CN102199118B - Oxo-bi(N-Methylphthalimide) synthesis method - Google Patents
Oxo-bi(N-Methylphthalimide) synthesis method Download PDFInfo
- Publication number
- CN102199118B CN102199118B CN2011100632065A CN201110063206A CN102199118B CN 102199118 B CN102199118 B CN 102199118B CN 2011100632065 A CN2011100632065 A CN 2011100632065A CN 201110063206 A CN201110063206 A CN 201110063206A CN 102199118 B CN102199118 B CN 102199118B
- Authority
- CN
- China
- Prior art keywords
- methyl
- oxo
- alkyl guanidine
- phthalimides
- halogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Indole Compounds (AREA)
Abstract
An oxo-bi(N-Methylphthalimide) synthesis method, which solves problems existing in prior art, such as long reaction time, incomplete reaction and low yield. The method comprises the following steps: adding N-methyl-4-nitrophthalimide, sodium carbonate, potash, N- methyl pyrrolidone, toluene and alkyl guanidine haloid into a three-neck flask; then heating for refluxing; cooling to room temperatureand pouring into water; filtering solid; washing and drying to finish. The method of the invention has moderate reaction conditions without requiring a waterless condition or an inert gas protection,a short reaction time, a complete reaction, and a simple post treatment. The product, which is easy to separate, has a yield higher than 85%, a melting point of 269-271 DEG C, and a high purity. In addition, the method with a reduced production costs is environment-friendly and suitable for large scale production.
Description
Technical field
The present invention relates to the synthetic method of a kind of oxo-two (N-methyl phthalimides).
Background technology
Oxo-two (N-methyl phthalimide) (OBI) be synthesis of polyimides important monomer 3,3 ', 4,4 '-intermediate of diphenyl ether tetraformic dianhydride (ODPA).By the synthetic polyimide of ODPA because the introducing of flexible ehter bond except having high heat resistance, outside favorable mechanical performance and the dielectric properties, also has meltability.ODPA is be used for the synthetic ether acid anhydride class monomer consumption maximum of polyimide at present a kind of.
The method of tradition synthesizing oxo-two (N-methyl phthalimides) is in the presence of nitrite, carbonate or Potassium monofluoride, the Sodium Fluoride at inorganic base metal, alkaline-earth metal, add phase-transfer catalyst such as tetraethylammonium bromide, Tetrabutyl amonium bromide, tetrabenzyl brometo de amonio, Tetraphenylphosphonium Bromide etc., under polar aprotic solvent, carry out self-condensation reaction.Though this operational path is comparatively ripe, but the solubleness in non-proton property polar solvent under heated condition such as used catalyzer such as Sodium Nitrite is less in the traditional technology, cause reaction times prolongation and reaction not exclusively, product yield is lower, is generally 65%～75%.
Summary of the invention
The present invention seeks to for the method that solves existing synthesizing oxo-two (N-methyl phthalimides) exists long reaction time, reaction not exclusively and the low problem of product yield, and the method for a kind of synthesizing oxo-two (N-methyl phthalimides) is provided.
The method of synthesizing oxo-two (N-methyl phthalimide) is implemented according to the following steps: to having agitator, condenser, add 80～90gN-methyl-4-nitro phthalic imidine in the there-necked flask of thermometer, 20～25g yellow soda ash, 8～12g salt of wormwood, 200～500mlN-methyl-2-pyrrolidone, 30～100ml toluene and 0.1～1g alkyl guanidine halogen, then at 150～190 ℃ of following reflux 3～7h, pour in the water of 500～2000ml after being cooled to room temperature, filter out the brown solid, after washing and drying, namely get oxo-two (N-methyl phthalimides); Wherein the alkyl guanidine halogen is five alkyl guanidine halogens or six alkyl guanidine halogens.
Reaction conditions among the present invention is relatively gentleer, does not need anhydrous condition or protection of inert gas, and is short with the reaction time, react completely, product separates easily, and product yield is up to more than 85%, fusing point is 269～271 ℃, and post-reaction treatment is simple, product purity is high, can reach more than 99%; The method of synthesizing oxo of the present invention-two (N-methyl phthalimide), because the product yield height, the therefore less relatively discharging of the three wastes, free from environmental pollution, also reduced production cost simultaneously, be applicable to scale operation.
Embodiment
Embodiment one: the method for present embodiment synthesizing oxo-two (N-methyl phthalimide) is implemented according to the following steps: to having agitator, condenser, add 80～90gN-methyl-4-nitro phthalic imidine in the there-necked flask of thermometer, 20～25g yellow soda ash, 8～12g salt of wormwood, 200～500mlN-methyl-2-pyrrolidone, 30～100ml toluene and 0.1～1g alkyl guanidine halogen, then at 150～190 ℃ of following reflux 3～7h, pour in the water of 500～2000ml after being cooled to room temperature, filter out the brown solid, after washing and drying, namely get oxo-two (N-methyl phthalimides); Wherein the alkyl guanidine halogen is five alkyl guanidine halogens or six alkyl guanidine halogens.
