CN110483477A - A kind of diamine monomer and preparation method thereof containing pyridine and indole structure - Google Patents
A kind of diamine monomer and preparation method thereof containing pyridine and indole structure Download PDFInfo
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- CN110483477A CN110483477A CN201910648525.9A CN201910648525A CN110483477A CN 110483477 A CN110483477 A CN 110483477A CN 201910648525 A CN201910648525 A CN 201910648525A CN 110483477 A CN110483477 A CN 110483477A
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- diamine monomer
- nitro
- preparation
- ethyl alcohol
- boronic acid
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 150000004985 diamines Chemical class 0.000 title claims abstract description 46
- 239000000178 monomer Substances 0.000 title claims abstract description 45
- 125000001041 indolyl group Chemical group 0.000 title claims abstract description 34
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 144
- 235000019441 ethanol Nutrition 0.000 claims abstract description 71
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 71
- 239000003054 catalyst Substances 0.000 claims abstract description 45
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 41
- 150000002828 nitro derivatives Chemical class 0.000 claims abstract description 39
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 39
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims abstract description 37
- 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 36
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 36
- KZJPVUDYAMEDRM-UHFFFAOYSA-M silver;2,2,2-trifluoroacetate Chemical compound [Ag+].[O-]C(=O)C(F)(F)F KZJPVUDYAMEDRM-UHFFFAOYSA-M 0.000 claims abstract description 36
- SFUIGUOONHIVLG-UHFFFAOYSA-N (2-nitrophenyl)boronic acid Chemical compound OB(O)C1=CC=CC=C1[N+]([O-])=O SFUIGUOONHIVLG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229940126062 Compound A Drugs 0.000 claims abstract description 7
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 131
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 96
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 66
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 64
- 238000013019 agitation Methods 0.000 claims description 64
- 239000000203 mixture Substances 0.000 claims description 63
- 229910052739 hydrogen Inorganic materials 0.000 claims description 47
- 239000001257 hydrogen Substances 0.000 claims description 47
- 239000003960 organic solvent Substances 0.000 claims description 44
- 230000015572 biosynthetic process Effects 0.000 claims description 41
- 239000003208 petroleum Substances 0.000 claims description 32
- 238000010898 silica gel chromatography Methods 0.000 claims description 31
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- NSFJAFZHYOAMHL-UHFFFAOYSA-N (4-nitrophenyl)boronic acid Chemical compound OB(O)C1=CC=C([N+]([O-])=O)C=C1 NSFJAFZHYOAMHL-UHFFFAOYSA-N 0.000 claims description 17
- ZNRGSYUVFVNSAW-UHFFFAOYSA-N 3-nitrophenylboronic acid Chemical compound OB(O)C1=CC=CC([N+]([O-])=O)=C1 ZNRGSYUVFVNSAW-UHFFFAOYSA-N 0.000 claims description 17
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 14
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 14
- 229910052794 bromium Inorganic materials 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- -1 methoxyl group Chemical group 0.000 claims description 10
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 6
- 125000004076 pyridyl group Chemical group 0.000 claims description 4
- 125000003368 amide group Chemical group 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 229960001866 silicon dioxide Drugs 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 229920005575 poly(amic acid) Polymers 0.000 abstract description 3
- 150000002431 hydrogen Chemical class 0.000 description 41
- 239000000463 material Substances 0.000 description 17
- 239000004642 Polyimide Substances 0.000 description 16
- 229920001721 polyimide Polymers 0.000 description 16
- 239000010408 film Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 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 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- QEWYKACRFQMRMB-UHFFFAOYSA-N fluoroacetic acid Chemical compound OC(=O)CF QEWYKACRFQMRMB-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical compound O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- VEQOALNAAJBPNY-UHFFFAOYSA-N antipyrine Chemical compound CN1C(C)=CC(=O)N1C1=CC=CC=C1 VEQOALNAAJBPNY-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000003949 imides Chemical group 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229960005222 phenazone Drugs 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical fields of organic synthesis, disclose a kind of diamine monomer and preparation method thereof containing pyridine and indole structure.The preparation method is by compound A, nitrobenzene boronic acid, silver trifluoroacetate, catalyst [RhCp*Cl2]2It reacts in ethanol, obtains nitro compound B；Nitro compound B is flowed back under the conditions of catalyst palladium carbon, hydrazine hydrate, ethyl alcohol and is reacted, nitro is reduced to amino, obtains the diamine monomer C with pyridine and indole structure.Using the polyamic acid of diamine monomer preparation, its elongation at break can achieve 15% or more.
Description
Technical field
The invention belongs to the technical fields of organic synthesis, and in particular to a kind of diamine monomer containing pyridine and indole structure and
Preparation method.
Background technique
Polyimides is a kind of high molecular polymer on main chain with imide ring structure.Due to high heat resistance
And mechanical performance, excellent electrical property and durability, in aerospace, electronic information, automobile industry, in the fields such as chemical
It is widely used.In recent years, the lighting of display, enlargement, ultra-thin with the fast development of photoelectric display technology
Change the inexorable trend that future development is had become with flexibility.Therefore, traditional hard glass is replaced to make using Kapton
Become focus concerned by people for the research of flexible display substrates material.
The method of synthesis of polyimides is more than ten, wherein most common method is using diamines and dianhydride as monomer, In
Polar solvent, such as DMF, DMAc first carry out low-temperature polycondensation in NMP or THE/ methanol mixed solvent, obtain soluble polyamic acid.
Then film or spinning are carried out and temperature programming dehydration cyclization is changed into polyimides.Currently, being used for flexible display substrates material
Although polyimide polymer have excellent thermal stability and mechanical performance.But molecule chain rigidity is big, elongation at break
Low, material is not only crisp but also flexible difference.Therefore, design composite structure different diamines or dianhydride monomer, passes through different combinations
Mode can obtain the polyimides of Various Functions, be of great significance for developing polyimide flex display base plate material.
Application No. is: 201910389637.7, denomination of invention are as follows: a kind of diamine monomer containing pyrimidine and indole structure and its
Preparation method.Patent No.: ZL 20171063926.2, denomination of invention are as follows: the diamine monomer of the indole structure of pyrimidine containing N- and its
Preparation method.The diamine monomer obtained using two patent preparation methods can prepare Kapton, which can make
For flexible display substrates material.
Application No. is: 201910389637.7 patents have the following problems: (1) what is be prepared contains pyrimidine and indole structure
Diamine monomer in pyrimidine group be symmetrical structure, cause strand that there is a degree of regularity, main chain and side group it is resistance to
It is hot relatively poor, it is not able to maintain the high heat resistance and high glass-transition temperature of polyimides；The symmetrical junction of pyrimidine group simultaneously
Structure makes the interaction force of intramolecular become larger, and intermolecular free volume becomes smaller, and molecular packing density is got higher, so as to cause polyamides Asia
The elongation at break of amine material reduces.(2) hydrogen has been used in nitro reduction catalyst system used in synthetic method, hydrogen is
A kind of combustibility explosive gas, needs high pressure reaction assembly, special reaction under high pressure and experiments Hydrogen room is needed, to experiment
Equipment and site requirements are higher, and risk is high, complicated for operation.
