CN107573352B - Cyclic annular bisbenzimidazole hexafluorophosphate compound and the preparation method and application thereof - Google Patents
Cyclic annular bisbenzimidazole hexafluorophosphate compound and the preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a kind of preparation method and applications of cyclic annular bisbenzimidazole salt compound.It is in organic solvent with 2,3,5,6- durol is raw material, obtains-two bromomethyl -2 of Isosorbide-5-Nitrae with paraformaldehyde, glacial acetic acid, the concentrated sulfuric acid and bromination nak response, 3,5,6- durols, it is reacted with benzimidazole again, intermediate (Y) is obtained, by itself and 1, the reaction of (2- bromine oxethyl) anthraquinone of 8- bis-, the bromide (1) of cyclic annular bis-benzimidazole salt is obtained, then it is exchanged to obtain cyclic annular bisbenzimidazole hexafluorophosphate compound (2) with hexafluorophosphate.Cyclic annular bisbenzimidazole hexafluorophosphate compound of the invention prepares succinct, fluorescence photosensitive effect clear advantage, can be used to make fluorescent molecule identification system, be mainly used in fluorescence identification technique field.
Description
About the statement for subsidizing research or development
The present invention is in Tianjin Normal University's youth fund (fund number: 52XQ1402), state natural sciences fund (base
Jin Hao: 21572159) it and the subsidy of Tianjin Natural Science Fund In The Light (fund number: 11JCZDJC22000) under carries out.
Technical field
The invention belongs to technical field of organic chemistry, it is related to through benzimidazole, 2,3,5,6- durols, 1,8- dihydroxy
In particular base anthraquinone and 1, cyclic annular bisbenzimidazole hexafluorophosphate compound of the 2- Bromofume as raw material are cyclic annular
The preparation method of bisbenzimidazole hexafluorophosphate compound and its research in fluorescence identifying performance.
Background technique
Benzimidazoles compound is a kind of heterocyclic compound containing two nitrogen-atoms, have good bioactivity and
Corrosion stability, such as anticancer, antimycotic, anti-inflammatory, treatment hypoglycemia and physiologic derangement, have very important in pharmaceutical chemistry
Meaning.And it can be used for simulating the active site research bioactivity of natural superoxide dismutase (SOD), and epoxy resin
Novel curing agent, catalyst and certain metallic surface inorganic agents, are alternatively arranged as the intermediate of organic synthesis.For benzene
And imidazole ring is luxuriant, more and more researchers have carried out the work of many explorations.Why benzimidazole ring is luxuriant becomes concern
Hot spot, derived from the construction of own Complex Flexible.Currently, having there is the ring from the benzimidazole ion containing 2 to 4 luxuriant
It is reported in succession, molecular volume is increasing, its own performance also changes therewith.In general, being set carrying out preparatory experiment
During counting route, most common is exactly the bridge chain different by introducing, and changes the luxuriant originally included inherent characteristic of ring, makes it
Play itself more advantage.With deeply being opened with the expansion of research range, benzimidazole salt compound as fluorescence for research
The motif compound of pass will be applied in fields such as chemistry subject, life science, environmental analysis and clinical medicine.
Summary of the invention
The purpose of the present invention is to provide cyclic annular bisbenzimidazole hexafluorophosphate compounds and preparation method thereof.
The present invention has further related to cyclic annular bisbenzimidazole hexafluorophosphate compound in fluorescence identifying field
Using.
To complete above-mentioned every goal of the invention, technical solution of the present invention is as follows:
The compound of cyclic annular bis-benzimidazole salt with following structures:
2
The preparation method of ring-type bisbenzimidazole hexafluorophosphate compound of the present invention, it is characterised in that by as follows
The step of carry out:
(1) after mixing 2,3,5,6- durols, paraformaldehyde and glacial acetic acid, the concentrated sulfuric acid is added drop-wise in potassium bromide,
Bromination hydrogen is generated, is passed through in glacial acetic acid mixed liquor, obtains-two bromomethyl -2,3 of Isosorbide-5-Nitrae, 5,6- durols；Wherein 2,3,
The molar ratio of 5,6- durol and paraformaldehyde is 1:2；
(2) it in organic solvent with 1,8- dihydroxy anthraquinone for raw material, reacts to obtain 1,8-, bis- (2- with 1,2- Bromofume
Bromine oxethyl) anthraquinone reacts with benzimidazole in organic solvent using durol as raw material, obtains in durol imidazoles
Mesosome (Y)；Wherein 1,8- bis- (2- bromine oxethyl) anthraquinone and 1, the molar ratio of 2- Bromofume are 1:2, equal tetramethyl and benzo miaow
The molar ratio of azoles is 1:2；
(3) in organic solvent by obtained durol imidazole intermediates (Y) and 1,8-(2- bromine oxethyl) anthraquinone is anti-
It should obtain the bromide (1) of cyclic annular bis-benzimidazole salt；
(4) by the bromide (1) and NH of cyclic annular bis-benzimidazole salt4PF6It is added to molar ratio for the ratio of 1-1.5mol
It in reaction vessels, after being dissolved with organic solvent, reacts 3 days, filters under ambient temperature, washing obtains cyclic annular bisbenzimidazole
Hexafluorophosphate (2).
