CN1603317A - Process for preparation of 4-phenylacetylene phthalic anhydride - Google Patents
Process for preparation of 4-phenylacetylene phthalic anhydride Download PDFInfo
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- CN1603317A CN1603317A CN 200410053378 CN200410053378A CN1603317A CN 1603317 A CN1603317 A CN 1603317A CN 200410053378 CN200410053378 CN 200410053378 CN 200410053378 A CN200410053378 A CN 200410053378A CN 1603317 A CN1603317 A CN 1603317A
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- phenylacetylene
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Abstract
This invention relates to a preparation method of 4-phenylacetylene benzene anhydride. The procedures are that (1) 4-bromobenzene anhydride reacts with acetylene for 19~21 hours in spasmolytol solvent with cuprous iodide catalyst and dichlor double triphenyl phosphor and palladium, the reaction temperature is 75~850C. (2) Spasmolytol is separated and solid precipitation is mixed with acetic anhydride, the mole ratio of acetic anhydride and 4-bromobenzene anhydride is 1.5~6.0:1. Acetic acid and acetic anhydride are evaporated by heating and reflowing 30 minutes, the 4-phenylacetylene benzene anhydrite is got after recrystal of isochoric toluene and normal hexane component solvent, melting point is 151.6~152.30C, gain ratio is 90~91%.
Description
Technical field
The present invention relates to the preparation method of 4-phenylacetylene phthalic anhydride, relate to method or rather by 4-bromobenzene acid anhydride and phenylacetylene prepared in reaction 4-phenylacetylene phthalic anhydride.
Background technology
4-phenylacetylene phthalic anhydride and derivative thereof are with the necessary cementability of polyimide, thermotolerance and physical strength, its utility value is high, it is the raw materials of aerospace with the matrix material parent resin, the matrix material made of polyimide precursor resins by its preparation, higher more than 30 ℃ than epoxy resin composite material use temperature, be the desired configuration material of subsonic aircraft.Prior art spy opens flat JP11-180970,6jul.1999 by phenylacetylene or its derivative and bromo phthalic anhydride, reaction in the presence of cuprous iodide and divalence or zeroth order palladium complex, then use the alkaline solution hydrolysis, with excessive equivalent aqueous hydrochloric acid precipitation product, filtration drying obtains 4-phenylacetylene phthalic anhydride with chemical closed loopization or hot closed loopization, fusing point is 151.8～152.8 ℃, the 4-phenylacetylene phthalic anhydride of omnidistance yield 92.3～92.5%.
In the prior art in order to prepare highly purified 4-phenylacetylene phthalic anhydride, the reactor product of 4-bromobenzene acid anhydride and phenylacetylene is become 4-phenylacetylene phosphorus benzene bis-acid potassium with the aqueous hydrolysis of sodium hydroxide, and then become 4-phenylacetylene phthalic anhydride with aceticanhydride chemistry closed loop, this basic hydrolysis, hydrochloric acid water precipitation and organic acid carry out the method for chemical closed loopization, step is many, and separate complex is need be improved on industrial production.
Summary of the invention
Preparation method of the present invention only in the triethylamine solvent, and does not have 4-bromobenzene acid anhydride and phenylacetylene under the existence of benzene, uses dichlorobis triphenylphosphine palladium PdCl
2[P (C
6H
5)
3]
2Cuprous iodide and triphenylphosphine are made catalyzer, the solid precipitation that back flow reaction makes directly mixes with aceticanhydride, reflux makes that issuable 4-phenylacetylene phthalic acid all changes into 4-phenylacetylene phthalic anhydride in the reaction, has got rid of in the background technology solid precipitation and has used earlier the aqueous sodium hydroxide solution hydrolysis, precipitate this step with excessive equivalent aqueous hydrochloric acid again, simplified production technique, separated simply, and suitable suitability for industrialized production.
The preparation method's of 4-phenylacetylene phthalic anhydride of the present invention step comprises:
(1) under nitrogen atmosphere, at the catalyzer cuprous iodide, divalence palladium complex and triphenylphosphine exist down, with 4-bromobenzene acid anhydride and phenylacetylene back flow reaction 19～21 hours in organic bases triethylamine solvent, temperature of reaction is 75～85 ℃, and the mol ratio of phenylacetylene and 4-bromobenzene acid anhydride is 1.06～1.10: 1.
(2) separate triethylamine, suction filtration, solid precipitation mixed stirring, reflux 20～40 minutes with aceticanhydride, made that issuable 4-phenylacetylene phthalic acid all changes into 4-phenylacetylene phthalic anhydride in the reaction.Add equal-volume toluene then and normal hexane mixed solvent recrystallization makes 4-phenylacetylene phthalic anhydride, fusing point: 151.6～152.3 ℃, yield 90～91%.
Among the preparation method of the present invention, the add-on of catalyzer is 0.8～2.4 weight % of 4-bromobenzene acid anhydride add-on, and catalyzer divalence palladium complex is a dichlorobis triphenylphosphine palladium, and its molecular formula is: PdCl
2[P (C
6H
5)
3]
2, dichloro bi triphenyl phosphorus cooperates the mol ratio of palladium and cuprous iodide to be: 1: 3～4.8, and the mol ratio of triphenyl phosphorus and cuprous iodide is 1.6～2.0: 1.