Patent No.: 20171063926.2 patent of ZL has the following problems: (1) pyrimidine containing N- obtained using this method
The elongation at break that the diamine monomer of indole structure prepares polyimide material is lower.(2) nitro reduction uses in synthetic method
Catalyst system be technique of activated ferrous powder with and acetic acid, diamine compound have amino and pyrimidine radicals basic group, acid catalytic body
System can damage product, and not environmentally, spatter property is lower, and the rate of recovery reduces, and post-processing is complicated.
Summary of the invention
The present invention provides a kind of diamine monomer and preparation method thereof containing pyridine and indole structure, utilizes the diamine monomer system
Its elongation at break of standby polyamic acid can achieve 15% or more.
In order to solve the above technical problems, a kind of diamine monomer containing pyridine and indole structure, structural formula are as follows:
Wherein, R2For hydrogen, methyl, butyl, bromine, one of phenyl；R3For hydrogen, methyl, trifluoromethyl, methoxyl group, in bromine
One kind；R5For amino, and R54,5 or 6 of indole ring can be located at；R6For amino, and R6The 3 or 4 of phenyl ring can be located at
Position.
Preferably, the diamine monomer is dissymmetrical structure, and the asymmetry side group is pyridyl group.
A kind of preparation method of the diamine monomer containing pyridine and indole structure, synthetic route are as follows:
Wherein, R1For nitro, and R14,5 or 6 of indole ring can be located at；R2For hydrogen, methyl, butyl, bromine, in phenyl
One kind；R3For hydrogen, methyl, trifluoromethyl, methoxyl group, one of bromine；R4For nitro, and R4The 3 or 4 of phenyl ring can be located at
Position；R5For amido, and R54,5 or 6 of indole ring can be located at；R6For amino, and R63 or 4 of phenyl ring can be located at.
Further, synthesis step are as follows:
(1) by compound A, nitrobenzene boronic acid, silver trifluoroacetate, catalyst [RhCp*Cl2]2It reacts, obtains in ethanol
Nitro compound B；
(2) nitro compound B is flowed back under the conditions of catalyst palladium carbon, hydrazine hydrate, ethyl alcohol and is reacted, nitro is restored
For amino, the diamine monomer C with pyridine and indole structure is obtained.
Preferably, the compound A, nitrobenzene boronic acid, silver trifluoroacetate, catalyst [RhCp*Cl2]2, ethyl alcohol mole
Than for 1:(2~3): (2~4): (0.005~0.05): (5~10).
It is highly preferred that the nitrobenzene boronic acid is 3- nitrobenzene boronic acid or 4- nitrobenzene boronic acid.
Further, it is carried out in pressure-resistant reaction flask in the synthesis step (1), by compound A, nitrobenzene boronic acid, three
Fluoroacetic acid silver, catalyst [RhCp*Cl2]2, ethyl alcohol magnetic agitation 4~8 hours at 80~100 DEG C.
Further, the synthesis step (1) further include: by mixture after suction filtered through kieselguhr, be removed under reduced pressure organic
Solvent obtains pure nitro compound B with silica gel column chromatography separating purification；Petroleum ether and ethyl acetate in the silicagel column
Volume ratio be 8:1.
Further, it in the synthesis step (2), is carried out in reaction flask, by nitro compound B, catalyst palladium carbon, water
Close hydrazine and ethyl alcohol magnetic agitation back flow reaction 20 minutes~2 hours.
Further, organic solvent is removed under reduced pressure after suction filtered through kieselguhr in mixture, obtains pure diamine monomer C.
One or more technical solutions provided in the embodiments of the present application have at least the following technical effects or advantages:
It (1) is a kind of completely new diamines using the diamine monomer containing pyridine and indole structure that the method for the present invention is prepared
Monomer, is dissymmetrical structure, and asymmetric side group is pyridyl group.Main chain and side group are able to maintain poly- with excellent heat resistance
Imido high heat resistance and high glass-transition temperature, while the dissymmetrical structure introduced breaks the regularity of strand, reduces
The outer interaction force of intramolecular, while intermolecular free volume is increased, molecular packing density reduces, and can be improved the disconnected of material
Split elongation.
(2) diamine monomer containing pyridine and indole structure and 3,3 ' -4,4 ' bibenzene tetracarboxylic dianhydrides hair of the present invention
Raw polycondensation reaction, the polyimides with pyridine side group of formation, elongation at break reach 15% or more.
(3) preparation method of the invention, raw material sources are extensive, and nitrobenzene boronic acid can be commercially available, simultaneous reactions condition
Mildly.
(4) it is palladium carbon and hydrazine hydrate that nitro of the present invention, which restores used catalyst system, reacts green cleaning, yield is more
Height, post-processing is simple, while lower to experimental facilities and site requirements, easy to operate without any risk.
Detailed description of the invention
It is thin that Fig. 1 is that the diamine monomer that is prepared of embodiment 3 with 3,3 ' -4,4 ' bibenzene tetracarboxylic dianhydrides prepares polyimides
The Mechanics Performance Testing of film；
It is thin that Fig. 2 is that the diamine monomer that is prepared of embodiment 8 with 3,3 ' -4,4 ' bibenzene tetracarboxylic dianhydrides prepares polyimides
The Mechanics Performance Testing of film；
Fig. 3 is that the diamine monomer that embodiment 23 is prepared and 3,3 ' -4,4 ' bibenzene tetracarboxylic dianhydrides prepare polyimides
The Mechanics Performance Testing of film；
Fig. 4 is that the diamine monomer that embodiment 27 is prepared and 3,3 ' -4,4 ' bibenzene tetracarboxylic dianhydrides prepare polyimides
The Mechanics Performance Testing of film.
Specific embodiment
In order to better understand the above technical scheme, in conjunction with appended figures and specific embodiments to upper
It states technical solution to be described in detail, it should be understood that the specific features in the embodiment of the present invention and embodiment are to the application skill
The detailed description of art scheme, rather than the restriction to technical scheme, in the absence of conflict, the embodiment of the present application
And the technical characteristic in embodiment can be combined with each other.
Embodiment 1
In the present embodiment: R1For nitro, R2For hydrogen, R3For hydrogen, R4For nitro, R5, R6For amino.
Its synthesis step are as follows: (1) in pressure-resistant reaction flask, A-1 (239mg, 1mmol), 4- nitrobenzene boronic acid is added
(334mg, 2mmol), silver trifluoroacetate (884mg, 4mmol), catalyst [RhCp*Cl2]2(6.1mg, 0.01mmol), ethyl alcohol
(10mL), magnetic agitation are heated to 80 DEG C of reaction 6h.Organic solvent is removed under reduced pressure after suction filtered through kieselguhr in mixture, uses silica gel
Column chromatography [V (petroleum ether): V (ethyl acetate)=8:1] isolates and purifies, and obtains pure product, yield 79%.
(2) in reaction flask, above-mentioned nitro compound B-1 (360mg, 1mmol), palladium carbon (50mg), hydrazine hydrate is added
(2.5mL), ethyl alcohol (10mL), magnetic agitation back flow reaction 0.5h.Mixture is removed under reduced pressure organic molten after suction filtered through kieselguhr
Agent obtains pure product, yield 100%.
