CN108314653A - Azacyclo- thione compounds and the preparation method and application thereof - Google Patents
Azacyclo- thione compounds and the preparation method and application thereof Download PDFInfo
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- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- G—PHYSICS
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- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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Abstract
The invention discloses azacyclo- thione compounds and the preparation method and application thereof.It is to be reacted in organic solvent with bromine with triphenylamine, and product (Y) is obtained by the reaction in three obtained (4 ' bromo phenyl) amine with imidazoles again.(Y) and bromopropane reaction are obtained into bromide (W), final product three [4 ' (N propyl imidazoles base) phenyl] amine thioketones is obtained by the reaction in bromide (W) and elemental sulfur（1）.1 is used as main body, uses different types of nitrate as object, at 25 DEG C, in organic solvent by subject and object dissolving, under a certain concentration, bulk solution is mixed with different object solution respectively, its fluorescence spectrum is measured, the object that main body can identify is found out.For the object that main body can identify, main body is titrated with the object of different concentration, measures its fluorescence spectrum.The azacyclo- thione compounds of the present invention have adjustable structure, prepare succinct, fluorescence photosensitive effect clear advantage, can be used for making fluorescent molecular identification system, be expected to be applied in fluorescence chemical field.
Description
About the statement for subsidizing research or development
The present invention is in state natural sciences fund（Fund number：21572159）, Tianjin Normal University's youth fund (fund number：
52XQ1402) and Tianjin Natural Science Fund In The Light（Fund number：11JCZDJC22000）Subsidy under carry out.
Technical field
The invention belongs to technical field of organic chemistry, it is related to through imidazoles, triphenylamine, bromine, elemental sulfur and N-Propyl Bromide alkane
As the azacyclo- thione compounds of raw material, in particular it is the preparation method of azacyclo- thione compounds and its knows in fluorescence
The research of other performance.
Background technology
Glyoxaline compound is a kind of heterocyclic compound containing two nitrogen-atoms, has good bioactivity and against corrosion
Property, such as anticancer, antimycotic, anti-inflammatory, treatment hypoglycemia and physiologic derangement, it has very important significance in pharmaceutical chemistry.
And can be used for simulating the active site research bioactivity of natural superoxide dismutase (SOD), and epoxy resin is novel solid
Agent, catalyst and certain metallic surface inorganic agents, are alternatively arranged as the intermediate of organic synthesis.For benzimidazole
Ring is luxuriant, and more and more researchers have carried out the work of many explorations.In general, carrying out advance experimental design route process
In, most common is exactly by introducing different bridge chains, by changing bridge chain, thus it is possible to vary original inherent characteristic makes its hair
Wave itself more advantage.With research deeply and research range expansion, azacyclo- thione compounds with adjustable structure,
Succinct, fluorescence photosensitive effect clear advantage is prepared, can be used for making fluorescent molecular identification system, therefore glyoxaline compound
Motif compound as fluorescent switch will obtain in fields such as chemistry subject, life science, environmental analysis and clinical medicine
Using.
Invention content
The invention discloses a kind of azacyclo- thione compounds with following structures：
N indicates the alkyl of straight chain（1）.
Azacyclo- thioketones complex preparation method disclosed by the invention, it is characterised in that carried out by following step：
（1）It is reacted in organic solvent with bromine with triphenylamine, three obtained (4 '-bromo phenyl) amine are obtained by the reaction with imidazoles again
Product (Y).(Y) and bromopropane reaction are obtained into bromide (W), final product three is obtained by the reaction in bromide (W) and elemental sulfur
[4 '-(N- propyl imidazoles base) phenyl] amine thioketones（1）；Wherein the molar ratio of triphenylamine and bromine is 1:3；Three (4 '-bromobenzenes
Base) amine again with the molar ratio of imidazoles be 1:3,（W）Molar ratio with N- ethyl imidazol(e)s is 1:3；
（2）By bromide (W) and elemental sulfur with molar ratio for 1:3 ratio is added in reaction vessels, is dissolved with organic solvent
Afterwards, reaction reflux 1 day, obtains final product three [4 '-(N- propyl imidazoles base) phenyl] amine thioketones（1）.
