CN106928090A - Two（4 methoxybenzylidenes）The preparation and use of the diamines of propane 1,3 - Google Patents
Two（4 methoxybenzylidenes）The preparation and use of the diamines of propane 1,3 Download PDFInfo
- Publication number
- CN106928090A CN106928090A CN201710195125.8A CN201710195125A CN106928090A CN 106928090 A CN106928090 A CN 106928090A CN 201710195125 A CN201710195125 A CN 201710195125A CN 106928090 A CN106928090 A CN 106928090A
- Authority
- CN
- China
- Prior art keywords
- crystal
- schiff base
- propane
- chemistry
- base dimer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
- C07C251/24—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to carbon atoms of six-membered aromatic rings
-
- 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
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The present invention relates to a kind of Schiff base dimer crystal of propyl group connection, outward appearance is block in water white transparency, 76.4 77.6 DEG C of fusing point, molecular formula C19H22N2O2, molecular weight is 310.39, and chemistry is entitled：(N1E,N3E)‑N1,N3The diamines of two (4 methoxybenzylidene) propane 1,3, its structure is as follows：The crystal belongs to tetragonal crystal system, P43212 space groups,α=β=γ=90 °,
Description
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
Synthesis 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 also has good application preceding in optical material and medicinal chemistry art
Scape.
The content of the invention
1st, structural characterization
Present disclosure is to have prepared one kind with propyl group (i.e.-(CH by various methods2)3-) it is the west of connects chain
Not alkali conjugated dimmer crystal, the structure of the dimer crystal and relevant characterization parameter are as follows：
The compound outward appearance is in water white transparency bulk crystals, 76.4-77.6 DEG C of fusing point, molecular formula C19H22N2O2, molecular weight
It is 310.39, chemistry is entitled：(N1E,N3E)-N1,N3- two (4- methoxybenzylidenes) propane -1,3- diamines, english system life
It is entitled：(N1E,N3E)-N1,N3- bis (4-methoxybenzylidene) propane-1,3-diamine, its structure is as follows：
Elementary analysis shows that the percentage composition of the dimer C, H, N is respectively 61.71%, 4.96% and 7.62% and (presses and divide
Minor C19H22N2O2The theoretical value of calculating is respectively 61.75%, 5.03% and 7.57%)；Ray crystallographic analysis show that it is crystallized
It is tetragonal crystal system, P43212 space groups,α=β=γ=90 °,Z=4, accompanying drawing 1, accompanying drawing 2 are respectively the hot ellipsoid crystal structure figure and crystal structure heap of the compound
Product figure, it is relevant1HNMR spectrums,13CNMR spectrums are shown in accompanying drawing 3 and accompanying drawing 4 respectively.
2nd, synthetic method
It is characterised by the compound synthesis method：With P-methoxybenzal-dehyde and propane diamine as raw material, using solution
Synthesis or solid-phase synthesis.Step is as follows：
1) P-methoxybenzal-dehyde and propane diamine are dissolved in suitable organic solvent respectively, then by certain mol ratio
Mix, at a certain temperature stirring reaction certain hour；Two kinds of reactants can also directly be mixed without organic solvent, ground
Mill reaction.
2) during liquid phase reactor, the solution that will be obtained removes most of solvent using certain method, can obtain powder or knot
Crystalline thing, as target product；During solid phase reaction, grinding certain hour can obtain target product.
3) target product can be recrystallized with purified product in suitable organic solvent.
Preferably, above-mentioned reaction dissolvent or recrystallization are selected from solvent：Methyl alcohol, ethyl acetate, dichloromethane, ethanol, second
Nitrile, acetone, chloroform, tetrahydrofuran, toluene, N,N-dimethylformamide.
Preferably, the reaction mol ratio of P-methoxybenzal-dehyde and propane diamine is 1:2 to 4:1.
Preferably, the reaction temperature is room temperature to being heated to reflux.
Preferably, the reaction time be：0.5-12 hours.