Embodiment 2
In the present embodiment: R1For nitro, R2For hydrogen, R3For hydrogen, R4For nitro, R5For nitro, R6For amino.
Its synthesis step are as follows: (1) in pressure-resistant reaction flask, A-2 (239mg, 1mmol), 3- nitrobenzene boronic acid is added
(334mg, 2mmol), silver trifluoroacetate (884mg, 4mmol), catalyst [RhCp*Cl2]2(6.1mg, 0.01mmol), ethyl alcohol
(10mL), magnetic agitation are heated to 100 DEG C of reaction 8h.Organic solvent is removed under reduced pressure after suction filtered through kieselguhr in mixture, uses silica gel
Column chromatography [V (petroleum ether): V (ethyl acetate)=8:1] isolates and purifies, and obtains pure product, yield 79%.
(2) in reaction flask, above-mentioned nitro compound B-2 (360mg, 1mmol), palladium carbon (50mg), hydrazine hydrate is added
(2.5mL), ethyl alcohol (10mL), magnetic agitation back flow reaction 2h.Organic solvent is removed under reduced pressure after suction filtered through kieselguhr in mixture,
Obtain pure product, yield 100%.
Embodiment 3
In the present embodiment: R1For nitro, R2For hydrogen, R3For hydrogen, R4For nitro, R5, R6For amino.
Its synthesis step are as follows: (1) in pressure-resistant reaction flask, A-3 (239mg, 1mmol), 4- nitrobenzene boronic acid is added
(334mg, 2mmol), silver trifluoroacetate (884mg, 4mmol), catalyst [RhCp*Cl2]2(6.1mg, 0.01mmol), ethyl alcohol
(10mL), magnetic agitation are heated to 80 DEG C of reaction 4h.Organic solvent is removed under reduced pressure after suction filtered through kieselguhr in mixture, uses silica gel
Column chromatography [V (petroleum ether): V (ethyl acetate)=8:1] isolates and purifies, and obtains pure product, yield 79%.
(2) in reaction flask, above-mentioned nitro compound B-3 (360mg, 1mmol), palladium carbon (50mg), hydrazine hydrate is added
(2.5mL), ethyl alcohol (10mL), magnetic agitation back flow reaction 20 minutes.Mixture is removed under reduced pressure organic molten after suction filtered through kieselguhr
Agent obtains pure product, yield 100%.
Embodiment 4
In the present embodiment: R1For nitro, R2For methyl, R3For hydrogen, R4For nitro, R5, R6For amino.
Its synthesis step are as follows: (1) in pressure-resistant reaction flask, A-4 (253mg, 1mmol), 4- nitrobenzene boronic acid is added
(334mg, 2mmol), silver trifluoroacetate (884mg, 4mmol), catalyst [RhCp*Cl2]2(6.1mg, 0.01mmol), ethyl alcohol
(10mL), magnetic agitation are heated to 90 DEG C of reaction 6h.Organic solvent is removed under reduced pressure after suction filtered through kieselguhr in mixture, uses silica gel
Column chromatography [V (petroleum ether): V (ethyl acetate)=8:1] isolates and purifies, and obtains pure product, yield 79%.
(2) in reaction flask, above-mentioned nitro compound B-4 (374mg, 1mmol), palladium carbon (50mg), hydrazine hydrate is added
(2.5mL), ethyl alcohol (10mL), magnetic agitation back flow reaction 1h.Organic solvent is removed under reduced pressure after suction filtered through kieselguhr in mixture,
Obtain pure product, yield 100%.
Embodiment 5
In the present embodiment: R1For nitro, R2For butyl, R3For hydrogen, R4For nitro, R5, R6For amino.
Its synthesis step are as follows: (1) in pressure-resistant reaction flask, A-5 (295mg, 1mmol), 4- nitrobenzene boronic acid is added
(334mg, 2mmol), silver trifluoroacetate (884mg, 4mmol), catalyst [RhCp*Cl2]2(6.1mg, 0.01mmol), ethyl alcohol
(10mL), magnetic agitation are heated to 80 DEG C of reaction 6h.Organic solvent is removed under reduced pressure after suction filtered through kieselguhr in mixture, uses silica gel
Column chromatography [V (petroleum ether): V (ethyl acetate)=8:1] isolates and purifies, and obtains pure product, yield 79%.
(2) in reaction flask, above-mentioned nitro compound B-5 (416mg, 1mmol), palladium carbon (50mg), hydrazine hydrate is added
(2.5mL), ethyl alcohol (10mL), magnetic agitation back flow reaction 0.5h.Mixture is removed under reduced pressure organic molten after suction filtered through kieselguhr
Agent obtains pure product, yield 100%.
Embodiment 6
In the present embodiment: R1For nitro, R2For bromine, R3For hydrogen, R4For nitro, R5, R6For amino.
Its synthesis step are as follows: (1) in pressure-resistant reaction flask, A-6 (318mg, 1mmol), 4- nitrobenzene boronic acid is added
(334mg, 2mmol), silver trifluoroacetate (884mg, 4mmol), catalyst [RhCp*Cl2]2(6.1mg, 0.01mmol), ethyl alcohol
(10mL), magnetic agitation are heated to 80 DEG C of reaction 5h.Organic solvent is removed under reduced pressure after suction filtered through kieselguhr in mixture, uses silica gel
Column chromatography [V (petroleum ether): V (ethyl acetate)=8:1] isolates and purifies, and obtains pure product, yield 79%.
(2) in reaction flask, above-mentioned nitro compound B-6 (439mg, 1mmol), palladium carbon (50mg), hydrazine hydrate is added
(2.5mL), ethyl alcohol (10mL), magnetic agitation back flow reaction 1.5h.Mixture is removed under reduced pressure organic molten after suction filtered through kieselguhr
Agent obtains pure product, yield 100%.
Embodiment 7
In the present embodiment: R1For nitro, R2For phenyl, R3For hydrogen, R4For nitro, R5, R6For amino.
Its synthesis step are as follows: (1) in pressure-resistant reaction flask, A-7 (315mg, 1mmol), 4- nitrobenzene boronic acid is added
(334mg, 2mmol), silver trifluoroacetate (884mg, 4mmol), catalyst [RhCp*Cl2]2(6.1mg, 0.01mmol), ethyl alcohol
(10mL), magnetic agitation are heated to 100 DEG C of reaction 7h.Organic solvent is removed under reduced pressure after suction filtered through kieselguhr in mixture, uses silica gel
Column chromatography [V (petroleum ether): V (ethyl acetate)=8:1] isolates and purifies, and obtains pure product, yield 79%.
(2) in reaction flask, above-mentioned nitro compound B-7 (436mg, 1mmol), palladium carbon (50mg), hydrazine hydrate is added
(2.5mL), ethyl alcohol (10mL), magnetic agitation back flow reaction 2h.Organic solvent is removed under reduced pressure after suction filtered through kieselguhr in mixture,
Obtain pure product, yield 100%.
Embodiment 8
In the present embodiment: R1For nitro, R2For hydrogen, R3For hydrogen, R4For nitro, R5, R6For amino.