Yellow soda ash and salt of wormwood belong to alkaline carbonate in the present embodiment, use as catalyzer; The alkyl guanidine halogen also uses as catalyzer; N-Methyl pyrrolidone belongs to polar aprotic solvent.
What carry out in the present embodiment is self-condensation reaction.
Embodiment two: not being both in the there-necked flask that has agitator, condenser, thermometer of present embodiment and embodiment one adds 80gN-methyl-4-nitro phthalic imidine, 20g yellow soda ash, 8g salt of wormwood, 200mlN-methyl-2-pyrrolidone, 30ml toluene and 0.1g alkyl guanidine halogen.Other step and parameter are identical with embodiment one.
Embodiment three: not being both in the there-necked flask that has agitator, condenser, thermometer of present embodiment and embodiment one adds 890gN-methyl-4-nitro phthalic imidine, 25g yellow soda ash, 12g salt of wormwood, 500mlN-methyl-2-pyrrolidone, 100ml toluene and 1g alkyl guanidine halogen.Other step and parameter are identical with embodiment one.
Embodiment four: not being both in the there-necked flask that has agitator, condenser, thermometer of present embodiment and embodiment one adds 82～88gN-methyl-4-nitro phthalic imidine, 21～24g yellow soda ash, 9～11g salt of wormwood, 300～400mlN-methyl-2-pyrrolidone, 40～80ml toluene and 0.3～0.8g alkyl guanidine halogen.Other step and parameter are identical with embodiment one.
Embodiment five: not being both in the there-necked flask that has agitator, condenser, thermometer of present embodiment and embodiment one adds 85gN-methyl-4-nitro phthalic imidine, 23g yellow soda ash, 10g salt of wormwood, 350mlN-methyl-2-pyrrolidone, 60ml toluene and 0.5g alkyl guanidine halogen.Other step and parameter are identical with embodiment one.
Embodiment six: not being both at 150 ℃ of following reflux 7h of one of present embodiment and embodiment one to five, pour in the water of 500ml after being cooled to room temperature.Other step and parameter are identical with one of embodiment one to five.
Embodiment seven: not being both at 190 ℃ of following reflux 3h of one of present embodiment and embodiment one to five, pour in the water of 2000ml after being cooled to room temperature.Other step and parameter are identical with one of embodiment one to five.
Embodiment eight: not being both at 160～180 ℃ of following reflux 4～6h of one of present embodiment and embodiment one to five, pour in the water of 800～1500ml after being cooled to room temperature.Other step and parameter are identical with one of embodiment one to five.
Embodiment nine: not being both at 170 ℃ of following reflux 5h of one of present embodiment and embodiment one to five, pour in the water of 1000ml after being cooled to room temperature.Other step and parameter are identical with one of embodiment one to five.
Embodiment ten: the method for present embodiment synthesizing oxo-two (N-methyl phthalimide) is implemented according to the following steps: to having agitator, condenser, add 82.4gN-methyl-4-nitro phthalic imidine in the there-necked flask of thermometer, 21.2g yellow soda ash, 10g salt of wormwood 250mlN-methyl-2-pyrrolidone, 50ml toluene and 0.36g alkyl guanidine halogen, then at 160 ℃ of following reflux 5h, pour in the water of 500ml after being cooled to room temperature, filter out the brown solid, after washing and drying, namely get oxo-two (N-methyl phthalimides); Wherein the alkyl guanidine halogen is six alkyl guanidine halogens.
Present embodiment gained oxo-two (N-methyl phthalimide) is 58.3g, yield 86.76%, and surveying its fusing point is 269.4～269.9 ℃.
Embodiment 11: the method for present embodiment synthesizing oxo-two (N-methyl phthalimide) is implemented according to the following steps: to having agitator, condenser, add 84gN-methyl-4-nitro phthalic imidine in the there-necked flask of thermometer, 22g yellow soda ash, 12g salt of wormwood, the 300mlN-methyl-2-pyrrolidone, 60ml toluene and 0.5g alkyl guanidine halogen, then at 180 ℃ of following reflux 4.5h, pour in the water of 600ml after being cooled to room temperature, filter out the brown solid, after washing and drying, namely get oxo-two (N-methyl phthalimides); Wherein the alkyl guanidine halogen is five alkyl guanidine halogens.
Present embodiment gained oxo-two (N-methyl phthalimide) is 58.6g, and yield reaches 85.5%, and surveying its fusing point is 269.8～271 ℃.
