CN102363607A - Method for synthesizing maleimide by using strongly acidic room-temperature ionic liquid as medium - Google Patents

Method for synthesizing maleimide by using strongly acidic room-temperature ionic liquid as medium Download PDF

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CN102363607A
CN102363607A CN 201110385605 CN201110385605A CN102363607A CN 102363607 A CN102363607 A CN 102363607A CN 201110385605 CN201110385605 CN 201110385605 CN 201110385605 A CN201110385605 A CN 201110385605A CN 102363607 A CN102363607 A CN 102363607A
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acid
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list
ionic liquid
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房强
李凯
陈星鹏
金凯凯
赖华
李竟
袁超
刁屾
吴建平
洪家
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Shanghai Institute of Organic Chemistry of CAS
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Abstract

The invention relates to a method for synthesizing a monomaleimide or bismaleimide derivative. In the method, monomaleamic acid or bimaleamic acid is used as a raw material, and a cyclization reaction is performed in the strongly acidic room-temperature ionic liquid medium, and a target product of which the yield is over 80 percent can be obtained. Unlike the conventional synthesis method, the synthesis route avoids using an acetic anhydride dehydrating agent and a strongly corrosive mineral acid catalyst. After reaction, the reaction mixture is extracted by an organic solvent, and the high-purity target product can be obtained by simple separation. The step of washing the product with a large volume of water for removing the catalyst and dehydrating agent in the conventional process is avoided. Because the catalyst provided by the invention can be used repeatedly and the synthesis method avoids discharging waste water, water gas and waste residue, the method can be used to synthesize the monomaleimide or bismaleimide derivative in a green, environment-friendly and low-cost way.