Among the preparation method of the present invention, the mol ratio of used triethylamine solvent and raw material 4-bromobenzene acid anhydride is 50～70: 1.
The amount of adding aceticanhydride and the mol ratio of raw material 4-bromobenzene acid anhydride are among the preparation method of the present invention: 1.5～6.0: 1.
The present inventor by analysis, think in the process of 4-bromobenzene acid anhydride and phenylacetylene prepared in reaction 4-phenylacetylene phthalic anhydride, under the sour water condition, partly acid anhydride may hydrolysis, if but add organic acid such as acetic acid, aceticanhydride carries out chemical ring-closure reaction and just can make highly purified 4-phenylacetylene phthalic anhydride.
In the prior art, when making solvent with organic bases such as triethylamine, add benzene or toluene etc. simultaneously, purpose is to remove the contained moisture content of triethylamine.The present invention does not use these solvents, and the triethylamine of use is water content not on substantially, and it obtains through pre-treatment, as distillation or molecular sieve dehydration etc.
The present invention is applicable to that 4-bromobenzene acid anhydride and derivative thereof and phenylacetylene and derivatives reaction thereof prepare phenylacetylene phthalic anhydride derivative.
The present invention except that adding the organic bases triethylamine, no longer adds other dewatering agent in reactive system, got rid of NaOH aqueous hydrolysis operation of the prior art, and the manufacturing operation process is simple.The inventive method can prepare high quality, high yield product 4-phenylacetylene phthalic anhydride, and its yield is 90～91%, fusing point is 151.6～152.3 ℃
Embodiment
In order to implement the present invention better, especially exemplified by following embodiment, but embodiment is not a limitation of the present invention.
Embodiment 1
Be equipped with the 500ml flask of nitrogen ingress pipe, spherical condensation tube, drying tube, dropping funnel and magnetic stirring apparatus, vacuumize earlier, with nitrogen replacement air three times, and always under nitrogen atmosphere, in there-necked flask, add 27.24g (0.12 mole) 4-bromobenzene acid anhydride, (0.1g 0.52 mmole) cuprous iodide, (0.1g 0.15 mmole) dichlorobis triphenylphosphine palladium, (0.24g 0.92 mmole) triphenylphosphine and 380ml exsiccant triethylamine, stirring, heating, at 85 ℃ down with dripping 13.5g (0.13 mole) phenylacetylene that is dissolved in the 10ml triethylamine in 1 hour.After dripping, continued heated and stirred 20 hours, decantation goes out triethylamine, and suction filtration, merges all solids, aceticanhydride mixes for solid and 70ml (0.74 mole), stirring, reflux 30 minutes, boil off acetic acid, aceticanhydride, add 70ml toluene then and equal-volume normal hexane recrystallization gets 4-phenylacetylene phthalic anhydride, dry weight 26.8 grams, productive rate 90.1%, 151.8 ℃ of fusing points.
1HNMR (CDCl
3, 300Hz), δ: 7.39 (1H), 7.41 (2H), 7.57 (dd, J=8.4Hz, 2H).
13CNMR (CDCl
3, 300HZ), δ: 86.9,96.0,121.5,125.6,128.1,128.6,129.5,129.7,131.7,131.9,138.6,162.1.IR (KBr) v:2210.4 (vs, C ≡ C), 1844.6[vs, (CO)
2O], 1775.0 (vs, CO) cm
-1. ultimate analysis C
16H
8O
3Calculated value: C, 77.42; H, 3.25. measured value: C, 77.20; H, 3.39.
Embodiment 2
Remove and add phenylacetylene 13.7 grams (0.132 mole), 80 ℃ of reactions 19 hours, and adding cuprous iodide 0.138 gram (0.72 mmole), outside the aceticanhydride 45ml (0.48 mole), all the other prescriptions and operation steps and embodiment 1 are just the same, the result removes 4-phenylacetylene phthalic anhydride yield 90%, 151.6 ℃ of fusing points, and other analytical results is the same with embodiment 1.
Embodiment 3
Remove and add phenylacetylene 13.19 grams (0.127 mole), 85 ℃ of reactions 20 hours, and adding cuprous iodide 0.087 gram (0.45 mmole), outside the aceticanhydride 18ml (0.19 mole), other operation is fully the same with embodiment 1 with prescription, the yield that the result removes 4-phenylacetylene phthalic anhydride is 91%, and outside 152 ℃ of the fusing points, other analytical results is the same with embodiment 1.