A kind of typical cyclic annular bisbenzimidazole hexafluorophosphate compound:
2
The molecular formula of typical ring-type bisbenzimidazole hexafluorophosphate is C46H44F12N4O4P2。
What is be especially illustrated is the following (use of single crystal data of cyclic annular bisbenzimidazole hexafluorophosphate compound
Bruker APEX II CCD diffractometer is measured):
The preparation method of ring-type bisbenzimidazole hexafluorophosphate compound crystal of the present invention, it is characterised in that by ring
Shape bisbenzimidazole hexafluorophosphate compound (2) is put into test tube after being dissolved in acetonitrile, and diffusion enables it slow in non-benign solvent
Slow crystallization obtains its light yellow crystal.
The present invention further discloses cyclic annular bisbenzimidazole hexafluorophosphate compound answering in fluorescence identifying field
With；The fluorescence identifying is referred to tetrabutyl ammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutyl phosphoric acid
Ammonium dihydrogen, 4-butyl ammonium hydrogen sulfate, tetrabutylammonium acetate ammonium and tetrabutyl ammonium nitrate fluorescence identifying, the results showed that main body 2 is right
OAc-With Selective recognition ability；
At 25 C, divide in water/acetonitrile solution (v:v=1:1) of cyclic annular bisbenzimidazole hexafluorophosphate compound
Not Jia Ru tetrabutyl ammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutyl ammonium dihydrogen phosphate, tetrabutyl hydrogen sulfate
Its fluorescence spectrum is measured after ammonium, tetrabutylammonium acetate ammonium and tetrabutyl ammonium nitrate, and absorption peak is selected to increase maximum tetrabutylammonium acetate
Ammonium is titrated.It uses cyclic annular bisbenzimidazole hexafluorophosphate compound as main body, is added thereto with micro syringe dense
Spend the tetrabutylammonium acetate ammonium salt solution (1 × 10 being gradually increased-5 mol/L).The excitation wavelength of bulk solution is 254nm, emits light
Spectrum has emission peak in 375-475 nm.Every time after addition, reaching within 8-10 minutes reaction balance just can record corresponding fluorescence spectrum,
Gradually increase its fluorescence intensity.See attached drawing 2 and 3.
Ring-type bisbenzimidazole hexafluorophosphate compound proposed by the present invention is a kind of can to stablize in normal conditions
Existing advanced fluorescent material, has that preparation is succinct, fluorescence photosensitive effect clear advantage, can be used to make fluorescent material and
Fluorescent molecule identifies system, is expected to be applied in fluorescence chemical field.
Detailed description of the invention
Fig. 1 is the crystal structure figure containing cyclic annular bisbenzimidazole hexafluorophosphate compound (embodiment 1)；
Fig. 2 is the water/acetonitrile solution containing cyclic annular bisbenzimidazole hexafluorophosphate compound (embodiment 1) at 25 C
Addition tetrabutyl ammonium fluoride in (v:v=1:1), tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutyl ammonium dihydrogen phosphate, four
Fluorescence spectra after butyl ammonium hydrogen sulfate, tetrabutylammonium acetate ammonium and tetrabutyl ammonium nitrate；The result shows that main body 2 is to OAc-Tool
Selective recognition capability；
Fig. 3 is cyclic annular bisbenzimidazole hexafluorophosphate compound (embodiment 1) at 25 C, water/acetonitrile solution (v:v
=1:1) in be added various concentration tetrabutylammonium acetate ammonium salt solution after fluorescence titration spectrogram；The result shows that with OAc-Concentration
The fluorescence of increase main body gradually increase, work as OAc-There is no apparent enhancings for fluorescence after concentration reaches certain numerical value.