Preferably, the method for removing solvent is nature volatilization or often/vacuum distillation.
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 213nm and 269nm
Outer absworption peak, as shown in Figure 5；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 6；It can be found that calculating gained spectrogram with experiment
It is fine that result is coincide, and such as calculates two main strong absworption peaks of gained and is located at 219nm and 267nm respectively, with experimental result only phase
Difference 6nm and 2nm；Found by orbit analysis, the two absworption peaks are produced by π → π * transition.
10-5In mol/L ethanol solutions, the ultraviolet excitation of 353nm and 369nm is respectively with wavelength, tests this chemical combination
The photoluminescent property of thing, it is found that it has strong fluorescent emission between 400~500nm, and fluorescence spectrum is shown in accompanying drawing 7；Shone with uviol lamp
Penetrate, naked eyes visible blue fluorescence.
Synthesis, such as following documents it is worth noting that, the dimer compound is reported in many documents：a)
(report fusing point is 79.0-79.5 to J.H.Billman, J.L.Meisenheimer, J.Med.Chem.6 (1963) 682-683
℃)；b)K.N.Zelenin,V.V.Alekseyev,I.V.Ukraintsev,I.V.Tselinsky,
Org.Prep.Proced.Int.30 (1998) 53-61 (report fusing point is 81 DEG C)；c)J.M.Locke,R.Griffith,
T.D.Bailey, R.L.Crumbie, 65 (2009), 10685-10692 (report fusing point is 81-82 DEG C)；d)S.Alina,
S.Cristian,K.Tadeshige,N.Satoko,M. Yoshiharu,Y.Tomoko,M.Keisuke,T.Masashi,
J.Chem.Soc.Perkin Trans.1 (2001) 2071-2078 (report fusing point is 74-76 DEG C)；e)M.S.Singh,
A.K.Singh,Pratibha Singh,Ruchi Jain,Org.Prep.Proced.Int.New J.Org.Synthesis
37 (2005) 173-177 (report fusing point be 78-80 DEG C), but the high purity single crystal of so far there are no someone the obtains compound, because
The crystal that the fusing point of this document report is obtained with us is different from；We compared for the head product and recrystallization of non-crystallization purifying
The photoluminescent property of crystal afterwards, it is found that the fluorescence intensity difference of the two is very big, tests the solid fluorescence of same quality, crystal it is glimmering
Luminous intensity is probably more than the twice of head product；With ultra violet lamp, head product cannot observe with the naked eye obvious fluorescence, i.e.,
Make increase solid consumption, its fluorescence intensity is also nothing like crystal state.
4th, anti tumor activity in vitro.
By the A549 lung carcinoma cells in logarithmic phase growth, 0.25% trypsin digestion cell is used, become unicellular, use
It is 1.25 × 10 that F12K nutrient solutions containing 10% hyclone are made concentration7The single cell suspension of individual/L, 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 of testing compound is respectively 5 μM, 10 μM, 50 μM, 100 μM, 200 μM, 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).After suctioning out whole supernatants, the DMSO of 200 μ L is added per hole, shake 15min, after first a ceremonial jade-ladle, used in libation is fully dissolved, 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 214.0 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.
Specific embodiment
In order to be better understood from present invention, technology of the 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 propane diamine 0.37g (0.005mol), is heated to reflux under stirring 6 hours, is filtered after being cooled to room temperature, and filtrate is placed in beaker
Middle standing volatilization, can obtain a large amount of lenticulars precipitations, will obtain head product after gained precipitation filtering, and this head product can again be tied with methyl alcohol
Crystalline substance, obtains colourless bulk crystals, as target product.
Embodiment 2.
P-methoxybenzal-dehyde 1.36g (0.01mol) is weighed, propane diamine 0.37g (0.005mol) is added, ground under normal temperature
8 hours, pastel is obtained, be subsequently adding 20ml absolute ethyl alcohols, heating for dissolving obtains colourless bulk crystals after cooling, as target is produced
Thing, recrystallization can make purifying products.