Claims (4)
1, a kind of preparation method of 4-phenylacetylene phthalic anhydride is characterized in that step comprises:
(1) under nitrogen atmosphere, in the presence of catalyzer cuprous iodide, divalence palladium complex and triphenylphosphine, with 4-bromobenzene acid anhydride and phenylacetylene back flow reaction 19～21 hours in organic bases triethylamine solvent, temperature of reaction is 75～85 ℃, and the mol ratio of phenylacetylene and 4-bromobenzene acid anhydride is 1.06～1.10: 1;
(2) separate triethylamine, suction filtration, solid precipitation mixes with aceticanhydride, stirring, reflux 20～40 minutes, boils off acetic acid and aceticanhydride, add equal-volume toluene then and normal hexane mixed solvent recrystallization makes 4-phenylacetylene phthalic anhydride, fusing point: 151.6～152.3 ℃.
2, preparation method according to claim 1 is characterized in that: the add-on of catalyzer is 0.8～2.4 weight % of 4-bromobenzene acid anhydride add-on, and described catalyzer divalence palladium complex is a dichlorobis triphenylphosphine palladium, and its molecular formula is PdCl
2[P (C
6H
5)
3]
2, the mol ratio of dichlorobis triphenylphosphine palladium and cuprous iodide is 1: 3～4.8, the mol ratio of triphenylphosphine and cuprous iodide is 1.6～2.0: 1.
3, preparation method according to claim 1 is characterized in that: the mol ratio of used triethylamine solvent and 4-bromobenzene acid anhydride is 50～70: 1.
4, preparation method according to claim 1 is characterized in that: adding the amount of aceticanhydride and the mol ratio of 4-bromobenzene acid anhydride is 1.5～6.0: 1.
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|---|---|---|---|
| CNB2004100533784A CN1312145C (en) | 2004-08-03 | 2004-08-03 | Process for preparation of 4-phenylacetylene phthalic anhydride |
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| CNB2004100533784A CN1312145C (en) | 2004-08-03 | 2004-08-03 | Process for preparation of 4-phenylacetylene phthalic anhydride |
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| CN1312145C CN1312145C (en) | 2007-04-25 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102099349A (en) * | 2008-07-31 | 2011-06-15 | 玛奈克股份有限公司 | Process for producing phthalic anhydride derivative |
| CN101550122B (en) * | 2008-04-01 | 2012-01-04 | 四川大学 | Method for preparing 4-phenylethynylphthalic anhydride by taking water as solvent |
| CN103641806A (en) * | 2013-11-19 | 2014-03-19 | 常州市天华制药有限公司 | Preparation method of 4-phenylethynylphthalic anhydride |
| JP2015514730A (en) * | 2012-04-20 | 2015-05-21 | ネクサム ケミカル エイビー | Method for producing (ethyne-1,2-diyl) bis (isobenzofuran-1,3-dione) |
| CN113024496A (en) * | 2021-03-24 | 2021-06-25 | 天津市泰合利华材料科技有限公司 | Method for preparing 4-p-trifluoromethyl phenyl alkynyl phthalic anhydride |
| CN113603662A (en) * | 2021-06-15 | 2021-11-05 | 陕西泰合利华工业有限公司 | Method for preparing 4- (1-ketone-2-propargyl phenyl propane) phthalic anhydride |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5567800A (en) * | 1994-10-28 | 1996-10-22 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Imide oligomers endcapped with phenylethynyl phthalic anhydrides and polymers therefrom |
| CN1324794A (en) * | 2000-05-19 | 2001-12-05 | 黑龙江省石油化学研究院 | Prepn. of diphenyl ether tetraformic dianhydride |
-
2004
- 2004-08-03 CN CNB2004100533784A patent/CN1312145C/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101550122B (en) * | 2008-04-01 | 2012-01-04 | 四川大学 | Method for preparing 4-phenylethynylphthalic anhydride by taking water as solvent |
| CN102099349A (en) * | 2008-07-31 | 2011-06-15 | 玛奈克股份有限公司 | Process for producing phthalic anhydride derivative |
| JP2015514730A (en) * | 2012-04-20 | 2015-05-21 | ネクサム ケミカル エイビー | Method for producing (ethyne-1,2-diyl) bis (isobenzofuran-1,3-dione) |
| CN103641806A (en) * | 2013-11-19 | 2014-03-19 | 常州市天华制药有限公司 | Preparation method of 4-phenylethynylphthalic anhydride |
| CN113024496A (en) * | 2021-03-24 | 2021-06-25 | 天津市泰合利华材料科技有限公司 | Method for preparing 4-p-trifluoromethyl phenyl alkynyl phthalic anhydride |
| CN113603662A (en) * | 2021-06-15 | 2021-11-05 | 陕西泰合利华工业有限公司 | Method for preparing 4- (1-ketone-2-propargyl phenyl propane) phthalic anhydride |
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| Publication number | Publication date |
|---|---|
| CN1312145C (en) | 2007-04-25 |
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Effective date of registration: 20210128 Address after: No. 1251, Zhulu West Road, Xujing Town, Qingpu District, Shanghai, 201702 Patentee after: SHANGHAI PLASTICS RESEARCH INSTITUTE Co.,Ltd. Address before: 200235 No. 36, Shanghai, Caobao Road Patentee before: SHANGHAI RESEARCH INSTITUTE OF SYNTHETIC RESINS Co.,Ltd. |
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