CN105733561B - 9,9 ' (diphenyl ether base of 3,3 ' dihydroxy 4,4 ') double fluorone reagents and its preparation method and application - Google Patents
9,9 ' (diphenyl ether base of 3,3 ' dihydroxy 4,4 ') double fluorone reagents and its preparation method and application Download PDFInfo
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Abstract
The invention belongs to Fluorone reagent series compound technical, it is not ideal enough to solve existing its sensitivity of Fluorone reagent series compound and selectivity, it cannot function as the problem of fluorometric reagent is used for the fluoroscopic examination of metal ion, one kind 9 is provided, 9'(3,3' dihydroxy 4,4' diphenyl ether bases) double fluorone reagents and its preparation method and application.Two pyranose ring structure units are introduced in molecule, metallic ion coordination points add 1 times, enhance the coordination ability of reagent and metal ion, the fluorometric reagent that sensitivity is high, selectivity is good.Preparation method is simple, it is with low cost, property is stable, in the presence of surfactant, fluorophotometric quenching method surveys nickel detection limit and is quenched method less than other reagents in alkaline medium, the sensitivity that AAS surveys cobalt is higher than other fluorone reagents, and the detection limit that Catalytic Photometry surveys cobalt is less than other class fluorone reagents.Detection speed for nickel and cobalt ions is fast, the good, sensitivity of selectivity is high, Stability of Metal Complexes is strong.
Description
Technical field
The invention belongs to Fluorone reagent series compound technical, and in particular to 9,9'- of one kind (3,3'- dihydroxy -4,
4'- diphenyl ether bases) double fluorone reagents and its preparation method and application.
Background technology
Fluorones reagent refers to the class triphenyl containing 2,3,7- trihydroxies -6- ketone groups-pyranose ring structure in molecule
Methane Derivatives.The compound formed after 9- hydrogen atoms are substituted by phenyl, also known as phenylfluorone（Structure is shown in Fig. 1）.
Phenylfluorone is generally orange or red crystal, is insoluble in water and cold ethanol, is soluble in the ethanol after acidifying.Such compound
Molecule have rigidity, planar conjugate it is bigBond structure, easily absorbs ultraviolet-visible light and excites generation fluorescence.It develops the color anti-
Answer o-dihydroxy or adjacent hydroxyl quinonyl that functional group is molecule two ends.Because oxygen atom has 2 lone pair electrons in hydroxyl, quinonyl, easily
With the unoccupied orbital formation coordinate bond of metal ion, it is possible to which generating stable complex with high volence metal ion, [Huang Liping opens
The Huashan, 3,5- bis- bromo- 4- aminophenyls fluorones and chromium chromogenic reaction and application, metallurgical analysis, 1997,17（4）：4-6].
In strong acid medium, the high valence ion generation chromogenic reaction that fluorone reagent can be with d areas, p areas in the periodic table of elements forms stable
Blueness or red complex, be widely used to photometry determine and some metal ions of Fluorimetric Quenching Method for Determination [Zhou Mingcheng,
Raise high-strength, analytical chemistry, 1987,15（4）, 361].Research is found, hydroxyl, halogen, ammonia are introduced at the ortho position of phenyl ring or contraposition
The electron-donating groups such as base, methoxyl group or expansion conjugated system such as carboxyl, azo group etc. can improve the sensitivity [Zhang Xu of reagent
Frame, fluorone reagent and lead, the spectrum behavioral study of palladium and application, Nanjing University of Technology, outstanding Master's thesis in 2003].Cause
This, the conjugated system that substituent or increase molecule are introduced in molecule is the basic of the highly sensitive Fluorone reagent series reagent of design synthesis
Method.
Fluorone reagent has the advantages that to be easily-synthesized, analyze stable system, paid close attention to extensively by people because of it.But its spirit
Sensitivity is high not enough, and such reagent is generally only used for photometric analysis, and the fluorescence for being used for metal ion as fluorometric reagent is examined
Observe and predict less.
The content of the invention
The present invention is not ideal enough in order to solve existing its sensitivity of Fluorone reagent series compound and selectivity, generally only uses
In photometric analysis, it is impossible to which the problem of being used for the fluoroscopic examination of metal ion as fluorometric reagent, there is provided one kind 9,9'- (3,3'-
Dihydroxy -4,4'- diphenyl ether bases) double fluorone reagents and its preparation method and application.
