CN102993207B - Rhodamine B-triazine compounds and preparation method and application thereof - Google Patents
Rhodamine B-triazine compounds and preparation method and application thereof Download PDFInfo
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- CN102993207B CN102993207B CN201210559241.0A CN201210559241A CN102993207B CN 102993207 B CN102993207 B CN 102993207B CN 201210559241 A CN201210559241 A CN 201210559241A CN 102993207 B CN102993207 B CN 102993207B
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Abstract
The invention discloses Rhodamine B-triazine compounds and a preparation method and application thereof, belonging to the field of organic synthesis and analytical chemistry. The Rhodamine B-triazine compounds have a structure general formula described in the specification, wherein R1 represents a Rhodamine B diaminoethane group, R2 represents a Rhodamine B hydrazide group and R3 represents a diethanol amine group. The preparation method comprises the steps of: in the presence of different acid-binding agents and selective solvents, carrying out step-by-step reaction by using Rhodamine B diaminoethane or Rhodamine B hydrazide for substituting one or two helium atoms on a cyanuric chloride ring, or substituting remained un-substituted helium atoms by using diethanol amine, thus respectively synthesizing series Rhodamine B-triazine compounds. The Rhodamine B-triazine compounds are used as fluorescence or colorimetric reagents of fluorescence spectrum or ultraviolet-visible spectroscopy, and are used for detecting metal ions by an ion probe.
Description
Technical field
The present invention one class rhodamine B-triaizine compounds and its preparation method and application belongs to organic synthesis and analytical chemistry field.
background technology:metallic element has inseparable contacting with fields such as life science, environmental science, medical science.In vivo, metal ion participates in vital process, plays a part extensive and important in many physiological processs.The detection by quantitative of trace metal ion is very important in medicine, food, clinical and environment measuring, develops highly selective, the metal-ion fluorescent probe of high sensitivity then has great significance.
Fluorescent probe technique as highly sensitive, selectivity good, fast, important means that is convenient, visual detection metal ion is widely used in chemical related discipline.Fluorescent probe by with target substance selectively acting, make the Fluorescence Increasing before and after combination or quencher, wavelength and the Parameters variation such as peak shape, fluorescence lifetime, the effect of microscopic fields is showed by optical information, thus the original position realized on a molecular scale detects in real time, reach the effective identification to metal ion, molecule.Due to the highly sensitive of fluorometric analysis and highly selective, real-time in-situ detects, equipment is simple, and abundant spectral information can be provided, play an important role in various ion detection, DNA and protein molecular marker, cell imaging, immunoassay etc. in the fields such as analytical chemistry, biological chemistry, environmental science, medicine and pharmacology.
Rhodamine is as the fluorescence dye of classics, and fluorescence quantum yield is high, spectrum property is superior, structure is simple, be easy to modify, be probe compound design in often select fluorophor, metal-ion fluorescent probe research in receive much concern.The more Fluorescence Increasing type rhodamine probe of bibliographical information mainly concentrates on Hg
2+, Cu
2+, Fe
3+isoionic recognition detection.Aluminium, chromium, copper etc. are as environment and biological coherent element, and the detection method research of its novelty, particularly structure are simple, the Al that highly sensitive, selectivity is superior
3+and Cr
3+fluorescent probe design studies is significant.Bibliographical information introduces triethylene tetramine or diethylenetriamine on rhodamine molecule, has synthesized Cr respectively
3+or Fe
3+fluorescent probe; Also report and can make Cr in cell
3+the rhodamine probe of ferrocene replacement of imaging and the naphthalimide-Rhodamine fluorescent probe based on resonance energy transfer mechanism.It is that the serial Tripod of precursor group design and synthesis, calixarene type and schiff's base type are to the fluorescent probe of special metal ion selective recognition that our study group reports with rhodamine B.
In fields such as living things system, physiological process, environment and food safeties, highly sensitive, the highly selective detection and Identification research of trace metal ion are with a wide range of applications.Find to be different from traditional organic fluorescent dye molecule, make that its testing cost is cheap, sample preparation is simple, measuring method is quick, and many kinds of metal ions can be detected simultaneously, the fluorescent probe of superior performance has researching value.Fluorescent spectrometry, due to simple to operate, do not need expensive plant and instrument, has more using value.But because most developer needs could be used for detecting through the pre-treatment that extraction, separation etc. are complicated, the sensitivity crucially detected and selectivity can not meet more and more higher demand.Fluorescent signal has unrivaled superiority in sensitivity, at present, detects Al
3+rhodamine fluorescence probe have no report, and Cr
3+fluorescent probe research is very limited, Cu
2+the selectivity of probe and sensitivity need to improve.Development structure is simple, simple synthetic method, cheap, sensitivity and the superior fluorescent probe reagent of selectivity have using value multi-field.
Cyanuric chloride in compound in triazine class is nitrogenous hexa-member heterocycle, 3 nitrogen-atoms on ring can with metallic ion coordination.Carbon atom very easily reacts with amine nucleophilic reagent as electrophilic center, utilize the reactive behavior difference of 3 chlorine atoms on cyanuric chloride ring, control reaction conditions can realize carrying out classification substitution reaction, thus realize on triazine ring, optionally introducing fluorescence substituting group carrying out molecular designing and structural modification.
summary of the invention:the object of the invention is to synthesize sensitivity and the superior rhodamine B-triazine fluorescence of selectivity or colorimetric reagent, and for the fluorescence of metal ion and colorimetric estimation or as ion probe, by controlling temperature of reaction, using different acid binding agents and selective solvent, with rhodamine B quadrol or rhodamine B hydrazides stepwise reaction, replace 1 or 2 chlorine atoms on cyanuric chloride ring, or with diethanolamine, the unsubstituted chlorine atom of residue is replaced again, synthesis obtains the different rhodamine-triaizine compounds replaced of series respectively.Under specific ambient condition, utilize fluorescence spectrum and uv-visible absorption spectra, compound can highly sensitive, highly selective detection special metal ion as fluorescence and colorimetric reagent.
