CN106146265A - A kind of 2, the synthetic method of 2-dialkoxy propane - Google Patents
A kind of 2, the synthetic method of 2-dialkoxy propane Download PDFInfo
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- CN106146265A CN106146265A CN201510199549.2A CN201510199549A CN106146265A CN 106146265 A CN106146265 A CN 106146265A CN 201510199549 A CN201510199549 A CN 201510199549A CN 106146265 A CN106146265 A CN 106146265A
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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
- C07C41/48—Preparation of compounds having groups
- C07C41/50—Preparation of compounds having groups by reactions producing groups
- C07C41/56—Preparation of compounds having groups by reactions producing groups by condensation of aldehydes, paraformaldehyde, or ketones
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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
- C07C41/01—Preparation of ethers
Abstract
The present invention provides a kind of 2,2-dialkoxy propane synthetic method and the method for coproduction 2-alkoxy propone.This law uses acetone, alcohol and positive esters of silicon acis to be raw material, under certain condition, can highly selective synthesis 2,2-dialkoxy propane, or make reaction simultaneously generate 2,2-dialkoxy propane and two kinds of products of 2-alkoxy propone.The advantage of this law is that synthesis technique is simple and safety and environmental protection, and product separates easily, and energy consumption is low, and product purity and yield are high.
Description
Technical field
The present invention relates to a kind of 2,2-dialkoxy propane synthetic method and the method for coproduction 2-alkoxy propone.
Background technology
2,2-dialkoxy propane compounds are important fine chemicals, and they have in the development and commercial production of the fine chemical products such as medicine, pesticide, natural product and have been widely used.As, 2,2-dimethoxypropane and 2,2-di ethyl propyl ether all can be prepared different types of acetal, can be used as protective agent, condensing agent, cyclizing agent, dehydrant etc. in organic synthesis.
2-alkoxy propone (such as 2-methoxyl group propylene and 2-ethoxy propylene) is important medicine intermediate, is the important source material of synthesis clarithromycin, AIDS-treating medicine etc., applies quite varied in the industrial circles such as fine chemistry industry, medicine, material.
The traditional synthetic method of 2,2-dialkoxy propanes has direct synthesis technique and indirect synthesis technique two kinds.Direct synthesis technique is synthesize 2 under catalyst action by acetone and alcohol, 2-dialkoxy propane, but this method is restricted by molecular balance, and separation and purification of products is difficult, and yield is extremely low.Additionally, also employing acetone is had to be synthesized 2 with ortho-formate under acidic catalyst effect, the method of 2-dialkoxy propane, but acetone is also a balancing response with the reaction of ortho-formate, ortho-formate cannot convert completely, and react by-product methyl formate, and cause product to separate difficulty, post processing is complicated.Indirect synthesis technique is divided into two steps, first step synthetic mesophase product acetone contracting polyhydric alcohol, and second step is intermediate product and alcohol is synthesized 2,2-dialkoxy propane, but this method production procedure is longer, and product separates more difficult so that production cost is higher.Additionally, either direct method or indirect method, being required for the existence at catalyst could react, and this also increases the production cost of product.
The method that 2-methoxyl group propylene or 2-ethoxy propylene mainly use 2,2-dimethoxypropane or 2,2-di ethyl propyl ether high temperature pyrolysis to eliminate a part methanol or ethanol produces.But this method first has to obtain 2,2-dimethoxypropane or 2,2-di ethyl propyl ether raw material.
Polysiloxanes can be used for producing nano silicon, and heat-resisting, the coating of chemically-resistant effect, organic silicon solvent and hot investment casting binding agent etc., be also the organic synthesis intermediate that purposes is wider.
Summary of the invention
It is an object of the present invention to provide a kind of simpler, economical 2,2-dialkoxy propane and 2-alkoxy propone synthetic method.Owing to acetone and alcohol react generation 2, water can be generated while 2-dialkoxy propane, and the existence of water not only can suppress the carrying out of reaction, bring difficulty also can to product separation purification, cause product yield the lowest.This law is to synthesize 2 at acetone and alcohol, and on the basis of the reaction of 2-dialkoxy propane, in reaction raw materials, addition positive esters of silicon acis corresponding to alcohol is as deicer, can be greatly improved the equilibrium conversion of reaction.And due in course of reaction silicic ester hydrolysate there is faintly acid, make reaction have autocatalysis, so typically need not additionally add catalyst, but in course of reaction, add a certain amount of acidic catalyst reaction be may also function as facilitation.If it addition, during only with acetone and positive esters of silicon acis for raw material, without reacting hardly under catalysts conditions, after adding a certain amount of catalyst (such as sulphuric acid, sulfonic acid etc.), reaction can be smoothed out, and except generating 2, outside 2-dialkoxy propane, also can generate more 2-alkoxy propone.Additionally, due to azeotropic mixture can be formed between reactor product and raw material, affect product separation yield, therefore can add the suitable atent solvent azeotropic with destruction product with raw material in reaction system, improve product yield.
