CN107118147A

CN107118147A - Preparation, structure and the purposes of the acetylindole Schiff base of 4-acetylbiphenyl hydrazone 3

Info

Publication number: CN107118147A
Application number: CN201710468213.0A
Authority: CN
Inventors: 谭学杰; 卜凡志; 邢殿香
Original assignee: Qilu University of Technology
Current assignee: Haicheng Leach Carbon Materials Co ltd
Priority date: 2017-06-20
Filing date: 2017-06-20
Publication date: 2017-09-01
Anticipated expiration: 2037-06-20
Also published as: CN107118147B

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 yellow powdery solid, 282.1 283.8 DEG C of fusing point, molecular formula C₂₄H₂₁N₃, it is chemical entitled：The H indoles of 3 ((E) ((E) (base of 1 biphenyl 4) ethylidene) hydrazine fork) ethyl 1, structure is as follows：

Description

Preparation, structure and the purposes of 4-acetylbiphenyl hydrazone -3- acetylindole 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 -3- acetylindole Schiff base compounds, the compound Outward appearance is in yellow powdery solid, 282.1-283.8 DEG C of fusing point, molecular formula C₂₄H₂₁N₃, it is chemical entitled：3-((E)-((E)-(1- Biphenyl -4- bases) ethylidene)-hydrazine fork)-ethyl -1-H indoles, [english system is named as：3-((E)-((E)-(1- (biphenyl-4-yl) ethylidene)-hydrazono) ethyl) -1H-indole), it is abbreviated as 3-BEHEI；Structure is such as Under.

1st, Structural Identification.

Elementary analysis shows, its C, H, N percentage composition is respectively 82.11%, 6.07% and 12.03% (to be based on molecule Formula C₂₄H₂₁N₃Theoretical value be respectively 82.02%, 6.02% and 11.96%)；Relevant¹HNMR spectrums,¹³CNMR spectrums are shown in attached respectively Fig. 1 and accompanying drawing 2.

2nd, synthetic method.

It is characterised by the compound synthesis method：Using 4-acetylbiphenyl hydrazone and 3- acetylindoles as raw material, using molten Liquid is synthesized or solid-phase synthesis；Step is as follows：

1) 4-acetylbiphenyl hydrazone and 3- acetylindoles are dissolved in suitable organic solvent respectively, then by certain mole Than mixing, at a certain temperature stirring reaction certain time；Two kinds of reactants can also be directly mixed without organic solvent, Griding reaction.

2) during liquid phase reactor, obtained solution is removed into most of solvent using certain method, be can obtain powdered solid Body, 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 3- acetylindoles 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 that it has two at 204nm and 301nm Individual main ultraviolet absorption peak, ultraviolet spectrogram is shown in accompanying drawing 3.

10^-5In mol/L ethanol solutions, the photoluminescent property of this compound is tested, it is found that it has in the range of 300-380nm Strong fluorescent emission, fluorescence spectrum is shown in accompanying drawing 4.

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, and every group sets 3 multiple holes, culture 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 50.5 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 52.0 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 3- acetylindoles 0.15g (0.95mmol), be heated to reflux stirring 6 hours, be then filtrated to get filtrate, be placed in quiet in beaker Volatilization is put, largely powdered precipitation can be obtained, head product (yield is about 78%) will be obtained after gained precipitation filtering, this head product can use Ethyl alcohol recrystallization, obtains yellow powdery solid, as 3-BEHEI Schiff bases.

Embodiment 2.

Weigh 4-acetylbiphenyl hydrazone 0.40g (1.9mmol) to be put into mortar, add 3- acetylindoles 0.30g (1.9mmol), grinds 3 hours, obtains target product crude product；By gained powder ethyl alcohol recrystallization, yellow powdery solid is obtained, As 3-BEHEI Schiff bases.

Brief description of the drawings

Accompanying drawing 1 is 4-acetylbiphenyl hydrazone -3- acetylindole Schiff bases¹HNMR spectrograms.

Accompanying drawing 2 is 4-acetylbiphenyl hydrazone -3- acetylindole Schiff bases¹³CNMR spectrograms.

Accompanying drawing 3 is the ultraviolet spectrogram (10 of 4-acetylbiphenyl hydrazone -3- acetylindole Schiff bases^-6Mol/L ethanol solutions).

Accompanying drawing 4 is the fluorescence spectra (10 of 4-acetylbiphenyl hydrazone -3- acetylindole Schiff bases^-5Mol/L ethanol solutions).

Claims

1. a kind of compound, outward appearance is in faint yellow bulk crystals, 282.1-283.8 DEG C of fusing point, molecular formula C₂₄H₂₁N₃, chemical name For：3- ((E)-((E)-(1- biphenyl -4- bases) ethylidene)-hydrazine fork)-ethyl -1-H indoles, structure is as follows：

2. the preparation method of compound crystal as described in the appended claim 1, it is characterised in that：With 4-acetylbiphenyl hydrazone and 3- acetyl group Indoles is raw material, and using solution synthetic method, step is as follows：

1) 4-acetylbiphenyl hydrazone and 3- acetylindoles are dissolved in methanol, ethyl acetate, dichloromethane, ethanol, acetonitrile, third respectively In ketone, chloroform or tetrahydrofuran organic solvent, then by 1:4 to 4:1 mixed in molar ratio, is stirred in room temperature at a temperature of being heated to reflux Mix reaction 0.5-12 hours；

2) obtained solution is volatilized using nature or often/vacuum distillation method removes most of solvent, can obtain powdered solid Body, 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.

3. the preparation method of compound crystal as described in the appended claim 1, it is characterised in that：With 4-acetylbiphenyl hydrazone and 3- acetyl group Indoles is raw material, and using solid-phase synthesis, step is as follows：

1) 4-acetylbiphenyl hydrazone and 3- acetylindoles are pressed 1:4 to 4:1 mixed in molar ratio, griding reaction 0.5-12 is small at room temperature When, gained powder is 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.

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.