Description

With the strongly-acid ionic liquid at room temperature is the method for the synthetic maleimide of medium
Technical field
The present invention relates to the preparation method of list or bismaleimides, utilize the strongly-acid ionic liquid at room temperature to be reaction medium, make list or span come the amido acid cyclisation and obtain title product.Catalyzer proposed by the invention is repeatedly reusable, and the reaction process three-waste free discharge is a green, environmental protection and synthetic route cheaply.
Background technology
List or bismaleimides are one type of important fine chemical products, have purposes widely.Wherein, single maleimide be mainly used in tree elastomer and elastomeric vulcanizing agent, thermoplastic resin modified dose.Resin after its modification has good thermotolerance and processibility, has been widely used in the macromolecular materials such as ABS, Vestolen PP 7052, PVC, PMMA.In addition, single maleimide also has good antibacterial activity, as the marine equipment stain control agent; Be applied in the equipment such as steamer, warship, sewer line; Can prevent that effectively harmful organism breeds in the sealing on equipment, then nontoxic to other biological, do not pollute the marine site.But autohemagglutination when bismaleimides heats because of it; Can't emit the small molecules volatile matter; Polymerisate has higher heat resisting temperature and electrical insulation capability preferably, as fibre composite matrix resin, packaged material etc., has been widely used in industries such as aerospace and electronic apparatus.
Yet; Loaded down with trivial details synthesis technique and the expensive reaction reagent of use; Cause the price of single (two) maleimide high (6.8 ten thousand yuan/ton of the average prices of the single maleimide in area, East China in 2011), increased user's use cost, also limited the application widely of these materials.Therefore, the developing low-cost synthesis technique is single (two) maleimide production and the department of application problem demanding prompt solution.
Usually, single (two) maleimide obtains through two-step reaction.That is, at first maleic anhydride and organic amine reaction are generated single (two) maleinamic acid, again the latter is generated product through dehydration closed-loop.One step of back is the key of synthetic single (two) maleimide.In most cases, it is catalyzer that metal-salt or organic amine are adopted in reaction, is dewatering agent with the acetic anhydride, uses polar organic solvent such as acetone and N (DMF) etc.Relevant building-up process has detailed description in U.S. Pat 3127414 and US4193747, Japanese Patent JP9268174.Owing in the post-reaction treatment process, must remove the dewatering agent diacetyl oxide for water, can cause the generation of a large amount of acid-bearing wastewaters, cause huge environmental stress.Importantly, diacetyl oxide is as being prone to system toxogen material, and various countries have all formulated strict buying and used regulation, cause it to cost an arm and a leg, and transport, use and manage all to be very limited, and this also is the major cause that causes single (two) maleimide expensive.In order to overcome these defectives, the technology of diacetyl oxide as dewatering agent is not used in existing extensive work research.Be typically azeotropic dehydration closed loop method.Adopting toluene like Japanese Patent JP5368770 is azeotropic aqua, in the presence of mineral acid (phosphoric acid, the vitriol oil, tosic acid, Vanadium Pentoxide in FLAKES etc.) catalyzer, has obtained the title product of high yield.U.S. Pat 4705866 has reported also that with the organic tin compound as catalyzer, ETHYLE ACETATE, toluene etc. is the method for azeotropic aqua.Although these technologies have been avoided the use diacetyl oxide, yet the last handling process of product is removed catalyzer because of needs and is become loaded down with trivial details, and can produce great amount of wastewater inevitably.
Ionic liquid at room temperature is the focus of Recent study, be called as green synthetic agent (referring to, Amanda C.Cole etc., J.Am.Chem.Soc.2002,124,5962-5963), and be applied at industrial sector.In the ionic liquid at room temperature, strong Bu Laosite acidic ion liquid enjoys the investigator to favor.Because it at room temperature is flow state, non-volatile, particularly it does not dissolve each other with most organic solvent, for the aftertreatment of reacting provides greatly convenience, can be used for many organic reactions.Typical example is its catalytic esterification.Common esterification is carried out under the acid catalysis of ore deposit, and reaction needs finishing sequences such as neutralization, washing after finishing.And when using ionic liquid, only need reaction product is simply separated with ionic liquid, just can obtain product, ionic liquid can be repeatedly used simultaneously, can save production cost the minimizing environmental stress greatly.