In course of reaction, esters of silicon acis can be converted into high boiling polysiloxanes so that it is is easy to product separation.
The technical solution used in the present invention is:
Acetone, alcohol, positive esters of silicon acis and atent solvent mix in loading reactor by a certain percentage, reaction can be carried out under without catalyst action, can also carry out under having catalyst action, control certain reaction temperature, response time is 0.5h～24h, by changing acetone, alcohol and the ratio of positive esters of silicon acis three, 2 can be synthesized by highly selective, 2-dialkoxy propane, also reaction can be made to obtain 2 simultaneously, 2-dialkoxy propane and two kinds of products of 2-dialkoxy propylene, product separates through simple rectification can obtain the 2 of purity more than 99.5%, 2-dialkoxy propane product and the 2-alkoxy propone of more than 99.5%, the low polysiloxanes of coproduction simultaneously.
Alcohol described in technical scheme can be methanol, ethanol or propanol, and it is alcohol/acetone=1/2～5/1 with acetone molar ratio conveniently.Synthesizing 2 to highly selective, during 2-dialkoxy propane, alcohol and acetone molar ratio conveniently are alcohol/acetone=1/2～5/1；To make reaction obtain 2 simultaneously, 2-dialkoxy propane and two kinds of products of 2-alkoxy propone, then, when feeding intake, the consumption of alcohol is generally 0.
Positive esters of silicon acis described in technical scheme can be methyl silicate, tetraethyl orthosilicate or positive silicic acid propyl ester, and it is positive esters of silicon acis/acetone=1/5～2/1 with the suitable molar ratio of acetone.
Atent solvent in synthetic method described in technical scheme refer to not with the material of other any component reaction in reaction system, such as: alkane, cycloalkane, aromatic hydrocarbons, ether etc..Reaction system can add atent solvent, it is possible to without atent solvent, and reaction system is added suitable atent solvent and separated product favourable, and its consumption accounts for the 0～50% of reaction system gross mass.
Reactor described in technical scheme can be fixed bed reactors, it is also possible to is tank reactor.When using fixed bed reaction technique, general feedstock mass space velocity is 0.5 h-1～5.0 h-1。
Reaction in synthetic method described in technical scheme can be carried out under without catalysts conditions, it is also possible to carries out under having catalysts conditions.Synthesizing 2 to highly selective, 2-dialkoxy propane, then reaction can carried out without catalyst or under having catalysts conditions；To make reaction obtain 2 simultaneously, 2-dialkoxy propane and two kinds of products of 2-alkoxy propone, then reaction needs to carry out under having catalysts conditions.
Catalyst described in technical scheme can be solid acid, such as sulfonic resin, acidic molecular sieve, support type Bronsted acid and ackd salt etc.；Can also be liquid acid, such as organic acid and heteropoly acids such as the mineral acid such as acidic ion liquid, sulphuric acid, sulfonic acid, when using liquid acid as catalyst, its consumption be the 0.01%～1% of reactant liquor gross mass.
Reaction described in technical scheme all can be carried out between-30 DEG C～60 DEG C of temperature, and preferable temperature is-20 DEG C～40 DEG C, and reaction pressure is not crucial, carries out the most at ambient pressure.
It is an advantage of the invention that synthesis technique is simple and safety and environmental protection, product separates easily, and energy consumption is low, and product yield is high, and product purity is high.
Detailed description of the invention
Embodiment
1
With magnetic agitation, thermometer, condensing tube 2000 milliliters of there-necked flasks in add ethanol 46g, acetone 116g and tetraethyl orthosilicate 832g, add phosphotungstic acid 9g, reaction temperature controls at about 10 DEG C, reaction 0.5h, product is through analyzing, and acetone conversion is 92.1%, the selectivity of 2,2-di ethyl propyl ethers is 96.4%.Product takes off ethanol and acetone through rectification, obtains 2 after re-refining, and the purity of 2-di ethyl propyl ether is 99.7%.
Embodiment
2
With magnetic agitation, thermometer, condensing tube 1000 milliliters of there-necked flasks in add methanol 320g, acetone 116g and methyl silicate 61g, reaction temperature controls at about-20 DEG C, reaction 24h, product is through analyzing, acetone conversion is 52.4%, and the selectivity of 2,2-dimethoxypropane is 98.3%.Product is through rectification separating methanol and acetone, and the purity obtaining 2,2-dimethoxypropane after re-refining is 99.6%.
