CN1184189C - Process for synthesizing 2-(4-hydroxylphenoxyl) butyl propionate - Google Patents
Process for synthesizing 2-(4-hydroxylphenoxyl) butyl propionate Download PDFInfo
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- CN1184189C CN1184189C CNB001229427A CN00122942A CN1184189C CN 1184189 C CN1184189 C CN 1184189C CN B001229427 A CNB001229427 A CN B001229427A CN 00122942 A CN00122942 A CN 00122942A CN 1184189 C CN1184189 C CN 1184189C
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- hydroxyphenoxy
- synthetic method
- butyl ester
- butyl propionate
- transfer catalyst
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Abstract
The present invention relates to a synthetic method for2-(4-hydroxyphenoxy) butyl propionate, which is characterized in that the compound is prepared by the reaction of hydroquinone and chloropropionic butyl ester under the existence of a phase transfer catalyst; the mol proportion of the hydroquinone to the chloropropionic butyl ester as reactant raw materials is from 4/1 to 1/1, the chloropropionic butyl ester is added in a dropping mode, and the dropping time is from 1 to 20 hours; the phase transfer catalyst is an anionic surfactant of alkyl sodium sulfonate, nacconol and alkyl sodium sulfate or is a cationic surfactant of tetrabutyl mmonium iodide, tetrabutyl romine ammonium bromide and octadecy l dimethylbenzyl quaternary amine chloride, the addition of the phase transfer catalyst is 0.1/1000 to 1% of the weight of the raw materials, and the temperature of the synthetic reaction is from 50 to 200 DEG C. The synthetic method can make the selectivity for generating the 2-(4-hydroxyphenoxy) butyl propionate reach more than 80%.
Description
The invention relates to the synthetic of 2-(4-hydroxyphenoxy) butyl propionate, refer in particular in the process of Synthetic 2-(4-hydroxyphenoxy) butyl propionate, the generation of control side reaction bis ether improves the selectivity and the yield that generate 2-(4-hydroxyphenoxy) butyl propionate.
2-(4-hydroxyphenoxy) butyl propionate be the weedicide of producing efficient, highly selective, low toxicity surely kill with the important intermediate (US4,046,553, US4,531,969) of cover grass energy.Molecular formula is as follows
It is by Resorcinol and chloropropionic acid butyl ester in the presence of alkali, temperature of reaction 20-200 ℃, the solvent of aprotic, polar such as the existence of acetone reaction down form.Square formula I.
Equation I
But should reaction be very easy to take place side reaction, square formula II.
In order to stop the generation of our undesirable bis ether, normal p methoxy phenol and the chloropropionic acid butyl ester of adopting reacts on the document, splits protecting group after having reacted again, as the equation formula III.(US4,324,627,2,926,093,3,240,706) but this method technology are complicated, influence yield.
The equation formula III
The object of the present invention is to provide the synthetic method of a kind of 2-(4-hydroxyphenoxy) butyl propionate, it has higher product yield.
The invention provides the synthetic method of a kind of 2-(4-hydroxyphenoxy) butyl propionate, it is characterized in that: this compound is to react synthetic by Resorcinol and chloropropionic acid butyl ester in the presence of phase-transfer catalyst; The molar ratio of reactant feed Resorcinol and chloropropionic acid butyl ester is 4/1-1/1, and best proportioning is 2/1-1.2/1, and the chloropropionic acid butyl ester adds in the dropping mode, and the dropping time is 1-20 hour, and the best dropping time is 5-10 hour; Phase-transfer catalyst is the anion surfactant of alkyl sodium sulfonate, sodium alkylarysulfonate, sodium alkyl sulfate, the perhaps cationic surfactant of tetrabutylammonium iodide, Tetrabutyl amonium bromide, octadecyl dimethyl benzyl aliquat, the add-on of phase-transfer catalyst is 0.1 ‰-1% of a raw material weight, and optimal addn is 1 ‰-5 ‰; Synthesis reaction temperature is 50-200 ℃, and optimal reaction temperature is 50-140 ℃.Adding owing to phase-transfer catalyst among the present invention can make selectivity of product improve about 10%.
Synthetic reaction process of the present invention carries out in the aprotic polar solvent of acetone, dioxane, N, N-N,N-DIMETHYLACETAMIDE.
