CN103641806A - Preparation method of 4-phenylethynylphthalic anhydride - Google Patents
Preparation method of 4-phenylethynylphthalic anhydride Download PDFInfo
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- CN103641806A CN103641806A CN201310585581.5A CN201310585581A CN103641806A CN 103641806 A CN103641806 A CN 103641806A CN 201310585581 A CN201310585581 A CN 201310585581A CN 103641806 A CN103641806 A CN 103641806A
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
- C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
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Abstract
The invention discloses a preparation method of 4-phenylethynylphthalic anhydride. A coupling reaction of a raw material 4-chlorophthalic anhydride and phenylacetylene is carried out with dichlorobis(triphenyl-phosphine) palladium(II) generated through an in situ reaction of palladium dichloride and triphenyl phosphine as a catalyst, and acetic anhydride cyclization is carried out, so the production cost of 4-phenylethynylphthalic anhydride is greatly reduced.
Description
Technical field
The invention relates to a kind of preparation method of 4-phenylacetylene benzoic anhydride.
Background technology
As a kind of special engineered material, polyimide, because its good thermotolerance, mechanical property and electric property are used widely in fields such as aerospace, microelectronics, laser, is called as one of most potential engineering plastics of 21 century.With respect to usining the composite polyimide material of norbornylene as end-capping reagent, the phenylacetylene base phthalic anhydride of usining is better as the new type polyimide material thermal resistance of end-capping reagent, resistance to solvent stability and chemical stability, vitrifying conversion temp is high, processing forming is also more outstanding, receives increasing concern.
The production technology complex procedures of tradition 4-phenylacetylene base phthalic anhydride, first alkaline hydrolysis is the process flow steps redundancy of acidolysis again, and separating step complexity and environmental pollution are larger.Directly use two (triphenylphosphine) palladium chlorides as catalyzer, preparation method is complicated, expensive, for environment for use, requires also very harsh; Bromo-derivative price goes up gradually, and is difficult for commercialization, and cost is higher.
Summary of the invention
In view of this, one of object of the invention is to provide a kind of preparation method of 4-phenylacetylene benzoic anhydride with low cost.
The invention solves the technical scheme that its technical problem adopts: a kind of preparation method of 4-phenylacetylene benzoic anhydride, comprises the steps:
(1) under nitrogen protection, 4-chloro-o-phthalic acid, phenylacetylene, triphenylphosphine, potassiumiodide are mixed;
(2) add non-protonic solvent and neutralization bases after substituting gas, add Palladous chloride, cuprous iodide after again substituting gas, cooling react 10-14h at 110 ℃ of 70 – after, revolve to steam and obtain 4-phenylacetylene phthalic acid except recrystallization after desolventizing; Described 4-chloro-o-phthalic acid, every 1mol is used non-protonic solvent 400-600mL;
(3) described 4-phenylacetylene phthalic acid and aceticanhydride are mixed to rear backflow, revolve to steam and remove after acetic acid and acetic anhydride, by toluene/hexane, gained solid is carried out to recrystallization, and carrying out vacuum-drying, obtain 4-phenylacetylene Tetra hydro Phthalic anhydride;
The mol ratio of described 4-chloro-o-phthalic acid, Palladous chloride, potassiumiodide is 1:(0.05-0.5): (0.1-0.3);
The mol ratio of described 4-chloro-o-phthalic acid, neutralization bases is 1:3-7;
The mol ratio of described Palladous chloride, triphenylphosphine, cuprous iodide is 1:(5-10): (2-4);
The mol ratio of described 4-phenylacetylene phthalic acid, aceticanhydride is 1:1.5-3.5.
Preferably, described step (2) is: after substituting gas, add non-protonic solvent and neutralization bases, add Palladous chloride, cuprous iodide after again substituting gas, and cooling react 12h at 80 ℃ after, revolve to steam and obtain 4-phenylacetylene phthalic acid except recrystallization after desolventizing; Described 4-chloro-o-phthalic acid, every 1mol is used non-protonic solvent 400-600mL.
Preferably, described neutralization bases is organic bases, and the mol ratio of described 4-chloro-o-phthalic acid, neutralization bases is 1:3-5; Described organic bases is preferably triethylamine, pyridine.
