CN106366087A - 4-(dimethylamino)-benzaldehyde-rhodamine B acylhydrazone condensation product and its preparation method and use - Google Patents

4-(dimethylamino)-benzaldehyde-rhodamine B acylhydrazone condensation product and its preparation method and use Download PDF

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CN106366087A
CN106366087A CN201610686319.3A CN201610686319A CN106366087A CN 106366087 A CN106366087 A CN 106366087A CN 201610686319 A CN201610686319 A CN 201610686319A CN 106366087 A CN106366087 A CN 106366087A
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rhodamine
dimethylamino
acylhydrazone
benzaldehyde
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朱军
徐景燕
卓馨
李晓玲
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Suzhou University
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Abstract

The invention discloses a 4-(dimethylamino)-benzaldehyde-rhodamine B acylhydrazone condensation product. The condensation product has nuclear magnetic resonance parameters such as m. p. of 160.5-162.0 DEG C, and <1>H NMR (500MHz, CDCl3), delta (ppm): 8.48 (s, 1H, N=CN), 7.43-6.20 (m, 14H Ar-H), 3.32 (q, 8H, CH2), 2.91 (s, 6H, NCH3) and 1.13 (t, 15H, CH2CH3). The invention also discloses a preparation method and a use of the 4-(dimethylamino)-benzaldehyde-rhodamine B acylhydrazone condensation product. The 4-(dimethylamino)-benzaldehyde-rhodamine B acylhydrazone condensation product as a fluorescent probe can realize naked eye colorimetric identification detection and content determination of Cd<2+> in soil and water and realize high sensitivity and high selectivity detection of Cd<2+> at pH greater than 4.5.

Description

4- (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone and preparation, application
Technical field
The present invention relates to Rhodamine Derivatives technical field, more particularly, to 4- (dimethylamino)-benzaldehyde contracting rhodamine b acyl Hydrazone and preparation method thereof, application.
Background technology
Cadmium (cadmium) is one of metal ion of generally existing in environment, extensively applies in the industrial production, such as closes The production of gold, plastics, plating etc. and use.It as a kind of very strong heavy metal of toxicity, early in 1974 just by the United Nations's ring Border Planning Department is set to priority pollutant.Half-life is twenty or thirty year to cadmium ion in the environment, and degradation rate is extremely low, thus with The development of industrial and agricultural production, the cadmium content in the environment such as polluted soil, water body also rises year by year.Therefore, research and development can Cd in the environment such as high selectivity, high-sensitivity detection soil, water body2+Method cause the highest attention of people.
The main method of detection cadmium ion has at present: atomic absorption method, chemoluminescence method, inductively coupled plasma atom Emission spectrometry and fluorimetry etc..Though these methods have its advantage in actual applications, there is also deficiency, such as chemistry Luminescence method selectivity ratios poor it is impossible to detection low concentration sample；Set needed for ICP-AES Standby price is high, and the pretreatment of sample is more complicated, complex operation etc..Wherein fluorimetry because detection limit low, simple to operate, sensitive Degree is high, response time is short, can the remarkable advantage such as on-site measurement, receive in the identification of metal ion is studied with detection and generally close Note.
Fluorescent molecular probe (fluorescent molecular probe) refers in certain system, certain system or When a certain property of material changes, also there is corresponding change, thus reflecting analyzed body in its fluorescence signal therewith The property of system or material, concentration, one-tenth grading information, this molecule can be referred to as the fluorescent molecular probe of a certain material or property. So far, existing is parent synthesis metal with regard to coumarin, rhodamine, naphthalimide, quinoline, pyrene, fluorine boron pyrroles etc. The report of ion fluorescence probe, is more especially capable of identify that transition and heavy metal ion such as fe3+、hg2+、cu2+Isoionic Fluorescent probe.
Rhodamine b precursor structure formula is as follows:
Understood by above formula: rhodamine b parent is the basic stain that the oxa- anthracene nucleus that a class is connected by " oxygen bridge " is constituted.Luo Dan Bright b is colourless in itself and does not have fluorescence phenomenon, but after its lactam nucleus is by particulate metal ion induction open loop, will produce strong Strong fluorescence, its color also can be changed into rose-red from colourless.Additionally, such dyestuff also has good water solublity, higher disappears Backscatter extinction logarithmic ratio and fluorescence quantum yield, insensitive to ph, nontoxic, the advantages of cheap and easy to get.In recent years, rhodamine b class dyestuff is because of it The research report having unique structure and being used for metal-ion fluorescent probe also gets more and more, and has been widely used in environment and has divided The fields such as analysis.