Step（1） 、（2）Described in organic solvent be selected from methanol, ethyl alcohol, chloroform, N,N-dimethylformamide,
The mixture of one or more of ether, acetonitrile, acetone.
The present invention further discloses azacyclo- thioketones complex crystal, crystal parameters are as follows：
The present invention further discloses application of the azacyclo- thione compounds in terms of preparing fluorescence identifying.Fluorescence therein is known
It does not refer to Cu2+Identification.
The present invention can prepare imidazole salt compound by imidazoles, triphenylamine, N-Propyl Bromide, bromine as raw material.It is
It is reacted in organic solvent with bromine with triphenylamine, product is obtained by the reaction with imidazoles again in three obtained (4 '-bromo phenyl) amine
(Y).(Y) and bromopropane reaction are obtained into bromide (W), final product three [4 '-is obtained by the reaction in bromide (W) and elemental sulfur
(N- propyl imidazoles base) phenyl] amine thioketones（1）.
The invention further relates to be used as application of the main body in fluorescence identifying field by azacyclo- thione compounds.
The azacyclo- thione compounds of the present invention have adjustable structure, prepare succinct, fluorescence photosensitive effect clear advantage, Ke Yiyong
System is identified to make fluorescent molecular, is expected to be applied in fluorescence chemical field.
The synthetic route of the present invention is as follows:
N indicates the alkyl of straight chain；
The molecular formula of typical azacyclo- thione compounds is C36H39N7S3.The assay method of the monocrystalline of azacyclo- thione compounds
It is as follows：
Crystal data and structure refinement parameter are included in supportive information.On 1000 CCD diffractometers of Bruker SMART
Carry out, experimental temperature is 113 (2) K, at 50kV and 20mA, with Mo-Ka radiation (0.71073) operation, with SMART and
SAINT softwares carry out data collection and reduction, and the range of q is 1.8< q < 25º.Experience is carried out using SADABS programs
Absorb correction.Crystal structure is solved by direct method, with SHELXTL packets to whole non-hydrogen atom coordinate anisotropy thermal parameters into
Row complete matrix least square method amendment.
One preferred embodiment of the present invention is example 1.
Presently preferred embodiment is application example 1.
The present invention further discloses the applications by azacyclo- thione compounds in fluorescence identifying field.
Experiments have shown that：It uses azacyclo- thione compounds as main body, uses different types of nitrate as object（Different nitre
Hydrochlorate, such as：Li+, Na+, K+, NH4 +, Ca2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Cr3+, Al3+, Pb2+ and
Hg2+）, in organic solvent by subject and object dissolving, under a certain concentration, bulk solution is respectively and different at 25 DEG C
Object solution mixing, measure its fluorescence spectrum, find out the object that main body can identify.For the object that main body can identify,
Main body is titrated with the object of different concentration（5.0 × 10-6 mol L-1）, measure its fluorescence spectrum.With micro note
Concentration gradually increased nitrate solution (0-400 × 10 are added in emitter-6 mol L-1).The excitation wavelength of bulk solution is
326 nm, emission spectrum have emission peak in 377 nm.Every time after addition, reaches within 8-10 minutes reaction balance and measure corresponding fluorescence
Intensity.Azacyclo- thione compounds of the present invention as main body（Especially crystal）To the fluorescence photosensitive effect of nitrate compound
Obviously, there is apparent fluorescent emission in 377 nm in fluorescence spectrum,（Fig. 2）It can be used for making fluorescence probe, be expected to
Fluorescence chemical field is applied.
Azacyclo- thione compounds crystal proposed by the present invention be it is a kind of can be stabilized in normal conditions it is advanced
Fluorescent material has fluorescence photosensitive effect clear advantage, can be used for making fluorescent molecular identification system, be expected to Fluoresceinated
Field is applied.
