CN108129352A - A kind of preparation method of 3- allyloxys propionitrile - Google Patents
A kind of preparation method of 3- allyloxys propionitrile Download PDFInfo
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- CN108129352A CN108129352A CN201711450572.XA CN201711450572A CN108129352A CN 108129352 A CN108129352 A CN 108129352A CN 201711450572 A CN201711450572 A CN 201711450572A CN 108129352 A CN108129352 A CN 108129352A
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- propionitrile
- preparation
- allyloxys
- reaction
- allyl alcohol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of preparation method of 3 allyloxy propionitrile, preparation method includes the following steps：S1, alkalize material；S2, synthetic reaction；S3, rectification under vacuum is to get 3 allyloxy propionitrile.The present invention provides a kind of reaction condition and mitigates, and preparation method safety, combined coefficient is high, and manufacturing cost is low, the high preparation method of 3 allyloxy propionitrile purity of gained.
Description
Technical field
The present invention relates to a kind of synthesis of organic compound and its Purity field, a kind of especially 3- allyloxys third
The preparation method of nitrile.
Background technology
3- allyloxy propionitrile is a kind of novel nonaqueous lithium ion battery electrolyte additive, the additive molecule structure
In due to simultaneously containing unsaturated carbon-carbon double bond and cyano, polymerisation can occur formed in electrode surface to contain multiple cyano
Compound, the compound can with the complexing of metal ion on positive electrode surface, so as to inhibit electrolyte electrode surface send out
Solution estranged improves the high-temperature storage and cycle performance of battery.
The preparation method of 3- allyloxy propionitrile reported at present is as follows：
It is reacted with lithium hydride with allyl alcohol, ether first obtains allyl alcohol anion, then react with 1,2- dichloroethanes for solvent
It to allyloxy chloroethanes, is finally reacted with Cymag, acetonitrile is solvent, obtains 3- allyloxy propionitrile.This method lacks
Point is that route is long, and yield is low, severe reaction conditions, and used hazardous chemical is more.
For above-mentioned technical problem, a kind of safety, low cost, high income are provided and can largely prepare 3- allyloxy propionitrile
Preparation method be at present it is in the urgent need to address the technical issues of.
Invention content
The invention the technical problem to be solved is that long for prior art 3- allyloxy propionitrile synthetic routes,
Yield is low, severe reaction conditions, and used hazardous chemical is more, and it is a large amount of to provide a kind of safety, low cost, high income and energy
Prepare the preparation method of 3- allyloxy propionitrile.
In order to achieve the above objectives, a kind of preparation method of 3- allyloxys propionitrile, the preparation method include the following steps：
S1, alkalize material：Allyl alcohol and the aqueous solution of alkaline reagent or alkaline reagent are added in into reaction vessel, is stirred evenly
Afterwards to get the allyl alcohol after alkalization；Alkaline reagent alkalization allyl alcohol is added in, is reacted conducive to next step acrylonitrile with allyl alcohol；
S2, synthetic reaction：Acrylonitrile is added dropwise in allyl alcohol after alkalization, and rear isothermal reaction is added dropwise to get 3- allyloxys
Propionitrile reaction solution；The rate of addition of control acrylonitrile ensures that allyl alcohol is fully reacted with acrylonitrile, and constant control reacts
Temperature makes the gentle progress of synthetic reaction, avoids reaction excessively fierce.
S3, rectification under vacuum:By the 3- allyloxy propionitrile reaction solution rectifications under vacuum of step S2, fraction is collected to get 3-
Allyloxy propionitrile.It is further purified by rectification under vacuum, obtains the high 3- allyloxy propionitrile of purity.If propenyl adds in alkali
The aqueous solution of reagent needs by 3- allyloxy propionitrile reaction solution carry out again after liquid separation removes water layer before rectification under vacuum
Rectification under vacuum.
Further, in step S1, the alkaline reagent is potassium carbonate, sodium carbonate, sodium hydroxide, lithium hydroxide, hydrogen-oxygen
Change one or more in potassium, sodium methoxide.Alkaline reagent is allyl alcohol and acrylonitrile, and alkaline reaction environment is provided for reaction.
Still further, in step S1, the aqueous solution of the alkaline reagent is the saturated aqueous solution of alkaline reagent.Add in alkali
The saturated aqueous solution of property reagent, which can be reduced, brings excessive water into reaction solution, influences the rectification under vacuum of subsequent step.
Still further, in step S1, the allyl alcohol is more than 1 with base reagent molar ratio:0.1.