In addition, in synthetic reaction process of the present invention, the Pd catalyzer be can also add, Pd/C, Pd/Al are selected from
2O
3, Pd/SiO
2One or more, the Pd add-on is the 0.05-0.5% of raw material weight, optimal addn is 0.05-0.1%.The adding of Pd catalyzer can make selectivity of product further improve about 10%
Give further instruction below by embodiment to the present invention.
Example 1
2.64g Resorcinol, 20mL acetone add in the there-necked flask that prolong and dropping pipe are housed, stirring and dissolving adds 1.38gK then
2CO
3, be warming up to 100 ℃, drip adding 3.29g chloropropionic acid butyl ester (being dissolved in 20mL acetone) in the pipe, begin to drip the chloropropionic acid butyl ester, 8 hours dropping time, dropwise, continue reaction 10 hours.React the vacuum filtration that finishes, filtrate is acidified to pH=1-2 with 10%HCl, and rotary evaporation is removed dioxane, and filter cake is water-soluble, and 10%HCl is acidified to pH=1-2, uses dichloromethane extraction three times, and solid-liquid mixes, and saturated sodium carbonate solution is given a baby a bath on the third day after its birth inferior.Selectivity of product 58%, feed stock conversion 100%.
The percentage composition % of selectivity %=product/(the percentage composition % of the percentage composition %+ by product of product)
Example 2
2.64g Resorcinol, 20mL acetone add in the there-necked flask that prolong and dropping pipe are housed, stirring and dissolving adds 1.38gK then
2CO
3, the 0.02g tetrabutylammonium iodide is warming up to 100 ℃, drips to add 3.29g chloropropionic acid butyl ester (being dissolved in 20mL acetone) in the pipe, begins to drip the chloropropionic acid butyl ester, 8 hours dropping time, dropwise, and continue reaction 10 hours.React the vacuum filtration that finishes, filtrate is acidified to pH=1-2 with 10%HCl, and rotary evaporation is removed dioxane, and filter cake is water-soluble, and 10%HCl is acidified to pH=1-2, uses dichloromethane extraction three times, and solid-liquid mixes, and saturated sodium carbonate solution is given a baby a bath on the third day after its birth inferior.Selectivity of product 70%, feed stock conversion 100%.
Example 3
2.64g Resorcinol, 20mL acetone add in the there-necked flask that prolong and dropping pipe are housed, stirring and dissolving adds 1.38gK then
2CO
3, the 0.02g tetrabutylammonium iodide, the Pd/C catalyzer of 0.30g5%Pd content is warming up to 100 ℃, drips to add 3.29g chloropropionic acid butyl ester (being dissolved in 20mL acetone) in the pipe, begins to drip the chloropropionic acid butyl ester, 8 hours dropping time, dropwise, continue reaction 10 hours.React the vacuum filtration that finishes, filtrate is acidified to pH=1-2 with 10%HCl, and rotary evaporation is removed dioxane, and filter cake is water-soluble, and 10%HCl is acidified to pH=1-2, uses dichloromethane extraction three times, and solid-liquid mixes, and saturated sodium carbonate solution is given a baby a bath on the third day after its birth inferior.Selectivity of product 88%, feed stock conversion 100%.
Example 4
2.64g Resorcinol, 20mL acetone add in the there-necked flask that prolong and dropping pipe are housed, stirring and dissolving adds 1.38gK then
2CO
3, the 0.02g sodium lauryl sulphate is warming up to 100 ℃, drips to add 3.29g chloropropionic acid butyl ester (being dissolved in 20mL acetone) in the pipe, begins to drip the chloropropionic acid butyl ester, 8 hours dropping time, dropwise, and continue reaction 10 hours.React the vacuum filtration that finishes, filtrate is acidified to pH=1-2 with 10%HCl, and rotary evaporation is removed dioxane, and filter cake is water-soluble, and 10%HCl is acidified to pH=1-2, uses dichloromethane extraction three times, and solid-liquid mixes, and saturated sodium carbonate solution is given a baby a bath on the third day after its birth inferior.Selectivity of product 71%, feed stock conversion 100%.
The mole proportioning of example 5 Resorcinol and chloropropionic acid butyl ester is to generating the influence of product selectivity
In example 2 described reaction systems, change the mole proportioning of Resorcinol and chloropropionic acid butyl ester, it sees Table 1 to the influence that generates selectivity of product.