Fluorescence or the colorimetric compound general structure of preparation are as follows:
In formula, substituent R
1for rhodamine B quadrol base, R
2for rhodamine B hydrazide group, R
3for di-alcohol amido.
R
1or R
2to the replacement of cyanuric chloride chlorine in ring atom by differential responses temperature, be controlledly made as monosubstituted or two replacement, be twoly substituted by identical group and replace.Monosubstitutedly refer to R
1or R
2to the replacement of the chlorine of on cyanuric chloride, two replacement refers to R
1or R
2or R
3in arbitrary group to the replacement of the chlorine of two in triazine, R
3replacement refer to above-mentioned monosubstituted or two replacement after replacement to chlorine remaining on cyanuric chloride, obtain a class rhodamine B-triaizine compounds.
The present invention with cyanuric chloride, rhodamine B quadrol, rhodamine B hydrazides, diethanolamine for raw material, salt of wormwood, cesium carbonate, N, N-diisopropylethylamine is acid binding agent, anhydrous tetrahydro furan, dioxane are solvent, control temperature of reaction, select different acid binding agent and solvent, through stepwise reaction, synthesis is obtained.Synthetic route is as follows:
（1）
Control temperature of reaction, replace a chlorine on cyanuric chloride ring with rhodamine B hydrazides or rhodamine B quadrol, carry out monosubstituted;
（2）
With aforementioned (1) reaction product for raw material, then replace remaining two chlorine on cyanuric chloride ring with diethanolamine, carry out three replacements;
（3）
With aforementioned (1) reaction product for raw material, then replace another chlorine on cyanuric chloride ring with identical substituting group (rhodamine B hydrazides or rhodamine B quadrol), carry out two replacement;
（4）
With aforementioned (3) reaction product for raw material, then replace a remaining chlorine on cyanuric chloride ring with diethanolamine, carry out three replacements;
According to said synthesis route, the preparation method of each compound is as follows:
Compound
1-a(2,4-bis-chloro-6-rhodamine B hydrazides--1,3,5-triazines
)synthesis
At N
2under protection, cyanuric chloride, salt of wormwood and anhydrous tetrahydro furan are mixed, control temperature, stir the lower anhydrous tetrahydrofuran solution dripping rhodamine B hydrazides, stirring and refluxing, reaction terminates, and filter, filtrate is spin-dried for, and silica gel chromatographic column is separated, and obtains white object product
1-a:
Time for adding: 30min
Temperature of reaction: 0 ~ 5 DEG C
Reaction times: 9h
Acid binding agent: salt of wormwood
Reaction solvent: anhydrous tetrahydro furan, add-on can dissolve corresponding solute
Eluent: sherwood oil: ethyl acetate: chloroform (
v:V:
v=3:1:4)
Mol ratio: cyanuric chloride: salt of wormwood: rhodamine B hydrazides=1: 4 ~ 5: 1
Compound
1-b(the chloro-6-of 2,4-bis-(N-amine Super sensitive color reac-tion acid amides)-1,3,5-triazines
)synthesis
At N
2under protection, cyanuric chloride, salt of wormwood and anhydrous tetrahydro furan are mixed, control temperature, stir the lower anhydrous tetrahydrofuran solution dripping rhodamine B quadrol, stirring and refluxing, reaction terminates, and filter, filtrate is spin-dried for, and silica gel chromatography is separated, and obtains white object compound
1-b:
Time for adding: 30min
Temperature of reaction: 0 ~ 5 DEG C
Reaction times: 9h
Acid binding agent: salt of wormwood
Reaction solvent: anhydrous tetrahydro furan, add-on can dissolve corresponding solute
Eluent: sherwood oil: ethyl acetate (
v:V=3:2)
Mol ratio: cyanuric chloride: salt of wormwood: rhodamine B quadrol=1 ~ 1.2: 4 ~ 4.5: 1
Compound
2-a(two diethanolamine-6-rhodamine B hydrazides-the 1,3,5-triazines of 2,4-
)synthesis
At N
2under protection, diethanolamine and DIPEA are dissolved in anhydrous tetrahydro furan, control temperature, drip compound
1-aanhydrous tetrahydrofuran solution, stirring and refluxing, reaction terminate, filter, filtrate is spin-dried for, silica gel chromatographic column be separated, obtain white object compound
2-a:
Time for adding: 30min
Temperature of reaction: the first step reacts 50 DEG C, second step reacts 66 DEG C
Reaction times: 9 ~ 10h
Acid binding agent: DIPEA
Reaction solvent: anhydrous tetrahydro furan, add-on can dissolve corresponding solute
Eluent: ethanol: chloroform (
v:V=1:4)
Mol ratio: diethanolamine: DIPEA: compound
1-a=10: 4 ~ 5: 1
Compound
2-b(two diethanolamine-6-(N-amine Super sensitive color reac-tion the acid amides)-1,3,5-triazines of 2,4-
)synthesis
At N
2under protection, diethanolamine and DIPEA are dissolved in dioxane, compound
1-bbe dissolved in dioxane, control dropping temperature, stirring and refluxing, reaction terminates, and filters, and filtrate is spin-dried for silica gel chromatographic column and is separated, and obtains white object compound
2-b:
Time for adding: 30min