Content of the invention
The technical problem being existed based on background technology, the present invention proposes a kind of 4- (dimethylamino)-benzaldehyde contracting Luo Dan Bright b acylhydrazone and preparation method thereof, application, using 4- (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone as fluorescent probe, tentatively Achieve to content cd certain in the environment such as soil, water body2+Bore hole colorimetric recognition detection, and 5.0 × 10-6～1.0 × 10-4In the range of mol/l, can effective detection cd2+, cd2+Detection is limited to 5.45 × 10-7mol/l；4- (dimethylamino)-benzaldehyde simultaneously Contracting rhodamine b acylhydrazone is to cd2+Identification process irreversible, insensitive to ph, can be in ph > in the range of 4.5 highly sensitive, high selection ground Detection cd2+.
4- (dimethylamino) proposed by the present invention-benzaldehyde contracting rhodamine b acylhydrazone, its structural formula is as follows:
Preferably, its nuclear magnetic resonance parameter is as follows: m.p.160.5-162.0 DEG C；
1h nmr(500mhz,cdcl3), δ (ppm): 8.48 (s, 1h, n=ch), 7.43-6.20 (m, 14h, ar-h), 3.32(q,8h,ch2),2.91(s,6h,nch3),1.13(t,15h,ch2ch3)；
13c nmr(125mhz,cdcl3),δ(ppm):165.0,153.4,152.3,151.8,149.2,148.8, 133.2,129.9,129.3,128.4,124.0,123.7,123.5,111.9,108.3,106.7,98.2,66.2,44.6, 40.6,13.0.
The present invention also proposes the preparation method of above-mentioned 4- (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone, by rhodamine b Hydrazides and 4- (dimethylamino) benzaldehyde react generation 4- (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone, and it reacts signal formula As follows:
Preferably, rhodamine b hydrazides is added mix homogeneously in dehydrated alcohol to obtain solution a, then solution a is stirred Mix, to the ethanol solution of Deca 4- (dimethylamino) benzaldehyde in solution a in whipping process, then heating in water bath backflow, Stand and separate out to yellow mercury oxide, sucking filtration, washing, it is dried to obtain 4- (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone.
Preferably, rhodamine b hydrazides is added mix homogeneously in dehydrated alcohol to obtain solution a, then solution a is stirred Mix 25～35min, to the ethanol solution of Deca 4- (dimethylamino) benzaldehyde in solution a, then water-bath in whipping process It is heated to reflux 10～14h, water bath heating temperature is 75～85 DEG C, standing 22～26h separates out to yellow mercury oxide, sucking filtration, washing, It is dried to obtain 4- (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone.
Preferably, rhodamine b hydrazides and the mol ratio of 4- (dimethylamino) benzaldehyde are 1:1.
Preferably, the preparation method of rhodamine b hydrazides is as follows: with rhodamine b as raw material, with excessive hydration hydrazine reaction life Become rhodamine b hydrazides, its reaction signal formula is as follows:
Preferably, the preparation method of rhodamine b hydrazides is as follows: rhodamine b is added mix homogeneously in dehydrated alcohol, room temperature Stirring, Deca hydrazine hydrate in whipping process, heating in water bath flows back, distillation, after adding hydrochloric acid solution mix homogeneously, Deca hydrogen-oxygen Changing sodium solution to ph is 9～10, does not stop to stir during Deca, after sucking filtration, washing, and it is dried to obtain light pink solid rhodamine B hydrazides.
Preferably, the preparation method of rhodamine b hydrazides is as follows: rhodamine b is added mix homogeneously in dehydrated alcohol, room temperature Stirring 25～35min, Deca hydrazine hydrate in whipping process, heating in water bath backflow 2～4h, water bath heating temperature is 75～85 DEG C, Solution gradually becomes the light orange of clear by aubergine, and ethanol is distilled off, and adds hydrochloric acid solution mix homogeneously and obtains After the red liquid of clear, Deca sodium hydroxide solution to ph is 9～10, does not stop stirring and obtain milky during Deca Solid, after sucking filtration, it is colourless for washing to filtrate, is dried to obtain light pink solid rhodamine b hydrazides.
