阅读说明：本技术 双(2-邻苯二甲酰亚胺)胺及其制备方法 (Bis- (2- phthalimide) amine and preparation method thereof ) 是由 郭睿 徐康 张晓飞 闫育蒙 马丽娟 于 2019-09-12 设计创作，主要内容包括：本发明提供双(2-邻苯二甲酰亚胺)胺及其制备方法,所述方法包括步骤1,将二乙烯三胺、邻苯二甲酸酐和冰乙酸组成的混合体系加热至90～100℃,得到混合体系A；步骤2,将混合体系A升温至115～130℃后反应1～4h,在升温过程中持续加入甲苯,得到混合体系B；步骤3,依次将混合体系B中的冰乙酸和杂质去除后,得到产物,将产物依次洗涤、烘干得到双(2-邻苯二甲酰亚胺)胺。邻苯二甲酸酐上羰基带有的部分正电荷与二乙烯三胺伯胺N原子上的未共用电子对相互作用先形成过度络合物,之后会形成酰胺酸,最后升高温度,酰胺酸分子中的酸与伯胺中另一个H原子高温脱去一分子水,形成最终的酰亚胺结构,产物的产率和纯度较高。(The present invention provides bis- (2- phthalimide) amine and preparation method thereof, and the method includes the steps 1, and the mixed system that diethylenetriamine, phthalic anhydride and glacial acetic acid form is heated to 90~100 DEG C, obtains mixed system A；Step 2,1~4h is reacted after mixed system A being warming up to 115~130 DEG C, and toluene is continuously added into temperature-rise period, obtains mixed system B；Step 3, successively by mixed system B glacial acetic acid and impurity removal after, obtain product, product successively washed, dries and obtains bis- (2- phthalimide) amine.Unshared electron pair interaction on the part positive charge and diethylenetriamine primary amine N atom that carbonyl has on phthalic anhydride is initially formed excessive complex compound, it will form amic acid later, finally increase temperature, acid in amide acid molecule sloughs a molecular water with another H atom high temperature in primary amine, final imide structure is formed, the yield and purity of product are higher.)

1. the preparation method of bis- (2- phthalimide) amine, which is characterized in that include the following steps,

Step 1, the mixed system that diethylenetriamine, phthalic anhydride and glacial acetic acid form is heated to 90~100 DEG C, diethyl The ratio between volume of the quality of alkene triamine, the quality of phthalic anhydride and glacial acetic acid be (2.43~3.86) g:(9.27~ 12.95) g:(40~60) ml, obtain mixed system A；

Step 2,1~4h is reacted after mixed system A being warming up to 115~130 DEG C, and toluene, first are continuously added into temperature-rise period The ratio between volume of glacial acetic acid is (20~30) in benzene and step 1: (40~60) obtain mixed system B；

Step 3, successively by mixed system B glacial acetic acid and impurity removal after, obtain product, product successively washed, is dried Obtain bis- (2- phthalimide) amine.

2. the preparation method of bis- (2- phthalimide) amine according to claim 1, which is characterized in that in step 2 Toluene be added in mixed system A with constant rate.

3. the preparation method of bis- (2- phthalimide) amine according to claim 1, which is characterized in that in step 3 Glacial acetic acid is removed by rotating mixed system B, obtains the sticky mixed system of buff, removal buff is sticky later mixes Impurity in zoarium system, obtains product.

4. the preparation method of bis- (2- phthalimide) amine according to claim 3, which is characterized in that 60~80 Mixed system B is rotated at DEG C and removes glacial acetic acid.

5. the preparation method of bis- (2- phthalimide) amine according to claim 3, which is characterized in that in step 3 With the mixed system that 50~60 DEG C of ethanol washing buff is sticky, stand 12 after resulting cleaning solution stirring~for 24 hours, contained There is the cleaning solution of white precipitate, separates the white precipitate in the cleaning solution, obtain product.

6. the preparation method of bis- (2- phthalimide) amine according to claim 5, which is characterized in that will contain white The cleaning solution of color precipitating obtains product after filtering.

7. the preparation method of bis- (2- phthalimide) amine according to claim 6, which is characterized in that product exists 50~60 DEG C of dryings 12~weigh afterwards for 24 hours, later again by weighing after the drying of this condition, repeated several times obtain until constant weight To bis- (2- phthalimide) amine.

8. the preparation method of bis- (2- phthalimide) amine according to claim 7, which is characterized in that the perseverance of product Weight process repeats 3~4 times.

