CN1194968C - Aromatic tetramine compound containing pyridine structure and preparation method and use thereof - Google Patents
Aromatic tetramine compound containing pyridine structure and preparation method and use thereof Download PDFInfo
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 80
- -1 Aromatic tetramine compound Chemical class 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 30
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000005695 Ammonium acetate Substances 0.000 claims abstract description 9
- 229960000583 acetic acid Drugs 0.000 claims abstract description 9
- 229940043376 ammonium acetate Drugs 0.000 claims abstract description 9
- 235000019257 ammonium acetate Nutrition 0.000 claims abstract description 9
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 9
- 229920002480 polybenzimidazole Polymers 0.000 claims abstract description 9
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000003935 benzaldehydes Chemical class 0.000 claims abstract description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 3
- 238000010992 reflux Methods 0.000 claims description 36
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- 238000001914 filtration Methods 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 10
- 239000012043 crude product Substances 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- IMPIIVKYTNMBCD-UHFFFAOYSA-N 2-phenoxybenzaldehyde Chemical compound O=CC1=CC=CC=C1OC1=CC=CC=C1 IMPIIVKYTNMBCD-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- LDWLIXZSDPXYDR-UHFFFAOYSA-N 3,5-bis(trifluoromethyl)benzaldehyde Chemical compound FC(F)(F)C1=CC(C=O)=CC(C(F)(F)F)=C1 LDWLIXZSDPXYDR-UHFFFAOYSA-N 0.000 claims description 3
- NMTUHPSKJJYGML-UHFFFAOYSA-N 3-(trifluoromethyl)benzaldehyde Chemical compound FC(F)(F)C1=CC=CC(C=O)=C1 NMTUHPSKJJYGML-UHFFFAOYSA-N 0.000 claims description 3
- HUMNYLRZRPPJDN-KWCOIAHCSA-N benzaldehyde Chemical group O=[11CH]C1=CC=CC=C1 HUMNYLRZRPPJDN-KWCOIAHCSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 2
- 239000004693 Polybenzimidazole Substances 0.000 abstract description 8
- 230000009467 reduction Effects 0.000 abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 36
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 22
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- 238000010907 mechanical stirring Methods 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 15
- 238000000921 elemental analysis Methods 0.000 description 13
- 239000000843 powder Substances 0.000 description 13
- 239000013078 crystal Substances 0.000 description 12
- 238000004949 mass spectrometry Methods 0.000 description 11
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N DMSO-d6 Substances [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000001819 mass spectrum Methods 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 230000001376 precipitating effect Effects 0.000 description 5
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 3
- KSSJBGNOJJETTC-UHFFFAOYSA-N COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC Chemical class COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC KSSJBGNOJJETTC-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- ISDBWOPVZKNQDW-UHFFFAOYSA-N 4-phenylbenzaldehyde Chemical compound C1=CC(C=O)=CC=C1C1=CC=CC=C1 ISDBWOPVZKNQDW-UHFFFAOYSA-N 0.000 description 2
- CAMAADNLIGZSSD-UHFFFAOYSA-N 4-pyridin-2-ylbenzene-1,2-diamine Chemical compound C1=C(N)C(N)=CC=C1C1=CC=CC=N1 CAMAADNLIGZSSD-UHFFFAOYSA-N 0.000 description 2
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000006396 nitration reaction Methods 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- RQBIGPMJQUKYAH-UHFFFAOYSA-N 4-(3,4-diaminophenoxy)benzene-1,2-diamine Chemical compound C1=C(N)C(N)=CC=C1OC1=CC=C(N)C(N)=C1 RQBIGPMJQUKYAH-UHFFFAOYSA-N 0.000 description 1
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229920000292 Polyquinoline Polymers 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- ANUAIBBBDSEVKN-UHFFFAOYSA-N benzene-1,2,4,5-tetramine Chemical compound NC1=CC(N)=C(N)C=C1N ANUAIBBBDSEVKN-UHFFFAOYSA-N 0.000 description 1
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000010511 deprotection reaction Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- KHUXNRRPPZOJPT-UHFFFAOYSA-N phenoxy radical Chemical compound O=C1C=C[CH]C=C1 KHUXNRRPPZOJPT-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical group C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Landscapes
- Pyridine Compounds (AREA)
Abstract
The present invention relates to an aromatic tetramine compound containing a pyridine structure, which has the preparing steps that (1), 1 to 100 parts by weight of substituted benzaldehyde, 1 to 200 parts by weight of substituted 3-nitro-4-acetaminoacetophenone, and 1 to 130 parts by weight of ammonium acetate are dissolved in 1 to 100 parts by weight of glacial acetic acid for reaction to produce 3-nitro-4-acetamino compounds; (2), 1 to 100 parts by weight of the 3-nitro-4-acetamino compounds, and 1 to 200 parts by weight of 20 % aqueous slkali are mixed and hydrolyzed to obtain 3-nitro-4-acetamino compounds; (3), 1 to 100 parts by weight of the 3-nitro-4-acetamino compounds are mixed with 1 to 10 parts by weight of Pd/C, and 1 to 20 parts by weight of hydrazine hydrate, and the aromatic tetramine compound containing a pyridine structure can be obtained after reduction. The compound is used for preparing polybenzimidazole (PBI) and polypyridine.