Still further, in step S2, the allyl alcohol is 0.9 with acrylonitrile molar ratio:1~1:1.Acrylonitrile addition
Than or equal to allyl alcohol addition, ensure that the reaction was complete for allyl alcohol quilt, addition is avoided excessively to lead to material waste, increases life
Produce cost.
Still further, in step S2, temperature control is at 20 DEG C~80 DEG C when the acrylonitrile is added dropwise.
Still further, in step S2, after the acrylonitrile time for adding is 8 hours hereinafter, the acrylonitrile drips
Reaction time is less than 15 hours.The acrylonitrile that control acrylonitrile time for adding ensures to be added dropwise is sufficiently mixed with allyl alcohol to react.
Still further, in step S3, the temperature of the rectification under vacuum is 35 DEG C~120 DEG C.The temperature of rectification under vacuum is
Less than 35 DEG C then temperature it is too low can not will main point distill, higher than 120 DEG C, then temperature is excessively high easily causes in reaction for temperature
By-product can be distilled off.
Compared with prior art, the advantageous effects of the invention：
Firstth, reaction condition mitigates, preparation method safety.3- alkene can be realized using conventional heating, rectification under vacuum in the present invention
Propoxyl group propionitrile, reaction condition mitigate, without special processing, preparation method safety in reaction process.
Secondth, synthetic route is short, and preparation efficiency is high.Allyl alcohol and acrylonitrile are synthesized system by the present invention under alkaline condition
, synthetic route is short, and preparation efficiency is high.
Third, manufacturing cost are low, and product purity is high.Preparation method of the present invention is raw materials used and reagent is common agents,
It is at low cost, and the high 3- allyloxy propionitrile of purity is obtained by multiple temperature section rectifications under vacuum removal of impurities fractionation.
Specific embodiment
Technical scheme of the present invention is more fully understood for ease of those skilled in the art, in conjunction with specific embodiment to this
Invention is described further.
Embodiment 1
S1, alkalize material：522.5g allyl alcohols and sodium hydroxide saturated aqueous solution, allyl alcohol and hydrogen-oxygen are added in into reaction vessel
It is 1 to change sodium molar ratio:0.08 stir evenly after to get the allyl alcohol after alkalization；
S2, synthetic reaction：505g acrylonitrile is added dropwise in allyl alcohol under 40 DEG C of temperature conditions after alkalization, and control acrylonitrile is added dropwise
Time is 5 hours, rear isothermal reaction is added dropwise 6 hours to get 3- allyloxy propionitrile reaction solutions；
S3, rectification under vacuum:The 3- allyloxy propionitrile reaction solutions of step S2 are subjected to rectification under vacuum at 35 DEG C~120 DEG C,
Collect fraction, the total recovery 84.37% of 3- allyloxy propionitrile.
Embodiment 2
S1, alkalize material：893g allyl alcohols and sodium hydroxide saturated aqueous solution, allyl alcohol and hydroxide are added in into reaction vessel
Sodium molar ratio is 1:0.05, to get the allyl alcohol after alkalization after stirring evenly；
S2, synthetic reaction：840g acrylonitrile is added dropwise in allyl alcohol under 20 DEG C of temperature conditions after alkalization, and control acrylonitrile is added dropwise
Time is 5 hours, rear isothermal reaction is added dropwise 4 hours to get 3- allyloxy propionitrile reaction solutions；
S3, rectification under vacuum:The 3- allyloxy propionitrile reaction solutions of step S2 are subjected to rectification under vacuum at 35 DEG C~120 DEG C,
Collect fraction, the total recovery 83.55% of 3- allyloxy propionitrile.
Embodiment 3
S1, alkalize material：493g allyl alcohols and sodium hydroxide saturated aqueous solution, allyl alcohol and hydroxide are added in into reaction vessel
Sodium molar ratio is 1:0.03, to get the allyl alcohol after alkalization after stirring evenly；
S2, synthetic reaction：467g acrylonitrile is added dropwise in allyl alcohol under 70 DEG C of temperature conditions after alkalization, and control acrylonitrile is added dropwise
Time is 3 hours, rear isothermal reaction is added dropwise 6 hours to get 3- allyloxy propionitrile reaction solutions；
S3, rectification under vacuum:The 3- allyloxy propionitrile reaction solutions of step S2 are subjected to rectification under vacuum at 35 DEG C~120 DEG C,
Collect fraction, the total recovery 79.78% of 3- allyloxy propionitrile.