Temperature of reaction: the first step reacts 50 DEG C, second step reacts 101 DEG C
Reaction times: 8h
Acid binding agent: DIPEA
Reaction solvent: dioxane, add-on can dissolve corresponding solute
Eluent: ethanol: chloroform (
v:V=1:4)
Mol ratio: diethanolamine: DIPEA: compound
1-b=10: 1.5 ~ 2: 1
Compound
3-b(two (N-amine Super sensitive color reac-tion the acid amides)-1,3,5-triazines of 2-chloro-4,6-
)synthesis
By rhodamine B quadrol and compound
1-bbe dissolved in anhydrous tetrahydro furan, then add cesium carbonate, stirring and refluxing, cooling, filter, after filtrate is spin-dried for, silica gel chromatographic column is separated, and obtains target compound
3-b:
Temperature of reaction: 66 DEG C
Reaction times: 6h
Acid binding agent: cesium carbonate
Reaction solvent: anhydrous tetrahydro furan, add-on can dissolve corresponding solute
Eluent: sherwood oil: ethyl acetate (
v:V=1:1)
Mol ratio: rhodamine B quadrol: cesium carbonate: compound
1-b=1: 5 ~ 6: 1
In patent of the present invention, the gordian technique of building-up reactions is the reactive behavior difference utilizing 3 chlorine atoms on cyanuric chloride ring, control reaction conditions and realize classification substitution reaction, can obtain the different serial rhodamine-triaizine compounds replaced by one-step or two-step reaction, productive rate is all more than 60%.
Temperature controls: temperature of reaction controls at 0-5 DEG C, prepares the triaizine compounds that single rhodamine group replaces; Temperature of reaction controls at 50-66 DEG C (solvent boiling point), the triaizine compounds that the two rhodamine group of preparation replaces; Temperature of reaction controls at 66-101 DEG C (solvent boiling point), and preparation three replaces the triaizine compounds of (rhodamine group and diethanolamine).
Acid binding agent: acid binding agent when carrying out monosubstituted is salt of wormwood; Acid binding agent when carrying out two replacement is cesium carbonate; Acid binding agent when carrying out three replacements is DIPEA.
Solvent: adopt different reaction solvents during different substitution reaction, reaction times and productive rate differ greatly.Compound
2-bsynthesis, be acid binding agent with organic bases DIPEA, dioxane is solvent, and compared with when being solvent with tetrahydrofuran (THF), the reaction times shortens to 8h by 38h, and productive rate is increased to 79.4% from 65.7%.Compound
3-bsynthesis, be acid binding agent with inorganic salt cesium carbonate, tetrahydrofuran (THF) is reaction solvent, and compared with when being solvent with dioxane, the reaction times shortens to 6h by 44h, and productive rate brings up to 67.2% by 30.8%.
The proton nmr spectra data of part rhodamine-its chemical structure of triaizine compounds of the present invention's synthesis list in table 2, the carbon-13 nmr spectra data of compound list in table 3, the mass-spectrometric data of compound lists in table 4, and the infrared signature peak spectroscopic data of compound lists in table 5.
The hydrogen nuclear magnetic resonance modal data of table 2 compound
The above-claimed cpd of the inventive method synthesis, with fluorescence spectrum or uv-visible absorption spectra as detection Al
3+, Cr
3+, Cu
2+deng fluorescence or the colorimetric reagent of special metal ion.Detection working method is easy, highly sensitive, selectivity is superior.The compound of different structure can detect Al respectively
3+, Cr
3+, Cu
2+in different metal ion, Fluorometric assay concentration linearity range Da Keda 2 orders of magnitude, detectability is low to moderate 10
-8mol
.l
-1 .
Because reagent of the present invention has very high selectivity, sensitivity and low detectability to metal ion, can be used for ion probe, detect metal ion.
accompanying drawing explanation:
Fig. 1 concentration is 1.00 × 10
-5mol
.l
-1compound
1-bethanolic soln, in Tutofusin tris-hydrochloric acid pH ~ 4 buffered soln, do not add metal ion respectively or add 2.00 × 10
-4mol
.l
-1metal ion Al
3+, Cr
3+, Fe
3+, Hg
2+, Co
2+, Ni
2+, Cu
2+, Zn
2+, Cd
2+, Pb
2+, Mg
2+, Ca
2+, Sr
2+, Ag
+, K
+, Na
+after fluorescence spectrum.Al
3+add fluorescence significantly strengthened, be secondly Cr
3+.Excitation wavelength is 556, and emission wavelength is 578 nm.Ordinate zou represents fluorescence intensity, and X-coordinate represents wavelength.M
n+represent the metal ion of experiment.
Fig. 2 concentration is 1.00 × 10
-5mol
.l
-1compound
1-bethanolic soln, in Tutofusin tris-hydrochloric acid pH ~ 4 buffered soln, do not add metal ion respectively or add 2.00 × 10
-4mol
.l
-1metal ion Al
3+, Cr
3+, Fe
3+, Hg
2+, Co
2+, Ni
2+, Cu
2+, Zn
2+, Cd
2+, Pb
2+, Mg
2+, Ca
2+, Sr
2+, Ag
+, K
+, Na
+after visible absorption spectra.Al
3+add absorbancy significantly strengthened, be secondly Cr
3+.Ordinate zou represents absorbancy, and X-coordinate represents wavelength.M
n+represent the metal ion of experiment.
