CN106699524A - Synthetic method of triethyl orthoformate - Google Patents
Synthetic method of triethyl orthoformate Download PDFInfo
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- CN106699524A CN106699524A CN201510789328.0A CN201510789328A CN106699524A CN 106699524 A CN106699524 A CN 106699524A CN 201510789328 A CN201510789328 A CN 201510789328A CN 106699524 A CN106699524 A CN 106699524A
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- triethyl orthoformate
- dehydrating agent
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- ethanol
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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
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthetic method of triethyl orthoformate. According to the synthetic method, a dehydrating agent is used, and the dehydrating agent is prepared from glycerol, activated clay and a 4A molecular sieve according to the mass ratio of 10: (2-1):(2-1). By means of the dehydrating agent, moisture in the triethyl orthoformate synthesis process can be greatly reduced, the amount of loss of a triethyl orthoformate product in the separation stage is reduced, raw material waste and industrial energy consumption are reduced, and the method is suitable for large-scale industrial production.
Description
Technical field
The invention belongs to chemical field, it is related to a kind of synthetic method of triethyl orthoformate.
Background technology
Triethyl orthoformate, also known as acton, is a kind of colourless transparent liquid, and synthesis is widely used in as intermediate
The medicals such as chloroquine, quinoline piperazine, dichloroquinoline, orfloxacin, Ciprofloxacin, fluorine piperazine quinolinic acid, aminopyrimidine, also
For the fibers such as acrylic acid synthesizing and methine class dyestuff and cyanine dye；As antihalation material be widely used in photographic chemical and
In the photosensitive materials such as colour cinefilm.
The synthetic method of triethyl orthoformate is a lot, has one-step method, two step method, phase transfer method etc. according to foreign literature report,
Current most domestic insecticide factory and pharmaceutical factory use two step method.Two step method is first anti-with solid caustic soda with absolute ethyl alcohol benzene
Answer and ternary azeotropic is formed in tower, the condensed separation water outlet of gas phase, liquid phase thing is caustic alcohol-ethanol, solution.Second step is by second
Sodium alkoxide-ethanol solution and haloform reaction.Product filters desalination, reheats and collects between 80-160 DEG C, 140-146 DEG C
It is fractionated again after cut once and obtains product.
In triethyl orthoformate building-up process, ethyoxyl methylene amine hydrochlorate and triethyl orthoformate finished product are met water and can all be divided
Solution.So as to cause yield to reduce, so to the aqueous of the raw material such as Materials Absolute ethanol, HCL and solvent needed for production process
Amount requires as low as possible.Production system requirement is as far as possible closed, prevents from contacting humid air.
Generally, the water content (mass percent) of absolute ethyl alcohol is in 0.04-0.08% or so, HCl gases be by
After 98% concentrated sulfuric acid is dried, its water content is general all in 0.01% or so (mass percent).Except containing part in raw material
Outside moisture, in process of production, equipment (cooling coil, tower reactor reboiler etc.) often inevitably occurs slight
Leak and infiltration, system water content are higher, can also make the yield reduction of triethyl orthoformate.
In triethyl orthoformate synthetic reaction, the mass fraction of liquid reclaimed water is synthesized generally more than 1%, even if through
Moisture can be reduced to 0.5% or so after suitably drying, but also having makes more than 15% product be hydrolyzed destruction, therefore
The micro-moisture in Synthesis liquid can be thoroughly removed, is the key point for further improving triethyl orthoformate yield.Document
(removing of micro-moisture, Wang Xiangrong etc., Shanxi chemical industry 2008 in triethyl orthoformate Synthesis liquid) have studied primitive nail triethylenetetraminehexaacetic acid
The dehydrating agent and dehydration conditions of micro-moisture are removed in the reaction of ester one-step synthesis method, it is found that glycerine can be used as a kind of dehydrating agent
It is applied in one-step synthesis method, wherein the large usage quantity of glycerine, is the 7% of Synthesis liquid quality, and in Synthesis liquid
Water quality minimum 0.2% or so, the maximum yield of triethyl orthoformate is 98%；It can be seen that, glycerine is de- as one kind
Aqua, its large usage quantity, and dewatering efficiency is perfect not enough.
In order to overcome the defect of prior art, the content of moisture in triethyl orthoformate building-up process is reduced to greatest extent,
The yield of triethyl orthoformate is improved, we urgently need micro- in a kind of effectively removing triethyl orthoformate building-up process of research
The method for measuring moisture.
The content of the invention
It is low as far as possible in order to ensure the water content in triethyl orthoformate synthesis system, primitive nail is improved to greatest extent
The yield of triethylenetetraminehexaacetic acid ester, we have invented a kind of method for removing micro-moisture in triethyl orthoformate building-up process.
The present invention on the basis of existing technology, by development test for many years, obtains a kind of effectively removal orthoformic acid three
The dehydrating agent of micro-moisture in ethyl ester building-up process, its preferred method of application is：At the beginning of crystallization process, HCl is passed through
Before gas, scavenger, the moisture and system of the possible seepage of the moisture that raw material in course of reaction is contained, coil pipe are added
The moisture for contacting humid air is all removed.
The technical scheme is that realize in the following way：A kind of method of triethyl orthoformate synthesis, it includes
Following steps：
First to the solvent (1410kg) that crystallization kettle adds 60% is neutralized, 0 DEG C or so is cooled to, adds the ethanol of 8500mol,
When continuing to be cooled to subzero 5 DEG C, dehydrating agent is added, the addition of dehydrating agent is the 1-2% of solvent quality, is then passed to
The HCl gases of 9000mol, continue to be cooled to subzero 7 DEG C or so, add the imines of 10000mol, are then slowly added into
40% solvent (940kg), neutralizes crystallization and terminates after 1 hour, be discharged to alcoholysis kettle, is warming up to 20 DEG C or so, adds
The ethanol of 22000mol, insulation reaction is centrifuged and obtains mixed liquor after 10 hours, then be can obtain into through distillation
Product triethyl orthoformate, the solid being centrifugally separating to obtain is ammonium chloride, then as being sold outside byproduct.
