CN106946735A

CN106946735A - Two（4 methoxybenzylidenes）The preparation and use of the diamines of dodecane 1,12

Info

Publication number: CN106946735A
Application number: CN201710194945.5A
Authority: CN
Inventors: 谭学杰; 刘健敏; 邢殿香
Original assignee: Qilu University of Technology
Current assignee: Qilu University of Technology
Priority date: 2017-03-29
Filing date: 2017-03-29
Publication date: 2017-07-14

Abstract

The present invention relates to a kind of Schiff base dimer compound of dodecyl connection, outward appearance is in colorless microcrystalline, 76.8 77.0 DEG C of fusing point, molecular formula C₂₈H₄₀N₂O₂, molecular weight is 436.63, and chemistry is entitled：(N¹E,N¹²E)‑N¹,N¹²The diamines of two (4 methoxybenzylidene) dodecane 1,12, its structure is as follows：

Description

The preparation and use of two (4- methoxybenzylidenes) dodecane -1,12- diamines

Technical field：

The present invention relates to organic synthesis, optical material and medicinal chemistry art, better simply raw material and the step of method one are used Synthesize target product.

Background technology：

Symmetry plays important role in vital movement, therefore dimer is that one kind is generally deposited in natural products Structure type.In technical field of material chemistry, dimeric structure be often used in photoelectric material, supramolecular materials, functional dye, In the structure of the new materials such as fluorescent material；Fluorescent material based on organic dimeric structure is widely used in optics electricity Sub- device, DNA diagnosis, Optochemical sensor, organic pigment, dyestuff, fluorescent whitening agent, photooxidant, fluorescent paint, laser dye Material, organic electroluminescence device (ELD) chemistry and biochemical analysis, solar energy trap, anti-fake mark, pharmaceutical indications and laser etc. Field；In medicinal chemistry art, dimer often shows more preferable activity than corresponding monomer；With the new of excellent properties The design and synthesis of dimer material are always the direction that material scholar and Pharmaceutical Chemist are made great efforts.

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, sterilized, 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；In view of Schiff base dimerization The connects chain of body can have abundant change in itself, and it is before optical material and medicinal chemistry art also have good application Scape.

The content of the invention

1st, structural characterization

Present disclosure is to have prepared one kind by a variety of methods with dodecyl (i.e.-(CH₂)₁₂-) it is connection The Schiff base conjugated dimmer compound of chain, the structure of the dimer compound and relevant characterization parameter are as follows：

The compound outward appearance is in water white transparency crystallite, 76.8-77.0 DEG C of fusing point, molecular formula C₂₈H₄₀N₂O₂, molecular weight is 436.63, chemistry is entitled：(N¹E,N¹²E)-N¹,N¹²- two (4- methoxybenzylidenes) dodecane -1,12- diamines, english system It is named as：(N¹E,N¹²E)-N¹,N¹²- bis (4-methoxybenzylidene) dodecane-1,12-diamine, its structure It is as follows：

Elementary analysis shows, the dimer C, H, N percentage composition be respectively 77.11%, 9.28% and 6.46% (by point Minor C₂₈H₄₀N₂O₂The theoretical value of calculating is respectively 77.02%, 9.23% and 6.42%)；Relevant¹HNMR spectrums,¹³CNMR spectrums point Accompanying drawing 1 and accompanying drawing 2 are not seen.

2nd, synthetic method

It is characterised by the compound synthesis method：Using P-methoxybenzal-dehyde and 1,12- dodecyls diamines as original Material, using solution synthesis or solid-phase synthesis.Step is as follows：

1) by P-methoxybenzal-dehyde and 1,12- dodecyls diamines is dissolved in suitable organic solvent respectively, then presses Certain mixed in molar ratio, at a certain temperature stirring reaction certain time；Two can also be directly mixed without organic solvent Plant reactant, 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 solvent：Methanol, ethyl acetate, dichloromethane, ethanol, second Nitrile, acetone, chloroform, tetrahydrofuran, toluene, N,N-dimethylformamide.