Description of the drawings
Fig. 1 is azacyclo- thione compounds（Embodiment 1）Crystal structure figure；
Fig. 2 is azacyclo- thione compounds（Embodiment 1）At 25 DEG C, the nitre of different type same concentrations is added in ethanol solution
The fluorescence spectra of acid salt solution；As can be seen from the figure main body is to Cu2+With Selective recognition ability;
Fig. 3 is azacyclo- thione compounds（Embodiment 1）At 25 DEG C, the Cu of various concentration is added in ethanol solution2+Solution
Fluorescence spectra, as can be seen from the figure with Cu2+The increase fluorescence intensity of concentration continuously decreases, and works as Cu2+Concentration increases to
After certain numerical value, fluorescence is reduced there is no apparent.
Specific implementation mode
The present invention is described below by specific embodiment.Unless stated otherwise, technological means used in the present invention
It is method known in those skilled in the art.In addition, embodiment is interpreted as illustrative, it is not intended to limit the present invention
Range, the spirit and scope of the invention are limited only by the claims that follow.To those skilled in the art, without departing substantially from this
Under the premise of invention spirit and scope, various changes or change to material component and dosage progress in these embodiments
It belongs to the scope of protection of the present invention.
The raw materials used in the present invention and reagent are commercially available；It is especially illustrated, prepares the starting of the compounds of this invention
Substance triphenylamine, imidazoles, N-Propyl Bromide, bromine, elemental sulfur etc. can commercially or easily pass through known method
It is made.The reagent used in the compounds of this invention is prepared all from Tianjin Ke Ruisi Chemical Co., Ltd.s, rank is point
It analyses pure.
Additionally need be illustrated be：All experimental implementations use Schlenk technologies, solvent pure by normal process
Change.The reagent that is useful for synthesizing and analyze all is that analysis is pure, and there is no by further processing.Fusing point passes through Boetius
Block apparatus measures.1H and13C{1H } NRM spectrum by mercury variable V x400 spectrophotometers record, surveying range：400 MHz
and 100 MHz.Chemical shift, δ are measured with reference to the TMS of international standard.Fluorescence spectrum passes through Cary Eclipse fluorescence spectrophotometers
Photometric determination.
Embodiment 1
The preparation of three (4 '-bromo phenyl) amine
The triphenylamine for weighing (9.640 g, 39.1 mmol) is added in 250 mL there-necked flasks, measures 40 mL chloroform solns
It is added thereto, stirring is opened with acetone ice bath, 6 mL bromines are slowly added dropwise with constant pressure funnel in there-necked flask, control two seconds
One drop, dropwise addition process keep low temperature and are stirred continuously, and 10 mL chloroform solns are added into constant pressure funnel after dripping
Continue to be added dropwise, wash out unreacted bromine, after being all added dropwise, is stirred one hour under condition of ice bath, as agitating solution becomes
For green 100 mL absolute ethyl alcohols to 40 C are in addition heated in whipping process.After waiting for there-necked flask stirring, after heating
Absolute ethyl alcohol be added in there-necked flask, solution becomes clarifying at once, is sealed with preservative film, be put into refrigerator freezing stay overnight, filter,
