CN1330620C - Process for synthesizing 2-alkoxy propylene - Google Patents
Process for synthesizing 2-alkoxy propylene Download PDFInfo
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- CN1330620C CN1330620C CNB2006100441989A CN200610044198A CN1330620C CN 1330620 C CN1330620 C CN 1330620C CN B2006100441989 A CNB2006100441989 A CN B2006100441989A CN 200610044198 A CN200610044198 A CN 200610044198A CN 1330620 C CN1330620 C CN 1330620C
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Abstract
The present invention relates to a process for synthesizing 2-alkoxy propylene. 2, 2-dialkoxy propane is used as an initial raw material, benzoic acid and pyridine are mixed for catalysis, ethylene glycol dimethyl ether is used as a solvent, phthalic diamide is added to consume alcohol produced by reaction, and 2-alkoxy propylene is produced by the reaction. Reaction temperature is from 100 to 150 DEG C, reaction time is from 0.25 to 2 hours, and the mol ratio of the raw materials of 2, 2-dialkoxy propane: phthalic diamide: pyridine: benzoic acid: ethylene glycol dimethyl ether is 1:1.0 to 2.0:0.05 to 0.2:0.05 to 0.2:0.5 to 2.0. The process has the advantages of mild reaction condition, high yield, easy acquirement of the raw materials and low cost; moreover, the solvent and the catalyst can be recycled; dimethyl phthalate or diethyl phthalate produced by the further reaction of byproducts is a plasticizing agent with wide purposes, and thus, the reaction materials can be fully utilized. The process also has the advantages of normal pressure reaction and low equipment investment, and thus, the process is suitable for industrial production.
Description
Technical field
The present invention relates to 2, the 2-dialkoxy propane is the novel process of raw material Synthetic 2-alkoxy propone.
Background technology
The 2-alkoxy propone is because existing pair of key also has ehter bond, so character is very active.In fine chemical products such as medicine synthetic,, use more and more widely as the protection reagent of reactive group such as hydroxyl.
2-alkoxy propone synthetic has alkynol condensation method and 2, two kinds of 2-dialkoxy propane cracking processs.Wherein, the alkynol condensation method is a raw material with propine and alcohol, is catalyzer with highly basic, gives birth to condensation reaction in high temperature, elevated pressure, obtains the 2-alkoxy propone.The advantage of this method is only to need single step reaction, and yield is about 70%, and shortcoming is propine preparation, the transportation difficulty as starting raw material, is not easy to obtain, and reaction simultaneously need under high pressure be carried out, and is easy to generate by product.Cracking process is with 2, and the 2-dialkoxy propane is a raw material, and in the presence of an acidic catalyst, Pintsch process obtains the 2-alkoxy propone.As US 3,218,359, propose to use magnesium pyrophosphate to make catalyzer, 300 ℃ of Pintsch processs; Bogod etc. are an acidic catalyst with ZSM-5 type zeolite catalyst, through 350 ℃ of vapor-phase thermal cracking reactions; Wohl, report such as R.A uses protonic acid catalysis, 100～200 ℃ of temperature of reaction; Publication number CN1660742A (application number 200410082315.1) also is to use acid material catalysis synthetic.The advantage of high temperature cracking method is, the reaction conversion ratio height, and simple to operate, shortcoming is at high temperature to react, and side reaction is many, and separating difficulty is big and yield is low, and is also higher to the requirement of equipment.
(J.Org.Chem.2910 such as Melvin.S.Newman, V0l.38, No16,1973) propose to use phenylformic acid and pyridine to be catalyzer, with the diglyme is solvent, the alcohol that uses the succinyl oxide consumption reaction to generate, yield can reach 90～95%, but the price height of succinyl oxide and diglyme, the monomethyl succinate of by-product does not have practical use yet, and recycle difficulty, production cost height, no industrial application value.
Summary of the invention
Technical problem to be solved by this invention provides a kind of reaction yield height, production cost is low, by product can be recycled 2-alkoxy propone synthesis technique.
The synthesis technique of 2-alkoxy propone of the present invention, with 2 of following structural formula, the 2-dialkoxy propane is a starting raw material,
Wherein R is methyl or ethyl,
It is characterized in that with phenylformic acid and pyridine mixed catalytic, glycol dimethyl ether is a solvent, and the alcohol of adding Tetra hydro Phthalic anhydride consumption reaction generation, reaction generates the 2-alkoxy propone, temperature of reaction is 100～150 ℃, reaction times is 0.25～2 hour, and the mole proportioning of raw material is 2,2-dialkoxy propane: Tetra hydro Phthalic anhydride: pyridine: phenylformic acid: glycol dimethyl ether=1: 1.0～2.0: 0.05～0.2: 0.05～0.2: 0.5～2.0.