Description
Technical Field
The invention relates to an aromatic tetramine compound containing a pyridine structure.
The invention also relates to a method for preparing the compound.
The invention also relates to the application of the compound.
Background
Aromatic tetraamine compounds are widely used for synthesis of organic aromatic heterocyclic polymers, such as Polybenzimidazole (PBI), Polybenzquinoline (PQ), polybenzoquinoxaline (PPQ), polypyrrolone (Py), and the like. Organic aromatic heterocyclic polymers are developed gradually with the urgent need of heat-resistant polymer materials in industries such as aviation, aerospace, machinery, electronics and the like at the end of 50 s and the beginning of 60 s in the 20 th century. The polymer contains heterocyclic rings and aromatic rings in the molecular chain, and at least contains two or more than two conjugated ring structures at the same time, so that the molecular chain has high rigidity, and the free rotation of the molecular chain is greatly limited. On the other hand, the rigid chain arrangement of these molecules is regular, and both of them have very high glass transition temperature and thermal decomposition temperature (Lufeng, aromatic heterocyclic polymer, macromolecules, 1996, 1, 1-7).
Although studies on aromatic heterocyclic polymers have been carried out for decades, very few of them have been commercialized. This is due on the one hand to the limitations of the starting materials or monomers and on the other hand mainly to the harsh conditions required for processing these materials. Such materials are commonly referred to in the literature as "brick dust" materials, meaning that they are available only in the form of infusible orange, red or even black powders. Therefore, in recent years, the emphasis on aromatic heterocyclic Polymers has been almost no longer on the synthesis of new, more heat-resistant Polymers, but rather on the improvement of synthetic methods and procedures, the reduction of costs, and the discovery of new properties (Rabilloud G., High-Performance Polymers, 2, Polyquinolines and Polymers, chemistry and Applications, edition technique, Paris, 1999).
The current research on the processable aromatic heterocyclic polymer mainly focuses on the research and development of the soluble aromatic hybrid polymer. Measures for improving the solubility of such materials mainly include introducing flexible groups into the molecular chain thereof; introducing large side groups such as benzene rings, hexafluoroisopropyl and the like; the use of copolymerization to disrupt molecular chain regularity, and the use of non-coplanar polymerized monomers, among others (Abadie M.J.M., Sillon B., polyimines and other high-temperature polymers, Elsevier, New York, 1991). All the measures are realized by polymerizing monomers, so that the synthesis of the polymerized monomers with certain special structures, such as containing flexible groups and containing large side groups, is a hot research topic in the field of aromatic heterocyclic organic polymer modification at present. Among them, studies on the synthesis of aromatic tetraamine compounds are one of the most remarkable aspects.
Currently, the types of the industrialized tetraamine compounds are few, and only a few compounds are 1, 2, 4, 5-tetraaminobenzene, 3 ', 4, 4' -tetraaminobiphenyl, 3 ', 4, 4' -tetraaminodiphenyl ether and the like. Foster et al prepared 3, 3 ', 4, 4 ' -tetraaminodiphenyl ether by four-step reaction of amino protection, nitration, deprotection, and reduction starting from 4, 4 ' -diaminodiphenyl ether (ODA) with a total yield of 50.8% (Foster R.T., Marvel C.S., J.Polym.Sci.: Part A, 1965, 3, 417-421). Koros et al, using bisphenol A or hexafluorobisphenol A as the starting material, respectively, prepare 3, 3 ', 4, 4' -Tetraaminoisopropylidenediphenyl (TADPPIP) and 3, 3 ', 4, 4' -tetraaminohexafluoroisopropylidenediphenyl (6FTA) by three steps of nitration, high pressure or low temperature ammoniation, and reduction, with an overall yield of about 60% (Koros W.J., Walker D.R.B., U.S. patent 5262056). Although the aromatic tetraamine compound can be prepared by the above route, the synthesis route is complicated, or the synthesis conditions are harsh, or the purification of the compound is difficult, and it is difficult to obtain a product with high purity and achieve the purpose of mass production, which greatly limits the application. In addition, the introduction of ether bond or (hexafluoro) isopropyl bond into the tetramine structure can improve the solubility of the polymer product, but at the same time, the heat resistance of the polymer product is sacrificed to some extent (Hamciuc e., Hamciuc c., Sava i., Bruma m., European polymer.j., 2001, 37, 287-293).
Disclosure of Invention
The invention provides a novel aromatic tetramine compound containing a pyridine structure, and a preparation method and application thereof. The compound has simple synthetic route, easily obtained raw materials, easy purification and mass production.
