CN109485550B - Method for preparing styrene derivative by using ionic liquid - Google Patents
Method for preparing styrene derivative by using ionic liquid Download PDFInfo
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- CN109485550B CN109485550B CN201811361150.XA CN201811361150A CN109485550B CN 109485550 B CN109485550 B CN 109485550B CN 201811361150 A CN201811361150 A CN 201811361150A CN 109485550 B CN109485550 B CN 109485550B
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
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- C07C17/00—Preparation of halogenated hydrocarbons
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Abstract
The invention belongs to the technical field of chemical engineering and medical intermediate synthesis, and relates to a method for preparing a styrene derivative by using an ionic liquid. The method takes the ionic liquid as a solvent, and has high reaction catalysis efficiency. The ionic liquid can be repeatedly used for many times, so that the industrial production cost is saved, and the environmental problem caused by the traditional solvent is solved.
Description
Technical Field
The invention belongs to the technical field of chemical engineering and medical intermediate synthesis, and relates to a method for preparing a styrene derivative by using an ionic liquid. In particular to a method for preparing styrene derivatives by using ionic solution.
Background
The styrene derivative is one of important intermediates in the synthesis of medicines and materials. The positive chemically amplified resist generally adopts derivatives of poly-p-hydroxystyrene as acid-sensitive resin, and the polymer photoresist containing p-hydroxystyrene becomes a key technology for photoetching 0.11 mu m line width chips, see Mengshui, Liguangxi, Yangqi and Huangyajiang; "Synthesis of Poly-p-hydroxystyrene for Photoresist and its evolution", chemical evolution, 2004, 16(2) 243-.
The p-hydroxy-styrene and its derivative are prepared by Wittig reaction, in the method, p-hydroxy-benzaldehyde derivative, such as p-acetoxybenzaldehyde, reacts with methyl iodide and other reagents under the action of organic strong base, such as sodium methoxide or potassium tert-butoxide, to generate the required product. In the reaction process, the preparation process and the adopted raw materials are expensive, so that the price of the p-hydroxystyrene derivative is high, no special manufacturer is available in China for production, and the further application of the p-hydroxystyrene derivative in various fields is influenced due to the restriction of the raw material factors.
Due to the unique physical and chemical properties, good substrate compatibility and catalyst stability, the ionic liquid is widely applied to the fields of extraction separation, organic synthesis, catalysis and the like.
Aiming at the defects of the prior art, the invention provides a preparation method of a novel styrene derivative. The method takes the ionic liquid as a solvent, and has high reaction catalysis efficiency. The ionic liquid can be repeatedly used for many times, so that the industrial production cost is saved, and the environmental problem caused by the traditional solvent is solved.
Disclosure of Invention
The invention provides a preparation method of a styrene derivative, which comprises the following steps:
reacting the compound shown in the formula III with malonic acid in the presence of ionic liquid to obtain a compound shown in a formula II; reacting a compound shown in a formula II in the presence of ionic liquid to obtain a compound shown in a formula I;
wherein R is selected from F, Cl, Br, cyano, nitro, C1-4 alkyl, C1-4 alkoxy or hydroxyl.
In some embodiments of the invention, the ionic liquid acts as a solvent or catalyst.
In some embodiments of the invention, the ionic liquid is selected from N-butyl-N-methylpiperidine bromide, N-butyl-N-methylpiperidine bis (trifluoromethanesulfonyl) imide, N-butyl-N-methylpyrrolidine bromide, N-butyl-N-methylpyrrolidine bis (trifluoromethanesulfonyl) imide, tributylmethylammonium chloride, tributylmethylammonium bis (trifluoromethanesulfonyl) imide, tributylmethylammonium chloride, N-methoxyethyl-N-methyldiethylammonium tetrafluoroborate or mixtures thereof, preferably from N-butyl-N-methylpiperidine bromide, N-butyl-N-methylpiperidine bis (trifluoromethanesulfonyl) imide, N-butyl-N-methylpyrrolidine bromide, N-butylmethyl-dimethylmethane-yl bromide, N-butylmethyl-dimethylmethane-bromide, N-methyl-bromide, N-dimethylmethane-bromide, N-methyl-propyl bromide, N-methyl-propyl bromide, and mixtures thereof, N-butyl-N-methylpyrrolidine bis (trifluoromethanesulfonyl) imide salt or mixtures thereof, more preferably from N-butyl-N-methylpiperidine bromide, N-butyl-N-methylpyrrolidine bromide, tributylmethylammonium chloride or mixtures thereof.
In some embodiments of the present invention, the amount of ionic liquid used (in grams of weight) is 1-20 times the amount of compound of formula III (in grams of weight), preferably 2-15 times the amount, more preferably 2-10 times the amount. Alternatively, in some embodiments of the invention, the ionic liquid is used in an amount 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5 or 10 times the amount of the compound of formula III.