The structural formula of the resulting 2-alkoxy propone of the present invention is:
Wherein R is methyl or ethyl.
The present invention uses low-cost glycol dimethyl ether to make solvent, and boiling point is low, reclaims easily, can reuse.
The alcohol that the present invention uses low-cost Tetra hydro Phthalic anhydride consumption reaction to generate, thus impel reaction to generate the alkyl alkene ether.By product phthalic acid diformazan (second) ester is broad-spectrum softening agent, has industrial utilization and is worth.
The present invention is a synthesis under normal pressure, and facility investment is few, and solvent and catalyzer can reclaim repeated use, and by product further reacts and generates phthalic acid diformazan (second) ester, and of many uses, reaction mass can make full use of.
The preferred processing condition of the present invention are:
Temperature of reaction is 120～145 ℃.
Advantage of the present invention:
Reaction conditions gentleness, yield height, raw material be easy to get and cost low, and solvent and catalyzer can be recycled; By product further reacts and generates phthalic acid diformazan (second) ester, is broad-spectrum softening agent, and reaction mass can make full use of; Synthesis under normal pressure, facility investment is few, is fit to suitability for industrialized production.
Embodiment
Embodiment one: on the 1000ml four-hole bottle, induction stirring, thermometer, constant pressure funnel and 25 * 900mm fractional column are installed.In reaction flask, add Tetra hydro Phthalic anhydride 166g (content 98%, 1.1mol), glycol dimethyl ether 90g (1.0mol), phenylformic acid 6.2g (0.05mol), pyridine 8.0g (0.05mol), stir heat solid thing dissolving down, when temperature reaches 120～130 ℃, begin from constant pressure funnel, to add 2,2-Propanal dimethyl acetal 106g (content 98%, 1.0mol), 2, the 2-Propanal dimethyl acetal must be added to below the liquid level, and beginning after 15 minutes occurs refluxing drips, and the cut of collecting 36～37 ℃ of boiling points is a 2-methoxyl group propylene, yield 92%, content is more than 98%.
Material continues heating in the reaction flask, and reclaim under reduced pressure glycol dimethyl ether, pyridine reclaim when boiling point reaches 80 ℃/0.08MPa and finish, and apply mechanically for following batch.The reaction mass cooling adds the 100g methyl alcohol and the 5ml vitriol oil, reflux 24 hours, making the esterification of phthalic acid mono-methyl is dimethyl phthalate, and reaction finishes the back and reclaims excessive methyl alcohol, the yellow soda ash neutralization, wash neutrality, underpressure distillation obtains the plasticizer phthalic acid dimethyl ester.
Embodiment two: on the 1000ml four-hole bottle, induction stirring, thermometer, constant pressure funnel and 25 * 900mm fractional column are installed.In reaction flask, add Tetra hydro Phthalic anhydride 181g (content 98%, 1.2mol), go up crowd glycol dimethyl ether and pyridine 100g, the phenylformic acid 6.5g that reclaim, stir heat solid thing dissolving down, when temperature reaches 120～130 ℃, begin from constant pressure funnel, to add 2,2-Propanal dimethyl acetal 106g (content 98%, 1.0mol), 2, the 2-Propanal dimethyl acetal must be added to below the liquid level, and beginning after 15 minutes occurs refluxing drips, and the cut of collecting 36～37 ℃ of boiling points is a 2-methoxyl group propylene, yield 94%, content is more than 98%.
Material continues heating in the reaction flask, and reclaim under reduced pressure glycol dimethyl ether, pyridine reclaim when boiling point reaches 80 ℃/0.08MPa and finish, and apply mechanically for following batch.The reaction mass cooling adds the 100g methyl alcohol and the 5ml vitriol oil, reflux 24 hours, making the esterification of phthalic acid mono-methyl is dimethyl phthalate, and reaction finishes the back and reclaims excessive methyl alcohol, the yellow soda ash neutralization, wash neutrality, underpressure distillation obtains the plasticizer phthalic acid dimethyl ester.
Embodiment three: on the 1000ml four-hole bottle, induction stirring, thermometer, constant pressure funnel and 25 * 900mm fractional column are installed.In reaction flask, add Tetra hydro Phthalic anhydride 166g (content 98%, 1.1mol), glycol dimethyl ether 90g (1.0mol), phenylformic acid 6.2g (0.05mol), pyridine 8.0g (0.05mol), stir heat solid thing dissolving down, when temperature reaches 125～135 ℃, begin from constant pressure funnel, to add 2,2-di ethyl propyl ether 135g (content 98%, 1.mol), 2, the 2-di ethyl propyl ether must be added to below the liquid level, and beginning after 15 minutes occurs refluxing drips, and the cut of collecting 61～63 ℃ of boiling points is the 2-ethoxy propylene, yield 90%, content is more than 98%.
