CN107043344A - Preparation, structure and the purposes of the indolecarboxaldehyde Schiff base of 4-acetylbiphenyl hydrazone N methyl 3 - Google Patents

Preparation, structure and the purposes of the indolecarboxaldehyde Schiff base of 4-acetylbiphenyl hydrazone N methyl 3 Download PDF

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Publication number
CN107043344A
CN107043344A CN201710468263.9A CN201710468263A CN107043344A CN 107043344 A CN107043344 A CN 107043344A CN 201710468263 A CN201710468263 A CN 201710468263A CN 107043344 A CN107043344 A CN 107043344A
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methyl
compound
indolecarboxaldehydes
acetylbiphenyl
hydrazone
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CN107043344B (en
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谭学杰
王超
邢殿香
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Changning Changjiang Industrial Co.,Ltd.
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Qilu University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
    • C07D209/14—Radicals substituted by nitrogen atoms, not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13—Crystalline forms, e.g. polymorphs
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom

Abstract

The present invention relates to a kind of structure, preparation method and some properties of Schiff base compound.The compound outward appearance is in golden yellow bulk crystals, 168.5 169.0 DEG C of fusing point, molecular formula C24H21N3, it is chemical entitled：The H indoles of 3 ((E) ((E) (1 (base of biphenyl 4) ethylidene) hydrazine fork) methyl) 1 methyl 1, structure is as follows：It is monoclinic system, P2 that it, which is crystallized,1/ c space groups, β=90.252 (2) °,

