GaAs and bismuth telluride, the antimony tellurium of tellurium to be widely applied in electrothermic industry, such as space
Cosmos navigation thermoelectric generator, the cooling of flying suit etc., meteorological record and measurement, phone microwave device, energy conversion device with
And submarine and the cooler of guided missile etc..It can make chilling unit silent, it is without friction.It is set to be not easy to be found on submarine.
By tellurium and bismuth, lead, antimony etc. together ingredient, semiconducting alloy can be made, be applied to thermoelectric generator and all kinds of
Mini thermoelectric heat cold-heat exchanger in.
Metal as material of cooling has tellurium, selenium, bismuth, lead, wherein best material is bismuth telluride, can be made into p-type or N-type
Material.P-type material is made of powder metallurgy process, and n type material is to be purified to obtain with zone-melting process.
It is reported that though tellurium optical electro-chemistry thin-film solar cells also in developing stage, is proved, its is high-efficient, light
And it is competitive in expense.Cadmium telluride solar battery is taken seriously very much in national defence, can make nuclear radiation detector, infrared spy
Survey device such as night vision device etc..
Tellurium thin films for sunlight selective absorbent have very big future, the sunlight wavelength absorptivity of tellurium thin films with it is infrared
The ratio between emissivity of radiation area is 33:1, all higher than any other known materials, this unique performance is that tellurium turns in solar energy
Become opening important market in the application of thermal energy.
The development of two (dimethylamino) tellurium compounds is exactly directed to be carried out with semiconductor-on-insulator and solar battery purposes.
Document is few to the report of the preparation method of two (dimethylamino) telluriums at present, mainly disperses ether for the lithium salts of diformazan ammonia
In, system is cooled to -78 DEG C, and telluric chloride tetrahydrofuran compound is added portionwise, and directly extracts out under the premise of not filtering molten
Rectifying after agent.The shortcomings that this method is to use ethers as solvent, and ether solvent has certain toxicity, simultaneously as only
Filter is distillage, has a large amount of chlorination lithium salts and its ether complex in substrate, so that vapo(u)rizing temperature increases, product decomposes tight
Weight, to influence yield.Meanwhile the ether de-coordinated when distillation can be cooled down and is adsorbed on product, reduce the purity of product.
Summary of the invention
The technical issues of solution: present invention is generally directed to the synthesis technologies of in currently available technology two (dimethylamino) telluriums
Deficiency provides a kind of preparation method of two (dimethylaminos).
Technical solution: the preparation method of two (dimethylamino) telluriums, step are as follows: under an inert atmosphere, according to every 100 grams of diformazans
The ratio of 200~400mL alkane solvent is added in amine, dimethylamine and alkane solvent are added into reaction vessel, stirs evenly, and
Reaction vessel is placed between -20~-80 DEG C, according to dimethylamine: n-BuLi is the molar ratio of 1.2:1~2:1, to reaction
The hexane solution of n-BuLi is added dropwise in container, is stirred to react after dripping 16 hours；By telluric chloride: n-BuLi 1:
Solid telluric chloride is added in above-mentioned reaction system by the molar ratio of 3~1:5, keeps the temperature of reaction system at -80 DEG C
To between -40 DEG C, after adding telluric chloride, it is small that reaction system is stirred to react 8~24 under conditions of inert gas shielding
When；After reaction, normal pressure removes reaction dissolvent, after equal solvent completely removes, Decompression Sublimation, as two (dimethylamino) telluriums
Compound.
The alkane solvent is n-hexane.
The preparation method of preferred two (dimethylamino) tellurium: under an inert atmosphere, 135 gram two is added in 2000mL there-necked flask
System is cooled to -80 DEG C with liquid nitrogen acetone, then by the normal-butyl of 2.5mol/L by methylamine and 400mL n-hexane, mechanical stirring
The hexane solution 800mL of lithium is added drop-wise in system, and dropwise addition is completed in three hours, is restored room temperature after dripping and is stirred to react 16
Hour；135 grams of telluric chlorides are added portionwise in above-mentioned system, temperature of reaction system is kept to be no more than -40 DEG C, after adding,
Naturally it is warmed to room temperature, stirs 16 hours under protection of argon gas；After reaction, filtrate is filtered out, filtrate is placed in distilling apparatus
In, normal pressure removes reaction dissolvent, after equal solvent n-hexane all removes, 50 DEG C/0.5mmHg of Decompression Sublimation, and as two (diformazan ammonia
Base) tellurium compound.