The aromatic tetraamine of the present invention has a structure represented by general formula (1):
wherein, R is-H,
or
Wherein R is1＝-H，-CF3Or- (CF)3)2。
The aromatic tetraamine compound represented by the general formula (1) specifically includes tetraamine compounds of the following structure:
the aromatic tetramine compound containing the pyridine structure is synthesized by the following steps:
1. dissolving 1-100 parts of substituted benzaldehyde, 1-200 parts of substituted 3-nitro-4-acetamidoacetophenone and 1-130 parts of ammonium acetate in 1-100 parts of glacial acetic acid, reacting under reflux for 1-10 hours, filtering and collecting generated precipitate while the precipitate is hot, and repeatedly washing with water to obtain a crude product. Recrystallizing the crude product by absolute ethyl alcohol to obtain a 3-nitro-4-acetamido compound containing a pyridine structure;
the substituted benzaldehyde is benzaldehyde, 4-benzaldehyde, m-trifluoromethyl benzaldehyde, 3, 5-bis-trifluoromethyl benzaldehyde, 4- (4 ' -trifluoromethyl) phenoxybenzaldehyde and 4- (3 ', 5 ' -bis-trifluoromethyl) phenoxybenzaldehyde.
2. Mixing 1-100 parts of the 3-nitro-4-acetamido compound with 1-200 parts of 20% potassium hydroxide or sodium hydroxide aqueous solution, heating, refluxing and hydrolyzing to obtain a 3-nitro-4-amino compound;
3. mixing 1-100 parts of the 3-nitro-4-amino compound, 1-10 parts of Pd/C and 1-20 parts of hydrazine hydrate, carrying out reflux reaction for 1-48 hours, filtering to remove insoluble substances while the mixture is hot, and cooling and crystallizing the filtrate to precipitate the aromatic tetramine compound containing the pyridine structure.
The aromatic tetramine compound containing the pyridine structure is tested by analysis means such as Fourier infrared spectroscopy (FT-IR), Nuclear Magnetic Resonance (NMR), Mass Spectrum (MS), elemental analysis, chromatography-mass spectrometry and the like, and the structure of the tetramine compound is consistent with the expected structure, the purity of the tetramine compound can reach 99.5 percent, and the ion analysis and test show that the ion content of the compound with the structure is as follows: na (Na)+＜1ppm，Cl-＜1-2ppm，K+Less than 1 ppm. In addition, the compound has the advantages of easily available raw materials and high yield (60-75%), and is suitable for large-scale production.
The aromatic tetramine compound containing the pyridine structure is used for preparing Polybenzimidazole (PBI) and polypyrrolone (Py), and the structures of the aromatic tetramine compound containing the pyridine structure are respectively shown as a formula (8) and a formula (9).
Wherein,
R＝-H， 
or
Wherein R is1＝-H，-CF3Or- (CF)3)2。
Wherein,
R＝-H， 
or
Wherein R is1＝-H，-CF3Or- (CF)3)2。
Detailed Description
Example 1: in a machine equipped with a mechanical stirrerA250 ml three-necked flask equipped with a stirrer, condenser and thermometer was charged with 1.061g (10.0mmol) of benzaldehyde, 4.444g (20.0mmol) of 3-nitro-4-acetylaminoacetophenone, 10g of ammonium acetate and 30ml of glacial acetic acid. The reaction mixture was reacted at reflux for 3 hr. The resulting yellow precipitate was collected by filtration and washed repeatedly with water to give a crude product. Recrystallizing with anhydrous ethanol to obtain solid powder of 4-phenyl-2, 6-bis [ (3 '-nitro-4' -acetamido) phenyl group]Pyridine, yield 3.17g (62%). FTIR (KBr, cm)-1): 1597.2, 1514.7, 1345.8, 1171.0 Mass Spectrometry (MS): 511(M +, 100) elemental analysis C27H21N5O6Calculated values: c, 63.40%; h, 4.14%. N, 13.69%. found: c, 63.28%; h, 4.22% and N, 13.58%.
In a 250ml three-necked flask equipped with a mechanical stirrer, a condenser tube and a thermometer, 5.115g (10mmol) of 4-phenyl-2, 6-bis [ (3 '-nitro-4' -acetylamino) phenyl ] pyridine, 40ml of anhydrous methanol and 20ml of a 20% KOH solution were charged. The system was heated to reflux for 3 hr. The system was filtered while hot and cooled to give 4-phenyl-2, 6-bis [ (3 '-nitro-4' -amino) phenyl ] pyridine in a yield of 4.03g (95%).
In a 250ml three-necked flask equipped with a mechanical stirring, condenser and thermometer, 4.27g (10mmol) of 4-phenyl-2, 6-bis [ (3 '-nitro-4' -amino) phenyl ] were charged]Pyridine, 150ml absolute ethanol and 0.24g 5% Pd/C. The system was heated to reflux and 15ml of hydrazine monohydrate was added dropwise under reflux. After the addition, the reaction was maintained under reflux for 24 hr. Filtering to remove Pd/C while the solution is hot, cooling the filtrate, and precipitating colorless crystals of 4-phenyl-2, 6-bis [ (3 ', 4' -diamino) phenyl group]Pyridine, collected by filtration and dried in vacuo for 24hrs, to give 3.38g (92.0%) of colorless crystals. The structure is shown as formula (2). FT-IR (KBr, cm)-1)：3401.3，3331.1，1601.9，1503.4，1326.7，1246.9，1121.4，830.5。.1H-NMR(300MHz，DMSO-d6Ppm): 5.22 (s; 4H); 6.37-6.38 (d; 2H); 6.98-7.00 (d; 2H); 7.10-7.12 (m; 2H); 7.25 (m; 1H); 7.53 (m; 1H); 8.02 (s; 1H). Mass Spectrometry (MS): 367(M +, 100). elemental analysis C23H21N5Calculated values:c, 75.18%; h, 5.76%; n, 19.06%. found: c, 75.02%; h, 5.84%; n, 18.98 percent.