Fig. 3 concentration is 1.00 × 10
-5mol
.l
-1compound
3-bethanolic soln, in Tutofusin tris-hydrochloric acid pH ~ 4 buffered soln, do not add metal ion respectively or add 2.00 × 10
-4mol
.l
-1metal ion Al
3+, Cr
3+, Fe
3+, Hg
2+, Co
2+, Ni
2+, Cu
2+, Zn
2+, Cd
2+, Pb
2+, Mg
2+, Ca
2+, Sr
2+, Ag
+, K
+, Na
+after fluorescence spectrum.Al
3+add fluorescence significantly strengthened, be secondly Cr
3+.Excitation wavelength is 556, and emission wavelength is 578 nm.Ordinate zou represents fluorescence intensity, and X-coordinate represents wavelength.M
n+represent the metal ion of experiment.
Fig. 4 concentration is 1.00 × 10
-5mol
.l
-1compound
3-bethanolic soln, in Tutofusin tris-hydrochloric acid pH ~ 4 buffered soln, do not add metal ion respectively or add 2.00 × 10
-4mol
.l
-1metal ion Al
3+, Cr
3+, Fe
3+, Hg
2+, Co
2+, Ni
2+, Cu
2+, Zn
2+, Cd
2+, Pb
2+, Mg
2+, Ca
2+, Sr
2+, Ag
+, K
+, Na
+after visible absorption spectra.Al
3+add absorption significantly strengthened, be secondly Cr
3+.Ordinate zou represents absorbancy, and X-coordinate represents wavelength.M
n+represent the metal ion of experiment.
Fig. 5 coexistent metallic ion is to compound
3-
bfluorometric assay Al
3+impact
Be 1.00 × 10 in concentration
-5mol
.l
-1fluorescence or colorimetric compound
3-bethanolic soln in, Tutofusin tris-hydrochloric acid buffer solution control pH ~ 4, add 2.00 × 10
-4molL
-1al
3+after solution, fluorescence significantly strengthens.Again respectively to
3-b-al
3+other metal ions of isodose are added: Cr in solution
3+, Fe
3+, M
3+(La
3+, Ce
3+, Pr
3+, Eu
3+, Gd
3+, Dy
3+, Er
3+, Yb
3+, Lu
3+), Hg
2+, Co
2+, Ni
2+, Cu
2+, Zn
2+, Cd
2+, Pb
2+, Mg
2+, Ca
2+, Sr
2+, Ba
2+, K
+, Na
+after fluorescence intensity change.White bars represents at compound
3-bin add the emissive porwer of different metal ion.Black bar represents
3-b-al
3+solution adds the fluorescence intensity change after other coexistent metallic ions again.Show compound
3-bdetect Al
3+fluorescence not by Cr
3+and the impact of other common coexistent metallic ions.Ordinate zou represents fluorescence intensity, and X-coordinate represents metal ion.M
n+represent the metal ion of experiment.
Fig. 6 coexistent metallic ion is to compound
3-
babsorption spectroscopy detects Al
3+impact.
Be 1.00 × 10 in concentration
-5mol
.l
-1compound
3-bethanolic soln in, Tutofusin tris-hydrochloric acid buffer solution control pH ~ 4, add 2.00 × 10
-4molL
-1al
3+absorb after solution and significantly strengthen.Again respectively to
3-b-al
3+other metal ions of isodose are added: Cr in solution
3+, Fe
3+, M
3+(La
3+, Ce
3+, Pr
3+, Eu
3+, Gd
3+, Dy
3+, Er
3+, Yb
3+, Lu
3+), Hg
2+, Co
2+, Ni
2+, Cu
2+, Zn
2+, Cd
2+, Pb
2+, Mg
2+, Ca
2+, Sr
2+, Ba
2+, K
+, Na
+after absorbancy change.White bars represents at compound
3-bin add the absorbancy of different metal ion.Black bar represents
3-b-al
3+solution adds the change of the absorbancy after other coexistent metallic ions again.Show compound
3-bdetect Al
3+absorption not by Cr
3+and the impact of other common coexistent metallic ions.Ordinate zou represents absorbancy, and X-coordinate represents metal ion.M
n+represent the metal ion of experiment.
Fig. 7 coexistent metallic ion is to compound
3-
bfluorometric assay Cr
3+impact
Be 1.00 × 10 in concentration
-5mol
.l
-1compound
3-bethanolic soln in, Tutofusin tris-hydrochloric acid buffer solution control pH ~ 4, add 2.00 × 10
-4molL
-1cr
3+after solution, fluorescence significantly strengthens.Again respectively to
3-b-cr
3+other metal ions of isodose are added: Al in solution
3+, Fe
3+, M
3+(La
3+, Ce
3+, Pr
3+, Eu
3+, Gd
3+, Dy
3+, Er
3+, Yb
3+, Lu
3+), Hg
2+, Co
2+, Ni
2+, Cu
2+, Zn
2+, Cd
2+, Pb
2+, Mg
2+, Ca
2+, Sr
2+, Ba
2+, K
+, Na
+after fluorescence intensity change.White bars represents at compound
3-bin add the emissive porwer of different metal ion.Black bar represents
3-b-cr
3+solution adds the fluorescence intensity change after other coexistent metallic ions again.Show compound
3-bdetect Cr
3+fluorescence by other common coexistent metallic ions (except Al
3+impact outward).Ordinate zou represents fluorescence intensity, and X-coordinate represents metal ion.M
n+represent the metal ion of experiment.