Preferably, in the preparation method of rhodamine b hydrazides, rhodamine b with the w/v (g/ml) of hydrazine hydrate is 2.20～2.45:6～7, the concentration of hydrochloric acid solution is 0.8～1.2mol/l, the concentration of sodium hydroxide solution is 0.8～ 1.2mol/l.
The nuclear magnetic resonance parameter of rhodamine b hydrazides is as follows: m.p.111.5-113.0 DEG C；
1h nmr(500mhz,cdcl3),δ(ppm):7.44-6.27(m,10h,ar-h),3.31(q,8h, ch2),1.62 (m,2h,nh2),1.13(t,12h,ch3)；
13c nmr(125mhz,cdcl3),δ(ppm):166.5,154.2,151.9,149.2,132.9,130.4, 128.5,124.2,123.3,108.9,104.9,98.3,66.3,44.7,13.0.
The present invention also propose above-mentioned 4- (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone as fluorescent probe be used for cadmium from The application of son detection.
4- (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone is carried out standard substance mensure:
I, 4- (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone is dissolved in acetonitrile obtain concentration be 1.0 × 10-3Mol/l's 4- (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone probe standard solution；
Ii, cadmium nitrate or Caddy (Cleary) are dissolved in deionized water obtain concentration be 1.0 × 10-3The cadmium ion standard of mol/l Solution；
Iii, in 10ml volumetric flask, add 5ml acetonitrile solution, be subsequently adding a certain amount of 4- (dimethylamino)-benzaldehyde contracting Rhodamine b acylhydrazone probe standard solution and cadmium ion standard solution, and use distilled water diluting, it is settled to scale, shakes up, place 2.5h, takes appropriate irradiation under 365nm uviol lamp, sees whether fluorescence phenomenon；Then repeat the above steps detect other Metal ion (na+, k+, mg2+Deng)；
Iv, add 5ml acetonitrile in 10ml volumetric flask, add 5 μ l4- (dimethylamino)-benzaldehyde contracting with microsyringe Rhodamine b acylhydrazone probe standard solution and the cadmium ion standard solution of 1ml, deionized water is settled to scale, places 2.5h Afterwards, with 550nm as excitation wavelength, record the fluorescence emission spectrum in wave-length coverage at 530～750nm, its slit width is 5nm；The optimal launch wavelength recording the fluorescence spectrum of 4- (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone is 553nm.
As shown in fig. 7, Fig. 7 is 4- (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone and cd2+Reaction mechanism schematic diagram. As shown in Figure 7: the lactam nucleus in 4- (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone probe are first by cd2+Identification, forms Colourless coordinate intermediate r0 molecule, then cd2+Induce its molecule that electric charge transfer occurs, open loop forms r1 molecule, finally by cd2+It is catalyzed it and hydrolyze to form the r2 molecule of redness.
The present invention, with rhodamine b, hydrazine hydrate, 4- (dimethylamino) benzaldehyde as raw material, has synthesized a kind of new Luo Dan Bright b hydrazide derivative.Using1H nmr and13C nmr characterizes to its molecular structure, with 4- (dimethylamino)-benzaldehyde Contracting rhodamine b acylhydrazone, as fluorescent probe, adds a certain amount of cd in acetonitrile/water solvent2+Afterwards, this fluorescent molecular probe and solution Middle cd2+Quickly become rose-red after effect, under ultra violet lamp, obvious red fluorescence occur, thus tentatively achieve right Certain content cd in the environment such as soil, water body2+Bore hole colorimetric recognition detection；And pass through this fluorescent molecular probe and cd2+Before coordination The wavelength of fluorescence emission spectrum afterwards and the change of fluorescence intensity, 5.0 × 10-6～1.0 × 10-4In the range of mol/l, can have Effect detection cd2+, and cd2+Detection is limited to 5.45 × 10-7mol/l；And 4- (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone pair cd2+Identification process irreversible, insensitive to ph, can be in ph > highly sensitive in the range of 4.5, detect cd to high selection2+.The present invention By using 4- (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone as fluorescent probe and cd2+Ratio colour discrimination measure, quantitative point The research of analysis detection is it is desirable to set up finite concentration cd in the environment such as a kind of detection soil, water quality2+New method.