It uses (20 mL × 3) absolute ethyl alcohol to elute again, obtains three (4 '-bromo phenyl) amine white solids.Yield：9.470 g (80%),
M.p.: 140-142˚C。
Three [4 '-(imidazole radicals) phenyl] amine（Y）Preparation
(1.000 g, 2.0 mmol) tribromaniline, (0.850 g, 12.4 mmol) miaow are added into 250 mL three-necked flasks
Azoles, (1.500 g, 10.8 mmol) potassium carbonate and (0.170 g, 0.8 mmol) cuprous iodide, measuring 10mL DMF will be former
Material dissolves, and reaction temperature, which is warming up to 140 C, under nitrogen protection reacts 48h.Reaction system is put into rapidly water after the reaction was complete
Cooling 0.5h, has a large amount of blue and white solids to be precipitated in bath.It filters, obtains blue and white solid, dissolved with 100 mL absolute ethyl alcohols, taken out
The outstanding steaming of liquid pressure-reducing is obtained white solid, as product three [4 '-(imidazole radicals) phenyl] amine by filter.Yield：0.650 g
(70%), M.p.: 243-245˚C. 1H NMR (400MHz, DMSO-d 6): 8.20(s, 3H, PhH),7.69(s, 3H,
PhH), 7.62 (d, 6H, PhH), 7.20 (d, 6H, PhH), 7.11 (s, 3H, PhH)。
Three [4 '-(N- propyl imidazoles base) phenyl] amine bromides（W）Preparation
(0.500 g, 1.1 mmol) three [4 '-(imidazole radicals) phenyl] amine and (2.060 g, 16.7 mmol) N-Propyl Bromide is molten
In 25 mL n,N-Dimethylformamide, reaction temperature is warming up to 100 C and is stirred continuously, reacted 3-5 days, reaction life
At white solid, filters, washed to obtain product three [4 '-(N- propyl imidazoles base) phenyl] amine with a small amount of n,N-Dimethylformamide
Bromide.Yield：0.850 g (90%), M.p.: 215-217˚C.1H NMR (400MHz, DMSO-d 6): 9.87 (s,
3H, PhH), 8.32 (s, 3H, PhH), 8.07 (s, 3H, PhH), 7.83 (d, 6H, PhH), 7.32 (d,
6H, PhH), 4.23 (q, 6H, CH 2), 1.93 (t, 6H, CH 2), 0.92 (q, 9H, CH 3)。
The preparation of three [4 '-(N- propyl imidazoles base) phenyl] amine thione compounds (1)
By (0.500 g, 0.6 mmol) three [4 '-(N- propyl imidazoles base) phenyl] amine bromide with (0.140 g, 4.3
Mmol) sulphur simple substance is dissolved in 20 mL methanol, is heated to reflux, and 24 h are reacted, and reaction generates white solid, filters, obtains white
Solid, as product three [4 '-(N- propyl imidazoles base) phenyl] amine thioketones.Yield：0.300 g (75%), M.p.: 215-
217˚C.1H NMR (400MHz, DMSO-d 6):7.63(d, 6H,PhH), 7.38(d, 6H, PhH), 7.20 (d, 6H,
PhH),3.98 (t, 6H, CH 2), 1.78 (q, 6H, CH 2),0.90 (t, 9H, CH 3). 13C NMR (100 MHZ,
DMSO-d6): δ161.70(imi-NCN). 145.85(PhC), 133.53(PhC), 127.19(PhC). 123.80
(PhC), 118.51 (PhC), 118.09(PhC), 48.56 (CH2),21.45 (CH2), 10.84 (CH3), crystal knot
Structure is shown in Figure of description 1：
Embodiment 1, the crystal parameters of thione compounds
Crystal data and structure refinement parameter are included in supportive information.It is enterprising in Bruker APEX II CCD diffractometers
Row, experimental temperature is 296 (2) K, at 50kV and 20mA, with Mo-Ka radiation (0.71073) operation, with SMART and
SAINT softwares carry out data collection and reduction, and the range of q is 1.8< q < 25º.Experience is carried out using SADABS programs
Absorb correction.Crystal structure is solved by direct method, with SHELXTL packets to whole non-hydrogen atom coordinate anisotropy thermal parameters into
Row complete matrix least square method amendment.
Application example 1
At 25 DEG C, in the ethanol solution of azacyclo- thione compounds crystal（5 × 10-6mol/L）Variety classes are added
Same concentrations（10 × 10-6mol/L）The solution of nitrate（Li+, Na+, K+, NH4 +,, Ca2+, Co2+, Ni2+,
Cu2+, Zn2+, Cd2+, Cr3+, Al3+, Pb2+ and Hg2+）, its fluorescence spectrum is measured, sees attached drawing 2.
