CN106699522A - Production process of high-quality trimethyl orthoacetate - Google Patents
Production process of high-quality trimethyl orthoacetate Download PDFInfo
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- CN106699522A CN106699522A CN201510789390.XA CN201510789390A CN106699522A CN 106699522 A CN106699522 A CN 106699522A CN 201510789390 A CN201510789390 A CN 201510789390A CN 106699522 A CN106699522 A CN 106699522A
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- trimethyl orthoacetate
- methyl alcohol
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- reaction
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/60—Preparation of compounds having groups or groups
Abstract
The invention discloses a production process of high-quality trimethyl orthoacetate. The production process comprises the following steps: performing salification reaction on acetonitrile, methanol and chlorine hydride in the presence of a solvent unsym-trimethyl benzene, so as to obtain ethyleneimine methyl ether hydrochloride; then adding the ethyleneimine methyl ether hydrochloride into a methanol solution; dropwise adding an aminomethanol solution to regulate a pH value, performing alcoholysis reaction to obtain a trimethyl orthoacetate crude product; filtering out solid ammonium chloride, and recycling the solid ammonium chloride; adsorbing filtrate by use of strong-basicity macroporous ion-exchange resin so as to remove chloridion; and finally performing continuous rectification, thereby obtaining a trimethyl orthoacetate product with content greater than 999.5% and yield greater than 85%. The production process is simple in process, the product is stable and reliable, and the used unsym-trimethyl benzene solvent is low in toxicity and safe to use.
Description
Technical field
The present invention relates to chemical field, a kind of particularly production technology of high-quality trimethyl orthoacetate.
Background technology
Trimethyl orthoacetate is colourless liquid, there is special smell, in the middle of the chemistry of production medicine and agricultural chemicals
Body, the pharmaceutical intermediates such as synthetic vitamin B1, retinol1, sulfidin are mainly used in pharmaceuticals industry；Led in agricultural
Domain is the intermediate raw material for synthesizing the pyrethroids such as cypermethrin, cyhalothrin.
The equal production technology of trimethyl orthoacetate often reported at present, is to be with acetonitrile, absolute methanol and dry hydrogen chloride
Raw material, under solvent action, carries out salt-forming reaction, generates ethyleneimine amitraz hydrochloride, and adding methyl alcohol, to carry out alcoholysis anti-
Trimethyl orthoacetate should be prepared.Wherein, the selection of solvent influences very big for course of reaction, industrial conventional low boiling
Solvent such as n-hexane and carbon tetrachloride, toxicity is big, consumption is more, be unfavorable for save production cost.Meanwhile, chlorine in product
The remaining influence of the ion purity of trimethyl orthoacetate.
The content of the invention
It is an object of the invention to provide a kind of production technology of high-quality trimethyl orthoacetate.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is：A kind of life of high-quality trimethyl orthoacetate
Production. art, production process is carried out in three steps, and the first step is passed through dry hydrogen chloride gas in the presence of solvent by acetonitrile and methyl alcohol,
Salt-forming reaction generation ethyleneimine methyl ether hydrochlorate is carried out, second step is obtained trimethyl orthoacetate to add methyl alcohol to carry out alcoholysis reaction
Crude product, the 3rd step is subtractive process, it is characterised in that：The solvent is pseudocumene；The salt-forming reaction condition is：
The mol ratio of raw material acetonitrile, methyl alcohol, hydrogen chloride and solvent pseudocumene is 1：1.1：1.1-1.15：1.16-1.2, ventilation is anti-
Answer temperature：0-5 DEG C, lead to the hydrogen chloride time：10-12 hours, into salt insulation reaction temperature：It is 20-25 DEG C, anti-into salt insulation
Between seasonable：6-8 hours；The alcoholysis reaction condition is：On the basis of ethane nitrile content, the methyl alcohol and acetonitrile mole
Than being 2:1, alcoholysis pH value 5-6,37-39 DEG C of glycolysis temperature, 6-8 hours alcoholysis time；The subtractive process is：Will
Trimethyl orthoacetate crude product centrifugal filtration, filter residue is ammonium chloride, and ammonium chloride, the white ammonium chloride after drying are washed with solvent
Solid, filtrate removes chlorion with resin, then through continuous rectification, obtains the trimethyl orthoacetate of high-quality.
Preferably, the cleaning solvent is the methyl alcohol and the low-boiling-point substance of methyl acetate of methyl alcohol or continuous rectification recovery.
Preferably, the resin is strong basicity macroporous ion exchange resin.