Example 2: in a 250ml three-necked flask equipped with a mechanical stirring, condenser and thermometer, 1.822g (10.0mmol) of 4-phenylbenzaldehyde, 4.444g (20.0mmol) of 3-nitro-4-acetylaminoacetophenone, 10g of ammonium acetate and 30ml of glacial acetic acid were charged. The reaction mixture was reacted at reflux for 3 hr. The resulting yellow precipitate was collected by filtration and washed repeatedly with water to give a crude product. Recrystallizing with anhydrous ethanol to obtain solid powder of 4-biphenyl-2, 6-bis [ (3 '-nitro-4' -acetamido) phenyl group]Pyridine, yield 3.78g (64.3%). FTIR (KBr, cm)-1): 1588.2, 1518.7, 1352.6, 1118.0 Mass Spectrometry (MS): 587(M +, 100). elemental analysis C33H25N5O6Calculated values: c, 67.46%; h, 4.29%. N, 11.92%. found: c, 67.41%; h, 4.32% and N, 11.88%.
In a 250ml three-necked flask equipped with a mechanical stirring, a condenser tube and a thermometer, 5.115g (10mmol) of 4-biphenyl-2, 6-bis [ (3 '-nitro-4' -acetylamino) phenyl ] pyridine, 60ml of anhydrous methanol and 30ml of a 20% KOH solution were charged. The system was heated to reflux for 3 hr. The system was filtered while hot and cooled to give 4-biphenyl-2, 6-bis [ (3 '-nitro-4' -amino) phenyl ] pyridine in a yield of 4.88g (97%).
5.03g (10mmol) of 4-biphenyl-2, 6-bis [ (3 '-nitro-4' -amino) phenyl ] are placed in a 250ml three-necked flask with mechanical stirring, condenser and thermometer]Pyridine, 180ml absolute ethanol and 0.29g 5% Pd/C. The system was heated to reflux and 18ml of hydrazine monohydrate was added dropwise under reflux. After the addition, the reaction was maintained under reflux for 24 hr. Filtering to remove Pd/C while the solution is hot, cooling the filtrate, and precipitating colorless crystals of 4-biphenyl-2, 6-bis [ (3 ', 4' -diamino) phenyl group]Pyridine, collected by filtration and dried in vacuo for 24hrs, to give 4.17g (94.0%) of colorless crystals. The structure is shown as formula (3). FT-IR (KBr, cm)-1)：3396.7，3328.2，1606.9，1513.4，1328.7，1256.9，1128.4，823.5。1H-NMR(300MHz，DMSO-d6Ppm): 5.14 (s; 4H); 6.28-6.30 (d; 2H); 6.94-6.95 (d; 2H); 7.12-7.14 (m; 2H); 7.32-7.33 (m; 2H); 7.48-7.50 (m; 2H); 7.54-7.56 (m; 4H), 8.02 (s; 1H). Mass Spectrum (MS): 443(M +, 100) elemental analysis C29H25N5Calculated values: c, 78.53%; h, 5.68%; n, 15.79%. found: c, 78.49%; h, 5.72%; n, 15.71 percent.
Example 3: in a 250ml three-necked flask equipped with a mechanical stirring, condenser and thermometer, 1.7412g (10.0mmol) of m-trifluoromethylbenzaldehyde, 4.444g (20.0mmol) of 3-nitro-4-acetamidoacetophenone, 10g of ammonium acetate and 30ml of glacial acetic acid were charged. The reaction mixture was reacted at reflux for 3 hr. The resulting yellow precipitate was collected by filtration and washed repeatedly with water to give a crude product. Recrystallizing with anhydrous ethanol to obtain solid powder of 4- (3 ' -trifluoromethyl) phenyl-2, 6-bis [ (3 ' -nitro-4 ' -acetamido) phenyl]Pyridine, yield 3.78g (65.2%). FTIR (KBr, cm)-1): 1588.3, 1514.6, 1325.8, 1169.2. Mass Spectrum (MS): 579(M +, 100). elemental analysis C28H20F3N5O6Calculated values: c, 58.03%; h, 3.48%. N, 12.09%. found: c, 57.98%; h, 3.52% and N, 12.01%.
In a 250ml three-necked flask equipped with a mechanical stirrer, a condenser and a thermometer were charged 5.795g, (10mmol) of 4- (3 ' -trifluoromethyl) phenyl-2, 6-bis [ (3 ' -nitro-4 ' -acetylamino) phenyl ] pyridine, 50ml of anhydrous methanol and 25ml of a 20% KOH solution. The system was heated to reflux for 3 hr. The system was filtered while hot and cooled to give 4- (3 ' -trifluoromethyl) phenyl-2, 6-bis [ (3 ' -nitro-4 ' -amino) phenyl ] pyridine, yield 4.71g (95%).