Claims (5)
1. the method for synthesizing oxo-two (N-methyl phthalimides), the method that it is characterized in that synthesizing oxo-two (N-methyl phthalimides) is implemented according to the following steps: to having agitator, condenser, add 80～90gN-methyl-4-nitro phthalic imidine in the there-necked flask of thermometer, 20～25g yellow soda ash, 8～12g salt of wormwood, 200～500mlN-methyl-2-pyrrolidone, 30～100ml toluene and 0.1～1g alkyl guanidine halogen, reflux 3～7h then, pour in the water of 500～2000ml after being cooled to room temperature, filter out the brown solid, after washing and drying, namely get oxo-two (N-methyl phthalimides); Wherein the alkyl guanidine halogen is five alkyl guanidine halogens or six alkyl guanidine halogens.
2. the method for a kind of synthesizing oxo according to claim 1-two (N-methyl phthalimides) is characterized in that adding 82～88gN-methyl-4-nitro phthalic imidine, 21～24g yellow soda ash, 9～11g salt of wormwood, 300～400mlN-methyl-2-pyrrolidone, 40～80ml toluene and 0.3～0.8g alkyl guanidine halogen in the there-necked flask that has agitator, condenser, thermometer.
3. the method for a kind of synthesizing oxo according to claim 1-two (N-methyl phthalimides) is characterized in that adding 85gN-methyl-4-nitro phthalic imidine, 23g yellow soda ash, 10g salt of wormwood, 350mlN-methyl-2-pyrrolidone, 60ml toluene and 0.5g alkyl guanidine halogen in the there-necked flask that has agitator, condenser, thermometer.
4. according to the method for claim 1,2 or 3 described a kind of synthesizing oxos-two (N-methyl phthalimides), it is characterized in that reflux 4～6h, pour in the water of 800～1500ml after being cooled to room temperature.
5. the method for a kind of synthesizing oxo according to claim 4-two (N-methyl phthalimides) is characterized in that reflux 5h, pours in the water of 1000ml after being cooled to room temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100632065A CN102199118B (en) | 2011-03-16 | 2011-03-16 | Oxo-bi(N-Methylphthalimide) synthesis method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100632065A CN102199118B (en) | 2011-03-16 | 2011-03-16 | Oxo-bi(N-Methylphthalimide) synthesis method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102199118A CN102199118A (en) | 2011-09-28 |
| CN102199118B true CN102199118B (en) | 2013-09-25 |
Family
ID=44660139
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100632065A Expired - Fee Related CN102199118B (en) | 2011-03-16 | 2011-03-16 | Oxo-bi(N-Methylphthalimide) synthesis method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102199118B (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3992406A (en) * | 1976-04-14 | 1976-11-16 | General Electric Company | Preparation of aromatic bisimides |
| US4017511A (en) * | 1976-03-24 | 1977-04-12 | General Electric Company | Preparation of aromatic bisimides |
| US4054600A (en) * | 1975-06-27 | 1977-10-18 | General Electric Company | Method for making aromatic bis(ether dicarboxylic acid)s |
| US4933469A (en) * | 1988-12-16 | 1990-06-12 | General Electric Company | Method for preparing oxybisphthalimides |
| CN1079734A (en) * | 1992-06-06 | 1993-12-22 | 上海市合成树脂研究所 | The method for preparing two-(N-methyl phthalimide) ether |
| US6028203A (en) * | 1998-12-14 | 2000-02-22 | General Electric Company | Phase transfer catalyzed method for prepared oxybisphthalic compounds |
| CN1958583A (en) * | 2006-11-21 | 2007-05-09 | 郁伟新 | Method for preparing double (N-methyl phthalimide) oxide |
| CN101007782A (en) * | 2007-01-26 | 2007-08-01 | 上海应用技术学院 | Bi(N-methylphthalic imidine) ester preparation method |
| CN101139315A (en) * | 2007-10-09 | 2008-03-12 | 上海市合成树脂研究所 | Method for preparing di(N-methyl phthalimide) ether |
| CN101550102A (en) * | 2009-05-07 | 2009-10-07 | 西北农林科技大学 | Method for preparing di-(N-methyl phthalimide) ether |
| CN101696163A (en) * | 2009-10-28 | 2010-04-21 | 石家庄海力精化有限责任公司 | Method for preparing diphenyl ether tetraformic acid |
-
2011
- 2011-03-16 CN CN2011100632065A patent/CN102199118B/en not_active Expired - Fee Related
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4054600A (en) * | 1975-06-27 | 1977-10-18 | General Electric Company | Method for making aromatic bis(ether dicarboxylic acid)s |
| US4017511A (en) * | 1976-03-24 | 1977-04-12 | General Electric Company | Preparation of aromatic bisimides |