Embodiment
3
With magnetic agitation, thermometer, condensing tube 1000 milliliters of there-necked flasks in add normal propyl alcohol 240g, acetone 116g and positive silicic acid propyl ester 264g, reaction temperature controls at about 20 DEG C, reaction 4h, product is through analyzing, acetone conversion is 54.6%, and the selectivity of 2,2-dimethoxypropane is 95.7%.Product takes off propanol and acetone through rectification, obtains 2 after re-refining, and the purity of 2-dipropoxy propane is 99.5%.
Embodiment
4
With magnetic agitation, thermometer, condensing tube 1000 milliliters of there-necked flasks in add methanol 128g, acetone 116g and methyl silicate 152g, add the concentrated sulphuric acid 0.04g of 98%, reaction temperature controls at about 20 DEG C, reaction 2h, product is through analyzing, and acetone conversion is 75.9%, the selectivity of 2,2-dimethoxypropane is 97.6%.Product is through rectification separating methanol and acetone, and the purity obtaining 2,2-dimethoxypropane after re-refining is 99.6%.
Embodiment
5
By ethanol, acetone and tetraethyl orthosilicate be in molar ratio 2/1/1 ratio with being pumped into the band recirculated water chuck rustless steel fixed bed reactors equipped with 50g highly acid sulfonic resin catalyst, inlet amount mass space velocity controls at 5h-1, product is through analyzing, acetone conversion is 71.3%, the selectivity of 2,2-di ethyl propyl ethers is 97.6%.Product takes off ethanol and acetone through rectification, obtains 2 after re-refining, and the purity of 2-di ethyl propyl ether is 99.6%.
Embodiment
6
By methanol, acetone and methyl silicate be in molar ratio 1/1/1 ratio with being pumped into the band recirculated water chuck rustless steel fixed bed reactors equipped with 50g HY molecular sieve catalyst, inlet amount mass space velocity controls at 0.5h-1, product is through analyzing, acetone conversion is 46.9%, the selectivity of 2,2-dimethoxypropane is 98.1%.Product is through rectification separating methanol and acetone, and the purity obtaining 2,2-dimethoxypropane after re-refining is 99.7%.
Embodiment
7
With magnetic agitation, thermometer, condensing tube 1000 milliliters of there-necked flasks in add acetone 116g and tetraethyl orthosilicate 416g, add concentrated sulphuric acid 5g, reaction temperature controls at about 20 DEG C, reaction 8h, product is through analyzing, and acetone conversion is 91.2%, 2, the selectivity of 2-di ethyl propyl ether is 57.3%, and 2-ethoxy propylene selectivity is 42.7%.Product obtains 2 after rectified purified, and the purity of 2-di ethyl propyl ether is 99.5%, and 2-ethoxy propylene purity is 99.5%.
Embodiment
8
With magnetic agitation, thermometer, condensing tube 1000 milliliters of there-necked flasks in add acetone 232g and methyl silicate 304g, add chlorosulfonic acid 5g, reaction temperature controls at about 30 DEG C, reaction 5h, product is through analyzing, and acetone conversion is 77.4%, 2, the selectivity of 2-dimethoxy propane is 51.6%, and 2-methoxyl group Propylene Selectivity is 48.4%..It is 99.6% that product obtains the purity of 2,2-dimethoxypropane after rectified purified, and 2-ethoxy propylene purity is 99.5%.
Embodiment
9
With magnetic agitation, thermometer, condensing tube 1000 milliliters of there-necked flasks in add methanol 128g, acetone 116g, methyl silicate 152g and normal hexane 200g, reaction temperature controls at about 10 DEG C, reaction 5h, product is through analyzing, acetone conversion is 87.4%, and the selectivity of 2,2-dimethoxypropane is 98.3%.It is 99.5% that product obtains the purity of 2,2-dimethoxypropane after rectified purified.
Embodiment
10
With magnetic agitation, thermometer, condensing tube 1000 milliliters of there-necked flasks in add ethanol 92g, acetone 116g, tetraethyl orthosilicate 152g, with hexamethylene 100g, adding silico-tungstic acid 1g, reaction temperature controls at about 20 DEG C, reacts 5h, product is through analyzing, acetone conversion is 76.5%, and the selectivity of 2,2-di ethyl propyl ethers is 96.1%.Product obtains 2 after rectified purified, and the purity of 2-di ethyl propyl ether is 99.6%.
Claims (9)
1. one kind 2, the synthetic method of 2-dialkoxy propane, it is characterized in that: acetone, alcohol, positive esters of silicon acis and atent solvent mix in loading reactor by a certain percentage, reaction can be carried out under without catalyst action, can also carry out under having catalyst action, control certain reaction temperature, response time is 0.5h～24h, by changing acetone, alcohol and the ratio of positive esters of silicon acis three, 2 can be synthesized by highly selective, 2-dialkoxy propane, also reaction can be made to generate 2 simultaneously, 2-dialkoxy propane and two kinds of products of 2-alkoxy propone, product separates through rectification can obtain the 2 of purity more than 99.5%, 2-dialkoxy propane product and the 2-alkoxy propone of more than 99.5%.