Brief description
Fig. 1 carries out examining than colour discrimination for the embodiment of the present invention 5 gained 4- (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone The schematic diagram surveyed, wherein a is uviol lamp, and b is black box, and the corresponding metal ion of 1-11 is followed successively by na+、k+、mg2+、ca2+、zn2+、 cd2+、pb2+、fe2+、fe3+、cu2+、co+.
Fig. 2 is the embodiment of the present invention 5 gained 4- (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone probe under uviol lamp The corresponding metal ion of selectivity to metal ion, wherein 1-11 is followed successively by na+、k+、mg2+、ca2+、zn2+、cd2+、pb2+、 fe2+、fe3+、cu2+、co+.
Fig. 3 is the embodiment of the present invention 5 gained 4- (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone probe and different metal The fluorescence spectra of ion.
Fig. 4 is the embodiment of the present invention 5 gained 4- (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone probe to cd2+Fluorescence Response light spectrogram, wherein 1-8 correspond to cd2+Concentration is followed successively by: 0,5,10,25,40,60,80,100 μm of ol/l.
Fig. 5 is cd2+Concentration value and Standardization curve for fluorescence intensity.
Fig. 6 is variable concentrations cd2+Wavelength change and Standardization curve for fluorescence intensity.
Fig. 7 is 4- (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone and cd2+Reaction mechanism schematic diagram.
Specific embodiment
Below, by specific embodiment, technical scheme is described in detail.
Embodiment 1
The present invention proposes the preparation method of above-mentioned 4- (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone, by rhodamine b acyl Hydrazine and 4- (dimethylamino) benzaldehyde react generation 4- (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone.
Embodiment 2
The present invention proposes the preparation method of above-mentioned 4- (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone, by rhodamine b acyl Hydrazine adds mix homogeneously in dehydrated alcohol to obtain solution a, is then stirred solution a, to Deca in solution a in whipping process The ethanol solution of 4- (dimethylamino) benzaldehyde, then heating in water bath backflow, stand and separate out to yellow mercury oxide, sucking filtration, wash Wash, be dried to obtain 4- (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone.
Embodiment 3
The present invention proposes the preparation method of above-mentioned 4- (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone, by rhodamine b acyl Hydrazine adds mix homogeneously in dehydrated alcohol to obtain solution a, then solution a is stirred 25min, to solution a in whipping process The ethanol solution of middle Deca 4- (dimethylamino) benzaldehyde, then heating in water bath backflow 14h, water bath heating temperature is 75 DEG C, standing 26h separates out to yellow mercury oxide, sucking filtration, and washing is dried to obtain 4- (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone； Wherein rhodamine b hydrazides and the mol ratio of 4- (dimethylamino) benzaldehyde are 1:1.
Embodiment 4
The present invention proposes the preparation method of above-mentioned 4- (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone, by rhodamine b acyl Hydrazine adds mix homogeneously in dehydrated alcohol to obtain solution a, then solution a is stirred 35min, to solution a in whipping process The ethanol solution of middle Deca 4- (dimethylamino) benzaldehyde, then heating in water bath backflow 10h, water bath heating temperature is 85 DEG C, standing 22h separates out to yellow mercury oxide, sucking filtration, and washing is dried to obtain 4- (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone； Wherein rhodamine b hydrazides and the mol ratio of 4- (dimethylamino) benzaldehyde are 1:1.
Embodiment 5
The present invention proposes the preparation method of above-mentioned 4- (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone, by 2.32g (5.01mmol) rhodamine b adds mix homogeneously in dehydrated alcohol, 30min is stirred at room temperature, in whipping process, Deca 6ml mass is divided The hydrazine hydrate for 85% for the number, heating in water bath backflow 3h, water bath heating temperature is 80 DEG C, and solution gradually becomes clarification thoroughly by aubergine Bright light orange, is distilled off ethanol, adds the hydrochloric acid solution mix homogeneously that concentration is 1mol/l and obtains the red of clear After color liquid, Deca concentration be 1mol/l sodium hydroxide solution to ph be 9～10, do not stop during Deca stirring obtain milky white Color solid, after sucking filtration, it is colourless for washing to filtrate, is dried to obtain 1.8721g light pink solid rhodamine b hydrazides, and yield is 80.69%；
0.475g (1mmol) rhodamine b hydrazides is added mix homogeneously in dehydrated alcohol to obtain solution a, then by solution a It is stirred 25～35min, in whipping process, contain 0.168g (1mmol) 4- (dimethylamino) benzaldehyde to Deca in solution a Ethanol solution, then heating in water bath backflow 12h, water bath heating temperature is 80 DEG C, and standing 24h separates out to yellow mercury oxide, takes out Filter, washing, it is dried to obtain 0.2613g4- (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone, yield is 55.01%.