Its synthesis step are as follows: (1) in pressure-resistant reaction flask, A-8 (239mg, 1mmol), 3- nitrobenzene boronic acid is added
(334mg, 2mmol), silver trifluoroacetate (884mg, 4mmol), catalyst [RhCp*Cl2]2(6.1mg, 0.01mmol), ethyl alcohol
(10mL), magnetic agitation are heated to 95 DEG C of reaction 4h.Organic solvent is removed under reduced pressure after suction filtered through kieselguhr in mixture, uses silica gel
Column chromatography [V (petroleum ether): V (ethyl acetate)=8:1] isolates and purifies, and obtains pure product, yield 79%.
(2) in reaction flask, above-mentioned nitro compound B-8 (360mg, 1mmol), palladium carbon (50mg), hydrazine hydrate is added
(2.5mL), ethyl alcohol (10mL), magnetic agitation back flow reaction 40 minutes.Mixture is removed under reduced pressure organic molten after suction filtered through kieselguhr
Agent obtains pure product, yield 100%.
Embodiment 9
In the present embodiment: R1For nitro, R2For methyl, R3For hydrogen, R4For nitro, R5, R6For amino.
Its synthesis step are as follows: (1) in pressure-resistant reaction flask, A-9 (253mg, 1mmol), 3- nitrobenzene boronic acid is added
(334mg, 2mmol), silver trifluoroacetate (884mg, 4mmol), catalyst [RhCp*Cl2]2(6.1mg, 0.01mmol), ethyl alcohol
(10mL), magnetic agitation are heated to 80 DEG C of reaction 6h.Organic solvent is removed under reduced pressure after suction filtered through kieselguhr in mixture, uses silica gel
Column chromatography [V (petroleum ether): V (ethyl acetate)=8:1] isolates and purifies, and obtains pure product, yield 79%.
(2) in reaction flask, above-mentioned nitro compound B-9 (374mg, 1mmol), palladium carbon (50mg), hydrazine hydrate is added
(2.5mL), ethyl alcohol (10mL), magnetic agitation back flow reaction 0.5h.Mixture is removed under reduced pressure organic molten after suction filtered through kieselguhr
Agent obtains pure product, yield 100%.
Embodiment 10
In the present embodiment: R1For nitro, R2For butyl, R3For hydrogen, R4For nitro, R5, R6For amino.
Its synthesis step are as follows: (1) in pressure-resistant reaction flask, A-10 (295mg, 1mmol), 3- nitrobenzene boronic acid is added
(334mg, 2mmol), silver trifluoroacetate (884mg, 4mmol), catalyst [RhCp*Cl2]2(6.1mg, 0.01mmol), ethyl alcohol
(10mL), magnetic agitation are heated to 90 DEG C of reaction 5h.Organic solvent is removed under reduced pressure after suction filtered through kieselguhr in mixture, uses silica gel
Column chromatography [V (petroleum ether): V (ethyl acetate)=8:1] isolates and purifies, and obtains pure product, yield 79%.
(2) in reaction flask, above-mentioned nitro compound B-10 (416mg, 1mmol), palladium carbon (50mg), hydrazine hydrate is added
(2.5mL), ethyl alcohol (10mL), magnetic agitation back flow reaction 1h.Organic solvent is removed under reduced pressure after suction filtered through kieselguhr in mixture,
Obtain pure product, yield 100%.
Embodiment 11
In the present embodiment: R1For nitro, R2For bromine, R3For hydrogen, R4For nitro, R5, R6For amino.
Its synthesis step are as follows: (1) in pressure-resistant reaction flask, A-11 (318mg, 1mmol), 3- nitrobenzene boronic acid is added
(334mg, 2mmol), silver trifluoroacetate (884mg, 4mmol), catalyst [RhCp*Cl2]2(6.1mg, 0.01mmol), ethyl alcohol
(10mL), magnetic agitation are heated to 80 DEG C of reaction 6h.Organic solvent is removed under reduced pressure after suction filtered through kieselguhr in mixture, uses silica gel
Column chromatography [V (petroleum ether): V (ethyl acetate)=8:1] isolates and purifies, and obtains pure product, yield 79%.
(2) in reaction flask, above-mentioned nitro compound B-11 (439mg, 1mmol), palladium carbon (50mg), hydrazine hydrate is added
(2.5mL), ethyl alcohol (10mL), magnetic agitation back flow reaction 0.5h.Mixture is removed under reduced pressure organic molten after suction filtered through kieselguhr
Agent obtains pure product, yield 100%.
Embodiment 12
In the present embodiment: R1For nitro, R2For phenyl, R3For hydrogen, R4For nitro, R5, R6For amino.
Its synthesis step are as follows: (1) in pressure-resistant reaction flask, A-12 (315mg, 1mmol), 3- nitrobenzene boronic acid is added
(334mg, 2mmol), silver trifluoroacetate (884mg, 4mmol), catalyst [RhCp*Cl2]2(6.1mg, 0.01mmol), ethyl alcohol
(10mL), magnetic agitation are heated to 100 DEG C of reaction 8h.Organic solvent is removed under reduced pressure after suction filtered through kieselguhr in mixture, uses silica gel
Column chromatography [V (petroleum ether): V (ethyl acetate)=8:1] isolates and purifies, and obtains pure product, yield 79%.
(2) in reaction flask, above-mentioned nitro compound B-12 (436mg, 1mmol), palladium carbon (50mg), hydrazine hydrate is added
(2.5mL), ethyl alcohol (10mL), magnetic agitation back flow reaction 20 minutes.Mixture is removed under reduced pressure organic molten after suction filtered through kieselguhr
Agent obtains pure product, yield 100%.
Embodiment 13
In the present embodiment: R1For nitro, R2For hydrogen, R3For hydrogen, R4For nitro, R5, R6For amino.
Its synthesis step are as follows: (1) in pressure-resistant reaction flask, A-13 (239mg, 1mmol), 4- nitrobenzene boronic acid is added
(334mg, 2mmol), silver trifluoroacetate (884mg, 4mmol), catalyst [RhCp*Cl2]2(6.1mg, 0.01mmol), ethyl alcohol
(10mL), magnetic agitation are heated to 90 DEG C of reaction 4h.Organic solvent is removed under reduced pressure after suction filtered through kieselguhr in mixture, uses silica gel
Column chromatography [V (petroleum ether): V (ethyl acetate)=8:1] isolates and purifies, and obtains pure product, yield 79%.
(2) in reaction flask, above-mentioned nitro compound B-13 (360mg, 1mmol), palladium carbon (50mg), hydrazine hydrate is added
(2.5mL), ethyl alcohol (10mL), magnetic agitation back flow reaction 1h.Organic solvent is removed under reduced pressure after suction filtered through kieselguhr in mixture,
Obtain pure product, yield 100%.
Embodiment 14
In the present embodiment: R1For nitro, R2For methyl, R3For hydrogen, R4For nitro, R5, R6For amino.
Its synthesis step are as follows: (1) in pressure-resistant reaction flask, A-14 (253mg, 1mmol), 4- nitrobenzene boronic acid is added
(334mg, 2mmol), silver trifluoroacetate (884mg, 4mmol), catalyst [RhCp*Cl2]2(6.1mg, 0.01mmol), ethyl alcohol
(10mL), magnetic agitation are heated to 80 DEG C of reaction 6h.Organic solvent is removed under reduced pressure after suction filtered through kieselguhr in mixture, uses silica gel
Column chromatography [V (petroleum ether): V (ethyl acetate)=8:1] isolates and purifies, and obtains pure product, yield 79%.