Two (dimethylamino) tellurium compound of the present invention has the following structure:
Two (dimethylamino) tellurium Te (NMe2)2It is yellow needle-like crystals at room temperature, 35 DEG C of fusing point.
The utility model has the advantages that present invention is generally directed to the synthesis technologies of two (dimethylamino) telluriums to improve, operation is simple,
Equipment is common.Single hydrocarbon solvent n-hexane is used simultaneously, reduces costs and react toxicity, while improving yield, more
Facilitate large-scale production.This method from dimethylamine and butyl lithium simple and easy to get, generates the lithium salts of dimethylamine, so first
It is directly reacted in single solvent with solid telluric chloride afterwards, after reaction, the lithium salts that filtering removal generates then is subtracted
Pressure pumps solvent, then carries out Decompression Sublimation, obtains two (dimethylamino) telluriums, not only can more efficiently obtain target production
Object can also reduce reaction cost, simplify operation, be convenient for the production of scale.Reaction uses hydro carbons as solvent,
Not only toxicity is low, but also low boiling point, and impurity is few, simple and easy to get, is easy to remove after reaction.
Specific embodiment
Implement to further illustrate the contents of the present invention below, but should not be construed as limiting the invention.Without departing substantially from this
In the case where spirit and essence, to modification made by the method for the present invention, step or condition and replaces, belong to of the invention
Range.Unless otherwise specified, the conventional means that technological means used in case study on implementation is well known to those skilled in the art.
Normal pressure of the present invention is a standard atmospheric pressure.
The synthesis of embodiment 1: two (dimethylamino) tellurium
(1) under an inert atmosphere, 100 grams of dimethylamine of addition and 300mL n-hexane in 2000mL there-necked flask, mechanical stirring,
System is cooled to -40 DEG C with liquid nitrogen acetone, the hexane solution of 600mL (2.5mol/L) n-BuLi is then added drop-wise to body
In system, dropwise addition is completed in three hours, is restored room temperature after dripping and is stirred to react 16 hours；
(2) 135 grams of telluric chlorides are added portionwise in above-mentioned system, keep temperature of reaction system to be not higher than -40 DEG C, adds
It after complete, is warmed to room temperature, stirs 8 hours under protection of argon gas naturally.
(3) after reaction, filtrate is filtered out, filtrate is placed in distilling apparatus, normal pressure removes reaction dissolvent, equal solvent
After n-hexane all removes, 50 DEG C/0.5mmHg of Decompression Sublimation, as two (dimethylamino) tellurium compounds.Yield 65%.Product
The identification of nucleus magnetic hydrogen spectrum is passed through.1H NMR (300MHz, C6D6): 3.46 (s, CH3,12H).
The synthesis of embodiment 2: two (dimethylamino) tellurium
(1) under an inert atmosphere, 135 grams of dimethylamine of addition and 400mL n-hexane in 2000mL there-necked flask, mechanical stirring,
System is cooled to -60 DEG C with liquid nitrogen acetone, the hexane solution of 800mL (2.5mol/L) n-BuLi is then added drop-wise to body
In system, dropwise addition is completed in three hours, is restored room temperature after dripping and is stirred to react 16 hours；
(2) 135 grams of telluric chlorides are added portionwise in above-mentioned system, keep temperature of reaction system to be not higher than -40 DEG C, adds
It after complete, is warmed to room temperature, stirs 12 hours under protection of argon gas naturally.
(3) after reaction, filtrate is filtered out, filtrate is placed in distilling apparatus, normal pressure removes reaction dissolvent, equal solvent
After n-hexane all removes, 50 DEG C/0.5mmHg of Decompression Sublimation, as two (dimethylamino) tellurium compounds.Yield 74%.Product
The identification of nucleus magnetic hydrogen spectrum is passed through.1H NMR (300MHz, C6D6): 3.46 (s, CH3,12H).
The synthesis of embodiment 3: two (dimethylamino) tellurium
(1) under an inert atmosphere, 135 grams of dimethylamine of addition and 400mL n-hexane in 2000mL there-necked flask, mechanical stirring,
System is cooled to -80 DEG C with liquid nitrogen acetone, the hexane solution of 800mL (2.5mol/L) n-BuLi is then added drop-wise to body
In system, dropwise addition is completed in three hours, is restored room temperature after dripping and is stirred to react 16 hours；
(2) 135 grams of telluric chlorides are added portionwise in above-mentioned system, keep temperature of reaction system to be not higher than -40 DEG C, adds
It after complete, is warmed to room temperature, stirs 16 hours under protection of argon gas naturally.
