CN1036065C - Method of preparation of bis (N-methylbenzene o-diformimine) ether - Google Patents
Method of preparation of bis (N-methylbenzene o-diformimine) ether Download PDFInfo
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- CN1036065C CN1036065C CN92108448A CN92108448A CN1036065C CN 1036065 C CN1036065 C CN 1036065C CN 92108448 A CN92108448 A CN 92108448A CN 92108448 A CN92108448 A CN 92108448A CN 1036065 C CN1036065 C CN 1036065C
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Abstract
The present invention relates to a method for preparing bis (N-methyl phthalimide) ether by heating N-methyl-4-nitryl phthalimide, which uses nitrite-carbonate of alkali or alkaline earth metals as a catalyst, the catalyst is heated and inversely flowed for 4 to 8 hours at the temperature of 162 to 168 DEG C, the bis (N-methyl phthalimide) ether is obtained by adding water by the steps of stirring, filtering, filtered cake washing and drying at the end of the reaction, the yield is from 68.5% to 75%, and the melting point is from 268 to 270 DEG C.
Description
The present invention relates to preparation two-method of (N-methyl phthalimide) ether, or rather, the present invention relates to the monomer that ANALYSIS OF MOLDABLE POLYIMIDES uses two-N-methyl phthalimide) preparation method of ether.
At prior art U.S.P.4, disclose in 757,149 a kind of heating N-methyl-4-nitro phthalimide preparation two-method of (N-methyl phthalimide) ether, its equation is as follows:
It adopts the carbonate of alkali or alkaline-earth metal to make catalyzer, as the composite catalyst of salt of wormwood or yellow soda ash and salt of wormwood, make reaction solvent with polar aprotic solvent such as dimethyl formamide, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone or N-Methyl pyrrolidone and toluene mixed solvent.Reaction mixture is in 160-165 ℃, and reflux 1.5 hours is cooled to 50 ℃, topples in the entry, is settled out product, after filtration, to obtain yield be 65% thick product for washing, drying.This invention was not reported quality product except that the yield of having reported thick product.The smart product yield of this technology obviously is lower than 65%, remains further to be improved yield and quality product.In addition, because product and solvent are toppled in the entry together, be settled out product, solvent recovering yield is not high.
The objective of the invention is to improve the preparation method of prior art, use the composite synergistic catalyzer, improve yield and the quality and the solvent recovering yield of product.
The present invention realizes like this, this heating N-methyl-4-nitro phthalimide prepares the method for two-(N-methyl phthalimide) ether, be characterized in that the nitrite-carbonate with alkali or alkaline-earth metal is the composite synergistic catalyzer, transmitting organic solvent with aprotic, polar is solvent, under normal pressure, heating reflux reaction 4-8 hour, when reacting to terminal, steam solvent, add that water stirs, filters, washing filter cake, drying obtain that yield is 68.5～75%, molten point is smart two-(N-methyl phthalimide) ether product of 268～270 ℃.
The nitrite of alkali of the present invention or alkaline-earth metal-carbonate composite synergistic catalyzer can be selected arbitrarily from the nitrous acid-carbonate of lithium, sodium, potassium, caesium, magnesium, calcium, strontium, barium, and wherein nitrite-the carbonate with sodium, potassium is good.
When the nitrite of alkali of the present invention or alkaline-earth metal-carbonate composite synergistic catalyzer was a Sodium Nitrite-salt of wormwood composite synergistic catalyzer, the mol ratio of salt of wormwood and Sodium Nitrite was 10～40%, is good with 20～35% wherein.
The mol ratio of Sodium Nitrite of the present invention-salt of wormwood composite synergistic catalyzer and N-methyl-4-nitro phthalimide is 0.2～0.3: 1, and wherein with 0.25～0.45: 1 is good.
Polar aprotic solvent of the present invention can be from N, N-N,N-DIMETHYLACETAMIDE, N-methyl pyrrole is slightly selected arbitrarily in the mixed solvent of alkane ketone, N, dinethylformamide, dimethyl sulfoxide (DMSO), hexamethylphosphoramide, tetramethylene sulfone and toluene or dimethylbenzene, serves as better with the mixed solvent of N, N-N,N-DIMETHYLACETAMIDE-dimethylbenzene.