Experimental example 1
Embodiment 5 gained 4- (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone is carried out colorimetric recognition detection, as Fig. 1 institute Show, institute's metal ion is followed successively by from left to right: na+、k+、mg2+、ca2+、zn2+、cd2+、 pb2+、fe2+、fe3+、cu2+、co+, In each sample bottle, solution is all with, after 365nm ultra violet lamp certain time, result is as shown in Figure 2: under ultra violet lamp in Fig. 2 cd2+Strong red fluorescence phenomenon in fluorescent probe.But the same terms add other metal ions (na+, k+, mg2+Deng), all Obvious fluorescence phenomenon does not occur.
4- (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone probe solution is a kind of colourless solution, and adds na+, k+, mg2+Etc. equal unstressed configuration phenomenon.But as addition cd2+After standard solution, solution becomes rose-red by colourless rapidly.It is indicated above 4- (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone probe solution is to cd2+There is higher selectivity.Thus the method is certain Under the conditions of can realize whether bore hole colorimetric recognition detection contains cd2+, can be applicable to " water environment quality standard " (gb3838-2002) detection of class cadmium ion in.
Experimental example 2
5 μm of ol/l embodiments 5 gained 4- (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone is added acetonitrile/water (1:1) In mixed liquor, add the different types of common metal (cd of 50 μ l with microsyringe respectively2+、na+、k+、mg2+、ca2+、pb2+、 fe2+、fe3+、zn2+、cu2+、co+).After placing 2.5h under room temperature, measure its fluorescence intensity respectively, its result is as shown in figure 3, work as Add a certain amount of cd2+When, the fluorescence at 553.4nm is very strong, because rhodamine b class dyestuff has five membered lactams spiral shells of uniqueness Ring structure, itself colourless and unstressed configuration phenomenon, but adding finite concentration cd2+Afterwards, solution colour quickly becomes rose, Obvious fluorescence response occurs.
Other metal ions (na under the same conditions+、k+、mg2+、ca2+、pb2+Deng) do dependence test, but except cu2+ Exist outside weaker fluorescence response, other metal ions all do not show obvious fluorescence response phenomenon.Therefore 4- (diformazan ammonia Base)-benzaldehyde contracting rhodamine b acylhydrazone probe is to cd2+There is very strong selectivity and identity.
Experimental example 3
The cd of variable concentrations is added in 10ml acetonitrile/water (1:1) solution2+Standard solution, after placing 2.5h, with 550nm For excitation wavelength, measure respectively and add cd2+Fluorescence emission spectrum in 530～750nm wave-length coverage in front and back, as shown in Figure 4: When not adding cd2+When, 4- (dimethylamino)-fluorescence at 553nm for the benzaldehyde contracting rhodamine b acylhydrazone is very weak, now 4- (diformazan Amino)-benzaldehyde contracting rhodamine b acylhydrazone fluorescent probe is to be closed in solution in the form of rhodamine b lactams volution；When plus Enter cd2+When, being remarkably reinforced occurs in 4- (dimethylamino)-fluorescence at 553nm for the benzaldehyde contracting rhodamine b acylhydrazone, and certain In the range of with cd2+When concentration is continuously increased, fluorescence intensity increases also with continuous, is because lactams in rhodamine b molecule Volution is opened, and defines larger conjugated system.
With cd2+Variable concentrations value is abscissa, and at 553nm, fluorescence intensity level is vertical coordinate, Criterion curve, such as Fig. 5 Shown, Fig. 5 is cd2+Concentration value and Standardization curve for fluorescence intensity.
As shown in Figure 5: cd2+Concentration 5.0 × 10-6～1.0 × 10-4Have preferably with fluorescence intensity in the range of mol/l Linear relationship, its equation of linear regression is y=12.744x+700.74, and wherein x is cd2+Concentration, the unit of x is 10-6Mol/l, Correlation coefficient is 0.9991.
Defined according to detection limit, calculate detection and be limited to 5.54 × 10-7mol/l.4- under certain condition thus can be described (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone is to cd2+There is higher sensitivity, as cd in the environment such as soil, water body2+Dense Degree > 5.54 × 10-7Mol/l, being capable of effective detection.