Present situation based on ion liquid characteristics and above-mentioned list (two) maleimide synthesis technique; Particularly do not have so far and utilize the report of ionic liquid for the synthetic maleimide of medium; It is medium that the present invention proposes to adopt the strongly-acid ionic liquid at room temperature, makes single (two) maleinamic acid cyclisation generate the synthesis technique of title product.The present invention has not only got rid of the dewatering agent aceticanhydride that uses in the prior synthesizing method.After the reaction, reaction mixture through simple separation, just can obtain target product with high purity through organic solvent extraction, has avoided in the traditional technology, uses the water washing product to remove the operation of catalyzer in a large number.Because catalyzer proposed by the invention can repeat repeatedly, and this compound method three-waste free discharge, therefore adopt the present invention, list or bismaleimide sulfonamide derivatives can be green, environmental protection synthesized, and the cost of product will be reduced greatly.
Summary of the invention
The present invention aims to provide the novel method of a kind of green, environmental protection and synthetic at low cost list or bismaleimide sulfonamide derivatives.
List of the present invention or bismaleimides prepare through following method:
In acid ionic liquid at room temperature, add list or span and come amido acid, stir down reacting by heating number hour after, add organic solvent, will be divided into the biphase reaction mixture and separate, promptly get title product after organic solvent is removed in the organic phase distillation.
Single maleinamic acid that the present invention adopted has following chemical structure:
Figure BDA0000113250190000021
Wherein, R 1Be H, OH, C 1～C 6Alkyl, cyclopentyl, cyclohexyl, allyl group and aryl.When R1 was aryl, it had following structure:
In the formula, R is H, OH, F, Cl, Br, I ,-COOH ,-CHO ,-CN, trifluoromethyl, ethanoyl, nitro, allyloxy, C 1～C 6Alkyl, cyclopentyl, cyclohexyl, allyl group, vinyl.
The span that the present invention adopted comes amido acid to have following chemical structure:
Figure BDA0000113250190000032
Wherein,
Figure BDA0000113250190000033
Figure BDA0000113250190000034
In the following formula, n=1-6.
Above-mentioned list or span come the amido acid can be by the preparation of following method: in acetone, with maleic anhydride and organic amine mixing, behind the stoichiometric number hour, reaction mixture can obtain product through filtration, organic solvent washing, drying.Preferred reaction conditions is, 0 ℃ of temperature of reaction is to room temperature.
According to technology according to the invention, the structure of single maleimide derivatives of acquisition is:
Figure BDA0000113250190000041
In the formula, R 1Chemical structure identical with aforementioned R1.
According to technology according to the invention, the structure of the bismaleimide sulfonamide derivatives of acquisition is:
Figure BDA0000113250190000042
In the formula, R 2Chemical structure and aforementioned R 2Identical.
The acid ionic liquid at room temperature that the present invention adopted has following chemical structure:
Figure BDA0000113250190000043
In the formula, Z and R 3Be the alkyl of C1～C6, m=1,2, X is sulfuric acid, nitric acid, phosphoric acid, acetate, tosic acid, trifluoroacetic acid, trifluoromethanesulfonic acid.
Above-mentioned ion liquid synthetic, and the reference literature reported method (Amanda C.Cole etc., J.Am.Chem.Soc.2002,124,5962-5963).
The present invention adopts the organic solvent extracting access method to the separation of product.Used organic solvent is acetone, butanone, pimelinketone, ether, THF, DMF, DMAC, DMSO, NMP, tetramethylene sulfone, methyl alcohol, ethanol, propyl carbinol, toluene, YLENE, ETHYLE ACETATE, hexanaphthene.
The temperature of reaction that the present invention adopted is 40 ℃-160 ℃, and preferable reaction temperature is 80 ℃.
The reaction times that the present invention adopted is 2-8 hour, preferred 5-6 hour.
Reaction raw materials of the present invention and ion liquid weight ratio are 1.0: 0.5～1.0: 20.0.Preferred 1.0: 10.
Embodiment
Through embodiment the present invention is carried out concrete description below; Be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; Can not be interpreted as the restriction to protection domain of the present invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
Synthesizing of embodiment 1 N-aryl maleinamic acid
Place 200 milliliters of acetone in 500 milliliters of reaction flasks, stir the 98 gram maleic anhydrides (1.0 moles) of adding down, after stirring, slowly drip 93 gram aniline, the reaction mixture vigorous stirring is after 5 hours, and formed yellow mercury oxide filters, is drying to obtain product.
Likewise, adopt present embodiment, can come amido acid, N-(4-carboxyl phenyl) maleinamic acid by the synthesizing diphenyl methane span