Preferably, described neutralization bases is mineral alkali, and the mol ratio of described 4-chloro-o-phthalic acid, neutralization bases is 1:4-7; Described mineral alkali is preferably cesium carbonate, salt of wormwood.
Preferably, described non-protonic solvent is one or more in tetrahydrofuran (THF), DMF, N,N-dimethylacetamide, toluene.
The present invention is directly usingd 4-chloro-o-phthalic acid as raw material, cheap being easy to get; Using palladium chloride and two (triphenylphosphine) palladium chlorides of triphenylphosphine reaction in－situ generation as catalyzer, avoided expensive two (triphenylphosphine) palladium chlorides of direct use; Get rid of the first alkaline hydrolysis technical process of acidolysis again in traditional technology, directly used aceticanhydride cyclization after 4-chloro-o-phthalic acid and phenylacetylene linked reaction, greatly reduced the production cost of this ethynyl of 4-phthalic anhydride.
Embodiment
It is raw material that the present invention directly adopts 4-chloro-o-phthalic acid, take Palladous chloride and and on-the-spot two (triphenylphosphine) palladium chloride generating of triphenylphosphine be catalyzer, cuprous iodide is as promotor, by the katalysis of potassiumiodide, thereby make 4-chloro-o-phthalic acid and phenylacetylene carry out coupling and make 4-phenylacetylene phthalic acid, then closed loop obtains 4-phenylacetylene Tetra hydro Phthalic anhydride under aceticanhydride effect.
Preparation process is as follows:
Reaction raw materials is:
Phenylacetylene:
4-chloro-o-phthalic acid:
Reactions steps is:
(1) under nitrogen atmosphere, 4-chloro-o-phthalic acid, phenylacetylene, triphenylphosphine and potassiumiodide are added in flask, after substituting gas, add non-protonic solvent and triethylamine, after again substituting gas, add Palladous chloride, cuprous iodide, cooling react 12h at 70 ℃ after, revolve to steam and obtain 4-phenylacetylene phthalic acid except recrystallization after desolventizing.
(2) above-mentioned gained 4-phenylacetylene phthalic acid and aceticanhydride are mixed to rear backflow half an hour, revolve to steam and remove after acetic acid and acetic anhydride, with toluene-hexane (V:V=1:1), gained solid is carried out to recrystallization, and at 80 ℃ after vacuum-drying, obtain yellow crystalline solid, i.e. 4-phenylacetylene Tetra hydro Phthalic anhydride.
In preparation method of the present invention, add two (triphenylphosphine) palladium chloride that catalyzer is Palladous chloride and triphenylphosphine reaction in－situ gained, avoided using expensive two (triphenylphosphine) palladium chloride as direct catalyzer.The consumption of Palladous chloride is that 0.05%-0.5%(be take 4-chloro-o-phthalic acid as benchmark), the mol ratio of Palladous chloride and triphenylphosphine is 1:5 – 10, the ratio of Palladous chloride and cuprous iodide is 1:2 – 4.Potassiumiodide can generate 4-chloro-o-phthalic acid original position 4-iodine phthalic acid, accelerates the linked reaction of 4-chloro-o-phthalic acid and phenylacetylene, and its consumption is 10%-30%.
In preparation method of the present invention, non-protonic solvent can be tetrahydrofuran (THF), DMF, N,N-dimethylacetamide, toluene etc., and its consumption is the every 1mol4-chloro-o-phthalic acid of 400-600mL.
In preparation method of the present invention, alkali can adopt the mineral alkalis such as the organic basess such as triethylamine, pyridine or cesium carbonate, salt of wormwood, wherein with the effect of organic bases for well, the ratio of organic bases and 4-chloro-o-phthalic acid is 3 – 5:1, the ratio of mineral alkali and 4-chloro-o-phthalic acid is 4-7:1.
In preparation method of the present invention, linked reaction temperature can conversion between 110 ℃ of 70 –, and the reaction times is different according to temperature of reaction, and 10 – 14h can complete reaction.