Simultaneously as addition cd2+When 4- (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone fluorescence at 553nm occur bright Aobvious enhancing, and with cd2+When concentration is continuously increased, maximum emission wavelength is by 553nm red shift to 555.2nm.
With maximum emission wavelength as abscissa, corresponding fluorescence intensity level is vertical coordinate, and Criterion curve, as Fig. 6 institute Show, Fig. 6 is variable concentrations cd2+Wavelength change and Standardization curve for fluorescence intensity.
As shown in Figure 6: launch wavelength is mobile to assume good linear relationship with fluorescence intensity, its regression equation and phase relation Number is y=612.210x-337932.48, and wherein x is the change of wavelength, and the unit of x is nm, and correlation coefficient is 0.9995.
Due to the increase of 4- (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone concentration in solution, 4- (dimethylamino)-benzene Dimer or polymeric state, because of the energy ratio of its first electron emission singletstate in formaldehyde contracting rhodamine b acylhydrazone molecule Monomer emission single line is low, and therefore maximum emission wavelength occurs red shift.Due to 4- (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone Fluorescent probe solution is colourless in itself, as a certain amount of cd of addition2+Solution then becomes rose afterwards, under certain condition Tentatively realize to low concentration cd in the environment such as water body, soil2+Quantitative analyses detection.
The above, the only present invention preferably specific embodiment, but protection scope of the present invention is not limited thereto, Any those familiar with the art the invention discloses technical scope in, technology according to the present invention scheme and its Inventive concept equivalent or change in addition, all should be included within the scope of the present invention.

Claims (7)

1.4- (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone is it is characterised in that its structural formula is as follows:
2. according to claim 1 4- (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone it is characterised in that its nuclear magnetic resonance, NMR Parameter is as follows: m.p.160.5-162.0 DEG C；
1h nmr(500mhz,cdcl3), δ (ppm): 8.48 (s, 1h, n=ch), 7.43-6.20 (m, 14h, ar-h), 3.32 (q, 8h,ch2),2.91(s,6h,nch3),1.13(t,15h,ch2ch3)；
13c nmr(125mhz,cdcl3),δ(ppm):165.0,153.4,152.3,151.8,149.2,148.8,133.2, 129.9,129.3,128.4,124.0,123.7,123.5,111.9,108.3,106.7,98.2,66.2,44.6,40.6, 13.0.
3. the preparation method of a kind of 4- as claimed in claim 1 or 2 (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone, its feature It is, rhodamine b hydrazides and 4- (dimethylamino) benzaldehyde are reacted generation 4- (dimethylamino)-benzaldehyde contracting rhodamine b acyl Hydrazone.
4. according to claim 3 4- (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone synthetic method it is characterised in that By rhodamine b hydrazides add dehydrated alcohol in mix homogeneously obtain solution a, then solution a is stirred, in whipping process to The ethanol solution of Deca 4- (dimethylamino) benzaldehyde in solution a, then heating in water bath backflow, stand to yellow mercury oxide analysis Go out, sucking filtration, washing, be dried to obtain 4- (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone.
5. according to claim 3 or 4 4- (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone synthetic method, its feature exists In, rhodamine b hydrazides is added mix homogeneously in dehydrated alcohol to obtain solution a, then solution a is stirred 25～35min, To the ethanol solution of Deca 4- (dimethylamino) benzaldehyde in solution a in whipping process, then heating in water bath backflow 10～ 14h, water bath heating temperature is 75～85 DEG C, and standing 22～26h separates out to yellow mercury oxide, sucking filtration, and washing is dried to obtain 4- (two Methylamino)-benzaldehyde contracting rhodamine b acylhydrazone.
6. according to claim 3-5 4- (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone synthetic method, its feature exists In rhodamine b hydrazides is 1:1 with the mol ratio of 4- (dimethylamino) benzaldehyde.
7. a kind of 4- as claimed in claim 1 or 2 (dimethylamino)-benzaldehyde contracting rhodamine b acylhydrazone is used for as fluorescent probe The application of cadmium ion detection.
CN201610686319.3A 2016-08-18 2016-08-18 4-(dimethylamino)-benzaldehyde-rhodamine B acylhydrazone condensation product and its preparation method and use Pending CN106366087A (en)

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