9. the preparation method of bis- (2- phthalimide) amine according to claim 1, which is characterized in that the method The yield of obtained bis- (2- phthalimide) amine is 52.37%~75.02%.

10. the preparation method of (2- phthalimide) amine bis- as described in any one of claim 1~9 obtains double (2- phthalimide) amine.

Technical field

The invention belongs to imide analog compounds technical field, specially bis- (2- phthalimide) amine and its preparation Method.

Background technique

Imide analog compounds are a kind of widely used one in biology, synthesis chemistry, medicine and polymer chemistry Type organic, imide analog compounds have unique molecular structure, and the N atom of hybridized orbit has lone pair electrons, has good Good coordination ability, usually shows good anticancer, antibacterial and antiviral isoreactivity.Acid imide is living because of its faint fluorescence Property, it can be with mercaptan cysteine and the quantitative reactions such as glutathione with physiological activity, generating has intense fluorescence Substance can be used for monitoring and the clinic diagnosis of disease；Imide analog compounds can also be used to synthesize some important biologies naturally Product such as holomycin, pig gall red pigment etc. can be used as the monomer of synthesizing polyamides high polymer in polymer chemistry, therefore domestic Very active to the research of such compound outside, research emphasis is concentrated mainly in its synthesis.

Phthalimide derivative has anti-inflammatory, anti-epileptic, antibacterial and the bioactivity such as antitumor." Chinese degree Paper database " 2008, in the master thesis in the Agricultural University Of Nanjing Huang moon fragrant in June, 2008, Huang Yuefang is using adjacent benzene two Formic anhydride method has synthesized a series of grape glycopeptide compounds, and has carried out preliminary bactericidal activity experiment, it is expected that developing pair Environmental-friendly new and effective fungicide.In the article of " Shandong chemical industry " 2017,46 (17): 1-3, imperial court's steel etc. passes through research table Bright N- hydroxymethylphthalimide can be used as the intermediate of medicine and pesticide.In recent years, the application of the compound has very big Potential prospect, in pulp bio-bleaching technique frequently as mediator substance, therefore study the method for synthesizing the compound and seem Day by day important." thermosetting resin " 2017,32 (04): in the article of 15-19, Yang Zhao etc. passes through research shows that N- hydroxyl neighbour benzene two Carboximide benzene sulfonate can play the role of chemical amplification in deep-UV lithography, such compound is in the ultraviolet of some strength Acid can be generated under illumination, this acid product can promote breaking polymer chains in a heated condition, to enhance photoetching The difference of the solvability of glue material exposure front and back, decomposites acid again in the process, can continue to be catalyzed photoetching xanthan molecule hair Raw reaction, so that the light sensitivity of photoresist be greatly improved.Therefore, the synthesis of phthalimide derivatives is by pass Note.

In conclusion further research phthalimide derivatives are necessary；And in the prior art, it is adjacent The synthetic method of phthalimide class compound, generally makees solvent using triethylamine as catalyst or acetic anhydride, first passes through low Warm ring-opening reaction carries out high temperature ring-closure reaction again, and low yield is at high cost, and time-consuming, and post-processing is complicated, and product purity is low, no Suitable for mass production.

Summary of the invention

Aiming at the problems existing in the prior art, the present invention provides bis- (2- phthalimide) amine and its preparation side Method, easy to operate, production cost is low, and time-consuming is few, convenient post-treatment, synthetic route be readily produced and the yield of product and purity compared with It is high.

The present invention is to be achieved through the following technical solutions:

The preparation method of bis- (2- phthalimide) amine, includes the following steps,

Step 1, the mixed system that diethylenetriamine, phthalic anhydride and glacial acetic acid form is heated to 90~100 DEG C, The ratio between volume of the quality of diethylenetriamine, the quality of phthalic anhydride and glacial acetic acid be (2.43~3.86) g:(9.27~ 12.95) g:(40~60) ml, obtain mixed system A；

Step 2,1~4h is reacted after mixed system A being warming up to 115~130 DEG C, and first is continuously added into temperature-rise period The ratio between volume of glacial acetic acid is (20~30) in benzene, toluene and step 1: (40~60) obtain mixed system B；

Step 3, successively by mixed system B glacial acetic acid and impurity removal after, obtain product, product is successively washed, Drying obtains bis- (2- phthalimide) amine.

Preferably, the toluene in step 2 is added in mixed system A with constant rate.

Preferably, glacial acetic acid is removed by rotating mixed system B in step 3, obtains the sticky mixed system of buff, Impurity in the sticky mixed system of removal buff later, obtains product.