Fig. 8 coexistent metallic ion is to compound
3-
babsorption spectroscopy detects Cr
3+impact.
Be 1.00 × 10 in concentration
-5mol
.l
-1compound
3-bethanolic soln in, Tutofusin tris-hydrochloric acid buffer solution control pH ~ 4, add 2.00 × 10
-4molL
-1cr
3+absorb after solution and significantly strengthen.Again respectively to
3-b-cr
3+other metal ions of isodose are added: Al in solution
3+, Fe
3+, M
3+(La
3+, Ce
3+, Pr
3+, Eu
3+, Gd
3+, Dy
3+, Er
3+, Yb
3+, Lu
3+), Hg
2+, Co
2+, Ni
2+, Cu
2+, Zn
2+, Cd
2+, Pb
2+, Mg
2+, Ca
2+, Sr
2+, Ba
2+, K
+, Na
+after absorbancy change.White bars represents at compound
3-bin add the absorbancy of different metal ion.Black bar represents
3-b-cr
3+solution adds the change of the absorbancy after other coexistent metallic ions again.Show compound
3-bdetect Cr
3+absorption by other common coexistent metallic ions (except Al
3+impact outward).Ordinate zou represents fluorescence intensity, and X-coordinate represents metal ion.M
n+represent the metal ion of experiment.
Fig. 9 concentration is 1.00 × 10
-5mol
.l
-1compound
2-aacetonitrile-water (3:7) solution, in Tutofusin tris-hydrochloric acid pH ~ 6 buffered soln, do not add metal ion respectively or add 2.00 × 10
-4mol
.l
-1metal ion Cu
2+, Al
3+, Cr
3+, Fe
3+, Hg
2+, Co
2+, Ni
2+, Zn
2+, Cd
2+, Pb
2+, Mg
2+, Ca
2+, Sr
2+, Ba
2+, K
+, Na
+after fluorescence spectrum.Cu
2+add fluorescence significantly strengthened, other metal ions are without response.Excitation wavelength is 553, and emission wavelength is 578 nm.Ordinate zou is fluorescence intensity, and X-coordinate is wavelength.M
n+represent the metal ion of experiment.
Figure 10 is 1.00 × 10
-5mol
.l
-1compound
2-aacetonitrile-water (3:7) solution, in Tutofusin tris-hydrochloric acid pH ~ 6 buffered soln, do not add metal ion respectively or add 2.00 × 10
-4mol
.l
-1metal ion
Cu
2+, Al
3+, Cr
3+, Fe
3+, Hg
2+, Co
2+, Ni
2+, Zn
2+, Cd
2+, Pb
2+, Mg
2+, Ca
2+, Sr
2+, Ba
2+, K
+, Na
+after visible absorption spectra.Cu
2+add visible absorbance significantly strengthened, other metal ions are without response.Ordinate zou is absorbancy, and X-coordinate is wavelength.M
n+represent the metal ion of experiment.
Figure 11 coexistent metallic ion is to compound
2-afluorometric assay Cu
2+impact
Be 1.00 × 10 in concentration
-5mol
.l
-1fluorescence or colorimetric compound
2-aacetonitrile-water (3:7) solution in, Tutofusin tris-hydrochloric acid buffer solution control pH ~ 6, add 2.00 × 10
-4molL
-1cu
2+after solution, fluorescence significantly strengthens.Again respectively to
2-a-cu
2+other metal ions of isodose are added: Al in solution
3+, Cr
3+, Fe
3+, Hg
2+, Co
2+, Ni
2+, Zn
2+, Cd
2+, Pb
2+, Mg
2+, Ca
2+, Sr
2+, Ba
2+, K
+, Na
+after fluorescence intensity change.White bars represents at compound
2-ain add the emissive porwer of different metal ion.Black bar represents
2-a-cu
2+solution adds the fluorescence intensity change after other coexistent metallic ions again.Show compound
3-adetect Cu
2+fluorescence by the impact of other common coexistent metallic ions.Ordinate zou represents fluorescence intensity, and X-coordinate represents metal ion.M
n+represent the metal ion of experiment.
Figure 12 coexistent metallic ion is to compound
2-aabsorption spectroscopy detects Cu
2+impact.
Be 1.00 × 10 in concentration
-5mol
.l
-1fluorescence or colorimetric compound
2-aacetonitrile-water (3:7) solution in, Tutofusin tris-hydrochloric acid buffer solution control pH ~ 6, add 2.00 × 10
-4molL
-1cu
2+absorb after solution and significantly strengthen.Again respectively to
2-a-cu
2+other metal ions of isodose are added: Al in solution
3+, Cr
3+, Fe
3+, Hg
2+, Co
2+, Ni
2+, Zn
2+, Cd
2+, Pb
2+, Mg
2+, Ca
2+, Sr
2+, Ba
2+, K
+, Na
+after absorbancy change.White bars represents at compound
2-ain add the absorbancy of different metal ion.Black bar represents
2-a-cu
2+solution adds the change of the absorbancy after other coexistent metallic ions again.Show compound
3-adetect Cu
2+absorption by the impact of other common coexistent metallic ions.Ordinate zou represents absorbancy, and X-coordinate represents metal ion.M
n+represent the metal ion of experiment.