In above-mentioned technical proposal, the solvent is hydrocarbon mixture or kerosene；
In above-mentioned technical proposal, the dehydrating agent is made up of glycerine, atlapulgite and 4A molecular sieves, the mass ratio of three
It is 10: 2-1: 2-1.
The beneficial effect that the present invention brings：
Prepared by dehydrating agent of the present invention unique, and consumption is few, reduces wastage of material and industrial energy consumption；
Moisture can be down to 0.01% in triethyl orthoformate building-up process of the present invention, and triethyl orthoformate product is in separation phase
Loss amount be greatly decreased, yield is up to 99.7%.
After adding dehydrating agent of the present invention, original reaction condition, technological parameter are constant, and the glycerine for being added is (high with original solvent
Boiling point) dissolve each other, can recycle in systems.And atlapulgite and 4A molecular sieves are split into solid in centrifugal process
In body ammonium chloride, and product quality is not influenceed.
Triethyl orthoformate synthetic method simple possible of the present invention, it is adaptable to which large-scale industry chemical conversion is produced.
Specific embodiment
Hereinafter further explanation will be made to the present invention using specific embodiment, but it is not intended as innovating the present invention
The limitation of spirit.
Embodiment 1
A kind of synthetic method of triethyl orthoformate, it comprises the following steps：
First to the solvent that crystallization kettle adds 60% is neutralized, 0 DEG C or so is cooled to, adds ethanol, continue to be cooled to subzero 5 DEG C
When, dehydrating agent is added, the addition of dehydrating agent is the 1% of solvent quality, then passes to HCl gases, continues to be cooled to
Subzero 7 DEG C or so, imines is added, be then slowly added into other 40% solvent, crystallization neutralized after 1 hour and is terminated, put
Material is warming up to 20 DEG C or so to alcoholysis kettle, adds alcoholysis ethanol, and insulation reaction is centrifuged after 10 hours
Mixed liquor is obtained, then finished product triethyl orthoformate is can obtain through distillation, the solid being centrifugally separating to obtain is ammonium chloride, then make
To be sold outside byproduct.
Above-mentioned dehydrating agent, is made up of glycerine, atlapulgite and 4A molecular sieves, and the mass ratio of three is 10: 1: 1.
Glycerine can select analyzes pure, and the glycerine for being added dissolves each other with original solvent (higher boiling), recycles in systems.
And atlapulgite and 4A molecular sieves are split into solid ammonium chloride, and do not influence the product of ammonium chloride in centrifugal process
Quality.After testing, the moisture in mixed liquor is down to 0.02% or so, damage of the triethyl orthoformate product in separation phase
Vector is greatly decreased, and yield is up to 99.5%.
Raw material proportioning ginseng is shown in Table 1：
Table 1
Claims (3)
1. a kind of method that triethyl orthoformate synthesizes, it is characterised in that methods described comprises the following steps：
First to the solvent for neutralizing crystallization kettle 60% weight portion of addition, 0 DEG C is cooled to, adds the ethanol of 8500mol, continue to lower the temperature
During to subzero 5 DEG C, dehydrating agent is added, then pass to the HCl gases of 9000mol, continue to be cooled to subzero 7 DEG C, add 10000mol
Imines, be then slowly added into the solvent of 40% weight portion, after 1 hour neutralize crystallization terminate, be discharged to alcoholysis kettle, be warming up to
20 DEG C, the ethanol of 22000mol is added, insulation reaction is centrifuged and obtains mixed liquor after 10 hours, then can through distillation
Finished product triethyl orthoformate is obtained, the solid being centrifugally separating to obtain is ammonium chloride, then as being sold outside byproduct；Wherein, it is described molten
The gross mass of agent is 2350kg.
2. the method for a kind of triethyl orthoformate synthesis according to claim 1, it is characterised in that the dehydrating agent adds
Dosage is the 1-2% of solvent gross mass.
3. the method that a kind of triethyl orthoformate according to claim 1 synthesizes, it is characterised in that the dehydrating agent is by third
Triol, atlapulgite and 4A molecular sieves composition, the mass ratio of three is 10: 2-1: 2-1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510789328.0A CN106699524A (en) | 2015-11-16 | 2015-11-16 | Synthetic method of triethyl orthoformate |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510789328.0A CN106699524A (en) | 2015-11-16 | 2015-11-16 | Synthetic method of triethyl orthoformate |
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| CN106699524A true CN106699524A (en) | 2017-05-24 |
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| CN201510789328.0A Pending CN106699524A (en) | 2015-11-16 | 2015-11-16 | Synthetic method of triethyl orthoformate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114605234A (en) * | 2020-12-09 | 2022-06-10 | 南通天泽化工有限公司 | Preparation method of trimethyl orthoacetate |
-
2015
- 2015-11-16 CN CN201510789328.0A patent/CN106699524A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114605234A (en) * | 2020-12-09 | 2022-06-10 | 南通天泽化工有限公司 | Preparation method of trimethyl orthoacetate |
| CN114605234B (en) * | 2020-12-09 | 2023-12-26 | 南通天泽化工有限公司 | Preparation method of trimethyl orthoacetate |
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| PB01 | Publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170524 |
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| WD01 | Invention patent application deemed withdrawn after publication |