(2) in reaction flask, above-mentioned nitro compound B-14 (374mg, 1mmol), palladium carbon (50mg), hydrazine hydrate is added
(2.5mL), ethyl alcohol (10mL), magnetic agitation back flow reaction 0.5h.Mixture is removed under reduced pressure organic molten after suction filtered through kieselguhr
Agent obtains pure product, yield 100%.
Embodiment 15
In the present embodiment: R1For nitro, R2For butyl, R3For hydrogen, R4For nitro, R5, R6For amino.
Its synthesis step are as follows: (1) in pressure-resistant reaction flask, A-15 (295mg, 1mmol), 4- nitrobenzene boronic acid is added
(334mg, 2mmol), silver trifluoroacetate (884mg, 4mmol), catalyst [RhCp*Cl2]2(6.1mg, 0.01mmol), ethyl alcohol
(10mL), magnetic agitation are heated to 95 DEG C of reaction 7h.Organic solvent is removed under reduced pressure after suction filtered through kieselguhr in mixture, uses silica gel
Column chromatography [V (petroleum ether): V (ethyl acetate)=8:1] isolates and purifies, and obtains pure product, yield 79%.
(2) in reaction flask, above-mentioned nitro compound B-15 (416mg, 1mmol), palladium carbon (50mg), hydrazine hydrate is added
(2.5mL), ethyl alcohol (10mL), magnetic agitation back flow reaction 2h.Organic solvent is removed under reduced pressure after suction filtered through kieselguhr in mixture,
Obtain pure product, yield 100%.
Embodiment 16
In the present embodiment: R1For nitro, R2For bromine, R3For hydrogen, R4For nitro, R5, R6For amino.
Its synthesis step are as follows: (1) in pressure-resistant reaction flask, A-16 (318mg, 1mmol), 4- nitrobenzene boronic acid is added
(334mg, 2mmol), silver trifluoroacetate (884mg, 4mmol), catalyst [RhCp*Cl2]2(6.1mg, 0.01mmol), ethyl alcohol
(10mL), magnetic agitation are heated to 100 DEG C of reaction 6h.Organic solvent is removed under reduced pressure after suction filtered through kieselguhr in mixture, uses silica gel
Column chromatography [V (petroleum ether): V (ethyl acetate)=8:1] isolates and purifies, and obtains pure product, yield 79%.
(2) in reaction flask, above-mentioned nitro compound B-16 (439mg, 1mmol), palladium carbon (50mg), hydrazine hydrate is added
(2.5mL), ethyl alcohol (10mL), magnetic agitation back flow reaction 40 minutes.Mixture is removed under reduced pressure organic molten after suction filtered through kieselguhr
Agent obtains pure product, yield 100%.
Embodiment 17
In the present embodiment: R1For nitro, R2For phenyl, R3For hydrogen, R4For nitro, R5, R6For amino.
Its synthesis step are as follows: (1) in pressure-resistant reaction flask, A-17 (315mg, 1mmol), 4- nitrobenzene boronic acid is added
(334mg, 2mmol), silver trifluoroacetate (884mg, 4mmol), catalyst [RhCp*Cl2]2(6.1mg, 0.01mmol), ethyl alcohol
(10mL), magnetic agitation are heated to 80 DEG C of reaction 8h.Organic solvent is removed under reduced pressure after suction filtered through kieselguhr in mixture, uses silica gel
Column chromatography [V (petroleum ether): V (ethyl acetate)=8:1] isolates and purifies, and obtains pure product, yield 79%.
(2) in reaction flask, above-mentioned nitro compound B-17 (436mg, 1mmol), palladium carbon (50mg), hydrazine hydrate is added
(2.5mL), ethyl alcohol (10mL), magnetic agitation back flow reaction 2h.Organic solvent is removed under reduced pressure after suction filtered through kieselguhr in mixture,
Obtain pure product, yield 100%.
Embodiment 18
In the present embodiment: R1For nitro, R2For hydrogen, R3For hydrogen, R4For nitro, R5, R6For amino.
Its synthesis step are as follows: (1) in pressure-resistant reaction flask, A-18 (239mg, 1mmol), 3- nitrobenzene boronic acid is added
(334mg, 2mmol), silver trifluoroacetate (884mg, 4mmol), catalyst [RhCp*Cl2]2(6.1mg, 0.01mmol), ethyl alcohol
(10mL), magnetic agitation are heated to 80 DEG C of reaction 6h.Organic solvent is removed under reduced pressure after suction filtered through kieselguhr in mixture, uses silica gel
Column chromatography [V (petroleum ether): V (ethyl acetate)=8:1] isolates and purifies, and obtains pure product, yield 79%.
(2) in reaction flask, above-mentioned nitro compound B-18 (360mg, 1mmol), palladium carbon (50mg), hydrazine hydrate is added
(2.5mL), ethyl alcohol (10mL), magnetic agitation back flow reaction 0.5h.Mixture is removed under reduced pressure organic molten after suction filtered through kieselguhr
Agent obtains pure product, yield 100%.
Embodiment 19
In the present embodiment: R1For nitro, R2For methyl, R3For hydrogen, R4For nitro, R5, R6For amino.
Its synthesis step are as follows: (1) in pressure-resistant reaction flask, A-19 (253mg, 1mmol), 3- nitrobenzene boronic acid is added
(334mg, 2mmol), silver trifluoroacetate (884mg, 4mmol), catalyst [RhCp*Cl2]2(6.1mg, 0.01mmol), ethyl alcohol
(10mL), magnetic agitation are heated to 95 DEG C of reaction 5h.Organic solvent is removed under reduced pressure after suction filtered through kieselguhr in mixture, uses silica gel
Column chromatography [V (petroleum ether): V (ethyl acetate)=8:1] isolates and purifies, and obtains pure product, yield 79%.
(2) in reaction flask, above-mentioned nitro compound B-19 (374mg, 1mmol), palladium carbon (50mg), hydrazine hydrate is added
(2.5mL), ethyl alcohol (10mL), magnetic agitation back flow reaction 1h.Organic solvent is removed under reduced pressure after suction filtered through kieselguhr in mixture,
Obtain pure product, yield 100%.
Embodiment 20
In the present embodiment: R1For nitro, R2For butyl, R3For hydrogen, R4For nitro, R5, R6For amino.
Its synthesis step are as follows: (1) in pressure-resistant reaction flask, A-20 (295mg, 1mmol), 3- nitrobenzene boronic acid is added
(334mg, 2mmol), silver trifluoroacetate (884mg, 4mmol), catalyst [RhCp*Cl2]2(6.1mg, 0.01mmol), ethyl alcohol
(10mL), magnetic agitation are heated to 80 DEG C of reaction 6h.Organic solvent is removed under reduced pressure after suction filtered through kieselguhr in mixture, uses silica gel
Column chromatography [V (petroleum ether): V (ethyl acetate)=8:1] isolates and purifies, and obtains pure product, yield 79%.