In a 250ml three-necked flask equipped with a mechanical stirrer, a condenser and a thermometer, 4.954g (10mmol) of 4- (3 ' -trifluoromethyl) phenyl-2, 6-bis [ (3 ' -nitro-4 ' -amino) phenyl ] were charged]Pyridine, 160ml absolute ethanol and 0.28g 5% Pd/C. The system was heated to reflux and 15ml of hydrazine monohydrate was added dropwise under reflux. After the addition, the reaction was maintained under reflux for 24 hr. Filtering to remove Pd/C while the solution is hot, cooling the filtrateThen, colorless crystals of 4- (3 ' -trifluoromethyl) phenyl-2, 6-bis (4 ' -aminophenyl) pyridine were precipitated, collected by filtration, and dried under vacuum for 24hrs to give colorless crystals of 4- (3 ' -trifluoromethyl) phenyl-2, 6-bis [ (3 ', 4 ' -diamino) phenyl group]Pyridine 4.08g (93.8%). The structure is shown as a formula (4). FT-IR (KBr, cm)-1)：3398.2，3328.1，1610.9，1513.4，1316.7，1238.9，1118.4，835.6。1H-NMR(300MHz，DMSO-d6Ppm): 5.10 (s; 4H); 6.30-6.31 (d; 2H); 7.17-7.20 (t; 2H); 7.25-7.26 (m; 1H); 7.42-7.43 (m; 1H); 7.48-7.50 (m; 1H); 7.67-7.68 (m; 1H); 7.82 (s; 1H). Mass Spectrometry (MS): 435(M +, 100) elemental analysis C24H20F3N5Calculated values: c, 66.20%; h, 4.63%; n, 16.08%. found: c, 66.13%; h, 4.68%; and N, 15.99 percent.
Example 4: in a 250ml three-necked flask equipped with a mechanical stirring, condenser and thermometer, 2.4212g (10.0mmol) of 3, 5-bistrifluoromethylbenzaldehyde, 4.444g (20.0mmol) of 3-nitro-4-acetylaminoacetophenone, 10g of ammonium acetate and 30ml of glacial acetic acid were charged. The reaction mixture was reacted at reflux for 3 hr. The resulting yellow precipitate was collected by filtration and washed repeatedly with water to give a crude product. Recrystallizing with anhydrous ethanol to obtain solid powder of 4- (3 ', 5' -bis (trifluoromethyl) phenyl-2, 6-bis [ (3 '-nitro-4' -acetamido) phenyl]Pyridine, yield 4.66g (64.4%). FTIR (KBr, cm)-1): 1600.2, 1516.7, 1348.4, 1172.4 Mass Spectrometry (MS): 723(M +, 100) elemental analysis C35H23F6N5O6Calculated values: c, 58.10%; h, 3.20%. N, 9.68%. found: c, 58.02%; h, 3.24%, N, 9.44%.
In a 250ml three-necked flask equipped with a mechanical stirrer, a condenser and a thermometer were charged 5.795g, (10mmol)4- (3 ', 5' -bistrifluoromethyl) phenyl-2, 6-bis [ (3 "-nitro-4" -acetylamino) phenyl ] pyridine, 100ml anhydrous methanol and 40ml 20% KOH solution. The system was heated to reflux for 3 hr. The system was filtered while hot and cooled to give 4- (3 ', 5' -bistrifluoromethyl) phenyl-2, 6-bis [ (3 '-nitro-4' -amino) phenyl ] pyridine, yield 6.14g (94%).
In a 250ml three-necked flask equipped with a mechanical stirrer, a condenser and a thermometer, 6.3951g (10mmol) of 4- (3 ', 5' -bistrifluoromethyl) phenyl-2, 6-bis [ (3 '-nitro-4' -amino) phenyl ] were charged]Pyridine, 180ml absolute ethanol and 0.29g 5% Pd/C. The system was heated to reflux and 15ml of hydrazine monohydrate was added dropwise under reflux. After the addition, the reaction was maintained under reflux for 24 hr. Filtering to remove Pd/C while the solution is hot, cooling the filtrate, and precipitating colorless crystals of 4- (3 ', 5' -bis (trifluoromethyl) phenyl-2, 6-bis [ (3 ', 4' -diamino) phenyl)]Pyridine, collected by filtration and dried in vacuo for 24hrs, to give 5.56g (96.0%) of colorless crystals. The structure is shown as a formula (5). FT-IR (KBr, cm)-1)：3401.3，3334.5，1602.9，1518.4，1333.6，1120.4。1H-NMR(300MHz，DMSO-d6Ppm)5.31 (s; 4H) (ii) a 6.32-6.33 (d; 2H); 6.94-6.95 (d; 2H); 7.60-7.62 (m; 1H); 7.67-7.69 (m; 2H); 7.98 (s; 2H). Mass Spectrometry (MS): 579(M +, 100). elemental analysis C31H23F6N5Calculated values: c, 64.25%; h, 4.00%; n, 12.08%. found: c, 64.18%; h, 4.08%; and N, 12.02 percent.