Advantages of the present invention include it is following some：
1st, the lower boiling n-hexane of high poison is replaced using high boiling solvent pseudocumene, improves the safety of process of producing product
Property；
2nd, because pseudocumene is dissolved in methyl alcohol and methyl acetate, therefore, reclaimed during enabled production rectifying containing methyl alcohol and acetic acid
Ammonium chloride is reclaimed in the low-boiling-point substance of methyl esters, washing, removes wherein organic impurities, and the ammonium chloride byproduct of white is obtained after drying；
3rd, filtrate is processed with strong basicity macroporous ion exchange resin, it is to avoid trimethyl orthoacetate is washed with water when post-processing,
The problem that product yield is low, wastewater flow rate is big is caused, chlorion in filtrate can be effectively removed again, when increased product post processing
Stability, product yield is brought up to more than 85%, content >=99.5% makes product have wide applicability；
4th, present invention process is simple, product quality and stable yield reliability.
Specific embodiment
In order that the public can be fully understood by technical spirit of the invention and beneficial effect, applicant will be below to of the invention
Specific embodiment is described in detail, but description of the applicant to embodiment is not the limitation to technical scheme, any according to this
Inventive concept is changed in the form rather than substance should all be considered as protection scope of the present invention.
Embodiment 1
512.5Kg acetonitriles, 440Kg methyl alcohol, 1750Kg solvent pseudocumenes are put into the enamel reaction still of 5000L,
Stirring and chilled brine are opened, material in reactor is cooled to 0-5 DEG C, start to be passed through hydrogen chloride gas 502Kg, generally
About need 10-12 hours, at the end of ventilation is fast, chilled brine valve is entered in appropriate regulation, and reaction temperature is raised to 20-25 DEG C gradually
Start to be incubated, insulation reaction 8 hours, salt-forming reaction terminates, and obtains ethyleneimine methyl ether hydrochloride intermediate.Stirring and
Under the conditions of chilled brine, to 600Kg methyl alcohol is added in ethyleneimine methyl ether hydrochloride intermediate, reaction solution is cooled to
0-5 DEG C, between 0-5 DEG C, 15-20% ammonia methanol solutions are added dropwise, between reacting liquid pH value 5-6, then according in ammonia methyl alcohol
The usage amount of methyl alcohol, supplies the amount of methyl alcohol to 800Kg, slowly brings up between 37-39 DEG C the temperature of material in reactor,
And between 37-39 DEG C insulation reaction 6 hours, alcoholysis reaction terminates.By above reaction solution centrifugal filtration, ammonium chloride is reclaimed,
The methyl alcohol reclaimed with 700-1000Kg methyl alcohol or continuous rectification washs ammonium chloride with the low-boiling-point substance of methyl acetate, after drying, obtains
Obtain 730Kg white ammonium chlorides, content：99.0%, filtrate is processed through with strong basicity macroporous ion exchange resin, except dechlorination
Ion (is detected, do not produce white precipitate) with silver nitrate solution, then through continuous rectification, obtains trimethyl orthoacetate product：
1282.5Kg, content：99.7%, yield：85.5%.
Embodiment 2
512.5Kg acetonitriles, 440Kg methyl alcohol, 1800Kg solvent pseudocumenes are put to the enamel reaction still of 5000L
In, stirring and chilled brine are opened, material in reactor is cooled to 0-5 DEG C, start to be passed through hydrogen chloride gas 525Kg,
Normally about need 10-12 hours, at the end of ventilation is fast, chilled brine valve is entered in appropriate regulation, and reaction temperature is raised to gradually
20-25 DEG C starts to be incubated, insulation reaction 8 hours, and salt-forming reaction terminates, and obtains ethyleneimine methyl ether hydrochloride intermediate.
Under the conditions of stirring and chilled brine, to 600Kg methyl alcohol is added in ethyleneimine methyl ether hydrochloride intermediate, reaction solution is cooled down
To 0-5 DEG C, between 0-5 DEG C, 15-20% ammonia methanol solutions are added dropwise, between reacting liquid pH value 5-6, now, then basis
The usage amount of methyl alcohol in ammonia methyl alcohol, supplies the amount of methyl alcohol to 800Kg, slowly brings up to the temperature of material in reactor
Between 37-39 DEG C, and insulation reaction 8 hours between 37-39 DEG C, alcoholysis reaction terminates.By above reaction solution centrifugal filtration,
Ammonium chloride is reclaimed, the methyl alcohol reclaimed with 700-1000Kg methyl alcohol or continuous rectification washs chlorination with the low-boiling-point substance of methyl acetate
Ammonium, after drying, obtains 765Kg white ammonium chlorides, content：99.2%.Filtrate uses strong basicity macroporous ion exchange resin
Treatment, removes chlorion (being detected with silver nitrate solution, do not produce white precipitate), then through continuous rectification, obtain ortho-acetic acid
Trimethyl product：1305Kg, content：99.8%, yield：87%.