N-(4-trifluoromethyl) maleinamic acid and N-(4-hydroxy phenyl) maleinamic acid.
Synthesizing of embodiment 2 imidazole type sulfuric acid chamber temperature ionic liquids
The molecular structure of the said imidazole type sulfuric acid chamber of present embodiment geothermal liquid is following:
Figure BDA0000113250190000051
With reference to Amanda C.Cole etc., J.Am.Chem.Soc.2002,124, the 5962-5963 reported method is synthetic.In reaction flask, add 40 gram N-Methylimidazoles and 68 grams 1,4-butane group sultone, stirring reaction gets white solid.Add the vitriol oil 9.8 grams behind the purifying, stirring reaction 6 hours obtains colourless liquid, promptly gets object ion liquid after the ether washing. 1HNMR(300MHz，D 2O)δ8.52(s，1H)，7.25(d，J＝17.4Hz，2H)，4.03(t，J＝7.0Hz，2H)，3.67(s，3H)，2.81-2.64(m，2H)，1.79(dd，J＝15.0，7.4Hz，2H)，1.53(dd，J＝15.5，8.0Hz，2H).
Synthesizing of embodiment 3 triphenylphosphine type sulfuric acid chamber temperature ionic liquids
With reference to Amanda C.Cole etc., J.Am.Chem.Soc.2002,124, the 5962-5963 reported method is synthetic.In reaction flask, add the triphenylphosphine and 1 of equimolar amount, 3-propyl sultone adds toluene again, and stirring also refluxes and spends the night, and gets white solid.The vitriol oil that adds equimolar amount behind the purifying, 70 ℃ of stirring reactions 6 hours obtain colourless liquid, promptly get object ion liquid after the ether washing.
Synthesizing of embodiment 4 pyrrolidone type sulfuric acid chamber temperature ionic liquids
The molecular structure of the said imidazole type sulfuric acid chamber of present embodiment geothermal liquid is following:
Figure BDA0000113250190000062
With reference to Amanda C.Cole etc., J.Am.Chem.Soc.2002,124, the 5962-5963 reported method is synthetic.In reaction flask, add the pyrrolidone and 1 of equimolar amount, 3-propyl sultone adds toluene again, and stirring also refluxes and spends the night, and gets white solid.The vitriol oil that adds equimolar amount behind the purifying, 70 ℃ of stirring reactions 6 hours obtain colourless liquid, promptly get object ion liquid after the ether washing.
Synthesizing of embodiment 5 imidazole type tosic acid ionic liquid at room temperature
The molecular structure of the said imidazole type sulfuric acid chamber of present embodiment geothermal liquid is following:
Figure BDA0000113250190000071
With reference to Amanda C.Cole etc., J.Am.Chem.Soc.2002,124, the 5962-5963 reported method is synthetic.In reaction flask, add equimolar N-Methylimidazole and 1,4-butane group sultone, stirring reaction gets white solid.Add equimolar tosic acid behind the purifying, 70 ℃ of stirring reactions 6 hours obtain colourless liquid, promptly get object ion liquid after the ether washing.
Synthesizing of embodiment 6 N-phenylmaleimides
Add in 500 milliliters of reaction flasks by embodiment 1 synthetic N-phenyl maleimide acid (19 gram) with by embodiment 2 synthetic imidazole type sulfuric acid chamber temperature ionic liquids (190 gram), be warming up to 60 ℃, stirring reaction 5 hours; After reaction finishes; In reaction system, add ether, after stirring, isolate supernatant liquid; Remove and desolvate, be drying to obtain product.
Synthesizing of embodiment 7 N-(4-carboxyl phenyl) maleimide
Add 24 gram N-(4-carboxyl phenyl) maleinamic acids in 500 milliliters of reaction flasks, 240 grams are heated up 60 ℃ by embodiment 3 synthetic triphenylphosphine type sulfuric acid chamber geothermal liquid ionic liquids; Reacted 5 hours; Reaction adds ether after finishing in reaction system, isolate supernatant liquid; Remove and desolvate, obtain faint yellow solid. 1H?NMR(300MHz，DMSO)δ8.05(d，J＝8.7Hz，2H)，7.50(d，J＝8.6Hz，2H)，7.23(s，2H)。
Synthesizing of embodiment 8 N-(4-trifluoromethyl) maleimide
Add 26 gram N-(4-trifluoromethyl) maleinamic acids in 500 milliliters of reaction flasks, 260 grams are heated up 60 ℃ by embodiment 4 synthetic pyrrolidone type sulfuric acid chamber temperature ionic liquids; Reacted 7 hours; Reaction adds ether after finishing in reaction system, isolate supernatant liquid; Remove and desolvate, obtain white solid. 19F?NMR(300MHz，CDCl 3)δ-63； 1H?NMR(300MHz，CDCl 3)δ6.56(2H)，7.1(2H)，7.5(2H)。
Synthesizing of embodiment 9 N-(4-hydroxy phenyl) maleimide
Add 21 gram N-(4-hydroxy phenyl) maleinamic acids in 500 milliliters of reaction flasks, 210 grams are heated up 60 ℃ by embodiment 2 synthetic imidazole type sulfuric acid chamber temperature ionic liquids; Reacted 7 hours; Reaction adds ether after finishing in reaction system, isolate supernatant liquid; Remove and desolvate, obtain light yellow needle-like crystal.
Synthesizing of embodiment 10 diphenyl methane dimaleimides
Add 39 gram ditane spans in 500 milliliters of reaction flasks and come amido acid; 390 grams are heated up 80 ℃ by embodiment 5 synthetic imidazole type tosic acid ionic liquid at room temperature, react 9 hours; After reaction finishes; In reaction system, add N, isolate supernatant liquid, removing desolvates obtains faint yellow solid.Thin layer chromatography analysis and commercially available article indifference.

