CN109879902A - The synthetic method of cyano-containing organo-silicon compound - Google Patents
The synthetic method of cyano-containing organo-silicon compound Download PDFInfo
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Abstract
The present invention relates to organo-silicon compound synthesis technical fields, and in particular to a kind of synthetic method of cyano-containing organo-silicon compound.Synthetic method of the present invention, using chloro nitrile and containing methylchlorosilane as raw material, using Bromofume as initiator, by a step Grignard Reagent method, reaction generates cyano-containing organo-silicon compound；The skeleton symbol of chloro nitrile is ClCH2(CH2)nCN, wherein n is the integer of 0-6；Skeleton symbol containing methylchlorosilane is (CH3)mSiCl4‑m, wherein m is the integer of 1-3.Synthetic method of the invention, simple and easy, raw material reaction rate is fast, and synthesis cycle is short, and product can be easily separated, the yield and purity is high of target product.
Description
Technical field
The present invention relates to organo-silicon compound synthesis technical fields, and in particular to a kind of conjunction of cyano-containing organo-silicon compound
At method.
Background technique
Lithium battery is widely used in consumption electronic product as New Green Battery, and organo-silicon compound have excellent
The advantages that good thermal stability and low-temperature ion conductive performance, high conductivity, nontoxicity, low combustible and high de-agglomeration voltage, just
It is increasingly becoming the research hotspot of novel electrolyte material.The organo-silicon compound monomer of cyano-containing is electrolyte and electrochemical device
Important source material and intermediate.
Patent US9680185 has synthesized cyano silicon compound using Si―H addition reaction and Grignard, the raw material which uses
There are bromomethane (or methyl-magnesium-bromide) and dimethyl silicane hydroxide.Its processing disadvantages has: first, two steps are needed when preparing product
The i.e. first Si―H addition reaction of synthesis that can complete target product, then occurs Grignard Reagent reaction, reaction process is relatively cumbersome again；The
Two, using dimethyl silicane hydroxide as addition raw material, 36 DEG C of the boiling point substance is volatile, easily burns, material safety
Difference requires consersion unit high；Third, using methyl-magnesium-bromide, which can only be by Grignard Reagent now-making-now-using, and prepares
Process needs the gaseous matter of high activity as bromomethane (3.6 DEG C of boiling point), and safety operation control requirement is very high, to consersion unit
It is required that also high.4th, the temperature of hydrosilylation is higher, and catalyst is expensive, will improve reaction cost.
Patent CN2016110078285 discloses a kind of synthetic method of cyano-containing chlorosilane, by cyano-containing alkene with
Pass through dropwise addition using copper chloride as major catalyst, tertiary amines derived object as co-catalyst containing the addition reaction between silicane hydroxide
Method, under the conditions of relatively mild synthesize cyano-containing chlorosilane cpd.Its catalyst amount is larger, reaction temperature 70-
120 DEG C, reaction time 10-36h, synthesis temperature is higher, and synthesis cycle is longer, and low temperature is needed to be added dropwise containing silicane hydroxide,
It reacts at high temperature again, height is required to consersion unit, energy consumption is high, at high cost for industrial production.
Summary of the invention
In view of the deficiencies of the prior art, the object of the present invention is to provide a kind of synthesis sides of cyano-containing organo-silicon compound
Method, simple and easy, raw material reaction rate is fast, and synthesis cycle is short, and product can be easily separated, the yield and purity is high of target product.
The synthetic method of cyano-containing organo-silicon compound of the present invention is original with chloro nitrile and containing methylchlorosilane
Material, using Bromofume as initiator, by a step Grignard Reagent method, reaction generates cyano-containing organo-silicon compound.
The general structure of chloro nitrile is ClCH2(CH2)nCN, wherein n is the integer of 0-6, the preferably integer of 1-3.
General structure containing methylchlorosilane is (CH3)mSiCl4-m, wherein m is the integer of 1-3.
Chloro nitrile and the molar ratio containing methylchlorosilane are 1:2-4.
The dosage of Bromofume is the 0.2-0.5% of chloro nitrile quality.
Chemical equation is as follows:
Wherein, n is the integer of 0-6, and m is the integer of 1-3.
