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Preparation method of p-hydroxystyrene and derivates thereof

A technology for p-hydroxystyrene and p-hydroxybenzaldehyde, which is applied in the field of preparation of p-hydroxystyrene and its derivatives, can solve the problems of heavy odor of pyridine, harsh conditions, and over 100% yield, and achieves alleviation of odor and recovery of The effect of low yield, reducing residual problems and improving yield

Active Publication Date: 2011-04-06
五莲县计量检测服务中心
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0029] In the common report of synthesizing PHCA, common organic bases can promote this reaction, and the base with better actual effect is pyridine, and the general yield is about 50%, but the smell of pyridine is heavy, which is not conducive to industrial application
In the process of synthesizing PAS by PHCA, there have been reports of higher yields. Since dimethylformamide (DMF) is mostly used as a solvent in this process, there are more DMF residues in the final purification, and the yield may exceed 100%.
The synthesis of PTBOCS is currently reported to go through the witting reaction, and finally the product is purified through the column. The conditions are relatively harsh, and the yield is between 35-65%.

Method used

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  • Preparation method of p-hydroxystyrene and derivates thereof
  • Preparation method of p-hydroxystyrene and derivates thereof
  • Preparation method of p-hydroxystyrene and derivates thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0050] Weigh 10.0g of PHB, 12.8g of malonic acid, 17.0mL of p-picoline, and 2.0mL of piperidine, put them into a 100mL four-neck flask at one time, stir and heat to 85°C in an oil bath, keep the temperature for 1.5h, and pour into the feed solution after cooling Add 40mL of 20% potassium carbonate solution to the water layer and keep stirring, let it stand for layer separation, add 35mL dilute hydrochloric acid (prepared according to the volume ratio of dense fume hydrochloric acid and water 1:1) to the water layer to adjust the pH value to about 2 , filtered the precipitated solid, washed with water, and dried to obtain a crude product, which was recrystallized with distilled water to obtain 12.8 g of a light yellow solid, with a yield of about 95%.

Embodiment 2-5

[0055] Embodiment 2-5: the preparation of PAS

[0056] Weigh 10.0g of PHCA, 0.05g of potassium acetate, 0.005g of hydroquinone, and 40mL of DMF, put them into a 100mL four-neck flask at one time, measure 12mL of acetic anhydride and pour them into the dropping funnel, stir and heat in an oil bath to 130°C, constant temperature 1.5 h, add acetic anhydride dropwise to it, continue to react for 1.5h after the dropwise addition, cool the feed liquid to room temperature, pour it into 100mL cold water, extract with the extract, dry over anhydrous magnesium sulfate, and remove the solvent by rotary evaporation to obtain pure PAS . The final product obtained by extraction with different extracts is as follows through gas phase detection:

[0057] Example

[0058] Taking cyclohexane extraction as an example, 9.2 g of light yellow liquid PAS was finally obtained, with a yield of about 93%.

Embodiment 6

[0059] Embodiment 6: the preparation of PTBOCS

[0060] Take 10.0 g of the final liquid of Example 1, 150 mL of dichloromethane, and 9.3 g of potassium tert-butoxide, and put them into a 250 mL four-neck flask at one time, measure 18 mL of di-tert-butyl dicarbonate and pour them into the dropping funnel, and stir mechanically at room temperature for 10 min. Add di-tert-butyl dicarbonate dropwise thereto, continue stirring for 2.0 h after the dropwise addition, wash the feed solution with water, dry over anhydrous magnesium sulfate, and rotary evaporate to obtain 16.0 g of light yellow liquid PTBOCS. The yield is about 87%.

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Abstract

The invention relates to the field of organic synthesis, in particular to a preparation method of p-hydroxystyrene and derivates thereof. The preparation method is as follows: preparing p-hydroxycinnamic acid; preparing the p-hydroxystyrene; and finally preparing 4-vinyl phenyl acetate or 4-tert-butoxycarbonyloxystyrene. In the preparation process of the p-hydroxycinnamic acid, 4-picoline replaces pyridine to serve as a reaction catalyst, the yield of the p-hydroxycinnamic acid is improved to about 95%, and the problems of odor of pyridine and low recovery rate are alleviated. Cyclohexane is used as an extraction solvent to extract the p-hydroxystyrene derivate from a reaction liquid, and the residue of the solvent in the product is greatly reduced. The traditional synthetic route of the 4-tert-butoxycarbonyloxystyrene is changed, and the Witting reaction with rigorous conditions is avoided; and meanwhile the complex separation and purification problems such as column chromatography are simplified, and the yield is about 80% which is higher than that of current reports.

Description

technical field [0001] The invention relates to the field of organic synthesis, in particular to a preparation method of p-hydroxystyrene and derivatives thereof. Background technique [0002] Para-Hydroxystyrene (PHS) is an aromatic compound with potential utility in a wide range of industrial applications. Its polymers are widely used in solid phase synthesis, phase transfer catalysis and high performance liquid chromatography (HPLC) stationary phase, curing agent for epoxy resin, adsorbent for organic waste liquid, selective permeable membrane, free radical scavenger and anti Oxygen etc. The scope of application involves a wide range of fields such as resins, elastomers, adhesives, coatings, automotive finishes, inks and electronic materials. Its derivatives (such as 4-tert-butoxyacyloxystyrene, referred to as PTBOCS) are currently used to prepare expensive high-performance 248nm deep ultraviolet photoresists (resolution Up to 0.13μm) of the main film-forming resin mat...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C39/20C07C37/56C07C69/157C07C67/08C07C69/96C07C68/06B01J31/02
Inventor 宋国强林林曹引梅赵廷合
Owner 五莲县计量检测服务中心
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