Method for synthesizing 3,3'-(p-phenyleneoxy)di(2,4,5-triphenyl)cyclopentadiene

A technology of cyclopentadienone and phenylene oxide, which is applied in the direction of condensation preparation of carbonyl compounds, organic chemistry, etc., can solve problems such as difficult oxidation, difficulty in batch preparation of dicyclopentadienone, and existing problems, and achieves good processing performance Effect

Inactive Publication Date: 2008-01-09
INST OF CHEM CHINESE ACAD OF SCI
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  • Abstract
  • Description
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Problems solved by technology

[0007] In the above method, except that there is no special difficulty in the condensation reaction in the third step, there are problems in the first and second steps
Problems in the first step of operation: 1. The solvent CS2 used is highly toxic, flammable and smelly; 2. The solubility of the product in this solvent is not good; 3. Add HCl after the reaction When decomposed, it is easy to agglomerate, has high viscosity, and is difficult to stir; problems in purification: there are three main products, and it is difficult to separate them after repeated recrystallization. The literature uses recrystallization followed by column chromatography separation, and this method is not suitable for large quantities preparation of
[0008]There is a problem in the second oxidation reaction: when using SeO2 as the oxidant and Ac2O as the solvent, The reaction temperature is high and the time is long; SeO2 is a highly toxic inorganic product, volatile, and the reduced product selenium powder is difficult to remove; in addition, the oxidation product is viscous before drying, which is difficult to transfer , and under the conditions reported in the literature, there are considerable by-products
Use 4-nitroso-N, when N-diethylaniline is oxygenant, this oxygenant is poisonous, and its reduction product is also poisonous; And oxygenant consumption is big (molar ratio is 3-3.5 times of (formula I), weight is slightly higher In (formula I)), the price is more expensive; the oxidation product is black sticky matter, which is inconvenient to handle; oxidation is not easy to achieve complete
These problems have brought difficulties to the batch preparation of dicyclopentadienone

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] Embodiment 1, preparation 3,3'-(p-phenylene oxygen) two (2,4,5-triphenyl) cyclopentadienone

[0028] Step 1: In a 1000mL three-necked bottle, add 400mLCH 2 Cl 2 , add 42.67g (0.32mol) of anhydrous AlCl under stirring 3 , ice bath; 27.23g (0.16mol) diphenyl ether, 49.47g (0.32mol) phenylacetyl chloride and 100mLCH 2 Cl 2After mixing evenly in the triangular flask, transfer it to a 200mL dropping funnel; drop the mixture of diphenyl ether and dichloromethane into the three-necked flask, drop it in about 1 hour, and keep the temperature between 0.5-1.5°C; After completion, remove the ice bath, stir at room temperature for 2 hr; heat and reflux in a water bath for 1.5 hr; add a mixture of 50 mL of HCl and 50 mL of water dropwise under an ice bath, and stir while adding; The yellow filter cake was washed repeatedly with water and filtered several times to obtain a near white solid (a relatively pure product); the organic layer in the filtrate was separated and washed wit...

Embodiment 2

[0033] Embodiment 2, preparation 3,3'-(p-phenylene oxygen) two (2,4,5-triphenyl) cyclopentadienone

[0034] In a 1000mL three-necked bottle, add 400mLCH 2 Cl 2 , add 42.67g (0.32mol) of anhydrous AlCl under stirring 3 , ice bath; 27.23g (0.16mol) diphenyl ether, 49.47g (0.32mol) phenylacetyl chloride and 100mL CH 2 Cl 2 After mixing evenly in the triangular flask, transfer it to a 200mL dropping funnel; drop the mixture of diphenyl ether and dichloromethane into the three-necked flask, drop it in about 1 hour, and keep the temperature between 0.5-1.5°C; After completion, remove the ice bath, stir at room temperature for 2 hr; heat and reflux in a water bath for 3 hr; add a mixture of 50 mL of HCl and 50 mL of water dropwise under an ice bath, and stir while adding; The filter cake was repeatedly washed with water and suction filtered several times to obtain a nearly white solid (a relatively pure product); the organic layer in the filtrate was separated and washed with NaH...

Embodiment 3

[0036] Embodiment 3, preparation 3,3'-(p-phenylene oxygen) two (2,4,5-triphenyl) cyclopentadienone

[0037] The first step reacts with embodiment 2.

[0038] Step 2: Weigh 15.50g of 4-phenylacetylphenyl ether (I), add it into a 1000mL three-necked flask equipped with a condenser and a stirrer, add 350mL of dichloromethane, heat in a water bath, stir, and dissolve 7.4g of bicarbonate Dissolve sodium and 15.50g tetraethylammonium bromide in 220mL water, add this aqueous solution into a three-necked flask, and dissolve 15.50g KMnO 4 Add it into a three-necked flask, and react at the reflux temperature of dichloromethane for 12 hours. Point plate tracking found that there are still a small amount of raw material points and obvious intermediate product points at this time, add 11.00g KMnO 4 , continue to react for 1.5 hours, the raw material point disappears, and the intermediate product point is very light. After being treated according to the method of Example 1, 15.57 g of ye...

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Abstract

A method for synthesizing 3,3-(phenylene oxide)di(2, 4, 5-triphenyl)cyclopentadienyl ketone is carried out by Foury reacting phenyl ether with phenacerine with anhydrous aluminum muriate as catalyst and methylene dichloride as solvent to prepare 4-phenacelate withIstructure, oxidizing 4-phenacelate into 4-phenyl-oxalate withIIstructure with potassium permanganate as oxidant and under existence of phase-transferring catalyst, and condensing 4-phenyl-oxalate withIIstructure with 1,3-diphenyl acetone under alkali catalyzing. It's cheap, efficient and non-toxic.

Description

technical field [0001] The invention relates to a method for synthesizing 3,3'-(p-phenylene oxide)bis(2,4,5-triphenyl)cyclopentadienone. Background technique [0002] Synthesizing polymers with good thermal stability, processability, film formation and high hardness is a very meaningful and challenging subject ((1) Stone, D.S.; Martynenko, Z. Polymers in Electronics, Fundamentals and applications; Elsevier: New York, 1989. (2) Electronic and Photonic Applications of Polymers; Bowden, M.J., Turner, S.R., Eds.; ACS Advances in Chemistry Series 218; American Chemical Society: Washington, DC, 1988. (3) Kumar U., Neenan, T. X. Macromolecules, 1995, 28, 124-130.). Because polymers with these properties play a very important role in aviation, aerospace, electronics, machinery and other fields. Increasing the content of aromatic rings in the molecular structure, avoiding long aliphatic chains, and increasing crosslinking density are all effective means to improve the heat resistan...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C45/45C07C49/597
Inventor 赵彤魏柳荷张瑞玲李婉婉杨明
Owner INST OF CHEM CHINESE ACAD OF SCI
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