(2) in reaction flask, above-mentioned nitro compound B-20 (416mg, 1mmol), palladium carbon (50mg), hydrazine hydrate is added
(2.5mL), ethyl alcohol (10mL), magnetic agitation back flow reaction 0.5h.Mixture is removed under reduced pressure organic molten after suction filtered through kieselguhr
Agent obtains pure product, yield 100%.
Embodiment 21
In the present embodiment: R1For nitro, R2For bromine, R3For hydrogen, R4For nitro, R5, R6For amino.
Its synthesis step are as follows: (1) in pressure-resistant reaction flask, A-21 (318mg, 1mmol), 3- nitrobenzene boronic acid is added
(334mg, 2mmol), silver trifluoroacetate (884mg, 4mmol), catalyst [RhCp*Cl2]2(6.1mg, 0.01mmol), ethyl alcohol
(10mL), magnetic agitation are heated to 100 DEG C of reaction 5h.Organic solvent is removed under reduced pressure after suction filtered through kieselguhr in mixture, uses silica gel
Column chromatography [V (petroleum ether): V (ethyl acetate)=8:1] isolates and purifies, and obtains pure product, yield 79%.
(2) in reaction flask, above-mentioned nitro compound B-21 (439mg, 1mmol), palladium carbon (50mg), hydrazine hydrate is added
(2.5mL), ethyl alcohol (10mL), magnetic agitation back flow reaction 0.5h.Mixture is removed under reduced pressure organic molten after suction filtered through kieselguhr
Agent obtains pure product, yield 100%.
Embodiment 22
In the present embodiment: R1For nitro, R2For phenyl, R3For hydrogen, R4For nitro, R5, R6For amino.
Its synthesis step are as follows: (1) in pressure-resistant reaction flask, A-22 (315mg, 1mmol), 3- nitrobenzene boronic acid is added
(334mg, 2mmol), silver trifluoroacetate (884mg, 4mmol), catalyst [RhCp*Cl2]2(6.1mg, 0.01mmol), ethyl alcohol
(10mL), magnetic agitation are heated to 90 DEG C of reaction 8h.Organic solvent is removed under reduced pressure after suction filtered through kieselguhr in mixture, uses silica gel
Column chromatography [V (petroleum ether): V (ethyl acetate)=8:1] isolates and purifies, and obtains pure product, yield 79%.
(2) in reaction flask, above-mentioned nitro compound B-22 (436mg, 1mmol), palladium carbon (50mg), hydrazine hydrate is added
(2.5mL), ethyl alcohol (10mL), magnetic agitation back flow reaction 1.5h.Mixture is removed under reduced pressure organic molten after suction filtered through kieselguhr
Agent obtains pure product, yield 100%.
Embodiment 23
In the present embodiment: R1For nitro, R2For hydrogen, R3For methyl, R4For nitro, R5, R6For amino.
Its synthesis step are as follows: (1) in pressure-resistant reaction flask, A-23 (253mg, 1mmol), 4- nitrobenzene boronic acid is added
(334mg, 2mmol), silver trifluoroacetate (884mg, 4mmol), catalyst [RhCp*Cl2]2(6.1mg, 0.01mmol), ethyl alcohol
(10mL), magnetic agitation are heated to 80 DEG C of reaction 6h.Organic solvent is removed under reduced pressure after suction filtered through kieselguhr in mixture, uses silica gel
Column chromatography [V (petroleum ether): V (ethyl acetate)=8:1] isolates and purifies, and obtains pure product, yield 79%.
(2) in reaction flask, above-mentioned nitro compound B-23 (374mg, 1mmol), palladium carbon (50mg), hydrazine hydrate is added
(2.5mL), ethyl alcohol (10mL), magnetic agitation back flow reaction 0.5h.Mixture is removed under reduced pressure organic molten after suction filtered through kieselguhr
Agent obtains pure product, yield 100%.
Embodiment 24
In the present embodiment: R1For nitro, R2For hydrogen, R3For trifluoromethyl, R4For nitro, R5, R6For amino.
Its synthesis step are as follows: (1) in pressure-resistant reaction flask, A-24 (307mg, 1mmol), 4- nitrobenzene boronic acid is added
(334mg, 2mmol), silver trifluoroacetate (884mg, 4mmol), catalyst [RhCp*Cl2]2(6.1mg, 0.01mmol), ethyl alcohol
(10mL), magnetic agitation are heated to 85 DEG C of reaction 4h.Organic solvent is removed under reduced pressure after suction filtered through kieselguhr in mixture, uses silica gel
Column chromatography [V (petroleum ether): V (ethyl acetate)=8:1] isolates and purifies, and obtains pure product, yield 79%.
(2) in reaction flask, above-mentioned nitro compound B-24 (428mg, 1mmol), palladium carbon (50mg), hydrazine hydrate is added
(2.5mL), ethyl alcohol (10mL), magnetic agitation back flow reaction 0.5h.Mixture is removed under reduced pressure organic molten after suction filtered through kieselguhr
Agent obtains pure product, yield 100%.
Embodiment 25
In the present embodiment: R1For nitro, R2For hydrogen, R3For methoxyl group, R4For nitro, R5, R6For amino.
Its synthesis step are as follows: (1) in pressure-resistant reaction flask, A-25 (269mg, 1mmol), 4- nitrobenzene boronic acid is added
(334mg, 2mmol), silver trifluoroacetate (884mg, 4mmol), catalyst [RhCp*Cl2]2(6.1mg, 0.01mmol), ethyl alcohol
(10mL), magnetic agitation are heated to 90 DEG C of reaction 7h.Organic solvent is removed under reduced pressure after suction filtered through kieselguhr in mixture, uses silica gel
Column chromatography [V (petroleum ether): V (ethyl acetate)=8:1] isolates and purifies, and obtains pure product, yield 79%.
(2) in reaction flask, above-mentioned nitro compound B-25 (390mg, 1mmol), palladium carbon (50mg), hydrazine hydrate is added
(2.5mL), ethyl alcohol (10mL), magnetic agitation back flow reaction 2h.Organic solvent is removed under reduced pressure after suction filtered through kieselguhr in mixture,
Obtain pure product, yield 100%.
Embodiment 26
In the present embodiment: R1For nitro, R2For hydrogen, R3For bromine, R4For nitro, R5, R6For amino.
Its synthesis step are as follows: (1) in pressure-resistant reaction flask, A-26 (318mg, 1mmol), 4- nitrobenzene boronic acid is added
(334mg, 2mmol), silver trifluoroacetate (884mg, 4mmol), catalyst [RhCp*Cl2]2(6.1mg, 0.01mmol), ethyl alcohol
(10mL), magnetic agitation are heated to 80 DEG C of reaction 6h.Organic solvent is removed under reduced pressure after suction filtered through kieselguhr in mixture, uses silica gel
Column chromatography [V (petroleum ether): V (ethyl acetate)=8:1] isolates and purifies, and obtains pure product, yield 79%.
(2) in reaction flask, above-mentioned nitro compound B-26 (439mg, 1mmol), palladium carbon (50mg), hydrazine hydrate is added
(2.5mL), ethyl alcohol (10mL), magnetic agitation back flow reaction 0.5h.Mixture is removed under reduced pressure organic molten after suction filtered through kieselguhr
Agent obtains pure product, yield 100%.