Example 5: in a 250ml three-necked flask equipped with a mechanical stirring, condenser and thermometer, 2.6621g (10mmol) of the compound 4- (4' -trifluoromethyl) phenoxybenzaldehyde, 4.444g (20.0mmol) of 3-nitro-4-acetamidoacetophenone, 10g of ammonium acetate and 30ml of glacial acetic acid were charged. The reaction mixture was reacted at reflux for 3 hr. The resulting yellow precipitate was collected by filtration and washed repeatedly with water to give a crude product. Recrystallizing with anhydrous ethanol to obtain light yellow solid powder of 4- [ (4' -trifluoromethyl) phenoxy)]Phenyl-2, 6-bis [ (3 '-nitro-4' -acetylamino) phenyl]Pyridine, yield 4.58g (68.2%). FTIR (KBr, cm)-1): 1594.2, 1516.7, 1352.8, 1169.0 Mass Spectrometry (MS): 671(M +, 100) elemental analysis C34H24F3N5O7Calculated values: c, 60.81%; h, 3.60%. N, 10.43%. found: c, 60.62%; h, 3.66% and N, 10.38%.
A250 ml three-necked flask equipped with a mechanical stirrer, a condenser and a thermometer was charged with 6.72g (10mmol) of 4- [ (4 ' -trifluoromethyl) phenoxy ] phenyl-2, 6-bis [ (3 ' -nitro-4 ' -acetylamino) phenyl ] pyridine, 160ml of anhydrous methanol and 50ml of 20% KOH solution. The system was heated to reflux for 3 hr. The system was filtered while hot and cooled to give 4- [ (4' -trifluoromethyl) phenoxy ] phenyl-2, 6-bis [ (3 "-nitro-4" -amino) phenyl ] pyridine, yield 5.52g (94%).
In a 250ml three-necked flask equipped with a mechanical stirring, condenser and thermometer, 5.8751g (10mmol) of 4- [ (4' -trifluoromethyl) phenoxy) was charged]Phenyl-2, 6-bis [ (3 '-nitro-4' -amino) phenyl]Pyridine, 200ml absolute ethanol and 0.24g 5% Pd/C. The system was heated to reflux and 15ml of hydrazine monohydrate was added dropwise under reflux. After the addition, the reaction was maintained under reflux for 24 hr. Filtering to remove Pd/C while hot, cooling, precipitating colorless crystal, filtering, collecting, vacuum drying for 24hrs to obtain colorless crystal 4- [ (4' -trifluoromethyl) phenoxy)]Phenyl-2, 6-bis [ (3 ', 4' -diamino) phenyl]Pyridine with a yield of 4.70g (89.0%) and a structure according to formula (6). FT-IR (KBr, cm)-1)：3396.2，3328.1，1612.9，1508.4，1332.7，1246.9，1121.4。1H-NMR(300MHz，DMSO-d6Ppm)5.43 (s; 4H) (ii) a 6.31-6.32 (d; 2H); 6.85-6.86 (d; 2H); 6.94-6.95 (d; 2H); 7.41-7.42 (m; 2H); 7.48-7.49 (m; 2H); 7.81 (s; 2H). Mass Spectrometry (MS): 527(M +, 100). elemental analysis C30H24F3N5Calculated value of O: c, 68.30%; h, 4.59%; n, 13.28%. found: c, 68.26%; h, 4.62%; and N, 13.14%.
Example 6: in a 250ml three-necked flask equipped with a mechanical stirring, condenser and thermometer, 3.3422g (10mmol) of the compound 4- (3 ', 5' -bistrifluoromethyl) phenoxybenzaldehyde, 4.444g (20.0mmol) of 3-nitro-4-acetamidoacetophenone, 10g of ammonium acetate and 30ml of glacial acetic acid were added. The reaction mixture was reacted at reflux for 3 hr. The resulting yellow precipitate was collected by filtration and washed repeatedly with water to give a crude product. Recrystallizing with absolute ethyl alcohol to obtain light yellow solid powder 4- [ (3 ', 5' -bis-trifluoromethyl)Phenoxy radical]Phenyl-2, 6-bis [ (3 '-nitro-4' -acetylamino) phenyl]Pyridine, yield 4.91g (66.4%). FTIR (KBr, cm)-1): 1596.8, 1514.1, 1354.7, 1172.2 Mass Spectrometry (MS): 739(M +, 100). elemental analysis C55H23F6N5O7Calculated values: c, 56.84%; h, 3.13%. N, 9.47%. found: c, 56.72%; h, 3.22% and N, 9.38%.
In a 250ml three-necked flask equipped with a mechanical stirrer, a condenser and a thermometer, 7.39g (10mmol) of 4- [ (3 ', 5' -bistrifluoromethyl) phenoxy ] phenyl-2, 6-bis [ (3 "-nitro-4" -acetylamino) phenyl ] pyridine, 200ml of anhydrous methanol and 50ml of a 20% KOH solution were added. The system was heated to reflux for 3 hr. The system was filtered while it was hot, and cooled to give 4- [ (3 ', 5' -bistrifluoromethyl) phenoxy ] phenyl-2, 6-bis [ (3 '-nitro-4' -amino) phenyl ] pyridine in a yield of 6.23g (95%).