Embodiment
Embodiment one: compound
1-a(the chloro-6-rhodamine B hydrazides-1,3,5-triazines of 2,4-bis-
)synthesis
At N
2in the there-necked flask of the 250ml of protection, add 323mg (1.75mmol) cyanuric chloride, 604mg (4.38mmol) K
2cO
3with 10ml anhydrous tetrahydro furan, control temperature 0 ~ 5 DEG C, dropwise adds 800mg(1.75mmol under stirring) solution of rhodamine B hydrazides (being dissolved in 50ml anhydrous tetrahydro furan), add in 30min, continue to stir 9h (thin-layer chromatography tracking).Reaction terminates, and filter, filtrate is spin-dried for, and silica gel chromatographic column is separated, and developping agent is: sherwood oil: ethyl acetate: chloroform (
v:
v:
v=3:1:4) obtain 0.81g white object product
1-a, productive rate 76.6%.m.p. >300 ℃;
1H NMR(400MHz, CDCl
3) δ:1.16 (t, 12H, J=7.0Hz, NCH
2CH
3), 3.33(q, 8H, J=7.0Hz, NCH
2CH
3), 6.31-6.29(m, 4H, ArH), 6.66-6.63(m, 2H, ArH), 7.20(d, 1H, J=8Hz, ArH), 7.61-7.53(m, 2H, ArH), 8.01(d, 1H, J=8Hz, ArH); MS (ESI)
m/z: 604.5(M
+-1)。
Embodiment two: compound
1-b(the chloro-6-of 2,4-bis-(N-amine ethyl rhodamine acid amides)-1,3,5-triazines
)synthesis
At N
2in the there-necked flask of the 250ml of protection, add 365mg (1.98mmol) cyanuric chloride, 568mg (4.11mmol) K
2cO
3with 10ml anhydrous tetrahydro furan, control temperature 0 ~ 5 DEG C, dropwise adds 800mg(1.65mmol under stirring) solution of rhodamine B quadrol (being dissolved in 50ml anhydrous tetrahydro furan), add in 30min, continue to stir 5h (thin-layer chromatography tracking).Reaction terminates, and filter, filtrate is spin-dried for, and silica gel chromatography is separated, and developping agent is: sherwood oil: ethyl acetate (
v:V=3:2), obtain 0.66g white object compound
1-b, productive rate 63.3%.m.p. 148.4-150.3 ℃;
1H NMR(400MHz, CDCl
3) δ:1.17 (t, 12H, J=6.8Hz, NCH
2CH
3), 3.26-3.22(m, 2H, NCH
2CH
2N), 3.34(q, 8H, J=6.8Hz, NCH
2CH
3), 3.42-3.39(m, 2H, NCH
2CH
2N), 6.41-6.22(m, 12H, ArH), 7.11-7.09(m, 1H, ArH), 7.49-7.47(m, 2H, ArH), 7.93-7.91(m, 1H, ArH); MS (ESI)
m/z: 632.2(M
+-1)。
Embodiment three: compound
2-a(two diethanolamine-6-rhodamine B hydrazides-the 1,3,5-triazines of 2,4-
)synthesis
At N
2in the there-necked flask of the 250ml of protection, by 1.22g(11.6mmol) diethanolamine and 599mg(4.64mmol) DIPEA is dissolved in 20ml anhydrous tetrahydro furan, 700mg(1.16mmol) compound
1-abe dissolved in 70ml anhydrous tetrahydro furan, and dropwise add in there-necked flask 50 DEG C time, drip complete stirring and refluxing 9h (thin-layer chromatography tracking).Reaction terminates, and filter, filtrate is spin-dried for, and silica gel chromatographic column is separated, developping agent: ethanol: chloroform (
v:V=1:4), obtain 0.79g product, productive rate 91.9%.m.p. 73.6-75.5 ℃;
1H NMR(400MHz, CDCl
3) δ:1.25-1.08 (m, 12H, NCH
2CH
3), 3.39-3.28(m, 8H, NCH
2CH
3), 3.78-3.64(m, 20H, NCH
2CH
2N and CH
2CH
2OH), 6.39-6.27(m, 6H, ArH), 7.10-7.06(m, 1H, ArH), 7.48-7.44(m, 2H, ArH), 7.92-7.88(m, 1H, ArH); MS (ESI)
m/z: 742.5(M
+-1)。
Embodiment four: compound
2-b(two diethanolamine-6-(N-amine ethyl rhodamine the acid amides)-1,3,5-triazines of 2,4-
)synthesis
At N
2in the there-necked flask of the 250ml of protection; by 504mg (4.80mmol) diethanolamine and 248mg(1.92mmol) N; N-diisopropylethylamine is dissolved in 10ml dioxane (molecular sieve drying), 300mg (0.48mmol) compound
1-bbe dissolved in 30ml dioxane (molecular sieve drying), and dropwise add in there-necked flask 50 DEG C time, drip complete stirring and refluxing 8h (thin-layer chromatography tracking).Reaction terminates, and filter, filtrate is spin-dried for.Silica gel chromatographic column is separated (ethanol: chloroform=1:4 wash-out), obtains 0.29g product, productive rate 79.4%.m.p. 94.3-95.5℃;
1H NMR(400MHz, CDCl
3) δ:1.17 (t, 12H, J=6.8Hz,NCH
2CH
3), 3.34-2.82 (m, 12H, NCH
2CH
3 and NCH
2CH
2N), 3.78-3.64(m,16H,CH
2CH
2OH), 6.46-6.27(m, 6H, ArH), 7.10-7.07(m, 1H, ArH), 7.48-7.44(m, 2H, ArH), 7.90-7.88(m, 1H, ArH); MS (ESI)
m/z: 770.5(M
+-1)。
Embodiment five: compound
3-b(two (N-amine ethyl rhodamine the acid amides)-1,3,5-triazines of 2-chloro-4,6-
)synthesis
In the there-necked flask of 100ml, by 1.14g (1.80mmol) rhodamine B quadrol and 875mg(1.80mmol) compound