Further, mixed system B is rotated at 60~80 DEG C and removes glacial acetic acid.

Further, with the mixed system that 50~60 DEG C of ethanol washing buff is sticky, resulting cleaning solution in step 3 After stirring stand 12~for 24 hours, obtain the cleaning solution containing white precipitate, separate the white precipitate in the cleaning solution, produced Object.

Further, product is obtained after the cleaning solution containing white precipitate being filtered.

Further, by product 50~60 DEG C dry 12~weigh afterwards for 24 hours, later again by this condition it is dry after weigh, weight Again several times, until constant weight, bis- (2- phthalimide) amine are obtained.

Further, the constant weight process of product repeats 3~4 times.

Preferably, the yield for bis- (2- phthalimide) amine that the method obtains is 52.37%~75.02%.

Bis- (2- neighbour's benzene two that the preparation method of (2- phthalimide) amine bis- as described in above-mentioned any one obtains Carboximide) amine.

Compared with prior art, the invention has the following beneficial technical effects:

The preparation method of bis- (2- phthalimide) amine of the present invention, the acidity that phthalic anhydride is provided in glacial acetic acid Under the conditions of, parental materials-elimination reaction occurs with diethylenetriamine, the part positive charge that carbonyl has on phthalic anhydride with Unshared electron pair interaction on diethylenetriamine primary amine N atom is initially formed excessive complex compound, will form amic acid later, Temperature is finally increased, the acid in amide acid molecule sloughs a molecular water with another H atom high temperature in primary amine, forms final acyl Imine structure.The glacial acetic acid of use, diethylenetriamine, phthalic anhydride and toluene are from a wealth of sources, and production cost is low；With it is existing Triethylamine is used as catalyst or is compared with the synthetic method that acetic anhydride makees solvent in technology, and the side of solvent is done using glacial acetic acid Method can play proton catalysis ring closure and cost is relatively low, and uses toluene can be quick by the water generated in reaction as azeotropic agent It separates, keeps reaction mobile to forward direction, improve the yield of product, product purity is high, at low cost, time-consuming short, post-processing side Just.

Detailed description of the invention

Fig. 1 is the infrared figure of Fourier of bis- (2- phthalimide) amine prepared by the embodiment of the present invention 1.

Fig. 2 is bis- (2- phthalimide) amine prepared by the embodiment of the present invention 1¹H NMR figure.

Specific embodiment

Below with reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and It is not to limit.

Bis- (2- phthalimide) amine of the present invention, chemical formula is as follows,

Relative molecular mass is 363.37.

By phthalic anhydride and diethylenetriamine parent occurs for the preparation method of bis- (2- phthalimide) amine Electric substitution-elimination reaction obtains, wherein making solvent using glacial acetic acid, can play the role of proton catalysis in this way and cost is relatively low, It uses toluene as azeotropic agent, can be come out the water quick separating generated in reaction by ring closure in this way, make reaction to forward direction It is mobile, improve the yield of product.

Wherein parental materials-elimination principle is as follows,

The preparation method of bis- (2- phthalimide) amine of the present invention, specifically comprises the following steps,

Step 1, the three-necked flask that blender is housed is placed in oil bath, by 2.43~3.86g diethylenetriamine, 9.27~ 12.95g phthalic anhydride, 40~60ml glacial acetic acid are added in three-necked flask, are heated to 90~100 DEG C from room temperature later, this Shi Jinhang ring-opening reaction；

Step 2, it takes 20~30ml toluene to be packed into prepare to be added dropwise in dropping funel；

Step 3, in the case where heating always, toluene is added dropwise while stirring, is dripped off i.e. with constant rate in 30min Can, specific rate does not influence the progress of reaction, is warming up to 115~130 DEG C, and the temperature the high more is conducive to closed loop, and the reaction was continued 1~ 4h；

Step 4, after reaction, it is cooled to room temperature, the mixed system obtained at this time is yellow, by the mixed system 60 ~80 DEG C carry out revolving until flowing out without liquid, as remove solvent glacial acetic acid, obtain the sticky mixed system of buff；

Step 5, which is placed in a beaker, is washed with 50~60 DEG C of hot ethanol, so that other impurities can be with Dissolution stands 12 wherein, after stirring~for 24 hours, until white precipitate is not further added by；

Step 6, white precipitate is obtained after the mixed system that step 5 obtains being filtered, by the white precipitate at 50~60 DEG C Dry 12~for 24 hours, weighing, repetitive operation 3~4 times is to get arriving bis- (2- phthalimide) amine.