Description

Preparation, structure and the purposes of 4-acetylbiphenyl hydrazone-N- methyl -3- indolecarboxaldehyde Schiff bases
Technical field
The present invention relates to organic synthesis, optical material and medicinal chemistry art, better simply raw material and method one have been used Step synthesis target product.
Background technology
Schiff base is a kind of more special compound of structure, can synthesize different types of according to the difference for introducing group Schiff base.Schiff base has important application in medical science, catalysis, analytical chemistry, corrosion and the field such as photochromic.For example, Medical domain, Schiff base has antibacterial, sterilization, antitumor, antiviral bioactivity；In optical material field, because it is rich The characteristics of electronics and rigid plane, make it have good fluorescence property and nonlinear optical property.
4-acetylbiphenyl hydrazone class Schiff base report is less, but such compound has larger conjugated system, it is more held Special property is easily produced in optical material field；In drug design field, the cyclohexyl biphenyl stable system fragrance of drug molecule Hydrophobic interaction, therefore it is commonly used for the structure of drug molecule.
The content of the invention
Present disclosure is to have synthesized a kind of 4-acetylbiphenyl hydrazone-N- methyl -3- indolecarboxaldehyde Schiff base compounds, the change Compound outward appearance is in golden yellow bulk crystals, 168.5-169.0 DEG C of fusing point, molecular formula C24H21N3, it is chemical entitled：3-((E)-((E)- (1- (biphenyl -4- bases) ethylidene)-hydrazine is pitched)-methyl) -1- methyl isophthalic acid-H indoles, [english system is named as：3-((E)-((E)- (1- (biphenyl-4-yl) ethylidene) hydrazono) methyl) -1-methyl-1H-indole], it is abbreviated as 3- BEHMI；Structure is as follows.
1st, Structural Identification.
Elementary analysis shows, its C, H, N percentage composition is respectively 82.08%, 6.06% and 11.98% (to be based on molecule Formula C24H21N3Theoretical value be respectively 82.02%, 6.02% and 11.96%)；Ray crystallographic analysis shows that it is monocline that it, which is crystallized, Crystallographic system, P21/ c space groups,β=90.252 (2) °,Z=4, it is relevant1HNMR spectrums,13CNMR spectrums are shown in accompanying drawing 1 and accompanying drawing 2 respectively；Accompanying drawing 3 and accompanying drawing 4 be the hot ellipsoid crystal structure figure and crystal structure accumulation graph of the compound respectively.
2nd, synthetic method.
It is characterised by the compound synthesis method：Using 4-acetylbiphenyl hydrazone and N- methyl -3- indolecarboxaldehydes as raw material, adopt With solution synthesis or solid-phase synthesis.Step is as follows：
1) 4-acetylbiphenyl hydrazone and N- methyl -3- indolecarboxaldehydes are dissolved in suitable organic solvent respectively, then by certain Mixed in molar ratio, stirring reaction certain time at a certain temperature；Two kinds can also be directly mixed without organic solvent instead Answer thing, griding reaction.
2) during liquid phase reactor, obtained solution is removed into most of solvent using certain method, powder or knot is can obtain Crystalline thing, as target product；During solid phase reaction, grinding certain time can obtain target product.
3) target product can be recrystallized with purified product in suitable organic solvent.
It is preferred that, above-mentioned reaction dissolvent or recrystallization are selected from organic solvent：Methanol, ethyl acetate, dichloromethane, second Alcohol, acetonitrile, acetone, chloroform, tetrahydrofuran.
It is preferred that, the reaction mol ratio of 4-acetylbiphenyl hydrazone and N- methyl -3- indolecarboxaldehydes is 1:4 to 4:1.
It is preferred that, the reaction temperature is room temperature to being heated to reflux.
It is preferred that, the reaction time is：0.5-12 hours.
It is preferred that, the method for removing solvent is volatilized or often/vacuum distillation for nature.
The beneficial effects of the invention are as follows：Can be with fairly simple step and the more complicated function of reactant one-step synthesis Molecular material, and separation method is simple.
3rd, ultraviolet and photoluminescent property.
10-6The ultraviolet spectra of this compound is tested in mol/L ethanol solutions, it is found in 203nm, 222nm, 282nm, There are four main ultraviolet absorption peaks at 348nm, ultraviolet spectrogram is shown in accompanying drawing 5.
10-5In mol/L ethanol solutions, the photoluminescent property of this compound is tested, it is found that it has in the range of 300-500nm Strong fluorescent emission, fluorescence spectrum is shown in accompanying drawing 6.
4th, anti tumor activity in vitro：
The A549 lung carcinoma cells or 4T1 mouse mastopathy cells that will be grown in logarithmic phase, are digested thin with 0.25% pancreatin Born of the same parents, become unicellular, and concentration is made of the F12K nutrient solutions containing 10% hyclone for 1.25 × 107Individual/L's is unicellular Suspension, cell is inoculated in 96 well culture plates, per the μ L of hole 200 (per hole 2.5 × 103Individual cell).By 96 porocyte culture plates It is placed in CO2In incubator, in 37 DEG C, 5%CO2Under the conditions of, cultivate 48h.
When hole, inner cell covers with (90% is full), empirically packet adds this Schiff base solution (200 of various dose μ L/ holes), the final concentration for making testing compound is respectively 5 μM, 10 μM, 30 μM, 50 μM, 100 μM, 150 μM, 200 μM, and every group sets 3 Individual multiple holes, cultivate 96h.
The MTT that 20 μ L concentration are 0.5g/L is separately added into each hole, continues to cultivate 4h, MTT is reduced to first a ceremonial jade-ladle, used in libation (Formazan).Suction out after whole supernatants, 200 μ L DMSO is added per hole, 15min is shaked, make after first a ceremonial jade-ladle, used in libation fully dissolves, fortune The absorbance (OD values) at 490nm is determined with enzyme-linked immunosorbent assay instrument.Then calculated according to the following formula：
Cell inhibitory rate %=(control group OD values-experimental group OD values)/control group OD value × 100%
Test result shows that the Schiff base is 108.5 μ to the IC50 (half-inhibition concentration of medicine) of lung cell A549 M, the IC50 (half-inhibition concentration of medicine) to breast cancer cell 4T1 is 112.0 μM, and this shows the compound to both cancers Cell has certain inhibition.
Embodiment
In order to be better understood from present invention, the technology of the present invention is further illustrated below by two specific embodiments Scheme：
Embodiment 1.
4-acetylbiphenyl hydrazone 0.20g (0.95mmol) is weighed to be dissolved in 30mL absolute methanols, heating stirring to whole dissolvings, plus Enter N- methyl -3- indolecarboxaldehydes 0.15g (0.95mmol), be heated to reflux stirring 6 hours, be then filtrated to get filtrate, be placed in burning Standing volatilization in cup, can obtain a large amount of lenticulars precipitations, will obtain head product (yield is about 70%), this primiparity after gained precipitation filtering Product can use ethyl alcohol recrystallization, obtain golden yellow bulk crystals, as 3-BEHMI Schiff bases.
Embodiment 2.
Weigh 4-acetylbiphenyl hydrazone 0.40g (1.9mmol) to be put into mortar, add N- methyl -3- indolecarboxaldehydes 0.30g (1.9mmol), grinds 3 hours, obtains target product crude product；By gained powder ethyl alcohol recrystallization, golden yellow bulk crystals are obtained, As 3-BEHMI Schiff bases.
Brief description of the drawings
Accompanying drawing 1 is 4-acetylbiphenyl hydrazone-N- methyl -3- indolecarboxaldehyde Schiff bases1H NMR spectras.
Accompanying drawing 2 is 4-acetylbiphenyl hydrazone-N- methyl -3- indolecarboxaldehyde Schiff bases13CNMR spectrograms.
Accompanying drawing 3 is the crystal structure figure of 4-acetylbiphenyl hydrazone-N- methyl -3- indolecarboxaldehyde Schiff bases, ellipsoid probability 30%.
Accompanying drawing 4 is the crystal structure accumulation graph of 4-acetylbiphenyl hydrazone-N- methyl -3- indolecarboxaldehyde Schiff bases, ellipsoid probability 5%.
Accompanying drawing 5 is the ultraviolet spectrogram (10 of 4-acetylbiphenyl hydrazone-N- methyl -3- indolecarboxaldehyde Schiff bases-6Mol/L ethanol is molten Liquid).
Accompanying drawing 6 is the fluorescence spectra (10 of 4-acetylbiphenyl hydrazone-N- methyl -3- indolecarboxaldehyde Schiff bases-5Mol/L ethanol is molten Liquid).