In preparation method of the present invention, in chemical closed loop step, acetic anhydride used and the mol ratio of 4-phenylacetylene phthalic acid are 1.5 – 3.5:1, and temperature of reaction is for refluxing, and within general one hour, reaction can be carried out completely.
Feature of the present invention is to utilize the Palladous chloride of relative low price and triphenylphosphine original position to generate two (triphenylphosphine) palladium chloride, has improved the problem that direct use two (triphenylphosphine) palladium chloride condition is harsh, cost is higher; Adopt 4-chloro-o-phthalic acid cheap, that be easy to get directly to react with phenylacetylene, coupling and 4-phenylacetylene phthalic acid, through aceticanhydride cyclization, obtain 4-phenylacetylene Tetra hydro Phthalic anhydride again, improved and in background technology, usingd 4-bromobenzene acid anhydride as the higher problem of raw materials cost, the operation of aqueous sodium hydroxide solution hydrolysis for removal, simplify production technique, greatly reduced the production cost of 4-phenylacetylene benzoic anhydride.
Embodiment 1
(1) under nitrogen atmosphere by 4-chloro-o-phthalic acid (200.58g, 1.0mol), phenylacetylene (122.56g, 1.2mol), triphenylphosphine (2.63g, 10mmol) and potassiumiodide (33.2g, 0.2mol) add in flask, after substituting gas, add 500mL DMF and 303.57g triethylamine, after again substituting gas, add Palladous chloride (0.177g, 1mmol), cuprous iodide (0.571g, 3mmol), cooling react 12h at 70 ℃ after, revolve to steam and obtain 4-phenylacetylene phthalic acid except toluene/hexane (V:V=1:1) recrystallization after desolventizing.
(2) by above-mentioned gained 4-phenylacetylene phthalic acid and aceticanhydride (204.2g, 2.0mol) mix rear backflow half an hour, revolve to steam and remove after acetic acid and acetic anhydride, by toluene/hexane (V:V=1:1), gained solid is carried out to recrystallization, and at 80 ℃ after vacuum-drying, obtain yellow crystalline solid, i.e. 4-phenylacetylene Tetra hydro Phthalic anhydride (149.9 ℃ of m.p.=148.3 –, yield 81%).
Take the above-mentioned desirable embodiment according to the invention as enlightenment, and by above-mentioned description, relevant staff can, within not departing from the scope of this invention creation technological thought, carry out various change and modification completely.The technical scope that this invention is created is not limited to the content on specification sheets, must determine its technical scope according to claim scope.
Claims (5)
1. a preparation method for 4-phenylacetylene benzoic anhydride, is characterized in that, comprises the steps:
(1) under nitrogen protection, 4-chloro-o-phthalic acid, phenylacetylene, triphenylphosphine, potassiumiodide are mixed;
(2) add non-protonic solvent and neutralization bases after substituting gas, add Palladous chloride, cuprous iodide after again substituting gas, cooling react 10-14h at 110 ℃ of 70 – after, revolve to steam and obtain 4-phenylacetylene phthalic acid except recrystallization after desolventizing; Described 4-chloro-o-phthalic acid, every 1mol is used non-protonic solvent 400-600mL;
(3) described 4-phenylacetylene phthalic acid and aceticanhydride are mixed to rear backflow, revolve to steam and remove after acetic acid and acetic anhydride, with toluene-hexane, gained solid is carried out to recrystallization, and carrying out vacuum-drying, obtain 4-phenylacetylene Tetra hydro Phthalic anhydride;
The mol ratio of described 4-chloro-o-phthalic acid, Palladous chloride, potassiumiodide is 1:(0.05-0.5): (0.1-0.3);
The mol ratio of described 4-chloro-o-phthalic acid, neutralization bases is 1:3-7;
The mol ratio of described Palladous chloride, triphenylphosphine, cuprous iodide is 1:(5-10): (2-4);
The mol ratio of described 4-phenylacetylene phthalic acid, aceticanhydride is 1:1.5-3.5;
The V/V of described toluene-hexane is 1:1.