Specific embodiment
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, to the various changes or change of 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；Wherein
2,3,5,6- durol, paraformaldehyde, 1,8- dihydroxy anthraquinone, tetrabutylammonium bromide, benzimidazole, tetramethyl
Benzene, durol imidazoles, dihydroxy anthraquinone, potassium carbonate, potassium hydroxide, anhydrous magnesium sulfate, glycol dibromide, ammonium hexafluorophosphate
Deng can commercially or being easily made by known method.
It prepares reagent used in the compounds of this invention and all derives from Tianjin Ke Ruisi Chemical Co., Ltd., rank is
It analyzes pure.
Additionally need and be illustrated: all experimental implementations use Schlenk technology, and solvent is pure by normal process
Change.All reagents for synthesizing and analyzing all are that analysis is pure, and there is no by further processing.Fusing point passes through Boetius
Block apparatus measurement.1H and13C{1H } NRM spectrum by mercury variable V x400 spectrophotometer 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 spectrophotometer
Photometric determination.
Embodiment 1
The preparation of bis- bromomethyl -2,3,5,6- durol of 1,4-:
By 2,3,5,6- durol (13.420 g, 100.0 mmol), paraformaldehyde (6.150 g, 205.0
Mmol) and after glacial acetic acid (50 mL) mixing, the concentrated sulfuric acid that mass fraction is 31 % is added drop-wise in the KBr of drying, HBr is generated
Gas is passed through in glacial acetic acid mixed liquor, and 10 h are stirred under the conditions of 120 C, has reacted and 100 mL water are added, and solid is precipitated, and is taken out
Filter, vacuum drying, obtains-two bromomethyl -2,3 of white solid Isosorbide-5-Nitrae, 5,6- durols.Yield: 31.050 g (97%).It is molten
Point: 162-164 C.1H NMR (400 MHz, DMSO-d6): δ 2.21 ( p, J = -1 Hz, 4H, CH 2), δ
2.51 (t, J = -1 Hz, 4H, CH 2), 3.37 (s, J = 5.8 Hz, 4H, CH 2), 5.51 (m, J = 5.8
Hz, 4H, CH 2), 7.24-7.31 (m, J = 3.2 Hz, 2H, PhH), 7.61-7.72 (m, J = 2.8 Hz,
4H, PhH)。
The preparation of bis- (benzimidazole the methyl) -2,3,5,6- durols of 1,4-:
After benzimidazole (1.075 g, 9.1 mmol) is dissolved with acetonitrile, and addition KOH (1.000 g, 17.8
Mmol) and tetrabutylammonium bromide (0.130 g, 0.4 mmol), and 1 h is stirred under reflux conditions.Then 1,4- is slowly added dropwise
Two bromomethyls -2,3,5,6- durols (1.440 g, 4.5 mmol) drip continuation and react 3 d at 80 DEG C.Revolving
Afterwards, the product obtained is pale yellow powder, this faint yellow solid is dissolved in CH2Cl2In (100 mL), connected with the water of 100 mL
Continuous extraction 3 times, the anhydrous MgSO of organic layer4It is dry, it filters, revolving obtains bis- (the benzimidazole methyl) -2 of white solid Isosorbide-5-Nitrae -,
3,5,6- durol.Yield: 1.543 g (88%).Fusing point: 238-240 C.1H NMR(400 MHZ, DMSO-d 6): δ
2.21 (s, 12H, CH 3), 5.51 (s, 4H, CH 2), 7.23-7.31 (m, 4H, PhH), 7.64(d, J = 7.6
Hz, 2H, PhH), 7.71 (d, J = 7.6 Hz, 2H, PhH), 7.78 (s, 2H, 2-bimH)。
The preparation of 1,8- bis- (2- bromine oxethyl) anthraquinone:
By 50 mL1,8- dihydroxy anthraquinones (5.000 g, 20.8 mmol), anhydrous K2CO3 (14.384 g, 109.0
) and the treated CH of tetrabutylammonium bromide (0.162 g, 2.1 mmol) mmol3CN suspension is leading at a temperature of indoors
Stirring 30 minutes.Drop is held 1,2- Bromofume (20.300 g, 100.5 mmol) with constant pressure funnel, is added dropwise, is maintained the reflux for,
Sufficiently reaction 3 days.After the reaction was completed, system is cooling until room temperature, filtering, are spin-dried for excess of solvent, finally obtain yellow is in
The substance of existing oily property.Use CH2Cl2This oily mater is dissolved, and water is added sufficiently to wash, then mixes water layer and methylene chloride
Solution liquid separation is closed, anhydrous Mg is added2SO4The excessive moisture in organic phase is removed, drying is kept.It is spin-dried for solvent and with acetic acid second
Ester is recrystallized to give 1,8- bis- (2- bromine oxethyl) anthraquinone product faint yellow solid, 1.246 g of yield, yield: 61%, fusing point:
122-124 ˚C。1H NMR (400 MHz, DMSO-d 6): δ 3.84 (t, J = 5.8 Hz, 4H, CH 2), 4.49
(t, J = 5.8 Hz, 4H, CH 2), 7.57 (q, J = 3.2 Hz, 2H, ArH), 7.75 (t, J = 2.8 Hz,
4H, ArH). 13C NMR (100 MHz, DMSO-d 6): δ182.9 and 180.7 (C=O), 157.3, 134.2,
134.1, 124.2, 121.5 and 119.2 (ArC), 69.7 (OCH2CH2), 30.8 (OCH2 CH2).