Preferably, the synthetic method of cyano-containing organo-silicon compound, comprising the following steps:
(1) under nitrogen protection, add organic solvent, Bromofume, anhydrous Manganese chloride, chloro nitrile and containing methylchlorosilane
Enter in reactor, stir, heating magnesium chips is added for the first time, magnesium chips is added again, is reacted after reaction causes；
(2) after reaction, reaction product is separated by solid-liquid separation, it is siliconated to obtain cyano-containing by rectifying for liquid phase
Monomer adduct.
The molar ratio of chloro nitrile and magnesium chips is 1:1.05-1.1 in step (1).
The molar ratio of chloro nitrile and anhydrous Manganese chloride is 1:0.01-0.05 in step (1).
The quality that magnesium chips is added in step (1) for the first time is the 1-5% of magnesium chips gross mass.
Organic solvent is tetrahydrofuran, toluene or ether, preferably tetrahydrofuran in step (1).
The concentration of chloro nitrile in organic solvent is 1-4mol/L.
Reaction temperature in step (1) is 50-75 DEG C, reaction time 1-4h.
Synthetic method of the invention is that a step feeds intake completion, when forming Grignard Reagent, since the cyano in chloro nitrile is
Strong electron-withdrawing group group, the Cl on C-Cl key is more active, and in molecular structure containing methylchlorosilane on Si connection there are four group,
Steric hindrance is big, so magnesium, which can preferably select to react with chloro nitrile, generates Grignard Reagent, then the Grignard Reagent of high activity is gone again
Attack contains methylchlorosilane, to obtain cyano-containing silane compound.
Wherein, manganese chloride is able to suppress the reaction of Grignard Reagent and cyano, plays the role of protecting cyano, reduces side reaction
Generation.In addition, improving the dosage containing methylchlorosilane, the generation of two substitutions or polysubstituted product can greatly be reduced.
Compared with prior art, the invention has the following beneficial effects:
(1) present invention completes the synthesis of cyano-containing organo-silicon compound using a step grignard reagent method, and synthetic method is simple,
Synthesis cycle is short, and the boiling point of product and raw material differs greatly, and is easy to rectification and purification, reduces production energy consumption；
(2) present invention as synthesis material, is liquid under room temperature containing methylchlorosilane using containing methylchlorosilane and chloro nitrile
Body, charging are easy, and for consersion unit without pressure resistance, reaction temperature is lower, and the cyano of chloro nitrile has sucting electronic effect, so carbon chlorine
Key is more active, it is easier to grignard reaction occur, can promote the generation of target product；
(3) full recycling and reusing may be implemented in organic solvent of the invention, meets the theory of safety and environmental protection；
(4) yield of synthetic method of the invention synthesis target product reaches 95% or more, and purity is 99.5% or more.
Specific embodiment
The present invention will be further described with reference to embodiments, but protection scope of the present invention is not limited only to this, the neck
Domain professional changes to made by technical solution of the present invention, is within the scope of protection of the invention interior.
Embodiment 1
Under nitrogen protection, by 1L tetrahydrofuran, 89.5g (1mol) 3- chloroethyl nitrile, 1.26g (0.01mol) anhydrous chlorination
Manganese, 217g (2mol) trim,ethylchlorosilane, 0.179g Bromofume are added in reactor, and stirring is heated to 50 DEG C, first to be added
0.252g magnesium chips after reaction causes, is added 24.95g magnesium chips again, reacts 1.5h；After reaction, reaction product is consolidated
Liquid separation, liquid phase obtain cyano-containing organo-silicon compound monomer (i.e. 2- cyanogen second in suitable temperature collection fraction by rectifying
Base trimethyl silane).
The yield of gained cyano-containing organo-silicon compound monomer is 95.6%, purity 99.8%.
Embodiment 2
Under nitrogen protection, by 0.5L tetrahydrofuran, 103.5g (1mol) 4- chlorobutyronitrile, 2.52g (0.02mol) anhydrous chlorine
Change manganese, 387g (3mol) dimethyldichlorosilane, 0.31g Bromofume to be added in reactor, stirring is heated to 65 DEG C, for the first time
0.514g magnesium chips is added, after reaction causes, 25.17g magnesium chips is added again, reacts 2h；After reaction, reaction product is carried out
It is separated by solid-liquid separation, liquid phase obtains cyano-containing organo-silicon compound monomer (i.e. 3- cyanogen in suitable temperature collection fraction by rectifying
Propyl-dimethyl chlorosilane).
The yield of gained cyano-containing organo-silicon compound monomer is 96.1%, purity 99.6%.