Material continues heating in the reaction flask, and reclaim under reduced pressure glycol dimethyl ether, pyridine reclaim when boiling point reaches 80 ℃/0.08MPa and finish, and apply mechanically for following batch.The reaction mass cooling, add the 170g dehydrated alcohol and the 5ml vitriol oil, reflux 24 hours, making the esterification of phthalic acid mono ethyl ester is diethyl phthalate, reaction finishes the back and reclaims excess ethanol, neutrality is washed in the yellow soda ash neutralization, and underpressure distillation obtains the plasticizer phthalic acid diethyl ester.
Embodiment four: on the 1000ml four-hole bottle, induction stirring, thermometer, constant pressure funnel and 25 * 900mm fractional column are installed.In reaction flask, add Tetra hydro Phthalic anhydride 181g (content 98%, 1.2mol), go up crowd glycol dimethyl ether and pyridine 100g, the phenylformic acid 6.5g that reclaim, stir heat solid thing dissolving down, when temperature reaches 125～135 ℃, begin from constant pressure funnel, to add 2,2-di ethyl propyl ether 135g (content 98%, 1.mol), 2, the 2-di ethyl propyl ether must be added to below the liquid level, and beginning after 15 minutes occurs refluxing drips, and the cut of collecting 61～63 ℃ of boiling points is the 2-ethoxy propylene, yield 92%, content is more than 98%.
Material continues heating in the reaction flask, and reclaim under reduced pressure glycol dimethyl ether, pyridine reclaim when boiling point reaches 80 ℃/0.08MPa and finish, and apply mechanically for following batch.The reaction mass cooling, add the 170g dehydrated alcohol and the 5ml vitriol oil, reflux 24 hours, making the esterification of phthalic acid mono ethyl ester is diethyl phthalate, reaction finishes the back and reclaims excess ethanol, neutrality is washed in the yellow soda ash neutralization, and underpressure distillation obtains the plasticizer phthalic acid diethyl ester.
Claims (1)
1, a kind of synthesis technique of 2-alkoxy propone, with 2 of following structural formula, the 2-dialkoxy propane is a starting raw material,
Wherein R is methyl or ethyl,
It is characterized in that with phenylformic acid and pyridine mixed catalytic, glycol dimethyl ether is a solvent, and the alcohol of adding Tetra hydro Phthalic anhydride consumption reaction generation, reaction generates the 2-alkoxy propone, temperature of reaction is 120～145 ℃, reaction times is 0.25～2 hour, and the mole proportioning of raw material is 2,2-dialkoxy propane: Tetra hydro Phthalic anhydride: pyridine: phenylformic acid: glycol dimethyl ether=1: 1.0～2.0: 0.05～0.2: 0.05～0.2: 0.5～2.0.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100441989A CN1330620C (en) | 2006-05-18 | 2006-05-18 | Process for synthesizing 2-alkoxy propylene |
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| CNB2006100441989A CN1330620C (en) | 2006-05-18 | 2006-05-18 | Process for synthesizing 2-alkoxy propylene |
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| CN1850760A CN1850760A (en) | 2006-10-25 |
| CN1330620C true CN1330620C (en) | 2007-08-08 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110330412A (en) * | 2019-07-19 | 2019-10-15 | 安徽威驰化工有限责任公司 | A kind of reaction cleavage method of 2- ethyoxyl propylene |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1660742A (en) * | 2004-12-30 | 2005-08-31 | 浙江大学 | New technique for synthesizing 2-alkoxyl propylene |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1660742A (en) * | 2004-12-30 | 2005-08-31 | 浙江大学 | New technique for synthesizing 2-alkoxyl propylene |
Non-Patent Citations (4)
| Title |
|---|
| 2-乙氧基丙烯的合成 崔伟，上海化工，第2004年卷第11期 2004 * |
| 2-甲氧基丙烯的制备研究 杨淑敏等人，精细化工中间体，第32卷第1期 2002 * |
| 2-甲氧基丙烯的制备研究 杨淑敏等人，精细化工中间体，第32卷第1期 2002;2-乙氧基丙烯的合成 崔伟，上海化工，第2004年卷第11期 2004;医药中间体2-甲氧基丙烯的合成及应用 王海民，杨淑敏，安徽化工，第2000年卷第3期 2000 * |
| 医药中间体2-甲氧基丙烯的合成及应用 王海民，杨淑敏，安徽化工，第2000年卷第3期 2000 * |
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