1-bbe dissolved in 50ml anhydrous tetrahydro furan, then add 1.76g(5.4mmol) Cs
2cO
3, stirring and refluxing 6h (thin-layer chromatography tracking).Cooling, filters, and after filtrate is spin-dried for, silica gel chromatographic column is separated, developping agent: sherwood oil: ethyl acetate (
v:V=1:1 wash-out), obtain 1.31g product, productive rate 67.2%.m.p. 164.2-166.1℃;
1H NMR(400MHz, CDCl
3) δ:1.17-1.11(m, 24H, NCH
2CH
3), 3.14-3.10(q, 4H, NCH
2CH
2N), 3.32-3.28(m, 20H, NCH
2CH
2N and NCH
2CH
3), 6.42-6.15(m, 12H, ArH), 7.09-7.00(m, 2H, ArH), 7.45-7.42(m, 4H, ArH), 7.90-7.86(m, 2H, ArH); MS (ESI)
m/z: 1081.3(M
+-2)。
Embodiment six:
Compound is added in 10.0 mL volumetric flasks
1b-1(or
3b-1) ethanol storing solution (1.00 × 10
-4molL
-1, 0-3.0mL), add Tutofusin tris-hydrochloric acid buffer solution (5.00 × 10
-2molL-1, pH 4.0,1.0 mL), metal ion Al
3+(2.00 × 10
-3molL-1,0-3.75 mL) or Cr
3+(2.00 × 10
-3molL
-1, 0-4.25 mL).Be diluted to scale with ethanolic soln, shake up, at 40 DEG C of constant temperature 2h, the quartz colorimetric utensil moving into 1cm carries out fluorescence spectrum and uv-visible absorption spectra mensuration.Fluorescence spectrometry to excite with emission wavelength be 556/578 nm.
Agents useful for same is analytical reagent, and test water is redistilled water.
Spectrophotofluorometer model used is Cary Eclipse spectrophotofluorometer, and VARIAN company of the U.S. manufactures.Ultraviolet-visible spectrophotometer model is UV – vis TU-1901, and Beijing Pu Xi general instrument Corp. manufactures.
Compound is regulated with Tutofusin tris-hydrochloric acid buffer solution
1-b(or
3-b) ethanolic soln pH in 4 ~ 6 scopes, not observing compound itself has obvious fluorescent emission and ultraviolet-ray visible absorbing.Add metal ion Al
3+(or Cr
3+) after, be excitation wavelength with 556nm, observe significant fluorescent emission, maximum in the fluorescence intensity at 578 nm places, Al
3+and Cr
3+(Fig. 1 is compound to make compound fluorescence significantly strengthen respectively
1-b, Fig. 3 is compound
3-b), solution becomes pink from colourless, observes transmitting orange fluorescence under 365nm ultraviolet lamp.Meanwhile, (Fig. 2 is compound all to observe very strong visible absorbance at 556nm wavelength place
1-b, Fig. 4 is compound
3-b).Except Fe
3+add have feeble signal increase outside, other Experiment Metal ion-pair compounds, all without obvious response signal, show that these two kinds of compounds are to Al
3+and Cr
3+there is recognition detection performance.
Compound
3-bdetect Al
3+fluorescence (Fig. 5) and absorption intensity (Fig. 6) not by Cr
3+the impact coexisted.And Al
3+to compound when coexisting
3-bdetect Cr
3+fluorescence (Fig. 7) and absorption intensity (Fig. 8) have certain influence.Other common coexistent metallic ions when concentration is suitable with test ion, on detect fluorescence intensity and absorbancy impact relative deviation all within 5%.All not interference measurements.
In the ethanolic soln of Tutofusin tris-hydrochloric acid control pH ~ 4, be fluorescence excitation and emission wavelength with 556/578nm, be maximum absorption wavelength with 556nm, measure Al respectively
3+and Cr
3+change in concentration and compound
1-b(or
3-b) fluorescent emission and absorbancy strengthen working curve.By the slope of calibration curve and the standard deviation measuring 10 blank values, measure and calculate linearity range and detection limit lists in table 6.
Table 6 compound detects the analytical parameters of metal ion as fluorescence or colorimetric reagent
Embodiment seven:
Compound is added in 10.0 mL volumetric flasks
2-aacetonitrile storing solution (1.00 × 10
-4molL
-1, 0-3.0mL), add Tutofusin tris-hydrochloric acid buffer solution (5.00 × 10
-2molL-1, pH ~ 6,1.0 mL), metal ion Cu
2+(2.00 × 10
-3molL-1,0-1.0 mL).Be diluted to scale (making acetonitrile in solution: water=3:7) with acetonitrile-aqueous solution, shake up, place 2h in room temperature, the quartz colorimetric utensil moving into 1cm carries out fluorescence spectrum and uv-visible absorption spectra mensuration.Fluorescence spectrometry to excite with emission wavelength be 553/578 nm.