The most according to claim 1, the alcohol in synthetic method can be methanol, ethanol or propanol, synthesizes 2 to highly selective, and during 2-dialkoxy propane, alcohol and acetone molar ratio conveniently are alcohol/acetone=1/2～5/1；To make reaction obtain 2 simultaneously, 2-dialkoxy propane and two kinds of products of 2-alkoxy propone, then, when feeding intake, the consumption of alcohol is generally 0.
The most according to claim 1, the positive esters of silicon acis in synthetic method can be methyl silicate, tetraethyl orthosilicate or positive silicic acid propyl ester, and it is positive esters of silicon acis/acetone=1/5～2/1 with acetone molar ratio conveniently.
The most according to claim 1 the atent solvent in synthetic method refer to not with the material of other what component reaction in reaction system, as: alkane, cycloalkane, aromatic hydrocarbons, ether etc., reaction system can add atent solvent, also can be without atent solvent, reaction system is added suitable atent solvent and is separated product favourable, and its consumption accounts for the 0～50% of reaction system gross mass.
The most according to claim 1, the reactor in synthetic method can be fixed bed reactors, it is also possible to is tank reactor.
The most according to claim 5, when using fixed bed reaction technique, feedstock quality air speed conveniently is 0.5 h-1～5.0h-1。
The most according to claim 1, the reaction in synthetic method can be carried out under without catalysts conditions, can also carry out under having catalysts conditions, synthesizing 2 to highly selective, 2-dialkoxy propane, then reaction can carried out without catalyst or under having catalysts conditions；To make reaction obtain 2 simultaneously, 2-dialkoxy propane and two kinds of products of 2-alkoxy propone, then reaction needs to carry out under having catalysts conditions.
The most according to claim 7, catalyst can be solid acid, such as sulfonic resin, acidic molecular sieve, support type Bronsted acid and ackd salt etc.；Can also be liquid acid, such as organic acid and heteropoly acids such as the mineral acid such as acidic ion liquid, sulphuric acid, sulfonic acid, when using liquid acid as catalyst, its consumption be the 0.01%～1% of reactant liquor gross mass.
The most according to claim 1, the reaction temperature general control in synthetic method is between-30 DEG C～60 DEG C, and preferable temperature is-20 DEG C～40 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510199549.2A CN106146265A (en) | 2015-04-24 | 2015-04-24 | A kind of 2, the synthetic method of 2-dialkoxy propane |
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| CN201510199549.2A CN106146265A (en) | 2015-04-24 | 2015-04-24 | A kind of 2, the synthetic method of 2-dialkoxy propane |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109776287A (en) * | 2017-11-15 | 2019-05-21 | 江苏鼎烨药业有限公司 | A kind of preparation method of acetone dimethyl acetal |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11217346A (en) * | 1998-01-30 | 1999-08-10 | Agency Of Ind Science & Technol | Production of acetal |
| CN103772167A (en) * | 2014-01-08 | 2014-05-07 | 浙江胡涂硅有限公司 | Preparation method of 2, 2-dimethoxypropane |
| CN104326888A (en) * | 2014-09-27 | 2015-02-04 | 安徽华甬新材料有限公司 | Preparation method of 2,2-dimethoxyl propane |
-
2015
- 2015-04-24 CN CN201510199549.2A patent/CN106146265A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11217346A (en) * | 1998-01-30 | 1999-08-10 | Agency Of Ind Science & Technol | Production of acetal |
| CN103772167A (en) * | 2014-01-08 | 2014-05-07 | 浙江胡涂硅有限公司 | Preparation method of 2, 2-dimethoxypropane |
| CN104326888A (en) * | 2014-09-27 | 2015-02-04 | 安徽华甬新材料有限公司 | Preparation method of 2,2-dimethoxyl propane |
Non-Patent Citations (3)
| Title |
|---|
| NAZAROV, I. N等: "Synthesis of acetals and ketals with the aid of tetraalkoxysilanes", 《ZHURNAL OBSHCHEI KHIMII 》 * |
| 李小保等: "2- 乙氧基丙烯绿色合成技术的研究", 《精细化工中间体》 * |
| 王宏舍等: "缩醛(酮)类香料的合成方法研究", 《广西化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109776287A (en) * | 2017-11-15 | 2019-05-21 | 江苏鼎烨药业有限公司 | A kind of preparation method of acetone dimethyl acetal |
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