The present invention is with N, when N-N,N-DIMETHYLACETAMIDE-dimethylbenzene is solvent, and the temperature of heating reflux reaction is 162-168 ℃.
The present invention compared with prior art has following advantage: one, correctly implement to make smart pair-(N-methyl phthalimide) ether according to method of the present invention, its yield is 68.5-75%, and fusing point is 268-270 ℃, has improved the yield and the quality of product.Two, because solvent recuperation is used, improved solvent recovering yield.
In order to implement the present invention better, as follows especially exemplified by most preferred embodiment.
Embodiment 1
206 gram (1 mole) exsiccant N-methyl-4-nitro phthalimides, the mixture of 20 gram (0.29 mole) Sodium Nitrites and 10 gram (0.072 mole) salt of wormwood, 500ml N,N-DIMETHYLACETAMIDE and 150ml dimethylbenzene, in 162-168 ℃ of reflux 4-8 hour, steaming solvent adds water stirring, cooling again, filters, washes, 100 ℃ of vacuum-drying gets 115 gram brown two-(N-methyl phthalimide) ether, yield is 75%, and fusing point is 26 8-270 ℃.
Embodiment 2
Except the Sodium Nitrite consumption is 50 grams (0.72 mole), the salt of wormwood consumption is 10 grams (0.072 mole), and yield is beyond 65%, and other reaction conditionss and result are with embodiment 1.
Embodiment 3
Except the Sodium Nitrite consumption is 12.4 grams (0.18 mole), the salt of wormwood consumption is 10 grams (0.072 mole), and yield is beyond 70%, and other reaction conditionss and result are with embodiment 1.
The comparative example 1
The mixture of 206 gram (1 mole) exsiccant N-methyl-4-nitro phthalimides, 30 gram (0.43 mole) Sodium Nitrites and 765ml N,N-DIMETHYLACETAMIDE, in 162-168 ℃ of reflux 4-8 hour, cooling, filtration, washing, dry 65.5 gram brown are two-(N-methyl phthalimide) ether, yield is 39%, and fusing point is 264-269 ℃.
Contrast real Duo example 2
Except that doing the catalyzer with 60 gram (0.43 mole) salt of wormwood, other prescription operations are with implementing 1, and the result is two-(N-methyl phthalimide) ether yield 55%, fusing point is 264-269 ℃.
The comparative example 3
10.30 gram (0.05 mole) N-methyl-4 nitro phthalimide, 2.51 gram (0.0283 mole) yellow soda ash, 0.17 gram (0.0013 mole) salt of wormwood, the slurry mix that 100mlN-methyl pyrrole omits alkane ketone and 25ml toluene refluxed 1.5 hours in 160-165 ℃, postcooling to 50 ℃ continues, mixture pours in the 300ml water, filtering-depositing, use 500ml water and 500ml washed with isopropyl alcohol in succession, vacuum-drying then (100 ℃) is spent the night, obtain 4,4 of 65% yield '-two-(N-methyl phthalimide) ether.
Claims (10)
1. heating N-methyl-4-nitro phthalimide prepares the method for two-(N-methyl phthalimide) ether, transmitting organic solvent with aprotic, polar is solvent, it is characterized in that with alkali-metal nitrite-carbonate be the composite synergistic catalyzer, under normal pressure, heating reflux reaction 4～8 hours, when reacting to terminal, steam solvent, add water and stir, filter, wash filter cake, the dry product that gets.
2. preparation according to claim 1 is two-method of (N-methyl phthalimide) ether, it is characterized in that described alkali-metal nitrite-carbonate composite synergistic catalyzer selects arbitrarily from the nitrite-carbonate of lithium, sodium, potassium, caesium.
3. preparation according to claim 2 is two-method of (N-methyl phthalimide) ether, it is characterized in that described alkali-metal nitrite-carbonate composite synergistic catalyzer is the nitrite-carbonate of sodium, potassium.
4. preparation according to claim 3 is two-method of (N-methyl phthalimide) ether, when it is characterized in that described alkali-metal nitrite-carbonate composite synergistic catalyzer is a Sodium Nitrite-salt of wormwood composite synergistic catalyzer, the mol ratio of salt of wormwood and Sodium Nitrite is 10～40%.