Embodiment 27
In the present embodiment: R1For nitro, R2For hydrogen, R3For methyl, R4For nitro, R5, R6For amino.
Its synthesis step are as follows: (1) in pressure-resistant reaction flask, A-27 (253mg, 1mmol), 3- nitrobenzene boronic acid is added
(334mg, 2mmol), silver trifluoroacetate (884mg, 4mmol), catalyst [RhCp*Cl2]2(6.1mg, 0.01mmol), ethyl alcohol
(10mL), magnetic agitation are heated to 100 DEG C of reaction 8h.Organic solvent is removed under reduced pressure after suction filtered through kieselguhr in mixture, uses silica gel
Column chromatography [V (petroleum ether): V (ethyl acetate)=8:1] isolates and purifies, and obtains pure product, yield 79%.
(2) in reaction flask, above-mentioned nitro compound B-27 (374mg, 1mmol), palladium carbon (50mg), hydrazine hydrate is added
(2.5mL), ethyl alcohol (10mL), magnetic agitation back flow reaction 2h.Organic solvent is removed under reduced pressure after suction filtered through kieselguhr in mixture,
Obtain pure product, yield 100%.
Embodiment 28
In the present embodiment: R1For nitro, R2For hydrogen, R3For trifluoromethyl, R4For nitro, R5, R6For amino.
Its synthesis step are as follows: (1) in pressure-resistant reaction flask, A-28 (307mg, 1mmol), 3- nitrobenzene boronic acid is added
(334mg, 2mmol), silver trifluoroacetate (884mg, 4mmol), catalyst [RhCp*Cl2]2(6.1mg, 0.01mmol), ethyl alcohol
(10mL), magnetic agitation are heated to 80 DEG C of reaction 6h.Organic solvent is removed under reduced pressure after suction filtered through kieselguhr in mixture, uses silica gel
Column chromatography [V (petroleum ether): V (ethyl acetate)=8:1] isolates and purifies, and obtains pure product, yield 79%.
(2) in reaction flask, above-mentioned nitro compound B-28 (428mg, 1mmol), palladium carbon (50mg), hydrazine hydrate is added
(2.5mL), ethyl alcohol (10mL), magnetic agitation back flow reaction 0.5h.Mixture is removed under reduced pressure organic molten after suction filtered through kieselguhr
Agent obtains pure product, yield 100%.
Embodiment 29
In the present embodiment: R1For nitro, R2For hydrogen, R3For methoxyl group, R4For nitro, R5, R6For amino.
Its synthesis step are as follows: (1) in pressure-resistant reaction flask, A-29 (269mg, 1mmol), 3- nitrobenzene boronic acid is added
(334mg, 2mmol), silver trifluoroacetate (884mg, 4mmol), catalyst [RhCp*Cl2]2(6.1mg, 0.01mmol), ethyl alcohol
(10mL), magnetic agitation are heated to 90 DEG C of reaction 5.5h.Organic solvent is removed under reduced pressure after suction filtered through kieselguhr in mixture, uses silicon
Plastic column chromatography [V (petroleum ether): V (ethyl acetate)=8:1] isolates and purifies, and obtains pure product, yield 79%.
(2) in reaction flask, above-mentioned nitro compound B-29 (390mg, 1mmol), palladium carbon (50mg), hydrazine hydrate is added
(2.5mL), ethyl alcohol (10mL), magnetic agitation back flow reaction 50 minutes.Mixture is removed under reduced pressure organic molten after suction filtered through kieselguhr
Agent obtains pure product, yield 100%.
Embodiment 30
In the present embodiment: R1For nitro, R2For hydrogen, R3For bromine, R4For nitro, R5, R6For amino.
Its synthesis step are as follows: (1) in pressure-resistant reaction flask, A-30 (318mg, 1mmol), 3- nitrobenzene boronic acid is added
(334mg, 2mmol), silver trifluoroacetate (884mg, 4mmol), catalyst [RhCp*Cl2]2(6.1mg, 0.01mmol), ethyl alcohol
(10mL), magnetic agitation are heated to 80 DEG C of reaction 6h.Organic solvent is removed under reduced pressure after suction filtered through kieselguhr in mixture, uses silica gel
Column chromatography [V (petroleum ether): V (ethyl acetate)=8:1] isolates and purifies, and obtains pure product, yield 79%.
(2) in reaction flask, above-mentioned nitro compound B-30 (439mg, 1mmol), palladium carbon (50mg), hydrazine hydrate is added
(2.5mL), ethyl alcohol (10mL), magnetic agitation back flow reaction 0.5h.Mixture is removed under reduced pressure organic molten after suction filtered through kieselguhr
Agent obtains pure product, yield 100%.
Effect example: the diamine monomer and aromatic series two prepared using embodiment 3, embodiment 8, embodiment 23, embodiment 27
Acid anhydride prepares Kapton.
Specific steps are as follows: the diamine monomer (10mmol) for preparing embodiment 3, embodiment 8, embodiment 23, embodiment 27
With 3,3 ' -4,4 ' bibenzene tetracarboxylic dianhydrides (10mmol) in 1- methyl 2-Pyrrolidone (30mL) 55 DEG C polycondensation reaction 48 hours
Obtain brown color macromolecule resin slurry.Resin slurry film instrument is coated on glass plate, is placed in high temperature oven and carries out Asia
Amination obtains Kapton.
Film prepared by different diamines is respectively labeled as PI-1, PI-2, PI-3, PI-4, to prepared polyimides
Film carries out Mechanics Performance Testing using GB13022-1991, and the result is shown in following tables:
The mechanical experimental results of table 1 Kapton PI-1, PI-2, PI-3, PI-4
From table 1 it follows that fixed film sample width is 10mm, film thickness 0.02mm is adopted when length is 71mm
It is 50mm/min with rate of extension, test elongation at break is respectively 13.69%, 15.04%, 11.34%, 10.89%, greatly
In 10%, and highest can achieve 15% or more.Illustrate the dissymmetrical structure for introducing the diamine monomer containing pyridine and indole structure
The elongation at break that film can be effectively improved makes film have good toughness, while from the number of stretch modulus and tensile strength
From the point of view of, polyimides high intensity has been still maintained.
From figure 1 it appears that phase before the stretching, stress and strain is directly proportional, and sample shows the row of Hookean elasticity body
For.Then, the obvious turning point of stress-strain diagram, material continues deformation after surrender until fracture, is demonstrated by before fracturing
Biggish deformation, is fractured into ductile rupture, and PI-1 thin-film material has good toughness.
From figure 2 it can be seen that phase before the stretching, stress and strain is directly proportional, and sample shows the row of Hookean elasticity body
For.Then, the obvious turning point of stress-strain diagram, material continues deformation after surrender until fracture, is demonstrated by before fracturing
Biggish deformation, is fractured into ductile rupture, and PI-2 thin-film material has good toughness.
From figure 3, it can be seen that phase before the stretching, stress and strain is directly proportional, and sample shows the row of Hookean elasticity body
For.Then, the obvious turning point of stress-strain diagram, material continues deformation after surrender until fracture, is demonstrated by before fracturing
Biggish deformation, is fractured into ductile rupture, and PI-3 thin-film material has good toughness.