(3) after reaction, filtrate is filtered out, filtrate is placed in distilling apparatus, normal pressure removes reaction dissolvent, equal solvent
After n-hexane all removes, 50 DEG C/0.5mmHg of Decompression Sublimation, as two (dimethylamino) tellurium compounds.Yield 81%.Product
The identification of nucleus magnetic hydrogen spectrum is passed through.1H NMR (300MHz, C6D6): 3.46 (s, CH3,12H).
The synthesis of embodiment 4: two (dimethylamino) tellurium
(1) under an inert atmosphere, 165 grams of dimethylamine of addition and 500mL n-hexane in 2000mL there-necked flask, mechanical stirring,
System is cooled to -60 DEG C with liquid nitrogen acetone, is then added drop-wise to the hexane solution of 1000mL (2.5mol/L) n-BuLi
In system, dropwise addition is completed in three hours, is restored room temperature after dripping and is stirred to react 16 hours；
(2) 135 grams of telluric chlorides are added portionwise in above-mentioned system, keep temperature of reaction system to be not higher than -40 DEG C, adds
It after complete, is warmed to room temperature, stirs 24 hours under protection of argon gas naturally.
(3) after reaction, filtrate is filtered out, filtrate is placed in distilling apparatus, normal pressure removes reaction dissolvent, equal solvent
After n-hexane all removes, 50 DEG C/0.5mmHg of Decompression Sublimation, as two (dimethylamino) tellurium compounds.Yield 80%.Product
The identification of nucleus magnetic hydrogen spectrum is passed through.1H NMR (300MHz, C6D6): 3.46 (s, CH3,12H).
Claims (1)
1. the preparation method of two (dimethylamino) telluriums, it is characterised in that under an inert atmosphere, 135 are added in 2000 mL there-necked flasks
System is cooled to -80 DEG C with liquid nitrogen acetone, then by 2.5 mol/L's by gram dimethylamine and 400 mL n-hexanes, mechanical stirring
800 mL of hexane solution of n-BuLi is added drop-wise in system, and dropwise addition is completed in three hours, is restored room temperature after dripping and is stirred
Mix reaction 16 hours；135 grams of telluric chlorides are added portionwise in above-mentioned system, temperature of reaction system is kept to be no more than -40 DEG C,
It after adding, is warmed to room temperature, stirs 16 hours under protection of argon gas naturally；After reaction, filtrate is filtered out, filtrate is placed in steaming
In distillation unit, normal pressure removes reaction dissolvent, and equal solvent n-hexane is all after removal, Decompression Sublimation 50 DEG C/0.5mmHg, and as two
(dimethylamino) tellurium compound.
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Citations (3)
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| CN102417517A (en) * | 2011-08-31 | 2012-04-18 | 南京大学 | Synthetic method of tetra(dimethylamino)hafnium |
| CN103132050A (en) * | 2007-04-24 | 2013-06-05 | 气体产品与化学公司 | Tellurium (te) precursors for making phase change memory materials |
| CN103910640A (en) * | 2014-03-18 | 2014-07-09 | 南京大学 | Synthetic method of tetra(dimethylamino)zirconium |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103132050A (en) * | 2007-04-24 | 2013-06-05 | 气体产品与化学公司 | Tellurium (te) precursors for making phase change memory materials |
| CN102417517A (en) * | 2011-08-31 | 2012-04-18 | 南京大学 | Synthetic method of tetra(dimethylamino)hafnium |
| CN103910640A (en) * | 2014-03-18 | 2014-07-09 | 南京大学 | Synthetic method of tetra(dimethylamino)zirconium |
Non-Patent Citations (3)
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| application to the preparation of metalloorganic tellurium(II) compounds.《J.Chem.SOC.,Dalton Trans.》.1996,第1727-1730页. |
| Parametrization of a Force Field for Te-N Secondary Bonding Interactions and Its Application in the Design of Supramolecular Structures Based on Heterocyclic Building Blocks;Anthony F. Cozzolino 等;《Crystal Growth & Design》;20110119;第11卷;第668-677页 |
| Robert E. Allan 等.Structure and reactivity of [{Te(NMe2)2}∞] |
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