Compound is regulated with Tutofusin tris-hydrochloric acid buffer solution
2-aacetonitrile-aqueous solution (acetonitrile: water=3:7) pH is in 3 ~ 7 scopes, compound itself does not have obvious fluorescent emission and ultraviolet-ray visible absorbing.Add metal ion Cu
2+after, be excitation wavelength with 553nm, observe significant fluorescent emission, maximum in the fluorescence intensity at 578 nm places, Cu
2+compound fluorescence is significantly strengthened (Fig. 9), and solution becomes pink from colourless, observes transmitting orange fluorescence under 365nm ultraviolet lamp.Meanwhile, very strong visible absorbance (Figure 10) is observed at 553nm wavelength place.Other Experiment Metal ion-pair compounds, all without obvious response signal, show that these two kinds of reagent are to Cu
2+there is recognition detection performance.
Compound in embodiments of the invention
2-acu is detected as fluorescence or colorimetric reagent
2+time, when other common coexistent metallic ions that concentration is suitable exist, on the fluorescence intensity (Figure 11) detected and the relative deviation that affects of absorbancy (Figure 12) all within 5%.All not interference measurements.
In the ethanolic soln of Tutofusin tris-hydrochloric acid control pH ~ 6.0, be fluorescence excitation and emission wavelength with 553/578nm, be maximum absorption wavelength with 553nm, measure Cu respectively
2+change in concentration and compound
2-afluorescent emission and absorbancy strengthen working curve.By the slope of calibration curve and the standard deviation measuring 10 blank values, measure and calculate linearity range and detection limit lists in table 7.
Table 7 compound detects Cu as fluorescence or colorimetric reagent
2+analytical parameters
Claims (5)
1. rhodamine B-triaizine compounds, is characterized in that its structural formula is:
。
2. according to the preparation method of rhodamine B-triaizine compounds according to claim 1, it is characterized in that by controlling temperature of reaction, select acid binding agent and solvent, control substitution reaction with rhodamine B hydrazides and diethanolamine to cyanuric chloride chlorine in ring atom substep and obtain, synthetic route is as follows:
（1）
Control temperature of reaction, replace a chlorine on cyanuric chloride ring with rhodamine B hydrazides;
（2）
With compound
1-afor raw material, then replace remaining two chlorine on cyanuric chloride ring with diethanolamine, obtained compound
2-a.
3. the preparation method of rhodamine B-triaizine compounds according to claim 2, it is characterized in that concrete synthetic technological condition is for raw material with cyanuric chloride, rhodamine B hydrazides, diethanolamine, salt of wormwood, N, N-diisopropylethylamine is acid binding agent, anhydrous tetrahydro furan is solvent, control temperature of reaction, select different acid binding agent, obtain through stepwise reaction:
(1) compound
1-asynthesis
At N
2under protection, cyanuric chloride, salt of wormwood and anhydrous tetrahydro furan are mixed, control temperature, stir the lower anhydrous tetrahydrofuran solution dripping rhodamine B hydrazides, stirring and refluxing, reaction terminates, and filter, filtrate is spin-dried for, and silica gel chromatographic column is separated, and obtains white object product
1-a,described 1-a is the chloro-6-rhodamine B hydrazides-1,3,5-triazines of 2,4-bis-,
Time for adding: 30min
Temperature of reaction: 0 ~ 5 DEG C
Reaction times: 9h
Acid binding agent: salt of wormwood
Reaction solvent: anhydrous tetrahydro furan, add-on can dissolve corresponding solute
Eluent: sherwood oil: ethyl acetate: chloroform, volume ratio
v:V:
v=3:1:4
Mol ratio: cyanuric chloride: salt of wormwood: rhodamine B quadrol=1:4 ~ 5:1
(2) compound
2-asynthesis
At N
2under protection, diethanolamine and DIPEA are dissolved in anhydrous tetrahydro furan, control temperature, drip compound
1-aanhydrous tetrahydrofuran solution, stirring and refluxing, reaction terminate, filter, filtrate is spin-dried for, silica gel chromatographic column be separated, obtain white object compound
2-a,described 2-a is the two diethanolamine-6-rhodamine B hydrazides-1,3,5-triazines of 2,4-,
Time for adding: 30min
Temperature of reaction: the first step reacts 50 DEG C, second step reacts 66 DEG C
Reaction times: 9 ~ 10h
Acid binding agent: DIPEA
Reaction solvent: anhydrous tetrahydro furan, add-on can dissolve corresponding solute
Eluent: ethanol: chloroform, volume ratio
v:V=1:4
Mol ratio: diethanolamine: DIPEA: compound
1-a=10:4 ~ 5:1.
4., according to the application of rhodamine B-triaizine compounds according to claim 1, it is characterized in that using compound
2-ametal ion Cu is detected as fluorescence spectrum or uv-visible absorption spectra
2+fluorescence or colorimetric reagent.
5. the application of rhodamine B-triaizine compounds according to claim 4, is characterized in that using compound
2-aas detection metal ion Cu
2+fluorescent probe, Fluorometric assay Cu
2+concentration linearity range Da Keda 2 orders of magnitude, detectability is low to moderate 10
-8mol
.l
-1.
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