Embodiment 3
Comparative example 1：Solvent be n-hexane with step described in embodiment 1, difference be using 1400Kg solvents just
Hexane replace above-mentioned 1750Kg solvents pseudocumene, as a result for：Yellow ammonium chloride 730Kg, content：97.0%, most
Whole trimethyl orthoacetate product：1125Kg, content：99.3%, yield：75%.
Claims (3)
1. a kind of production technology of high-quality trimethyl orthoacetate, production process is carried out in three steps, and the first step is by acetonitrile and methyl alcohol in solvent
In the presence of be passed through dry hydrogen chloride gas, carry out salt-forming reaction generation ethyleneimine methyl ether hydrochlorate, second step for add methyl alcohol carry out alcohol
Solution reaction is obtained trimethyl orthoacetate crude product, and the 3rd step is subtractive process, it is characterised in that：The solvent is pseudocumene；Institute
Stating salt-forming reaction condition is：The mol ratio of raw material acetonitrile, methyl alcohol, hydrogen chloride and solvent pseudocumene is 1：1.1：1.1-1.15：
1.16-1.2, ventilatory response temperature：0-5 DEG C, lead to the hydrogen chloride time：10-12 hours, into salt insulation reaction temperature：20-25 DEG C,
Into the salt insulation reaction time：6-8 hours；The alcoholysis reaction condition is：On the basis of ethane nitrile content, the methyl alcohol and acetonitrile
Mol ratio is 2:1, alcoholysis pH value 5-6,37-39 DEG C of glycolysis temperature, 6-8 hours alcoholysis time；The subtractive process is：Will
Trimethyl orthoacetate crude product centrifugal filtration, filter residue is ammonium chloride, with solvent wash ammonium chloride, the white chloride solid after drying,
Filtrate removes chlorion with resin, then through continuous rectification, obtains the trimethyl orthoacetate of high-quality.
2. the production technology of a kind of high-quality trimethyl orthoacetate according to claim 1, it is characterised in that：The cleaning solvent
The methyl alcohol and the low-boiling-point substance of methyl acetate reclaimed for methyl alcohol or continuous rectification.
3. the production technology of a kind of high-quality trimethyl orthoacetate according to claim 1, it is characterised in that：The resin is strong
Basic macroporous ion exchange resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201510789390.XA CN106699522A (en) | 2015-11-16 | 2015-11-16 | Production process of high-quality trimethyl orthoacetate |
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| CN201510789390.XA CN106699522A (en) | 2015-11-16 | 2015-11-16 | Production process of high-quality trimethyl orthoacetate |
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| CN201510789390.XA Pending CN106699522A (en) | 2015-11-16 | 2015-11-16 | Production process of high-quality trimethyl orthoacetate |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111675607A (en) * | 2020-06-09 | 2020-09-18 | 杭州众立化工科技有限公司 | Method for producing trimethyl orthoacetate through differential circulation and continuous production |
| CN112316469A (en) * | 2020-11-20 | 2021-02-05 | 安徽鑫泰新材料有限公司 | Trimethyl orthoacetate continuous rectification device and continuous rectification process |
| TWI756470B (en) * | 2017-12-21 | 2022-03-01 | 日商奧璐佳瑙股份有限公司 | Method of refining non-aqueous substance, and ion exchange resin-filled cartridge with airproofing member |
-
2015
- 2015-11-16 CN CN201510789390.XA patent/CN106699522A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI756470B (en) * | 2017-12-21 | 2022-03-01 | 日商奧璐佳瑙股份有限公司 | Method of refining non-aqueous substance, and ion exchange resin-filled cartridge with airproofing member |
| US11607624B2 (en) | 2017-12-21 | 2023-03-21 | Organo Corporation | Method for purifying nonaqueous liquid substance and ion exchange resin-filled cartridge with external air blocking member |
| CN111675607A (en) * | 2020-06-09 | 2020-09-18 | 杭州众立化工科技有限公司 | Method for producing trimethyl orthoacetate through differential circulation and continuous production |
| CN112316469A (en) * | 2020-11-20 | 2021-02-05 | 安徽鑫泰新材料有限公司 | Trimethyl orthoacetate continuous rectification device and continuous rectification process |
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