The mole proportioning of table 1 Resorcinol and chloropropionic acid butyl ester is to generating the influence of product selectivity
| The mole proportioning of Resorcinol and chloropropionic acid butyl ester | Selectivity of product % |
| 1/1.2 | 70 |
| 1/1.3 | 72 |
| 1/1.5 | 85 |
| 1/1.8 | 85 |
| 1/2.0 | 88 |
The adding of example 6 phase-transfer catalysts and Pd/C catalyzer is to the influence of selectivity of product
In example 2 described reaction systems, add phase-transfer catalyst and Pd/C catalyzer, its influence to selectivity of product sees Table 2.
The adding of table 2 phase-transfer catalyst and Pd/C catalyzer is to the influence of selectivity of product
| Catalyzer | The add-on of catalyzer | Selectivity of product % |
| Tetrabutylammonium iodide (1 ‰) | 0 | 58 |
| 1 | 65 | |
| 3 | 70 | |
| 5 | 63 | |
| Pd/C (0.1%) 3% tetrabutylammonium iodide | 8 | 42 |
| 0 | 70 | |
| 3 | 72 | |
| 5 | 88 |
Claims (8)
1, the synthetic method of a kind of 2-(4-hydroxyphenoxy) butyl propionate, it is characterized in that: this compound is to react synthetic by Resorcinol and chloropropionic acid butyl ester in the presence of phase-transfer catalyst; The molar ratio of reactant feed Resorcinol and chloropropionic acid butyl ester is 4/1-1/1, and the chloropropionic acid butyl ester adds in the dropping mode, and the dropping time is 1-20 hour; Phase-transfer catalyst is the anion surfactant of alkyl sodium sulfonate, sodium alkylarysulfonate, sodium alkyl sulfate, the perhaps cationic surfactant of tetrabutylammonium iodide, Tetrabutyl amonium bromide, octadecyl dimethyl benzyl aliquat, the add-on of phase-transfer catalyst is 0.1 ‰-1% of a raw material weight; Synthesis reaction temperature is 50-200 ℃.
2, by the synthetic method of the described 2-of claim 1 (4-hydroxyphenoxy) butyl propionate, it is characterized in that: the molar ratio of reactant feed Resorcinol and chloropropionic acid butyl ester is 2/1-1.2/1.
3, by the synthetic method of the described 2-of claim 1 (4-hydroxyphenoxy) butyl propionate, it is characterized in that: the chloropropionic acid butyl ester dropping time is 5-10 hour.
4, by the synthetic method of the described 2-of claim 1 (4-hydroxyphenoxy) butyl propionate, it is characterized in that: the add-on of phase-transfer catalyst is a raw material weight 1 ‰-5 ‰.
5, by the synthetic method of the described 2-of claim 1 (4-hydroxyphenoxy) butyl propionate, it is characterized in that: synthesis reaction temperature is 50-140 ℃.
6, by the synthetic method of the described 2-of claim 1 (4-hydroxyphenoxy) butyl propionate, it is characterized in that: described synthetic reaction process carries out in the aprotic polar solvent of acetone, dioxane, N, N-N,N-DIMETHYLACETAMIDE.
7, by claim 1, the synthetic method of 2,3,4 or 5 described 2-(4-hydroxyphenoxy) butyl propionate is characterized in that: add the Pd catalyzer in described synthetic reaction process, be selected from Pd/C, Pd/Al
2O
3, Pd/SiO
2One or more, the Pd add-on is the 0.05-0.5% of raw material weight.
8, by the synthetic method of the described 2-of claim 7 (4-hydroxyphenoxy) butyl propionate, it is characterized in that: the Pd add-on is the 0.05-0.1% of raw material weight.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001229427A CN1184189C (en) | 2000-08-30 | 2000-08-30 | Process for synthesizing 2-(4-hydroxylphenoxyl) butyl propionate |
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|---|---|---|---|
| CNB001229427A CN1184189C (en) | 2000-08-30 | 2000-08-30 | Process for synthesizing 2-(4-hydroxylphenoxyl) butyl propionate |
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|---|---|
| CN1340497A CN1340497A (en) | 2002-03-20 |
| CN1184189C true CN1184189C (en) | 2005-01-12 |
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| CN109867601B (en) * | 2019-02-15 | 2021-05-28 | 湖南速博生物技术有限公司 | Preparation method of (R) -2- (4-hydroxyphenoxy) butyl propionate |
| CN112321428A (en) * | 2020-10-26 | 2021-02-05 | 安徽丰乐农化有限责任公司 | Synthesis method of R- (+) -2- (4-hydroxyphenoxy) ethyl propionate |
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