In some embodiments of the invention, the ratio of the amount of material of the compound of formula III to malonic acid is selected from 1: 1-5, preferably selected from 1:1 to 2.5, more preferably selected from 1:1 to 1.5. Alternatively, in some embodiments of the invention, the ratio of the amount of material of the compound of formula III to malonic acid is selected from 1: 1. 1: 1.5, 1: 2. 1: 2.5, 1: 3. 1: 3.5, 1: 4. 1: 4.5 or 1: 5.
in some embodiments of the present invention, in the step of preparing the compound of formula II by reacting the compound of formula III with malonic acid, the reaction temperature is selected from 10-60 ℃, preferably from 20-50 ℃, and more preferably from 30-50 ℃.
In some embodiments of the present invention, in the step of preparing the compound of formula I from the compound of formula II, the reaction temperature is selected from 80-200 ℃, preferably from 100-180 ℃, and more preferably from 120-160 ℃.
In some embodiments of the present invention, in the step of preparing the compound of formula II from the compound of formula III, the reaction time is selected from 1 to 6 hours, preferably from 2 to 4 hours, and most preferably from 3 hours.
In some embodiments of the present invention, in the step of preparing the compound of formula I from the compound of formula II, the reaction time is selected from 2 to 8 hours, preferably from 4 to 6 hours, and most preferably from 5 hours.
In some embodiments of the invention, the reaction to prepare the compound of formula II from the compound of formula III and the compound of formula I from the compound of formula II is a one-pot reaction. The one-pot reaction refers to the reaction for preparing the compound of the formula I from the compound of the formula II directly without post-treatment after the reaction for preparing the compound of the formula II from the compound of the formula III is finished.
In some embodiments of the invention, the R group of the compound of formula III, the compound of formula II, or the compound of formula I is attached at the para position of the phenyl ring.
In some embodiments of the invention, the compound of formula III is selected from the group consisting of p-hydroxyphenylacetaldehyde, p-C1-4 alkoxyphenylacetaldehyde; the compound of formula II is selected from p-hydroxyphenylacrylic acid, p-C1-4 alkoxy phenylacrylic acid; the compound of formula I is selected from p-hydroxystyrene and p-C1-4 alkoxy styrene.
The invention adopts the ionic liquid as the reaction solvent, and improves the reaction yield. The ionic liquid can be repeatedly used for many times, so that the industrial production cost is saved, and the environmental problem caused by the traditional solvent is solved.
Detailed Description
The present invention will be illustrated in detail by the following examples, which are merely illustrative and are not intended to limit the scope of the present invention.
Example 1
A1000 mL reaction bottle is added with 122.1g (1mol) of p-hydroxybenzaldehyde and 104.1g (1mol) of malonic acid, 500g of N-butyl-N-methylpiperidine bromide chloride as ionic liquid and 4g (0.1mol) of sodium hydroxide, the mixture reacts for 3 hours at the temperature of 40-50 ℃, then the mixture is heated to 160 ℃ for reaction for 5 hours, the temperature is reduced to normal temperature after the reaction is finished, the mixture is directly extracted by 500mLx3 of ethyl acetate, washed by brine and concentrated to obtain 119.2g of p-hydroxystyrene with the yield of 99.3%.
Example 2
140.6g (1mol) of p-chlorobenzaldehyde and 125.5g (1.2mol) of malonic acid, ionic liquid 500g N-butyl-N-methylpiperidine bis (trifluoromethanesulfonyl) imide salt and 4g (0.1mol) of sodium hydroxide are added into a 1000mL reaction bottle, the mixture is reacted for 3 hours at the temperature of 40-50 ℃, heated to 160 ℃ for reaction for 5 hours, cooled to normal temperature after the reaction is finished, directly extracted by ethyl acetate 500mLx3, washed by brine and concentrated to obtain the product of p-chlorostyrene 137.2g with the yield of 99.0 percent.
Example 3
A1000 mL reaction bottle is added with 131.1g (1mol) of p-cyanobenzaldehyde and 135.2g (1.3mol) of malonic acid, an ionic liquid of 400g N-butyl-N-methylpyrrolidine bromide and 4g (0.1mol) of sodium hydroxide, the mixture is reacted for 3 hours at the temperature of 40-50 ℃, the temperature is heated to 160 ℃ again for 5 hours, the temperature is reduced to normal temperature after the reaction is finished, the mixture is directly extracted by ethyl acetate 500mLx3, the salt solution is washed, and the product of p-cyanostyrene is obtained by concentration, wherein the yield is 127.2g, and 98.5%.
Example 4
151.0g (1mol) of p-nitrobenzaldehyde and 145.6g (1.4mol) of malonic acid, 400g N-butyl-N-methylpyrrolidine bis (trifluoromethanesulfonyl) imide salt serving as an ionic liquid and 4g (0.1mol) of sodium hydroxide are added into a 1000mL reaction bottle, the mixture is reacted for 3 hours at the temperature of 40-50 ℃, heated to 160 ℃ for reaction for 5 hours, cooled to the normal temperature after the reaction is finished, directly extracted by 500mLx3 of ethyl acetate, washed by brine and concentrated to obtain 146.5g of p-nitrostyrene product, and the yield is 98.2%.