Embodiment 3
Under nitrogen protection, by 0.25L toluene, 117.5g (1mol) 5- chlorine valeronitrile, 3.78g (0.03mol) anhydrous chlorination
Manganese, 448.5g (3mol) methyl trichlorosilane, 0.47g Bromofume are added in reactor, and stirring is heated to 70 DEG C, first to add
Enter 1.037g magnesium chips, after reaction causes, 24.88g magnesium chips is added again, reacts 4h；After reaction, reaction product is consolidated
Liquid separation, liquid phase obtain cyano-containing organo-silicon compound monomer (i.e. 4- hydrogen fourth in suitable temperature collection fraction by rectifying
Ylmethyl dichlorosilane).
The yield of gained cyano-containing organo-silicon compound monomer is 96.7%, purity 99.5%.
Embodiment 4
Under nitrogen protection, by 0.25L ether, 117.5g (1mol) 5- chlorine valeronitrile, 6.3g (0.05mol) anhydrous chlorination
Manganese, 598g (4mol) methyl trichlorosilane, 0.587g Bromofume are added in reactor, and stirring is heated to 75 DEG C, first to be added
1.32g magnesium chips after reaction causes, is added 25.08g magnesium chips again, reacts 3h；After reaction, reaction product is subjected to solid-liquid
Separation, liquid phase obtain cyano-containing organo-silicon compound monomer (i.e. 4- hydrogen butyl in suitable temperature collection fraction by rectifying
Dimethyl dichlorosilane (DMCS)).
The yield of gained cyano-containing organo-silicon compound monomer is 97.8%, purity 99.5%.
Embodiment 5
Under nitrogen protection, by 0.5L tetrahydrofuran, 89.5g (1mol) 3- chloroethyl nitrile, 5.04g (0.04mol) anhydrous chlorine
Change manganese, 299g (2mol) methyl trichlorosilane, 0.27g Bromofume to be added in reactor, stirring is heated to 50 DEG C, first to add
Enter 0.513g magnesium chips, after reaction causes, 25.17g magnesium chips is added again, reacts 2h；After reaction, reaction product is consolidated
Liquid separation, liquid phase obtain cyano-containing organo-silicon compound monomer in suitable temperature collection fraction by rectifying.
The yield of gained cyano-containing organo-silicon compound monomer is 96.6%, purity 99.6%.
Comparative example 1
Using first synthesizing Grignard Reagent, then the target product for the method synthetic example 1 reacted with containing methylchlorosilane, tool
Body synthesis step is as follows:
Under nitrogen protection, by 1L tetrahydrofuran, 89.5g (1mol) 3- chloroethyl nitrile, 1.26g (0.01mol) anhydrous chlorination
Manganese, 0.179g Bromofume are added in reactor, and stirring is heated to 50 DEG C, first that 0.252g magnesium chips is added, after reaction causes,
24.95g magnesium chips is added again, reacts 2h, obtains Grignard Reagent；
Grignard reagent dropwise is entered in 217g (2mol) trim,ethylchlorosilane, maintains the temperature at 50 DEG C, is put down after being added dropwise
Weigh 2h, stops reaction, reaction product is separated by solid-liquid separation, and liquid phase is contained by rectifying in suitable temperature collection fraction
Cyano organo-silicon compound monomer (i.e. 2- cyanoethyl trimethyl silane).
The yield of gained cyano-containing organo-silicon compound monomer is 97.5%, purity 99.7%.
Comparative example 2
The target product of the embodiment of the present invention 5 is synthesized using the synthetic method of patent CN2016110078285 embodiment 1,
Specific synthesis step is as follows:
With condensation reflux unit 500ml three neck round bottom flask in sequentially add 2.19g (0.016mol) copper chloride,
Then three-necked flask is placed in ice-water bath, weighs by 3.28g (0.032mol) triethylamine, 84.8g (1.60mol) acrylonitrile
235g (2.00mol) dimethyl dichlorosilane (DMCS), is added dropwise in flask, drips off in 2h, then system temperature < 10 DEG C when dropwise addition rise
Temperature is to 70 DEG C of reaction 30h.It is cooled to room temperature after completion of the reaction, then rises to suitable temperature and steam cyano-containing chlorosilane by decompression
It evaporates and steams, product yield 75%, purity 99.3%.