Brief description of the drawings
Accompanying drawing 1 is the crystal structure figure of target compound, ellipsoid probability 30%.
Accompanying drawing 2 is the crystal structure accumulation graph of target compound, is observed along a direction of principal axis.
Accompanying drawing 3 is target compound1H NMR spectras.
Accompanying drawing 4 is target compound13CNMR spectrograms.
Accompanying drawing 5 is the ultraviolet spectrogram (experimental result) of target compound.
Accompanying drawing 6 is the ultraviolet spectrogram (result of calculations of Gaussian 03) of target compound.
Accompanying drawing 7 is the fluorescence spectra (experimental result) of target compound.
Claims (2)
1. a kind of Schiff base dimer crystal of propyl group connection is in optical electron device, DNA diagnosis, Optochemical sensor, organic
Pigment, dyestuff, fluorescent whitening agent, photooxidant, fluorescent paint, laser dye, organic electroluminescence device, 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；The crystal
Outward appearance is block in water white transparency, 76.4-77.6 DEG C of fusing point, molecular formula C19H22N2O2, molecular weight is 310.39, and chemistry is entitled：
(N1E,N3E)-N1,N3- two (4- methoxybenzylidenes) propane -1,3- diamines, its structure is as follows：
The crystal belongs to tetragonal crystal system, P43212 space groups,α=β=
γ=90 °,Z=4.
2. a kind of Schiff base dimer crystal of propyl group connection or its preparing prevention and/or controlling in pharmaceutically acceptable salt
Treat the application in tumour medicine, it is characterised in that：The tumour is lung cancer；Molecular formula and the structure such as right of the compound crystal
It is required that shown in 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710195125.8A CN106928090A (en) | 2017-03-29 | 2017-03-29 | Two（4 methoxybenzylidenes）The preparation and use of the diamines of propane 1,3 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710195125.8A CN106928090A (en) | 2017-03-29 | 2017-03-29 | Two（4 methoxybenzylidenes）The preparation and use of the diamines of propane 1,3 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106928090A true CN106928090A (en) | 2017-07-07 |
Family
ID=59426182
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710195125.8A Pending CN106928090A (en) | 2017-03-29 | 2017-03-29 | Two（4 methoxybenzylidenes）The preparation and use of the diamines of propane 1,3 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106928090A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103626675A (en) * | 2013-11-04 | 2014-03-12 | 广东中烟工业有限责任公司 | Schiff base and preparation method thereof as well as application serving as cigarette free-radical scavenger |
| CN103694990A (en) * | 2013-11-29 | 2014-04-02 | 德州学院 | Schiff base zinc ion and magnesium ion fluorescent probe and preparation method thereof |
| CN103755590A (en) * | 2014-01-14 | 2014-04-30 | 昆明理工大学 | Preparation method of Schiff base and application thereof |
| CN104370770A (en) * | 2014-10-06 | 2015-02-25 | 桂林理工大学 | Bromosalicylaldehyde-based bis-schiff base and use thereof |
| CN106957242A (en) * | 2017-04-24 | 2017-07-18 | 四川省人民医院 | A kind of schiff base compounds and preparation method thereof and pharmaceutical applications |
-
2017
- 2017-03-29 CN CN201710195125.8A patent/CN106928090A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103626675A (en) * | 2013-11-04 | 2014-03-12 | 广东中烟工业有限责任公司 | Schiff base and preparation method thereof as well as application serving as cigarette free-radical scavenger |
| CN103694990A (en) * | 2013-11-29 | 2014-04-02 | 德州学院 | Schiff base zinc ion and magnesium ion fluorescent probe and preparation method thereof |