Claims (5)

1. the method for synthetic list or bismaleimide sulfonamide derivatives; It is characterized in that in temperature of reaction be 40-160 ℃; Coming amido acid with list or span is raw material, in acid room-temperature ion liquid body medium, reacts and makes list or span come the amido acid cyclisation to form list or bismaleimide sulfonamide derivatives in 2-8 hour:
Described reaction raw materials and ion liquid weight ratio are 1.0: 0.5～1.0: 20.0;
Described single maleinamic acid has following chemical structure:
Figure FDA0000113250180000011
Described span comes amido acid to have following chemical structure:
Figure FDA0000113250180000012
The structure of described single maleimide derivatives is:
Figure FDA0000113250180000013
The structure of described bismaleimide sulfonamide derivatives is:
Figure FDA0000113250180000014
Described strongly-acid ionic liquid at room temperature has following chemical structure:
Figure FDA0000113250180000021
Wherein, R 1Be H, OH, CH 2COOH, CH 2CH 2COOH, C 1～C 6Alkyl, cyclopentyl, cyclohexyl, allyl group or aryl; Described aryl has following structure:
In the formula, R be H, OH ,-CHO, F, Cl, Br, I ,-CHO ,-COOH ,-CN, trifluoromethyl, ethanoyl, nitro, allyloxy, C 1～C 6Alkyl, cyclopentyl, cyclohexyl, allyl group or vinyl;
Figure FDA0000113250180000023
Figure FDA0000113250180000031
Z and R 3Be the alkyl of C1～C6;
n＝1-6；
M=1 or 2;
X is sulfuric acid, nitric acid, phosphoric acid, acetate, tosic acid, trifluoroacetic acid or trifluoromethanesulfonic acid.
2. according to the said method of claim 1, it is characterized in that after reaction finished, reaction product was through the organic solvent extraction purifying; Described organic solvent is acetone, butanone, pimelinketone, ether, THF, N; Dinethylformamide, DMAC N,N, DMSO 99.8MIN., N-Methyl pyrrolidone, tetramethylene sulfone, methyl alcohol, ethanol, propyl carbinol, toluene, YLENE, ETHYLE ACETATE or hexanaphthene.
3. according to the said method of claim 1, it is characterized in that described temperature of reaction is 80 ℃.
4. according to the said method of claim 1, it is characterized in that the described reaction response time is 5-6 hour.
5. according to the said method of claim 1, it is characterized in that described reaction raw materials and ion liquid weight ratio are 1.0: 10.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103881069A (en) * 2014-04-01 2014-06-25 中国科学院上海有机化学研究所 Manufacturing method of low-dielectric-constant bismaleimide resin
CN105017127A (en) * 2015-07-08 2015-11-04 聊城大学 Preparation method for N,N'-4,4'-diphenylmethyene bismaleimide
CN113861094A (en) * 2021-11-12 2021-12-31 精晶药业股份有限公司 Preparation method of 3-maleimide propionic acid

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
《武汉工程大学学报》 20111115 魏宇等 N-苯基马来酰亚胺的制备与表征 55-58 1-5 第33卷, 第11期 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103881069A (en) * 2014-04-01 2014-06-25 中国科学院上海有机化学研究所 Manufacturing method of low-dielectric-constant bismaleimide resin
CN105017127A (en) * 2015-07-08 2015-11-04 聊城大学 Preparation method for N,N'-4,4'-diphenylmethyene bismaleimide
CN113861094A (en) * 2021-11-12 2021-12-31 精晶药业股份有限公司 Preparation method of 3-maleimide propionic acid

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