Claims (10)
1. the synthetic method of cyano-containing organo-silicon compound, it is characterised in that: using chloro nitrile and containing methylchlorosilane as raw material, with
Bromofume is initiator, and by a step Grignard Reagent method, reaction generates cyano-containing organo-silicon compound；
The skeleton symbol of the chloro nitrile is ClCH2(CH2)nCN, wherein n is the integer of 0-6；
The skeleton symbol containing methylchlorosilane is (CH3)mSiCl4-m, wherein m is the integer of 1-3.
2. the synthetic method of cyano-containing organo-silicon compound according to claim 1, it is characterised in that: chloro nitrile with contain first
The molar ratio of base chlorosilane is 1:2-4.
3. the synthetic method of cyano-containing organo-silicon compound according to claim 1, it is characterised in that: the use of Bromofume
Amount is the 0.2-0.5% of chloro nitrile quality.
4. the synthetic method of cyano-containing organo-silicon compound according to claim 1, it is characterised in that: be additionally added anhydrous chlorine
The molar ratio of change manganese, chloro nitrile and anhydrous Manganese chloride is 1:0.01-0.05.
5. the synthetic method of cyano-containing organo-silicon compound according to claim 1, it is characterised in that: including following step
It is rapid:
(1) under nitrogen protection, organic solvent, Bromofume, anhydrous Manganese chloride, chloro nitrile and the addition containing methylchlorosilane is anti-
It answers in device, stirs, heating magnesium chips is added for the first time, magnesium chips is added again, is reacted after reaction causes；
(2) after reaction, reaction product is separated by solid-liquid separation, liquid phase obtains cyano-containing organo-silicon compound by rectifying
Monomer.
6. the synthetic method of cyano-containing organo-silicon compound according to claim 5, it is characterised in that: chlorine in step (1)
It is 1:1.05-1.1 for the molar ratio of nitrile and magnesium chips.
7. the synthetic method of cyano-containing organo-silicon compound according to claim 5, it is characterised in that: step has in (1)
Solvent is tetrahydrofuran, toluene or ether.
8. the synthetic method of cyano-containing organo-silicon compound according to claim 5, it is characterised in that: chloro nitrile is organic
Concentration in solvent is 1-4mol/L.
9. the synthetic method of cyano-containing organo-silicon compound according to claim 5, it is characterised in that: in step (1)
Reaction temperature is 50-75 DEG C, reaction time 1-4h.
10. the synthetic method of cyano-containing organo-silicon compound according to claim 5, it is characterised in that: in step (1) just
The secondary quality that magnesium chips is added is the 1-5% of magnesium chips gross mass.
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Citations (4)
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|---|---|---|---|---|
| US3054817A (en) * | 1959-12-31 | 1962-09-18 | Union Carbide Corp | Process for the preparation of organosilicon compounds |
| GB948757A (en) * | 1959-12-30 | 1964-02-05 | Union Carbide Corp | Process of making cyanoalkylsilanes |
| CN1245807A (en) * | 1998-08-20 | 2000-03-01 | 瓦克化学有限公司 | Preparation method of silicane whose alpha-position related to silicon atom possesses tertiary alkyl radical |
| CN106117084A (en) * | 2016-06-26 | 2016-11-16 | 江苏中旗作物保护股份有限公司 | A kind of big production method of 4 chlorine 2 ' cyanobiphenyls |
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2019
- 2019-03-18 CN CN201910203349.8A patent/CN109879902B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB948757A (en) * | 1959-12-30 | 1964-02-05 | Union Carbide Corp | Process of making cyanoalkylsilanes |
| US3054817A (en) * | 1959-12-31 | 1962-09-18 | Union Carbide Corp | Process for the preparation of organosilicon compounds |
| CN1245807A (en) * | 1998-08-20 | 2000-03-01 | 瓦克化学有限公司 | Preparation method of silicane whose alpha-position related to silicon atom possesses tertiary alkyl radical |
| CN106117084A (en) * | 2016-06-26 | 2016-11-16 | 江苏中旗作物保护股份有限公司 | A kind of big production method of 4 chlorine 2 ' cyanobiphenyls |
Non-Patent Citations (2)
| Title |
|---|
| ZARGES，WOLFGANG等: "Dilithium (trimethylsilyl)cyanomethanediide [{Li2(Me3SiCCN)}12(Et2O)6(C6H14)]，a crystal structure with the (trimethylsilyl)acetonitrile dianion", 《CHEMISCHE BERICHTE》 * |
| 何若愚 等: "锰催化的碳碳键生成反应研究进展", 《化学通报》 * |
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