| CN103755590A (en) * | 2014-01-14 | 2014-04-30 | 昆明理工大学 | Preparation method of Schiff base and application thereof |
| CN104370770A (en) * | 2014-10-06 | 2015-02-25 | 桂林理工大学 | Bromosalicylaldehyde-based bis-schiff base and use thereof |
| CN106957242A (en) * | 2017-04-24 | 2017-07-18 | 四川省人民医院 | A kind of schiff base compounds and preparation method thereof and pharmaceutical applications |
Non-Patent Citations (2)
| Title |
|---|
| FIONA N.-F. HOW ET AL.: ""Synthesis and Characterization of Various Type of Azines as PotentialBioactive Agents"", 《INTERNATIONAL PROCEEDINGS OF CHEMICAL, BIOLOGICAL & ENVIRONMENTAL ENGINEERING》 * |
| XIAO-NA MA ET AL.: ""Two families of bis(imido) symmetrical Schiff bases: X-ray crystal structure and optical properties"", 《JOURNAL OF MOLECULAR STRUCTURE》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101580477B (en) | Dehydroabietylamine derivatives and application thereof in bactericidal and antineoplastic medicaments | |
| CN104945302B (en) | The structure of the double Schiff bases of 3 indolecarboxaldehyde of benzil dihydrazone, preparation and use | |
| CN107266348B (en) | Preparation, structure and the purposes of 4-acetylbiphenyl hydrazone -3- indolecarboxaldehyde Schiff base | |
| CN106866618B (en) | The preparation and use of two (thiophene -2- methylene) butane -1,4- diamines | |
| CN106749167A (en) | Two（The methylene of thiophene 2）The preparation and use of the diamines of propane 1,3 | |
| CN106928090A (en) | Two（4 methoxybenzylidenes）The preparation and use of the diamines of propane 1,3 | |
| Ooyama et al. | Photophysical properties and photostability of novel symmetric polycyclicphenazine-type fluorescent dyes and the dye-doped films | |
| CN106831485A (en) | Two（4 methoxybenzylidenes）The preparation and use of the diamines of butane 1,4 | |
| CN107043345A (en) | Preparation, structure and the purposes of the diketone Schiff base of 4-acetylbiphenyl hydrazone indoline 2,3 | |
| CN107266349B (en) | Preparation, structure and the purposes of 4-acetylbiphenyl hydrazone -2- indolecarboxaldehyde Schiff base | |
| CN106866619B (en) | The preparation and use of two (thiophene -2- methylene) dodecane -1,12- diamines | |
| CN111039925A (en) | Pyridine-based organic room temperature phosphorescent compound and preparation and application thereof | |
| CN105348146B (en) | Structure, preparation and use of benzil hydrazone-chlorobenzaldehyde bis-Schiff base | |
| CN110698383B (en) | Structure, synthesis and application of benzil hydrazone-3-acetyl indole | |
| CN106946735A (en) | Two（4 methoxybenzylidenes）The preparation and use of the diamines of dodecane 1,12 | |
| CN107118147A (en) | Preparation, structure and the purposes of the acetylindole Schiff base of 4-acetylbiphenyl hydrazone 3 | |
| CN105367445A (en) | Preparation, structure and application of benzyl dihydrazone-N-mono-(2-hydroxy-4-diethylin-1-formyl benzene) | |
| CN108079294B (en) | Ferrocene-lanthanide metal compound and preparation method and application thereof | |
| CN107033063B (en) | Preparation, structure and the purposes of 4-acetylbiphenyl hydrazone -4- indolecarboxaldehyde Schiff base | |
| CN104151194A (en) | Dibenzoyl dihydrazone-N,N'-di(4-methoxy-1-formylphenyl) structure, preparation and purpose thereof | |
| CN116969919B (en) | Quinoline-2-formaldehyde Schiff base derivative and preparation method and application thereof | |
| CN106188099B (en) | 1, 4-thiazepine derivative and synthetic method thereof | |
| CN108659015B (en) | Preparation and application of hexyl chain demethyl cantharidimide dimer | |
| CN108659011B (en) | Preparation and application of butyl chain demethyl cantharidimide dimer | |
| CN108659014B (en) | Preparation and application of ethyl chain demethyl cantharidimide dimer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170707 |