The foregoing is only a preferred embodiment of the present invention, not makees limitation in any form to the present invention；It is all
The those of ordinary skill of the industry can swimmingly implement the present invention by described above；But all technology people for being familiar with this profession
Member without departing from the scope of the present invention, a little change, the modification made using disclosed above technology contents
It is the equivalent embodiment of the present invention with the equivalent variations of differentiation；Meanwhile all substantial technologicals according to the present invention to implementing above
Variation, modification and evolution of any equivalent variations for being made of example etc., still fall within technical scheme of the present invention protection domain it
It is interior.
Claims (8)
1. a kind of preparation method of 3- allyloxys propionitrile, it is characterised in that the preparation method includes the following steps：
S1, alkalize material：Allyl alcohol and the aqueous solution of alkaline reagent or alkaline reagent are added in into reaction vessel, is stirred evenly
Afterwards to get the allyl alcohol after alkalization；
S2, synthetic reaction：Acrylonitrile is added dropwise in allyl alcohol after alkalization, and rear isothermal reaction is added dropwise to get 3- allyloxys
Propionitrile reaction solution；
S3, rectification under vacuum:By the 3- allyloxy propionitrile reaction solution rectifications under vacuum of step S2, fraction is collected to get 3- allyls
Oxygroup propionitrile.
2. the preparation method of 3- allyloxys propionitrile according to claim 1, it is characterised in that：In step S1, the alkali
Property reagent be potassium carbonate, it is sodium carbonate, sodium hydroxide, lithium hydroxide, potassium hydroxide, one or more in sodium methoxide.
3. the preparation method of 3- allyloxys propionitrile according to claim 1, it is characterised in that：In step S1, the alkali
Property reagent aqueous solution be alkaline reagent saturated aqueous solution.
4. the preparation method of the 3- allyloxy propionitrile according to claims 1 to 3 any claim, it is characterised in that：
In step S1, the allyl alcohol is more than 1 with base reagent molar ratio:0.1.
5. the preparation method of 3- allyloxys propionitrile according to claim 1, it is characterised in that：In step S2, the alkene
Propyl alcohol is 0.9 with acrylonitrile molar ratio:1~1:1.
6. the preparation method of 3- allyloxys propionitrile according to claim 5, it is characterised in that：In step S2, described third
Temperature control is at 20 DEG C~80 DEG C when alkene nitrile is added dropwise.
7. the preparation method of 3- allyloxys propionitrile according to claim 6, it is characterised in that：In step S2, described third
Alkene nitrile time for adding is 8 hours hereinafter, it is less than 15 hours that the acrylonitrile, which drips the rear reaction time,.
8. the preparation method of 3- allyloxys propionitrile according to claim 1, it is characterised in that：It is described to subtract in step S3
The temperature for pressing rectifying is 35 DEG C~120 DEG C.
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| CN201711450572.XA CN108129352A (en) | 2017-12-27 | 2017-12-27 | A kind of preparation method of 3- allyloxys propionitrile |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111613836A (en) * | 2020-05-28 | 2020-09-01 | 天能帅福得能源股份有限公司 | Electrolyte additive, electrolyte and lithium ion battery |
| CN114276254A (en) * | 2021-12-31 | 2022-04-05 | 万华化学集团股份有限公司 | Synthetic method of 3-methoxypropylamine |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE842194C (en) * | 1941-05-24 | 1952-06-23 | Basf Ag | Process for the preparation of esters, amides or nitriles of AEtherpropionsaeuren |
| CN1733702A (en) * | 2005-08-08 | 2006-02-15 | 扬州大学 | 3-(2-methoxyethoxy)-propylamine production process |
-
2017
- 2017-12-27 CN CN201711450572.XA patent/CN108129352A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE842194C (en) * | 1941-05-24 | 1952-06-23 | Basf Ag | Process for the preparation of esters, amides or nitriles of AEtherpropionsaeuren |
| CN1733702A (en) * | 2005-08-08 | 2006-02-15 | 扬州大学 | 3-(2-methoxyethoxy)-propylamine production process |
Non-Patent Citations (1)
| Title |
|---|
| HIEU-TRINH LUU等: "A Titanium(III)-Catalyzed Reductive Umpolung Reaction for the Synthesis of 1,1-Disubstituted Tetrahydroisoquinolines", 《ORGANIC LETTERS》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111613836A (en) * | 2020-05-28 | 2020-09-01 | 天能帅福得能源股份有限公司 | Electrolyte additive, electrolyte and lithium ion battery |
| CN114276254A (en) * | 2021-12-31 | 2022-04-05 | 万华化学集团股份有限公司 | Synthetic method of 3-methoxypropylamine |
| CN114276254B (en) * | 2021-12-31 | 2023-09-19 | 万华化学集团股份有限公司 | Synthesis method of 3-methoxypropylamine |
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Application publication date: 20180608 |