CN101967087A - Method for preparing (E)-4.4-dimethoxy-2-propylene aldehyde - Google Patents
Method for preparing (E)-4.4-dimethoxy-2-propylene aldehyde Download PDFInfo
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- CN101967087A CN101967087A CN2010102908573A CN201010290857A CN101967087A CN 101967087 A CN101967087 A CN 101967087A CN 2010102908573 A CN2010102908573 A CN 2010102908573A CN 201010290857 A CN201010290857 A CN 201010290857A CN 101967087 A CN101967087 A CN 101967087A
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Abstract
The invention relates to a method for preparing (E)-4.4-dimethoxy-2-propylene aldehyde, particularly comprising the following steps of: carrying out hydrolysis reaction on (2E)-1,1,4,4-tetramethoxy butylenes I and water under the action of an acid with the dosage enough for being used a catalyst and the conditions that the negative pressure is 50-200 mmHg and the reaction temperature is 40-80 DEG C, and removing methanol generated in the reaction process; after the reaction is finished, regulating the pH value of a reaction system to 7; then carrying out reduced pressure distillation to obtain the (E)-4.4-dimethoxy-2-propylene aldehyde, wherein the mole ratio of the (2E)-1,1,4,4-tetramethoxy butylenes I to H2O is 1:1-1:10, and the mole ratio of the acid to the (2E)-1,1,4,4-tetramethoxy butylenes I is 1:0.001-1:0.05. The synthesizing method has the advantage that the process condition does not need an organic solvent, thereby being beneficial to the amplification production of the process; in addition, the invention can obtain a product with the purity of 90-95 percent by distilling a reaction product, has higher yield coefficient and is suitable for industrialized production.
Description
Technical field:
The present invention relates to a kind of preparation method of (E)-4.4-dimethoxy-crotonic aldehyde.
Background technology:
(E)-4.4-dimethoxy-crotonic aldehyde (English name: (E)-4,4-Dimethoxybutenal) active aldehyde in the molecule can be with witting reagent, Grignard reagent, contain the N nucleophilic reagent, contain reactions such as O nucleophilic reagent, it is important synthesis intermediates, have purposes very widely, its structural formula is as follows:
α, the generation of beta-unsaturated aldehyde compounds and heart disease (as arteriosclerosis and diabetic syndrome) and neurodegenerative disease (as senile dementia, parkinson's syndrome and cerebral ischaemia) and develop relevant, trans-the 4-hydroxyl-2-nonenal IV is this class α, in the beta-unsaturated aldehyde compounds most important one.(E)-4.4-dimethoxy-crotonic aldehyde I is the key intermediate of synthesis of trans IV, its reaction formula following (fine chemistry industry, Vol 22,955 (2005)):
(Z)-2,4,6-Sencolaminic acid methyl esters VII is the main component of the assembly pheromone of the green net of tea wing stinkbug, has been used for observing and predicting and trapping and killing this insect in the orchard for E, E.(E)-4.4-dimethoxy-crotonic aldehyde I is a key intermediate during it synthesizes, reaction formula following (Tetrahedron, Vol 61,3651 (2005)):
Retrieve relevant patent both at home and abroad and publish document, find about (2E)-4.4-dimethoxy-crotonic aldehyde I synthetic method is less, usually will use organic solvents such as methylene dichloride, tetrahydrofuran (THF) or ether in the reaction, and productive rate is lower, two hydrolysis dialdehyde impurity are more.
About (2E)-4.4-dimethoxy-domestic and international patent of crotonic aldehyde I synthetic and publish document and comprise: Tetrahedron Letter, Vol 27,4983 (1986); Tetrahedron Letters, Vol 16,1749 (1975); Organic and Bio-Organic Chemistry, 1907 (1991); US 5386063; European Journal of Organic Chemistry, 2609 (1999); Fine chemistry industry, Vol 22,955 (2005); Tetrahedron, Vol 61,3651 (2005).
Summary of the invention:
The object of the invention is to provide a kind of preparation method of (2E)-4.4-dimethoxy-crotonic aldehyde.
For achieving the above object, the reaction mechanism that the present invention adopts is: the present invention is with 1,1,4, and 4-tetramethoxy-2-butylene I is a raw material, heating hydrolysis under acid catalysis, in reaction process and the post-reaction treatment all less than with an organic solvent.After reaction finishes, add the appropriate bases neutralizing acid, obtain (2E)-4.4-dimethoxy-crotonic aldehyde product by underpressure distillation again.Whole technology need not be with an organic solvent, and purity is (93%) better, productive rate higher (73%).Concrete reaction formula is:
According to above-mentioned reaction mechanism, the present invention adopts following technical scheme:
A kind of preparation method of (2E)-4.4-dimethoxy-crotonic aldehyde, the concrete steps that it is characterized in that this method are: (2E)-1,1,4,4-tetramethoxy butylene I under the effect of the acid of catalyst levels with water, in negative pressure is 50-200mmHg, and temperature of reaction is the reaction that is hydrolyzed under 40-80 ℃ the condition, and removes the methyl alcohol that generates in the reaction process; After reaction finished, the pH value of conditioned reaction system was 7, carries out underpressure distillation then, obtains (E)-4.4-dimethoxy-crotonic aldehyde; (2E)-1,1,4 wherein, 4-tetramethoxy butylene and H
2The mol ratio of O is 1: 1～1: 10; Acid with (2E)-1,1,4, the mol ratio of 4-tetramethoxy butylene is 1: 0.001～1: 0.05.
Above-mentioned acid is hydrochloric acid, sulfuric acid, phosphoric acid, methylsulfonic acid, tosic acid, Amberlyst solid acid, perchloric acid, at least a in hydrogen boron fluoric acid and the acetic acid.
The above-mentioned used alkali of conditioned reaction system pH is Na
2CO
3, K
2CO
3, KOH, K
3PO
4, NaOH, NaHCO
3Or KHCO
3
Technological merit of the present invention: the advantage of this synthetic method is to need not in the processing condition with an organic solvent, helps technology and amplifies production.Reaction product can obtain the product of purity 90-95%, and yield is higher by distillation, is fit to suitability for industrialized production.
Embodiment:
Embodiment one: one vacuum distillation apparatus is housed and gets adding (2E)-1,1,4 in 50 milliliters of round-bottomed flasks, 4-tetramethoxy butylene (15.7g, 89mmol), 3%H
3PO
4(1.64mL) and water (3.21g, 178mmol).Regulation system pressure is to about 120mmHg.Heat temperature raising to 60 ℃ is collected 40-45 ℃ of methanol-water cut.Behind about 50min, no cut steams.Be cooled to room temperature, add an amount of K
2CO
3Neutralising phosphoric acid.Regulation system pressure is to 10-15mmHg once more, and the heat temperature raising underpressure distillation gets (2E)-4.4-dimethoxy crotonaldehyde product 8.4g.Productive rate: 73%, purity: 93%.
Example two: one vacuum distillation apparatus is housed and gets adding (2E)-1,1,4 in 1000 milliliters of round-bottomed flasks, 4-tetramethoxy butylene (300g, 1.70mol), 3% tosic acid and water (64g, 3.5mol).Regulation system pressure is to about 120mmHg.Heat temperature raising to 60 ℃ is collected 40-45 ℃ of methanol-water cut.After about 2 hours, no cut steams.Be cooled to room temperature, add an amount of K
2CO
3Neutralising phosphoric acid.Regulation system pressure is to 10-15mmHg once more, and the heat temperature raising underpressure distillation gets (2E)-4.4-dimethoxy crotonaldehyde product 154g.Productive rate: 70%, purity: 93%.
Claims (3)
1. the preparation method of (2E)-4.4-dimethoxy-crotonic aldehyde is characterized in that the concrete steps of this method are:
(2E)-1,1,4,4-tetramethoxy butylene I under the effect of the acid of catalyst levels with water, be 50-200mmHg in negative pressure, temperature of reaction is the reaction that is hydrolyzed under 40-80 ℃ the condition, and removes the methyl alcohol that generates in the reaction process; After reaction finished, the pH value of conditioned reaction system was 7, carries out underpressure distillation then, obtains (E)-4.4-dimethoxy-crotonic aldehyde; (2E)-1,1,4 wherein, 4-tetramethoxy butylene and H
2The mol ratio of O is 1: 1～1: 10; Acid with (2E)-1,1,4, the mol ratio of 4-tetramethoxy butylene is 1: 0.001～1: 0.05.
2. according to the preparation method of (2E)-4.4-dimethoxy-crotonic aldehyde of claim 1, it is characterized in that described acid is hydrochloric acid, sulfuric acid, phosphoric acid, methylsulfonic acid, tosic acid, Amberlyst solid acid, perchloric acid, at least a in hydrogen boron fluoric acid and the acetic acid.
3. according to the preparation method of (2E)-4.4-dimethoxy-crotonic aldehyde of claim 1, it is characterized in that the used alkali of conditioned reaction system pH is Na
2CO
3, K
2CO
3, KOH, K
3PO
4, NaOH, NaHCO
3Or KHCO
3
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102908573A CN101967087A (en) | 2010-09-21 | 2010-09-21 | Method for preparing (E)-4.4-dimethoxy-2-propylene aldehyde |
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|---|---|---|---|
| CN2010102908573A CN101967087A (en) | 2010-09-21 | 2010-09-21 | Method for preparing (E)-4.4-dimethoxy-2-propylene aldehyde |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115135630A (en) * | 2020-02-28 | 2022-09-30 | 帝斯曼知识产权资产管理有限公司 | Sustainable process for the manufacture of 1,1,4, 4-tetramethoxy-2-butene |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1671643A (en) * | 2002-02-25 | 2005-09-21 | 扩散药品有限公司 | Bipolar trans carotenoid salts and their uses |
-
2010
- 2010-09-21 CN CN2010102908573A patent/CN101967087A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1671643A (en) * | 2002-02-25 | 2005-09-21 | 扩散药品有限公司 | Bipolar trans carotenoid salts and their uses |
Non-Patent Citations (2)
| Title |
|---|
| JAN RAAP ET AL.: "Synthesis of Isotopically Labelled L-Phenylalanine and L-Tyrosine", 《EUR.J.ORG.CHEM.》 * |
| 文珂等: "一种反式-4-羟基-2-壬烯醛的低成本合成方法", 《精细化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115135630A (en) * | 2020-02-28 | 2022-09-30 | 帝斯曼知识产权资产管理有限公司 | Sustainable process for the manufacture of 1,1,4, 4-tetramethoxy-2-butene |
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Application publication date: 20110209 |