Figure 4, it is seen that phase before the stretching, stress and strain is directly proportional, and sample shows the row of Hookean elasticity body
For.Then, the obvious turning point of stress-strain diagram, material continues deformation after surrender until fracture, is demonstrated by before fracturing
Biggish deformation, is fractured into ductile rupture, and PI-4 thin-film material has good toughness.
It is a kind of completely new diamines list using the diamine monomer containing pyridine and indole structure that the method for the present invention is prepared
Body, is dissymmetrical structure, and asymmetric side group is pyridyl group.Main chain and side group are able to maintain polyamides with excellent heat resistance
The high heat resistance and high glass-transition temperature of imines, while the dissymmetrical structure introduced breaks the regularity of strand, reduces and divides
Interaction force inside and outside son, while intermolecular free volume is increased, molecular packing density reduces, and can be improved the fracture of material
Elongation.Diamine monomer of the present invention containing pyridine and indole structure contracts with 3,3 ' -4,4 ' bibenzene tetracarboxylic dianhydrides
Poly- reaction, the polyimides with pyridine side group of formation, elongation at break reach 15% or more.Preparation side of the invention
Method, raw material sources are extensive, and nitrobenzene boronic acid can be commercially available, simultaneous reactions mild condition.Nitro reduction of the present invention is used
Catalyst system be palladium carbon and hydrazine hydrate, react green cleaning, yield is higher, and post-processing is simple, while to experimental facilities and
Site requirements is lower, easy to operate without any risk.
It should be noted last that the above specific embodiment is only used to illustrate the technical scheme of the present invention and not to limit it,
Although being described the invention in detail referring to example, those skilled in the art should understand that, it can be to the present invention
Technical solution be modified or replaced equivalently, without departing from the spirit and scope of the technical solution of the present invention, should all cover
In the scope of the claims of the present invention.
Claims (10)
1. a kind of diamine monomer containing pyridine and indole structure, which is characterized in that the structural formula is as follows:
Wherein, R2For hydrogen, methyl, butyl, bromine, one of phenyl；R3For hydrogen, methyl, trifluoromethyl, methoxyl group, one in bromine
Kind；R5For amino, and R54,5 or 6 of indole ring can be located at；R6For amino, and R63 or 4 of phenyl ring can be located at.
2. the diamine monomer according to claim 1 containing pyridine and indole structure, which is characterized in that the diamine monomer is
Dissymmetrical structure, the asymmetry side group is pyridyl group.
3. a kind of preparation method of the diamine monomer of any of claims 1 or 2 containing pyridine and indole structure, which is characterized in that
Synthetic route is as follows:
Wherein, R1For nitro, and R14,5 or 6 of indole ring can be located at；R2For hydrogen, methyl, butyl, bromine, one in phenyl
Kind；R3For hydrogen, methyl, trifluoromethyl, methoxyl group, one of bromine；R4For nitro, and R43 or 4 of phenyl ring can be located at；R5
For amido, and R54,5 or 6 of indole ring can be located at；R6For amino, and R63 or 4 of phenyl ring can be located at.
4. the preparation method of the diamine monomer according to claim 3 containing pyridine and indole structure, which is characterized in that synthesis
Step are as follows:
(1) by compound A, nitrobenzene boronic acid, silver trifluoroacetate, catalyst [RhCp*Cl2]2It reacts in ethanol, obtains nitro
Compound B；
(2) nitro compound B is flowed back under the conditions of catalyst palladium carbon, hydrazine hydrate, ethyl alcohol and is reacted, nitro is reduced to ammonia
Base obtains the diamine monomer C with pyridine and indole structure.
5. the preparation method of the diamine monomer according to claim 4 containing pyridine and indole structure, which is characterized in that described
Compound A, nitrobenzene boronic acid, silver trifluoroacetate, catalyst [RhCp*Cl2]2, ethyl alcohol molar ratio are as follows: 1:(2~3): (2~
4): (0.005~0.05): (5~10).
6. the preparation method of the diamine monomer according to claim 4 containing pyridine and indole structure, which is characterized in that described
Nitrobenzene boronic acid is 3- nitrobenzene boronic acid or 4- nitrobenzene boronic acid.
7. the preparation method of the diamine monomer according to claim 4 containing pyridine and indole structure, which is characterized in that
It is carried out in pressure-resistant reaction flask in the synthesis step (1), by compound A, nitrobenzene boronic acid, silver trifluoroacetate, catalysis
Agent [RhCp*Cl2]2With magnetic agitation 4~8 hours at 80~100 DEG C.
8. the preparation method of the diamine monomer according to claim 7 containing pyridine and indole structure, which is characterized in that described
Synthesis step (1) further include: by mixture after suction filtered through kieselguhr, organic solvent is removed under reduced pressure, is separated with silica gel column chromatography pure
Change, obtains pure nitro compound B；
The volume ratio of petroleum ether and ethyl acetate is 8:1 in the silicagel column.
9. the preparation method of the diamine monomer according to claim 4 containing pyridine and indole structure, which is characterized in that
It in the synthesis step (2), is carried out in reaction flask, by nitro compound B, catalyst palladium carbon, hydrazine hydrate and ethyl alcohol
Magnetic agitation back flow reaction 20 minutes~2 hours.
10. the preparation method of the diamine monomer according to claim 9 containing pyridine and indole structure, which is characterized in that mixed
Object is closed after suction filtered through kieselguhr, organic solvent is removed under reduced pressure, obtains pure diamine monomer C.
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| CN113150278A (en) * | 2021-04-26 | 2021-07-23 | 江汉大学 | Polyimide containing asymmetric indole structure and preparation method thereof |
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| CN105523986A (en) * | 2015-12-30 | 2016-04-27 | 江汉大学 | Synthetic method of efflux pump inhibitor N-hydrogen-2-arylindol and derivatives thereof |
| CN107445944A (en) * | 2017-07-31 | 2017-12-08 | 江汉大学 | Diamine monomer of the indole structure of pyrimidine containing N and preparation method thereof |
| CN109400536A (en) * | 2018-12-21 | 2019-03-01 | 东华大学 | A kind of N substituted benzimidazole diamines and preparation method thereof |
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| GB1161637A (en) * | 1966-08-25 | 1969-08-13 | Merck & Co Inc | Indole Derivatives |
| US4970218A (en) * | 1987-04-24 | 1990-11-13 | Hoechst-Roussel Pharmaceuticals Inc. | N-(pyridinyl)-1H-indol-1-amines |
| CN105523986A (en) * | 2015-12-30 | 2016-04-27 | 江汉大学 | Synthetic method of efflux pump inhibitor N-hydrogen-2-arylindol and derivatives thereof |
| CN107445944A (en) * | 2017-07-31 | 2017-12-08 | 江汉大学 | Diamine monomer of the indole structure of pyrimidine containing N and preparation method thereof |
| CN109400536A (en) * | 2018-12-21 | 2019-03-01 | 东华大学 | A kind of N substituted benzimidazole diamines and preparation method thereof |
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| CN113150278A (en) * | 2021-04-26 | 2021-07-23 | 江汉大学 | Polyimide containing asymmetric indole structure and preparation method thereof |
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