In a 250ml three-necked flask equipped with a mechanical stirring, condenser and thermometer, 6.5551g (10mmol) of 4- [ (3 ', 5' -bistrifluoromethyl) phenoxy]Phenyl-2, 6-bis [ (3 '-nitro-4' -amino) phenyl]Pyridine, 200ml absolute ethanol and 0.30g 5% Pd/C. The system was heated to reflux and 15ml of hydrazine monohydrate was added dropwise under reflux. After the addition, the reaction was maintained under reflux for 24 hr. Filtering to remove Pd/C while hot, cooling, precipitating colorless crystal, filtering, collecting, vacuum drying for 24hr to obtain colorless crystal 4- [ (3 ', 5' -bis-trifluoromethyl) phenoxy)]Phenyl-2, 6-bis [ (3 ', 4' -diamino) phenyl]Pyridine, yield 5.50g (92.0%), its structure is shown in formula (7). FT-IR (KBr, cm)-1)：3394.4，3318.2，1602.5，1511.4，1328.7，1248.4，1122.1。1H-NMR(300MHz，DMSO-d6Ppm)5.44 (s; 4H) (ii) a 6.32-6.33 (d; 2H); 6.98-7.00 (m; 2H); 7.11-7.13 (m; 4H); 7.36 (s; 1H); 7.81 (s; 2H). Mass Spectrometry (MS): 595(M +, 100). elemental analysis C31H23F6N5Calculated value of O: c, 62.52%; h, 3.89%; n, 11.76%. found: c, 62.48%; h, 4.02%; n, 11.64 percent.
Practice ofExample 7: in a 250ml three-necked flask equipped with mechanical stirring, nitrogen inlet and thermometer, 4.4424g (10mmol) of 4, 4 ' -hexafluoroisopropyl dianhydride (6FDA), 3.6745g (10mmol) of 4-phenyl-2, 6-bis [ (3 ', 4 ' -diamino) phenyl ] were added]Pyridine with 46ml of N, N-dimethylacetamide. The mixture was cooled in ice water and reacted under nitrogen for 24hr to give a viscous solution. The solution was filtered and poured onto a clean glass plate and cured in an oven at the following programmed temperature: 80 deg.C, 3 hr; 120 deg.C, 1hr, 180 deg.C, 1hr, 200 deg.C, 1hr, 250 deg.C, 1hr, 300 deg.C, 1hr to obtain brown polypyrrolone film. Yield 7.79g, 96%. FT-IR (film, cm)-1)：3318.2，1840.5，1511.4，1328.7，1288.5，1162.1。
Example 8: in a 250ml three-necked flask equipped with mechanical stirring, nitrogen inlet and thermometer, 3.1022g (10mmol) of 3, 3 ', 4, 4' -diphenylether tetracarboxylic dianhydride (ODPA), 3.6745g (10mmol) of 4-phenyl-2, 6-bis [ (3 ', 4' -diamino) phenyl ] phenyl]Pyridine with 38ml of N, N-dimethylacetamide. The mixture was cooled in ice water and reacted under nitrogen for 24hr to give a viscous solution. The solution was filtered and poured onto a clean glass plate and cured in an oven at the following programmed temperature: 80 deg.C, 3 hr; 120 deg.C, 1hr, 180 deg.C, 1hr, 200 deg.C, 1hr, 250 deg.C, 1hr, 300 deg.C, 1hr to obtain brown polypyrrolone film. Yield 6.64g, 98% yield. FT-IR (film, cm)-1)：3316.3，1820.5，1533.4，1336.7，1280.5，868.5。
Example 9: in a 250ml three-necked flask equipped with mechanical stirring, nitrogen inlet and thermometer, 4.4424g (10mmol) of 4, 4 '-hexafluoroisopropyl dianhydride (6FDA), 4.3545g (10mmol) of 4- (3' -trifluoromethyl) phenyl-2, 6-bis [ (3 ', 4' -diamino) phenyl ] was charged]Pyridine with 50ml of N, N-dimethylacetamide. The mixture was cooled in ice water and reacted under nitrogen for 24hr to give a viscous solution. The solution was filtered and poured onto a clean glass plate and cured in an oven at the following programmed temperature: 80 deg.C, 3 hr; 120 deg.C, 1hr, 180 deg.C, 1hr, 200 deg.C, 1hr, 250 deg.C, 1hr, 300 deg.C, 1hr to obtain brown polypyrrolone film. Yield 8.35g, 95%. FT-IR (fi)lm，cm-1)：3326.8，1819.5，1509.3，1332.7，1290.5，1160.1。
Example 10: in a 250ml three-necked flask equipped with mechanical stirring, nitrogen inlet and thermometer, 3.1022g (10mmol) of 3, 3 ', 4, 4 ' -diphenylether tetracarboxylic dianhydride (ODPA), 4.3545g (10mmol) of 4- (3 ' -trifluoromethyl) phenyl-2, 6-bis [ (3 ", 4" -diamino) phenyl ] were placed]Pyridine with 42ml of N, N-dimethylacetamide. The mixture was cooled in ice water and reacted under nitrogen for 24hr to give a viscous solution. The solution was filtered and poured onto a clean glass plate and cured in an oven at the following programmed temperature: 80 deg.C, 3 hr; 120 deg.C, 1hr, 180 deg.C, 1hr, 200 deg.C, 1hr, 250 deg.C, 1hr, 300 deg.C, 1hr to obtain brown polypyrrolone film. Yield 7.22g, 97%. FT-IR (film, cm)-1)：3308.1，1827.6，1510.4，1326.7，1300.5，1165.2。
Example 11: in a 250ml three-necked flask equipped with mechanical stirring, nitrogen inlet and thermometer, 3.9225g (10mmol) of 4, 4 ' -dicarboxyphenylhexafluoroisopropanol and 3.6745g (10mmol) of 4-phenyl-2, 6-bis [ (3 ', 4 ' -diamino) phenyl ] were charged]Pyridine reacts with 43ml polyphosphoric acid under the protection of nitrogen at 180 ℃ for 3 hours, and the viscous solution is obtained after cooling. This was poured into water to give a yellow powder, which was filtered off with suction and dried in vacuo to give 7.45g of a yellow powder in 98% yield. The powder was dissolved in N, N-dimethylacetamide to make a solution with 10% solid content, filtered and poured onto a clean glass plate, and cured in an oven at the following programmed temperature: 80 deg.C, 3 hr; 120 deg.C, 1hr, 180 deg.C, 1hr, 200 deg.C, 1hr, 250 deg.C, 1hr, 300 deg.C, 1hr to obtain yellow polybenzimidazole film. FT-IR (film, cm)-1)：3338.2，1860.5，1533.4，1308.7，1225.5。
Example 12: in a 250ml three-necked flask equipped with mechanical stirring, nitrogen inlet and thermometer, 2.5823g (10mmol) of 4, 4 '-dicarboxydiphenyl ether, 4.3545g (10mmol) of 4- (3' -trifluoromethyl) phenyl-2, 6-bis [ (3 ', 4' -diamino) phenyl ] were placed]Pyridine reacts with 39ml polyphosphoric acid under the protection of nitrogen at 180 ℃ for 3hr, and the viscous solution is obtained after cooling.This was poured into water to give a yellow powder, which was filtered off with suction and dried in vacuo to give 6.77g of a yellow powder in 98% yield. The powder was dissolved in N, N-dimethylacetamide to make a solution with 10% solid content, filtered and poured onto a clean glass plate, and cured in an oven at the following programmed temperature: 80 deg.C, 3 hr; 120 deg.C, 1hr, 180 deg.C, 1hr, 200 deg.C, 1hr, 250 deg.C, 1hr, 300 deg.C, 1hr to obtain yellow polybenzimidazole film. FT-IR (film, cm)-1)：3326.2，1858.5，1536.4，1325.7，1229.4。
Claims (5)
1. An aromatic tetramine compound containing a pyridine structure is characterized in that the general formula of the aromatic tetramine compound containing the pyridine structure is as follows:
wherein, R is-H,or
Wherein R is1＝-H，-CF3Or- (CF)3)2。
2. The compound of claim 1, wherein the aromatic tetraamine compound containing a pyridine structure is:
3. a process for the preparation of a compound according to claim 1, comprising the main steps of:
(a) dissolving 1-100 parts of optionally substituted benzaldehyde, 1-200 parts of 3-nitro-4-acetamidoacetophenone and 1-130 parts of ammonium acetate in 1-100 parts of glacial acetic acid, reacting under reflux for 1-10 hours, filtering and collecting generated precipitate while the precipitate is hot, and repeatedly washing with water to obtain a crude product; recrystallizing the crude product by absolute ethyl alcohol to obtain a 3-nitro-4-acetamido compound containing a pyridine structure;
the optionally substituted benzaldehyde is benzaldehyde, 4-benzaldehyde, m-trifluoromethyl benzaldehyde, 3, 5-bis-trifluoromethyl benzaldehyde, 4- (4 ' -trifluoromethyl) phenoxybenzaldehyde and 4- (3 ', 5 ' -bis-trifluoromethyl) phenoxybenzaldehyde;
(b) mixing 1-100 parts of the product prepared in the step a with 1-200 parts of 20% alkali solution, heating, refluxing and hydrolyzing to obtain a 3-nitro-4-amino compound;
(c) and C, mixing 1-100 parts of the product prepared in the step b, 1-10 parts of Pd/C and 1-20 parts of hydrazine hydrate, carrying out reflux reaction for 1-48 hours, filtering to remove insoluble substances while the solution is hot, and cooling and crystallizing the filtrate to separate out the aromatic tetramine compound containing the pyridine structure.
4. The method of claim 3, wherein the alkali solution is a potassium hydroxide or sodium hydroxide solution.
5. The use of the aromatic tetraamine compound containing a pyridine structure according to claim 1 for the preparation of polypyrrolones and polybenzimidazoles.
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