2. the preparation method of 4-phenylacetylene benzoic anhydride according to claim 1, is characterized in that, described step (2) is:
After substituting gas, add non-protonic solvent and neutralization bases, add Palladous chloride, cuprous iodide after again substituting gas, cooling react 12h at 80 ℃ after, revolve to steam and obtain 4-phenylacetylene phthalic acid except recrystallization after desolventizing; Described 4-chloro-o-phthalic acid, every 1mol is used non-protonic solvent 400-600mL.
3. the preparation method of 4-phenylacetylene benzoic anhydride according to claim 1, is characterized in that, described neutralization bases is organic bases, and the mol ratio of described 4-chloro-o-phthalic acid, neutralization bases is 1:3-5; Described organic bases is preferably triethylamine, pyridine.
4. the preparation method of 4-phenylacetylene benzoic anhydride according to claim 1, is characterized in that, described neutralization bases is mineral alkali, and the mol ratio of described 4-chloro-o-phthalic acid, neutralization bases is 1:4-7; Described mineral alkali is preferably cesium carbonate, salt of wormwood.
5. the preparation method of 4-phenylacetylene benzoic anhydride according to claim 1, is characterized in that, described non-protonic solvent is one or more in tetrahydrofuran (THF), DMF, N,N-dimethylacetamide, toluene.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107001308A (en) * | 2014-12-30 | 2017-08-01 | 陶氏环球技术有限责任公司 | Method for producing 4 azido sulfonyl o phthalate anhydrides |
| CN116143134A (en) * | 2023-02-17 | 2023-05-23 | 江苏海格新材料有限公司 | Preparation method of silicon micropowder for integrated circuit packaging |
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| CN1544424A (en) * | 2003-11-27 | 2004-11-10 | 中国科学院长春应用化学研究所 | 4-phenylacetylene benzoic anhydride preparation method |
| CN1603317A (en) * | 2004-08-03 | 2005-04-06 | 上海市合成树脂研究所 | Process for preparation of 4-phenylacetylene phthalic anhydride |
| US20050215820A1 (en) * | 2004-03-25 | 2005-09-29 | Fuji Photo Film Co., Ltd. | Aryl ethynyl phthalic acid derivative and method for producing the same |
| WO2008120839A1 (en) * | 2007-03-30 | 2008-10-09 | Gyeongsang National University Industrial And Academic Collaboration Foundation | Novel organic semiconductor compound, and organic thin film transistor using the same |
| CN101550122A (en) * | 2008-04-01 | 2009-10-07 | 四川大学 | Method for preparing 4-phenylethynylphthalic anhydride by taking water as solvent |
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2013
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Patent Citations (6)
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| US20050215820A1 (en) * | 2004-03-25 | 2005-09-29 | Fuji Photo Film Co., Ltd. | Aryl ethynyl phthalic acid derivative and method for producing the same |
| CN1603317A (en) * | 2004-08-03 | 2005-04-06 | 上海市合成树脂研究所 | Process for preparation of 4-phenylacetylene phthalic anhydride |
| WO2008120839A1 (en) * | 2007-03-30 | 2008-10-09 | Gyeongsang National University Industrial And Academic Collaboration Foundation | Novel organic semiconductor compound, and organic thin film transistor using the same |
| CN101550122A (en) * | 2008-04-01 | 2009-10-07 | 四川大学 | Method for preparing 4-phenylethynylphthalic anhydride by taking water as solvent |
| CN101550121A (en) * | 2008-04-01 | 2009-10-07 | 四川大学 | Method for preparing 4-phenylacetylene phthalic anhydride from 4-phenylacetylene phthalic anhydride |
Non-Patent Citations (2)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107001308A (en) * | 2014-12-30 | 2017-08-01 | 陶氏环球技术有限责任公司 | Method for producing 4 azido sulfonyl o phthalate anhydrides |
| CN116143134A (en) * | 2023-02-17 | 2023-05-23 | 江苏海格新材料有限公司 | Preparation method of silicon micropowder for integrated circuit packaging |
| CN116143134B (en) * | 2023-02-17 | 2023-10-20 | 江苏海格新材料有限公司 | Preparation method of silicon micropowder for integrated circuit packaging |
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Application publication date: 20140319 |