| US3992406A (en) * | 1976-04-14 | 1976-11-16 | General Electric Company | Preparation of aromatic bisimides |
| US4933469A (en) * | 1988-12-16 | 1990-06-12 | General Electric Company | Method for preparing oxybisphthalimides |
| CN1079734A (en) * | 1992-06-06 | 1993-12-22 | 上海市合成树脂研究所 | The method for preparing two-(N-methyl phthalimide) ether |
| US6028203A (en) * | 1998-12-14 | 2000-02-22 | General Electric Company | Phase transfer catalyzed method for prepared oxybisphthalic compounds |
| CN1958583A (en) * | 2006-11-21 | 2007-05-09 | 郁伟新 | Method for preparing double (N-methyl phthalimide) oxide |
| CN101007782A (en) * | 2007-01-26 | 2007-08-01 | 上海应用技术学院 | Bi(N-methylphthalic imidine) ester preparation method |
| CN101139315A (en) * | 2007-10-09 | 2008-03-12 | 上海市合成树脂研究所 | Method for preparing di(N-methyl phthalimide) ether |
| CN101550102A (en) * | 2009-05-07 | 2009-10-07 | 西北农林科技大学 | Method for preparing di-(N-methyl phthalimide) ether |
| CN101696163A (en) * | 2009-10-28 | 2010-04-21 | 石家庄海力精化有限责任公司 | Method for preparing diphenyl ether tetraformic acid |
Non-Patent Citations (5)
| Title |
|---|
| Markezich, R. L.;Zamek, O. S..Reactions of fluoride and nitrite ions with 4-nitrophthalimides.《Journal of Organic Chemistry》.1977, * |
| Zhang, Zhi Qiang;Tian, Zheng Hua.Nucleophilic aromatic substitution of nitrobenzenes with nitrite ion.《Chinese Chemical Letters》.1997, * |
| Zhang, Zhiqiang;Liu, Shumei;Tian, Zhenghua.Investigation on the new synthetic reactions and mechanisms of substituted diphenyl ethers.《Chinese Chemical Letters》.1991, * |
| 张志强,田正华.二苯醚系高分子单体的新合成路线.《化学通报》.1996, * |
| 田正华,张志强.取代二苯醚的新合成反应研究.《化学通报》.1989, * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102199118A (en) | 2011-09-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105037383A (en) | High-purity ptyltetracid dianhydride and synthesis method thereof, and polyimides synthesized on basis of ptyltetracid dianhydride | |
| CN105153085A (en) | Derivative of dibenzofuran and preparation method and application thereof | |
| CN101838225A (en) | Sulfonylation methods of amine and derivative thereof | |
| CN102199118B (en) | Oxo-bi(N-Methylphthalimide) synthesis method | |
| CN105712978A (en) | Preparation method of rupatadine fumarate | |
| US8461355B2 (en) | Preparation method of 3,4-ethylenedioxythiophene | |
| CN103601668A (en) | Preparation method of N-phenyl-3-bromocarbazole | |
| CN106117113A (en) | Polysubstituted carbazole, derivant and synthetic method thereof | |
| CN105085420B (en) | A kind of method that compound phenazine is catalyzed and synthesized under the microwave radiation in aqueous phase | |
| CN102351621B (en) | Method for preparing N-sulfonyl amidine | |
| CN102875463A (en) | Synthesis method for high-quality and low-cost bispyrithione | |
| CN106146496A (en) | A kind of gulf district cyclization synthetic method of double imide derivative | |
| CN111187240B (en) | Preparation method of 4, 4-diphenyl ether dianhydride | |
| CN104387407A (en) | 6-methyl-6H-benzo[4, 5]thiophene[2, 3-b]indole and derivatives thereof as well as synthesis method of 6-methyl-6H-benzo[4, 5]thiophene[2, 3-b]indole and derivatives thereof | |
| CN100460390C (en) | Bi(N-methylphthalic imidine) ester preparation method | |
| CN115093372A (en) | Synthesis method of imidazole derivative | |
| CN104592034A (en) | Synthetic method of 1, 3-diamidophenyl-5, 7-dimethyl adamantane | |
| Tünnermann et al. | A Straightforward Synthesis to Novel 1, 10-Phenanthrolines with Fused Thiophene Structure | |
| CN102476983A (en) | Method for synthesizing 6-methoxy-2-naphthaldehyde | |
| CN103073435A (en) | Synthesis method for 4-bromo-o-phenylenediamine | |
| CN108929217A (en) | A kind of preparation method of 2- methyl -5- fluobenzoic acid | |
| CN110305057A (en) | A kind of preparation method of bromo- 7H- benzo [c] carbazole of 10- | |
| CN103833635A (en) | Method for preparing safe and effective antibechic dimimorfan phosphate | |
| CN103833530A (en) | Preparation method of organic intermediate 3-phenoxyl-1, 2-propylene glycol | |
| CN102267980B (en) | Method for preparing 2,6-bis(2-benzimidazolyl)pyridine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130925 Termination date: 20160316 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |