CN107556182A - The preparation method of the methoxycinnamic aldehyde of 3 hydroxyl 4 - Google Patents
The preparation method of the methoxycinnamic aldehyde of 3 hydroxyl 4 Download PDFInfo
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- CN107556182A CN107556182A CN201710964777.3A CN201710964777A CN107556182A CN 107556182 A CN107556182 A CN 107556182A CN 201710964777 A CN201710964777 A CN 201710964777A CN 107556182 A CN107556182 A CN 107556182A
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Abstract
The preparation method of the methoxycinnamic aldehyde of 3 hydroxyl 4, it is related to the methoxycinnamic aldehyde of 3 hydroxyl 4.Using potassium hydroxide as catalyst, PolyTHF is co-catalyst, carries out condensation reaction by isovanillin and acetaldehyde, produces the methoxycinnamic aldehyde of 3 hydroxyl 4.The co-catalyst PolyTHF of use is a kind of polyether Glycols, can be complexed with potassium ion, so as to improve the activity of catalyst potassium hydroxide.Compared with the preparation method of the existing methoxycinnamic aldehyde of 3 hydroxyl 4, the dosage of alkali is greatly decreased, and so as to which caused wastewater flow rate also significantly reduces, the reaction time significantly shortens, and product yield is improved.
Description
Technical field
The present invention relates to 3- hydroxyl -4- methoxycinnamic aldehydes, more particularly, to by isovanillin in catalyst and co-catalysis
The lower method for being reacted with acetaldehyde and preparing 3- hydroxyl -4- methoxycinnamic aldehydes of agent effect.
Background technology
3- hydroxyl -4- methoxycinnamic aldehydes are a kind of important organic synthesis intermediates, available for synthesizing intense sweetener
N- [N- [3- (3- hydroxyl -4- methoxyphenyls) propyl group]-L- α-aspartoyl]-L-phenylalanine -1- methyl esters (trade names
Advantame).3- hydroxyl -4- methoxycinnamic aldehydes can be carried out in the presence of alkali metal hydroxide by isovanillin with acetaldehyde
Condensation reaction prepares (U.S.Patent No.:7141263B2), but this method to need the alkali number that adds be raw material isovanillin
10 times of mole, post processing need to add substantial amounts of hydrochloric acid and neutralized again, produce substantial amounts of waste water, and byproduct of reaction compared with
More, product yield is relatively low (53%), and the required reaction time is up to 46h, causes the preparation efficiency of 3- hydroxyl -4- methoxycinnamic aldehydes
It is very low, cost is very high.
The content of the invention
It is an object of the invention to provide a kind of production cost is low, high income and environment-friendly 3- hydroxyl -4- methoxyl groups
The preparation method of cinnamic acid.
The present invention's comprises the following steps that：
Using potassium hydroxide as catalyst, PolyTHF is co-catalyst, and condensation reaction is carried out by isovanillin and acetaldehyde,
Produce 3- hydroxyl -4- methoxycinnamic aldehydes.
The dosage of the catalyst potassium hydroxide can be the 5%~20% of isovanillin mole, and the co-catalyst gathers
The dosage of tetrahydrofuran can be the 1%~5% of isovanillin mass percent, and the mol ratio of the isovanillin and acetaldehyde can
For (0.4~1): 1.
The number-average molecular weight of the co-catalyst PolyTHF can be 200~1000.
The temperature of the condensation reaction can be -10~20 DEG C, and the time of condensation reaction can be 3~8h.
The co-catalyst PolyTHF that the present invention uses is a kind of polyether Glycols, can be complexed with potassium ion, so as to carry
The high activity of catalyst potassium hydroxide.It is of the invention compared with the preparation method of existing 3- hydroxyls -4- methoxycinnamic aldehydes
The dosage of method alkali is greatly decreased, and so as to which caused wastewater flow rate also significantly reduces, the reaction time significantly shortens, and product yield obtains
Improve.
Embodiment
The invention will be further described for following examples.
Embodiment 1：
1.008g (0.015mol) potassium hydroxide is dissolved in 100ml methanol aqueous solutions (methanol and water volume ratio 1: 1),
Then 15.2g (0.1mol) isovanillin and 0.456g PolyTHFs (number-average molecular weight 250) are added, is sufficiently stirred and is allowed to
It is well mixed.- 5 DEG C are cooled to, the acetaldehyde solution 35.36g that mass fraction is 28% is continuously added dropwise into reaction system
(0.225mol) proceeds by reaction, and process is added dropwise and continues 5h.Continue stirring reaction 2h after completion of dropwise addition, then add quality point
Number is neutralized to terminate to react for 36% hydrochloric acid 1.9ml.Filter, obtain light yellow crystal, this is 3- hydroxyl -4- methoxycinnamates
Aldehyde crude product.The crystal is added in 300ml methanol, stirs 2h, filters, filter cake is washed with 50ml methanol.Gained filter cake is added
In 1200ml methanol, heating, dissolved under reflux temperature (64 DEG C), after all dissolving, stop heating, be cooled at 15 DEG C and tie
Crystalline substance, filter, obtain light yellow crystal.Gained crystal is dried into 24h at 30 DEG C under vacuum produces 3- hydroxyl -4- methoxycinnamic aldehydes
Finished product, yield 70%.
Embodiment 2：
0.56g (0.010mol) potassium hydroxide is dissolved in 100ml methanol aqueous solutions (methanol and water volume ratio 1: 1),
Then 15.2g (0.1mol) isovanillin and 0.304g PolyTHFs (number-average molecular weight 650) are added, is sufficiently stirred and is allowed to
It is well mixed.0 DEG C is cooled to, the acetaldehyde solution 35.36g that mass fraction is 28% is continuously added dropwise into reaction system
(0.225mol) proceeds by reaction, and process is added dropwise and continues 4h.Continue stirring reaction 1h after completion of dropwise addition, then add quality point
Number is neutralized to terminate to react for 36% hydrochloric acid 1.1ml.Filter, obtain light yellow crystal, this is 3- hydroxyl -4- methoxycinnamates
Aldehyde crude product.The crystal is added in 300ml methanol, stirs 2h, filters, filter cake is washed with 50ml methanol.Gained filter cake is added
In 1200ml methanol, heating, dissolved under reflux temperature (64 DEG C), after all dissolving, stop heating, be cooled at 15 DEG C and tie
Crystalline substance, filter, obtain light yellow crystal.Gained crystal is dried into 24h at 30 DEG C under vacuum produces 3- hydroxyl -4- methoxycinnamic aldehydes
Finished product, yield 64%.
Embodiment 3：
0.336g (0.006mol) potassium hydroxide is dissolved in 100ml methanol aqueous solutions (methanol and water volume ratio 1: 1),
Then 15.2g (0.1mol) isovanillin and 0.304g PolyTHFs (number-average molecular weight 1000) are added, being sufficiently stirred makes
It is well mixed.10 DEG C are cooled to, the acetaldehyde solution 19.64g that mass fraction is 28% is continuously added dropwise into reaction system
(0.125mol) proceeds by reaction, and process is added dropwise and continues 3h.Continue stirring reaction 1h after completion of dropwise addition, then add quality point
Number is neutralized to terminate to react for 36% hydrochloric acid 0.65ml.Filter, obtain light yellow crystal, this is 3- hydroxyl -4- methoxyl group meat
Cinnamic aldehyde crude product.The crystal is added in 300ml methanol, stirs 2h, filters, filter cake is washed with 50ml methanol.Gained filter cake is added
Enter in 1200ml methanol, heat, dissolved under reflux temperature (64 DEG C), after all dissolving, stop heating, be cooled at 15 DEG C
Crystallization, filter, obtain light yellow crystal.Gained crystal is dried into 24h at 30 DEG C under vacuum produces 3- hydroxyl -4- methoxycinnamates
Aldehyde finished product, yield 58%.
Claims (4)
- The preparation method of 1.3- hydroxyl -4- methoxycinnamic aldehydes, it is characterised in that it is comprised the following steps that：Using potassium hydroxide as catalyst, PolyTHF is co-catalyst, carries out condensation reaction by isovanillin and acetaldehyde, produces 3- hydroxyl -4- methoxycinnamic aldehydes.
- 2. the preparation method of 3- hydroxyls -4- methoxycinnamic aldehydes as claimed in claim 1, it is characterised in that the catalyst hydrogen-oxygen The dosage for changing potassium is the 5%~20% of isovanillin mole, and the dosage of the co-catalyst PolyTHF is isovanillin The 1%~5% of mass percent, the mol ratio of the isovanillin and acetaldehyde is (0.4~1): 1.
- 3. the preparation method of 3- hydroxyls -4- methoxycinnamic aldehydes as claimed in claim 1, it is characterised in that the co-catalyst gathers The number-average molecular weight of tetrahydrofuran is 200~1000.
- 4. the preparation method of 3- hydroxyls -4- methoxycinnamic aldehydes as claimed in claim 1, it is characterised in that the condensation reaction Temperature is -10~20 DEG C, and the time of condensation reaction is 3~8h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108863745A (en) * | 2018-08-27 | 2018-11-23 | 上海华堇生物技术有限责任公司 | The preparation method of 3- hydroxycinnamaldehyde |
| CN109020793A (en) * | 2018-08-27 | 2018-12-18 | 上海华堇生物技术有限责任公司 | The preparation method of 4- hydroxycinnamaldehyde |
| CN109160875A (en) * | 2018-08-07 | 2019-01-08 | 华南理工大学 | A kind of sweetener intermediate 3- hydroxyl -4- methoxyl group-cinnamaldehyde and preparation method thereof |
-
2017
- 2017-10-17 CN CN201710964777.3A patent/CN107556182A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 吴美红: "超高甜度阿斯巴甜类似物的研究与开发", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109160875A (en) * | 2018-08-07 | 2019-01-08 | 华南理工大学 | A kind of sweetener intermediate 3- hydroxyl -4- methoxyl group-cinnamaldehyde and preparation method thereof |
| CN108863745A (en) * | 2018-08-27 | 2018-11-23 | 上海华堇生物技术有限责任公司 | The preparation method of 3- hydroxycinnamaldehyde |
| CN109020793A (en) * | 2018-08-27 | 2018-12-18 | 上海华堇生物技术有限责任公司 | The preparation method of 4- hydroxycinnamaldehyde |
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