The preparation of cyclic annular bisbenzimidazole hexafluorophosphate compound:
By 1,8- bis- (2- bromine oxethyl) anthraquinone (0.400 g, 1.0 mmol) and durol imidazoles (0.350 g, 1.0
Mmol it) is dissolved respectively with 200 mL acetonitriles, 1000 mL is slowly added drop-wise to similar rate of addition by constant pressure dropping funnel
In there-necked flask.The acetonitrile solution of 100 mL is added before testing in 1000 mL there-necked flasks to guarantee condition dilute enough.Drip after
It is continuous to react 48 h under reflux conditions.Revolving, obtains crude product, is purified with acetone, obtain the bromo of cyclic annular bis-benzimidazole salt
Compound (1).Again with NH4PF6It carries out anion exchange and obtains corresponding faint yellow cyclic annular bisbenzimidazole hexafluorophosphate chemical combination
Object (2).Yield: 0.570 g (83%).Fusing point: 282-284 C.1H NMR(400 MHZ, DMSO-d6): δ 2.11 (s,
6H, CH 3), 2.09 (s, 6H, CH3), 4.53 (s, 4H, CH2), 5.09 (s, 4H, CH 2), 5.83 (s,
4H, CH 2), 7.41-7.73 (m, 6H, PhH), 7.89 (d, J = 7.6 Hz, 2H, PhH), 8.34 (d, J =
7.6 Hz, 2H, PhH), 8.85 (s, 2H, 2-bimH)。13C NMR (100 MHz, DMSO-d6): δ158.1
(bimi-NCN), 142.6 (PhC), 134.9 (PhC), 134.5 (PhC), 131.1 (PhC), 126.2 (PhC),
121.7 (PhC), 120.3 (PhC), 119.0 (PhC), 113.5 (PhC), 67.8 (OCH2CH2), 44.7
(NCH2), 30.6 (NCH2), 16.3 (CH3), 15.82 (CH3)
Crystal structure is shown in Figure of description 1:
The crystal of the cyclic annular bisbenzimidazole hexafluorophosphoric acid compound of embodiment 1, crystal parameters are as follows:
Crystal data and structure refinement parameter are included in supportive information.In Bruker APEX II CCD diffractometer
Upper progress, experimental temperature is 293 (2) K, at 50kV and 20mA, with Mo-Ka radiation (0.71073) operation, uses SMART
Data collection is carried out with SAINT software and reduction, the range of q are 1.8 < q < 25o.Using SADABS program carry out through
Test absorption correction.Crystal structure is solved by direct method, with SHELXTL packet to whole non-hydrogen atom coordinate anisotropy thermal parameters
Carry out complete matrix least square method amendment.