The present invention is realized by following technical scheme：A kind of 9,9'- (3,3'- dihydroxy -4,4'- diphenyl ether bases) is double glimmering
Light ketone reagent, referred to as 9,9'-DHDPDF, its molecular structural formula is：
。
The preparation method of 9,9'- (3,3'- dihydroxy -4,4'- diphenyl ether base) double fluorone reagents, comprises the following steps：
(1) synthesis of triphenol triacetate partially：28mL acetic anhydrides and the dense H of 1mL2SO4Added under stirring mixing, stirring condition
11g 1,4-benzoquinone, 40 DEG C of -50 DEG C of reaction 1.5h, is poured into 100mL cold water under stirring, separates out white precipitate, suction filtration, which is obtained, slightly to be produced
Thing, ethyl alcohol recrystallization obtains the inclined triphenol triacetate of sterling；
(2) preparation of 3,3'- dihydroxy -4,4'- diphenyl ether base dicarbaldehydes：In the flask equipped with reflux condensing tube successively
Add 50mmol 3,3'- dihydroxy diphenyl ethers, 120mL absolute ethyl alcohols, 0.7mol sodium hydroxides, 57.55mmol triethylamines,
8h is reacted under 0.0248mol pyridines, 0.09952mol chloroforms, 85 DEG C of return stirrings, is cooled to room temperature, 1mol/L is added
Hydrochloric acid is neutralized, and modulation is neutral, suction filtration, and absolute ethyl alcohol is washed three times, is dried, is obtained 3,3'- dihydroxy -4,4'- diphenyl ether base diformazans
Aldehyde；
(3) preparation of 9,9'- (3,3'- dihydroxy -4,4'- diphenyl ether bases) double fluorones：Step（1）The sterling of acquisition
Inclined triphenol triacetate is dissolved in the ethanol that concentration is 50%, and dense H is added dropwise thereto2SO4, it is slow to add after mixture is completely dissolved
Enter 5g steps（2）3,3'- dihydroxy -4, the 4'- diphenyl ether base dicarbaldehydes obtained, stirring, 75-85 DEG C of back flow reaction 16h, cooling
To after room temperature, add 6g natrium nitrosums, stand 4d, separate out suction filtration after precipitation, obtain crude product, crude product be placed in 70ml ethyl acetate and
10ml concentration is in 1mol/L sulfuric acid solution, then 55-65 DEG C of heating 1h stands 4h, separates out sediment suction filtration, use acetic acid second
Ester is moved in beaker after washing 3 times, adds 70mL water, and 75-85 DEG C of heating 0.5h, cooling, suction filtration is washed 3 times；After washing
Precipitation is transferred in 70mL absolute ethyl alcohols and dissolved by heating, standing, separates out crystallization, repeats 70mL absolute ethyl alcohols and dissolves by heating precipitation knot
Brilliant process 2 times, dries, obtains sterling 9,9'- (3,3'- dihydroxy -4,4'- diphenyl ether base) double fluorones.
Product detection data are as follows：
Elementary analysis result：The theoretical value of each element is calculated by the molecular formula of synthetic product（w ℅）And and measured value（w
℅）Compare, two values are consistent（It is theoretical value in bracket）：C, 66.25 (66.47); H, 3.19(3.21); O, 30.13
(30.32)。
The ir data of reagent（KBr tablettings）： 3380cm-1Locate the stretching vibration absworption peak for hydroxyl; 3110
cm-1, 3020 cm-1Locate as phenyl ring C-H stretching vibration absworption peaks; 1140 cm-1, 1200 cm-1Locate as the flexible of C-O-C keys
Vibration absorption peak; 1600 cm-1, 1560 cm-1, 1450 cm-1Locate as phenyl ring framework characteristic absworption peak, 1640 cm-1Locate be
The stretching vibration absworption peak of carbonyl.0 through elementary analysis, infrared spectrum test, it can be verified that synthetic product is consistent with target molecule.
Advantages of the present invention and good effect：
（1）Phenylfluorone reagent（Molecular structure is shown in Fig. 1）It is that photometry determines Cu2+、Ti4+、Cr3+、Fe3+、W6+Deng from
The highly sensitive developer of son.Two pyrroles are introduced in 9,9'- (3,3'- dihydroxy -4,4'- diphenyl ether bases) double fluorone reagent molecules
Mutter ring structure unit, by the coordination site of metal ion by single fluorone 2,3 or 6,7 increases for 2,3 and 2', 3' or
6th, 7 and 6', 7', because coordination points add 1 times, the coordination ability of reagent and metal ion is enhanced, therefore, 9,
9'- (3,3'- dihydroxy -4,4'- diphenyl ether bases) double fluorone reagents have higher sensitivity.
（2）Two pyranose ring structure units are linked together by diphenyl ether base in reagent 9,9'-DHDPDF, formed more
Pi-electron mobility strengthens in big conjugated system, conjugated system, and the probability increase of electron transition, the absorption intensity to light strengthens,
Simultaneously as molecule net sectional area increases, it is that sensitivity is high, selective good so as to improve the fluorescence intensity of reagent molecule
Novel fluorescence reagent.