It is preferred that, the reaction mol ratio of P-methoxybenzal-dehyde and 1,12- dodecyl diamines is 1:2 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^-5The ultraviolet spectra of this compound is tested in mol/L ethanol solutions, it is found that it has purple at 208nm and 266nm Outer absworption peak, as shown in Figure 3；It is theoretical with TD-DFT by Gaussian03 softwares, b3lyp/6-311+g (d, p) method/ The ultraviolet spectra of the compound is calculated under base group, result of calculation is listed in accompanying drawing 4；It can be found that calculating gained spectrogram and experiment As a result identical is fine, such as calculates two main strong absworption peaks of gained and is located at 223nm and 277nm respectively, with experimental result only phase Poor 15nm and 11nm；Found by orbit analysis, the two absworption peaks are produced by π → π * transition.

10^-5In mol/L ethanol solutions, it is respectively 348nm and 366nm ultraviolet excitation with wavelength, tests this chemical combination The photoluminescent property of thing, it is found that it has strong fluorescent emission between 400~500nm, fluorescence spectrum is shown in accompanying drawing 5；Shone with uviol lamp Penetrate, naked eyes visible blue fluorescence.

4th, anti tumor activity in vitro.

The A549 lung carcinoma cells that will be grown in logarithmic phase, use 0.25% trypsin digestion cell, become unicellular, use It is 1.25 × 10 that concentration, which is made, in F12K nutrient solutions containing 10% hyclone⁷Individual/L single cell suspension, 96 are inoculated in by cell In well culture plate, per the μ L of hole 200 (per hole 2.5 × 10³Individual cell).96 porocyte culture plates are placed in CO₂In incubator, 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, 50 μM, 100 μM, 200 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 186.0 μ to the IC50 (half-inhibition concentration of medicine) of lung cell A549 M, this shows that the compound has gentle inhibition to lung carcinoma cell.

Embodiment

In order to be better understood from present invention, the technology of the present invention is further illustrated below by a specific embodiment Scheme：

Embodiment 1.

Weigh P-methoxybenzal-dehyde 1.36g (0.01mol) to be dissolved in 30mL absolute ethyl alcohols, heating stirring is molten to whole Solution, adds 1,12- dodecyl diamines 1.00g (0.005mol), is heated to reflux under stirring 6 hours, is cooled to after room temperature and filters, filter Liquid is placed in standing volatilization in beaker, can obtain a large amount of lenticulars precipitations, will obtain head product after gained precipitation filtering, this head product can use Recrystallizing methanol, obtains colourless powder crystal, as target product.

Embodiment 2.

P-methoxybenzal-dehyde 1.36g (0.01mol) is weighed, 1,12- dodecyl diamines 1.00g is added Ground 8 hours under (0.005mol), normal temperature, obtain pastel, then add 20ml absolute ethyl alcohols, heating for dissolving obtains nothing after cooling Toner is brilliant, as target product, and recrystallization can make purifying products.

Brief description of the drawings

Accompanying drawing 1 is target compound¹H NMR spectras.

Accompanying drawing 2 is target compound¹³CNMR spectrograms.

Accompanying drawing 3 is the ultraviolet spectrogram (experimental result) of target compound.

Accompanying drawing 4 is the ultraviolet spectrogram (result of calculations of Gaussian 03) of target compound.

Accompanying drawing 5 is the fluorescence spectra (experimental result) of target compound.

Claims

1. a kind of Schiff base dimer compound of dodecyl connection, the compound outward appearance is in colorless microcrystalline, fusing point 76.8- 77.0 DEG C, molecular formula C₂₈H₄₀N₂O₂, molecular weight is 436.63, and chemistry is entitled：(N¹E,N¹²E)-N¹,N¹²- two (4- methoxybenzenes Asias Methyl) dodecane -1,12- diamines, its structure is as follows：

2. compound is in optical electron device, DNA diagnosis, Optochemical sensor, organic pigment, dye as described in the appended claim 1 Material, fluorescent whitening agent, photooxidant, fluorescent paint, laser dye, organic electroluminescence device, chemistry and biochemical analysis, the sun Can trap, anti-fake mark, the purposes of pharmaceutical indications and laser field, the purposes is based on its photoluminescent property.

3. as described in the appended claim 1 compound or its pharmaceutically acceptable salt prepare prevention and/or treatment tumour Application in medicine, it is characterised in that：The tumour is lung cancer.