Example 5
A1000 mL reaction bottle is added with 120.1g (1mol) of p-tolualdehyde, 114.4g (1.1mol) of malonic acid, 400g of tributylmethylammonium chloride and 4g (0.1mol) of sodium hydroxide, the mixture is reacted for 3 hours at 40-50 ℃, the reaction is heated to 150 ℃ for 5 hours, the temperature is reduced to normal temperature after the reaction is finished, the mixture is directly extracted by ethyl acetate 500mLx3, the mixture is washed by saline solution, and the product p-methylstyrene is obtained by concentration, namely 117.2g, and the yield is 99.1%.
Example 6
A1000 mL reaction bottle is added with 136.1g (1mol) of p-methoxybenzaldehyde and 114.4g (1.1mol) of malonic acid, 600g of tributylmethylammonium bis (trifluoromethanesulfonyl) imide salt and 4g (0.1mol) of sodium hydroxide, the mixture is reacted for 3 hours at the temperature of 40-50 ℃, the temperature is heated to 160 ℃ again for 5 hours, the temperature is reduced to normal temperature after the reaction is finished, the mixture is directly extracted by 500mL of ethyl acetate x3, the product is washed by saline solution and concentrated to obtain 130.8g of p-methoxystyrene, and the yield is 97.5%.
Example 7
A1000 mL reaction flask was charged with 122.1g (1mol) of p-hydroxybenzaldehyde and 104.1g (1mol) of malonic acid, 500mL of dichloromethane, 4g (0.1mol) of sodium hydroxide, and reacted under reflux for 3 hours. After the reaction is finished, the product is concentrated, dichloromethane is removed, 500mL of toluene is added, the reaction is carried out for 5 hours under the reflux condition, and the temperature is reduced to the normal temperature after the reaction is finished. The product was concentrated, added with ethyl acetate and saturated saline solution for layer extraction, washed with saline solution, and concentrated to give 75.1g of p-hydroxystyrene, a yield of 62.5%.
Example 8
Adding 122.1g (1mol) of p-hydroxybenzaldehyde, 104.1g (1mol) of malonic acid, 500mL of toluene and 4g (0.1mol) of sodium hydroxide into a 1000mL reaction bottle, reacting at 50-60 ℃ for 3 hours, reacting under reflux for 5 hours, cooling to normal temperature after the reaction is finished, concentrating the product, adding ethyl acetate and saturated saline solution, performing layered extraction, washing with the saline solution, and concentrating to obtain 63.1g of p-hydroxystyrene product, wherein the yield is 53.2%.
Claims (5)
1. A method for preparing a styrene derivative, comprising:
adding a compound of formula III, malonic acid, ionic liquid and sodium hydroxide into a reaction vessel, reacting at 10-60 ℃, heating to 80-200 ℃ after the reaction is finished, reacting, cooling to normal temperature after the reaction is finished, and carrying out post-treatment to obtain a compound of formula I; the reaction for preparing the compound shown in the formula II from the compound shown in the formula III and the reaction for preparing the compound shown in the formula I from the compound shown in the formula II are one-pot reaction;
wherein:
r is selected from F, Cl, Br, cyano, nitro, C1-4 alkyl, C1-4 alkoxy or hydroxyl; the ionic liquid is selected from N-butyl-N-methylpiperidine bromide chloride, N-butyl-N-methylpiperidine bis (trifluoromethanesulfonyl) imide salt, N-butyl-N-methylpyrrolidine bromide salt, N-butyl-N-methylpyrrolidine bis (trifluoromethanesulfonyl) imide salt, tributylmethylammonium chloride and tributylmethylammonium bis (trifluoromethanesulfonyl) imide salt.
2. The process according to claim 1, wherein the ionic liquid is used in an amount of 1 to 20 times that of the compound of the formula III.
3. The method of claim 1, wherein the ratio of the amount of the compound of formula III to the amount of malonic acid is selected from 1:1 to 5.
4. The method of claim 1, wherein the R group of the compound of formula III, the compound of formula II, or the compound of formula I is attached at the para position of the phenyl ring.
5. The process according to claim 1, wherein the compound of formula III is selected from p-hydroxybenzaldehyde, p-C1-4 alkoxybenzaldehyde; the compound of formula II is selected from p-hydroxyphenylacrylic acid, p-C1-4 alkoxy phenylacrylic acid; the compound of formula I is selected from p-hydroxystyrene and p-C1-4 alkoxy styrene.
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Non-Patent Citations (2)
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| CO2 absorbing cost-effective ionic liquid for synthesis of commercially important alpha cyanoacrylic acids: A safe process for activation of cyanoacetic acid;Yogesh O. Sharma等;《Green Chem.》;20090211(第11期);526-530 * |
| N-Heterocyclic Carbene Promoted Decarboxylation of Lignin-Derived Aromatic Acids;Liu, Dajiang等;《ACS Sustainable Chemistry & Engineering》;20180416;第6卷(第6期);7232-7238 * |
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Denomination of invention: Preparation of styrene derivatives from ionic liquids Effective date of registration: 20220629 Granted publication date: 20220104 Pledgee: Ningbo Tianjin Enterprise Service Co.,Ltd. Pledgor: NINGBO WEIXIN NEW MATERIAL TECHNOLOGY Co.,Ltd. Registration number: Y2022330001154 |
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