Fluorescence titration is measured by the quartz cell of Cary Eclipse sepectrophotofluorometers 1cm path lengths.Titration
Carry out being by main body (5 × 10-6 mol L-1) be put into the cuvette of 4 mL, micro syringe be used in combination that concentration is added gradual
Increased Cu2+Solution (0-400 × 10-6 mol L-1).The excitation wavelength of bulk solution is 326 nm, and emission spectrum is 377
Nm has emission peak.Every time after addition, reaches within 8-10 minutes reaction balance and measure fluorescence intensity.Data analysis uses Origin
8.0, see Fig. 3.
In conclusion present disclosure is not limited in example, the knowledgeable people in same area can be in this hair
Can propose other examples within bright technological guidance's thought easily, but this example be included in the scope of the present invention it
It is interior.
Claims (6)
1. the azacyclo- thione compounds with following structures：
N indicates the alkyl of straight chain；（1）.
2. azacyclo- thione compounds preparation method described in claim 1, it is characterised in that carried out by following step：
（1）It is reacted in organic solvent with bromine with triphenylamine, three obtained (4 '-bromo phenyl) amine are obtained by the reaction with imidazoles again
Product (Y)；(Y) and bromopropane reaction are obtained into bromide (W), final product three is obtained by the reaction in bromide (W) and elemental sulfur
[4 '-(N- propyl imidazoles base) phenyl] amine thioketones（1）；Wherein the molar ratio of triphenylamine and bromine is 1:3；Three (4 '-bromobenzenes
Base) amine again with the molar ratio of imidazoles be 1:3,（W）Molar ratio with N- ethyl imidazol(e)s is 1:3；
（2）By bromide (W) and elemental sulfur with molar ratio for 1:3 ratio is added in reaction vessels, is dissolved with organic solvent
Afterwards, reaction reflux 1 day, obtains final product three [4 '-(N- propyl imidazoles base) phenyl] amine thioketones（1）
N indicates the alkyl of straight chain（1）.
3. the preparation method described in claim 2, wherein step（1） 、（2）Described in organic solvent be selected from methanol, ethyl alcohol,
The mixture of one or more of chloroform, N,N-dimethylformamide, ether, acetonitrile, acetone.
4. azacyclo- thione compounds crystal described in claim 1, crystal parameters are as follows：
。
5. application of the azacyclo- thioketones complex described in claim 1 in terms of preparing fluorescence identifying.
6. the application described in claim 5, wherein fluorescence identifying are referred to Cu2+Identification.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504806A (en) * | 2011-10-14 | 2012-06-20 | 大连理工大学 | Metal organic skeletal material for detecting nitrogen oxide based on paramagnetic metal center |
| CN105968051A (en) * | 2016-05-16 | 2016-09-28 | 天津大学 | Organic small molecular fluorescent probe for detecting methanol and preparation method of organic small molecular fluorescent probe |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504806A (en) * | 2011-10-14 | 2012-06-20 | 大连理工大学 | Metal organic skeletal material for detecting nitrogen oxide based on paramagnetic metal center |
| CN105968051A (en) * | 2016-05-16 | 2016-09-28 | 天津大学 | Organic small molecular fluorescent probe for detecting methanol and preparation method of organic small molecular fluorescent probe |
Non-Patent Citations (3)
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| M. LEBENTAL ET AL.: "Diffusion of triplet excitons in an operational organic light-emitting diode", 《PHYSICAL REVIEW B》 * |
| YUJIAN HUANG ET AL.: "Molecular organic conductors with triiodide/hole dual channels as efficient electrolytes for solid-state dye sensitized solar cells", 《RSC ADV.》 * |
| 杨杨等: "三苯胺类荧光探针的研究进展", 《材料报道A：综述篇》 * |
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