Application example 1
It is (dense in water/acetonitrile solution (v:v=1:1) of cyclic annular bisbenzimidazole hexafluorophosphoric acid compound under 25 C
Degree is 1 × 10-5 Mol/L is separately added into same concentrations (20 × 10-5 Mol/L tetrabutyl ammonium fluoride), tetrabutyl chlorine
Change ammonium, tetrabutylammonium bromide, tetrabutyl ammonium dihydrogen phosphate, 4-butyl ammonium hydrogen sulfate, tetrabutylammonium acetate ammonium and tetrabutyl nitric acid
Its fluorescence spectrum is measured after ammonium, sees attached drawing 2, it can be seen that main body 2 is to OAc from attached drawing 2-With Selective recognition ability；
Fluorescence titration is measured by the quartz cell of Cary Eclipse sepectrophotofluorometer 1cm path length.Titration
Carry out being by main body (1 × 10-5 Mol/L it) is put into the cuvette of 4 mL, and concentration is added with micro syringe and gradually increases
Big tetrabutylammonium acetate ammonium salt solution solution (0-60 × 10-5 mol L-1).The excitation wavelength of bulk solution is 254nm, emits light
Spectrum has emission peak in 375-475nm.Every time after addition, reach within 8-10 minutes the fluorescence intensity that reaction balance just has absorption, data
Analysis uses Origin 8.0, attached drawing 3 is seen, from attached drawing 3 it can be seen that with OAc-The fluorescence of the increase main body of concentration is gradually
Enhancing, works as OAc-There is no apparent enhancings for fluorescence after concentration reaches certain numerical value.
In conclusion the contents of the present invention are 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 cyclic annular bisbenzimidazole salt compound with following structures:
。
2. the preparation method of ring-type bisbenzimidazole salt compound described in claim 1, it is characterised in that by following step into
Row:
(1) after mixing 2,3,5,6- durols, paraformaldehyde and glacial acetic acid, the concentrated sulfuric acid is added drop-wise in potassium bromide, is generated
Bromination hydrogen is passed through in glacial acetic acid mixed liquor, obtains-two bromomethyl -2,3 of Isosorbide-5-Nitrae, 5,6- durols；Wherein 2,3,5,6-
The molar ratio of durol and paraformaldehyde is 1:2；
(2) it in organic solvent with 1,8- dihydroxy anthraquinone for raw material, reacts to obtain (the 2- bromine second of 1,8- bis- with 1,2- Bromofume
Oxygroup) anthraquinone, in organic solvent with-two bromomethyl -2,3 of Isosorbide-5-Nitrae, 5,6- durols are raw material, react, obtain with benzimidazole
To durol imidazole intermediates (Y)；Wherein 1,8- dihydroxy anthraquinone and 1, the molar ratio of 8- Bromofume are 1:2, Isosorbide-5-Nitrae-two
The molar ratio of bromomethyl -2,3,5,6- durol and benzimidazole is 1:2；
(3) obtained durol imidazole intermediates (Y) and (2- bromine oxethyl) anthraquinone of 1,8- bis- are reacted in organic solvent
Obtain cyclic annular bisbenzimidazole bromide (1)；
(4) by cyclic annular bisbenzimidazole bromide (1) and NH4PF6Reaction vessels are added to molar ratio for the ratio of 1-1.5mol
It is interior, it after being dissolved with organic solvent, reacts 3 days, filters under ambient temperature, washing obtains cyclic annular bisbenzimidazole hexafluorophosphoric acid
Salt (2)；
Described (1) represents: cyclic annular bisbenzimidazole bromine compounds
(2) it represents: cyclic annular bisbenzimidazole hexafluorophosphate compound
Y is represented: 1,4- bis- (benzimidazole methyl) -2,3,5,6- durol
。
3. preparation method as claimed in claim 2, wherein the organic solvent be selected from methylene chloride, acetone, methanol, ether,
The mixture of one or more of acetonitrile, ethyl acetate.
4. the crystal of ring-type bisbenzimidazole salt compound, crystal parameters described in claim 1 are as follows:
。
5. the preparation method of ring-type bis-benzimidazole salt compound crystal described in claim 4, it is characterised in that with obtained ring
Shape bisbenzimidazole hexafluorophosphate compound, is put into test tube after being dissolved in acetonitrile, and diffusion enables it in non-benign solvent
Slowly crystallization obtains its light yellow crystal.
6. application of the ring-type bisbenzimidazole salt compound in fluorescence identifying field described in claim 1；The fluorescence is known
It does not refer to tetrabutyl ammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutyl ammonium dihydrogen phosphate, tetrabutyl sulphur
Sour hydrogen ammonium, the identification of tetrabutylammonium acetate ammonium and tetrabutyl ammonium nitrate fluorescence.
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| CN104910138A (en) * | 2015-05-13 | 2015-09-16 | 天津师范大学 | Bis-benzimidazole salts based on sym-trimethylbenzene bridging, preparation method therefor and applications |
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| CN104910138A (en) * | 2015-05-13 | 2015-09-16 | 天津师范大学 | Bis-benzimidazole salts based on sym-trimethylbenzene bridging, preparation method therefor and applications |
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