5. preparation according to claim 4 is two-method of (N-methyl phthalimide) ether, and when it is characterized in that being the composite synergistic catalyzer with Sodium Nitrite-salt of wormwood, the mol ratio of salt of wormwood and Sodium Nitrite is 20～35%.
6. preparation according to claim 4 is two-method of (N-methyl phthalimide) ether, it is characterized in that the mol ratio of Sodium Nitrite-salt of wormwood composite synergistic catalyzer and N-methyl-4-nitro phthalimide is 0.2～0.8: 1.
7. preparation according to claim 6 is two-method of (N-methyl phthalimide) ether, it is characterized in that Sodium Nitrite-salt of wormwood is that the mol ratio of composite synergistic catalyzer and N-methyl-4-nitro phthalimide is 0.25～0.45: 1.
8. preparation according to claim 1 is two-method of (N-methyl phthalimide) ether, it is characterized in that aprotic, polar transmission organic solvent is from N, N-N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, N select arbitrarily in the mixed solvent of dinethylformamide, dimethyl sulfoxide (DMSO), hexamethylphosphoramide, tetramethylene sulfone and toluene or dimethylbenzene.
9. preparation according to claim 8 is two-method of (N-methyl phthalimide) ether, it is characterized in that it is the mixed solvent of N,N-dimethylacetamide-dimethylbenzene that aprotic, polar is transmitted organic solvent.
10. preparation according to claim 9 is two-method of (N-methyl phthalimide) ether, and when it is characterized in that being solvent with N,N-dimethylacetamide-dimethylbenzene, the temperature of heating reflux reaction is 162～168 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92108448A CN1036065C (en) | 1992-06-06 | 1992-06-06 | Method of preparation of bis (N-methylbenzene o-diformimine) ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92108448A CN1036065C (en) | 1992-06-06 | 1992-06-06 | Method of preparation of bis (N-methylbenzene o-diformimine) ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1079734A CN1079734A (en) | 1993-12-22 |
| CN1036065C true CN1036065C (en) | 1997-10-08 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN92108448A Expired - Lifetime CN1036065C (en) | 1992-06-06 | 1992-06-06 | Method of preparation of bis (N-methylbenzene o-diformimine) ether |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101139315B (en) * | 2007-10-09 | 2010-04-07 | 上海市合成树脂研究所 | Method for preparing di(N-methyl phthalimide) ether |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101550102B (en) * | 2009-05-07 | 2010-12-01 | 西北农林科技大学 | Method for preparing di-(N-methyl phthalimide) ether |
| CN102199118B (en) * | 2011-03-16 | 2013-09-25 | 黑龙江省科学院石油化学研究院 | Oxo-bi(N-Methylphthalimide) synthesis method |
| CN108117505A (en) * | 2016-11-27 | 2018-06-05 | 杜庶铭 | A kind of preparation method for synthesizing diphenyl ether imidodicarbonic diamide |
| CN108250168A (en) * | 2017-12-25 | 2018-07-06 | 上海固创化工新材料有限公司 | A kind of preparation method of diphenyl ether tetraformic dianhydride |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4757149A (en) * | 1986-12-31 | 1988-07-12 | General Electric Company | Synthesis of bis(N-substituted phthalimide)ethers |
| US4780544A (en) * | 1986-07-02 | 1988-10-25 | General Electric Company | Method for making oxybisphthalimides |
| US4933469A (en) * | 1988-12-16 | 1990-06-12 | General Electric Company | Method for preparing oxybisphthalimides |
-
1992
- 1992-06-06 CN CN92108448A patent/CN1036065C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4780544A (en) * | 1986-07-02 | 1988-10-25 | General Electric Company | Method for making oxybisphthalimides |
| US4757149A (en) * | 1986-12-31 | 1988-07-12 | General Electric Company | Synthesis of bis(N-substituted phthalimide)ethers |
| US4933469A (en) * | 1988-12-16 | 1990-06-12 | General Electric Company | Method for preparing oxybisphthalimides |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101139315B (en) * | 2007-10-09 | 2010-04-07 | 上海市合成树脂研究所 | Method for preparing di(N-methyl phthalimide) ether |
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| CN1079734A (en) | 1993-12-22 |
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Expiration termination date: 20120606 Granted publication date: 19971008 |