Claims (5)

1. a kind of compound, outward appearance is in golden yellow bulk crystals, 168.5-169.0 DEG C of fusing point, molecular formula C24H21N3, chemical name For：3- ((E)-((E)-(1- (biphenyl -4- bases) ethylidene)-hydrazine fork)-methyl) -1- methyl isophthalic acid-H indoles, structure is as follows：
It is monoclinic system, P2 that it, which is crystallized,1/ c space groups, β=90.252 (2) °,Z=4.
2. the preparation method of compound crystal as described in the appended claim 1, it is characterised in that：With 4-acetylbiphenyl hydrazone and N- methyl- 3- indolecarboxaldehydes are raw material, and using solution synthetic method, step is as follows：
1) 4-acetylbiphenyl hydrazone and N- methyl -3- indolecarboxaldehydes are dissolved in methanol, ethyl acetate, dichloromethane, ethanol, second respectively In nitrile, acetone, chloroform or tetrahydrofuran organic solvent, then by 1:4 to 4:1 mixed in molar ratio, in room temperature to being heated to reflux temperature Degree lower stirring reaction 0.5-12 hours；
2) obtained solution is volatilized using nature or often/vacuum distillation method removes most of solvent, can obtain powder or knot Crystalline thing, as target product；
3) target product can be organic in methanol, ethyl acetate, dichloromethane, ethanol, acetonitrile, acetone, chloroform or tetrahydrofuran Recrystallized in solvent with purified product and cultivate monocrystalline.
3. the preparation method of compound crystal as described in the appended claim 1, it is characterised in that：With 4-acetylbiphenyl hydrazone and N- methyl- 3- indolecarboxaldehydes are raw material, and using solid-phase synthesis, step is as follows：
1) 4-acetylbiphenyl hydrazone and N- methyl -3- indolecarboxaldehydes are pressed 1:4 to 4:1 mixed in molar ratio, at room temperature griding reaction 0.5-12 hours, gained powder was target product head product；
2) target product head product can be in methanol, ethyl acetate, dichloromethane, ethanol, acetonitrile, acetone, chloroform or tetrahydrochysene furan Mutter and recrystallize with purified product in organic solvent and cultivate monocrystalline.
4. compound as claimed in claim 1 is in organic pigment, Optical Bleaching Agent, photooxidant, coating, chemistry and biochemical point The purposes of analysis, solar energy trap, anti-fake mark, pharmaceutical indications and laser field, the purposes is based on its photoluminescent property.
5. as described in the appended claim 1 compound or its pharmaceutically acceptable salt prepare prevention and/or treatment tumour medicine Application in thing, it is characterised in that：The tumour is lung cancer or breast cancer.
CN201710468263.9A 2017-06-20 2017-06-20 Preparation, structure and the purposes of 4-acetylbiphenyl hydrazone-N- methyl -3- indolecarboxaldehyde Schiff base Active CN107043344B (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1987006133A1 (en) * 1986-04-07 1987-10-22 The Upjohn Company Anthelmintic acylhydrazones, method of use and compositions
CN1598698A (en) * 2003-09-16 2005-03-23 三星电子株式会社 Organophotoreceptor with charge transport compound with an azine group
WO2009155362A1 (en) * 2008-06-19 2009-12-23 Ligand Pharmaceuticals Inc. Small molecule hematopoietic growth factor mimetic compounds and their uses
CN104193650A (en) * 2014-08-12 2014-12-10 齐鲁工业大学 Structure, preparation and application of benzildihydrazone-N,N'-bis(1-formacylnaphthalene)
CN104945302A (en) * 2015-06-12 2015-09-30 齐鲁工业大学 Structure, preparation and application of benzil dihydrazone-indole-3-carboxaldehyde dual-Schiff base

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1987006133A1 (en) * 1986-04-07 1987-10-22 The Upjohn Company Anthelmintic acylhydrazones, method of use and compositions
CN1598698A (en) * 2003-09-16 2005-03-23 三星电子株式会社 Organophotoreceptor with charge transport compound with an azine group
WO2009155362A1 (en) * 2008-06-19 2009-12-23 Ligand Pharmaceuticals Inc. Small molecule hematopoietic growth factor mimetic compounds and their uses
CN104193650A (en) * 2014-08-12 2014-12-10 齐鲁工业大学 Structure, preparation and application of benzildihydrazone-N,N'-bis(1-formacylnaphthalene)
CN104945302A (en) * 2015-06-12 2015-09-30 齐鲁工业大学 Structure, preparation and application of benzil dihydrazone-indole-3-carboxaldehyde dual-Schiff base

Non-Patent Citations (2)

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MATTHIAS VOGEL,等: "Analytics of nonpeptidic erythropoietin mimetic agents in sports drug testing employing high-resolution/high-accuracy liquid chromatography-mass spectrometry", 《ANAL BIOANAL CHEM》 *
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