（3）Introduced in reagent 9,9'-DHDPDF between 2 hydroxyl substituents and two phenyl ring and introduce oxygen atom, because hydroxyl is
Electron-donating group and hydrophilic radical, so that the cloud density increase of conjugated system, the reduction of molecule ground state excitation energy, are conducive to
Reagent and metallic ion coordination and aqueous phase color development, and then improve the sensitivity of reaction and the water solubility of complex compound.
（4）Preparation method of reagent thereof of the present invention is simple, with low cost, and property is stable, available in the presence of surfactants,
The fluorophotometric quenching method detection of nickel ion in alkaline medium, detection limit is quenched the detection limit that method surveys nickel less than other reagents（See
Table 4）.AAS and catalytic decolourization Spectrophotometric determination of cobalt ion are can also be used for, AAS surveys the sensitivity of cobalt
Higher than other fluorone reagents（It is shown in Table 2）, Catalytic Photometry surveys the detection limit of cobalt, less than other class fluorone reagents（It is shown in Table 5）.
The characteristics of detection speed that reagent is used for nickel and cobalt ions is fast, the good, sensitivity of selectivity is high, Stability of Metal Complexes is strong.
Brief description of the drawings
Fig. 1 is phenylfluorone reagent precursor structure formula；Fig. 2 is 9,9'-DHDPDF of the present invention synthetic route stream
Cheng Tu.
Embodiment
Embodiment 1：9,9'- of one kind (3,3'- dihydroxy -4,4'- diphenyl ether base) double fluorone reagents, referred to as 9,9'-
DHDPDF, its molecular structural formula is：
。
The double fluorone preparation method of reagent thereof of the 9,9'- (3,3'- dihydroxy -4,4'- diphenyl ether bases) comprise the following steps：
(1) synthesis of triphenol triacetate partially：28 mL acetic anhydrides and the dense H of 1 mL are added in 100 mL beakers2SO4Stir
Mixing is mixed, lower addition 11g 1,4-benzoquinone is stirred vigorously, 40 DEG C of -50 DEG C of reaction 1.5h are poured under stirring in 100 mL cold water,
White precipitate is separated out, suction filtration obtains 22 g crude products, and ethyl alcohol recrystallization obtains the inclined g of triphenol triacetate 20 of sterling；
(2) preparation of 3,3'- dihydroxy -4,4'- diphenyl ether base dicarbaldehydes：In the 250mL flasks equipped with reflux condensing tube
Middle addition 10.1g (50 mmol) 3,3'- dihydroxy diphenyl ethers, 120 mL absolute ethyl alcohol, 28 g (0.7 mol) hydroxide
Sodium, 8 mL (57.55 mmol) triethylamine, 2 mL (0.0248 mol) pyridine, 8 mL (0.09952 mol) chloroform, 85 DEG C
8h is reacted under return stirring, is cooled to room temperature, 1mol/L hydrochloric acid is added and is neutralized, modulation neutrality, suction filtration, with anhydrous
Ethanol is washed three times, is dried, is obtained product 3, the g of 3'- dihydroxy -4,4'- diphenyl ether bases dicarbaldehyde 7；
(3) preparation of 9,9'- (3,3'- dihydroxy -4,4'- diphenyl ether bases) double fluorones：The inclined triphenol triacetates of 20g
It is dissolved in the 150mL ethanol that concentration is 50%, the dense H of 6 mL is added dropwise thereto2SO4, after mixture is completely dissolved, it is slowly added to 5 g
3,3'- dihydroxy -4,4'- diphenyl ether base dicarbaldehydes, are stirred continuously, 75-85 DEG C of backflow 16h, are cooled to after room temperature, add 6g
Natrium nitrosum, stands 4d, separates out suction filtration after precipitation, obtains 8g crude products, crude product then is placed in into 70ml ethyl acetate and 10 ml 1
In mol/L sulfuric acid solution, then 55-65 DEG C of heating 1h of control temperature place 4h, separate out precipitation, suction filtration uses ethyl acetate
Washing 3 times, precipitation is moved in beaker, adds 70mL water, and 75-85 DEG C of 0.5 h of heating, cooling, suction filtration is washed 3 times.Will be heavy
Shallow lake is transferred in 70 mL absolute ethyl alcohols and dissolved by heating, and stands, and separates out crystallization, and repetition 70mL absolute ethyl alcohols, which are dissolved by heating, separates out knot
Brilliant process 2 times, dries, obtains sterling 5g, gained sterling Yi Yi Chun ︰ Yi acyl Bing Tong ︰ glacial acetic acids=︰ 1 of 3 ︰ 2 are solvent, carries out thin layer
Chromatography, as a result display only has a spot,R f It is worth for 0.34.
Experimental example 1：9,9'- (3,3'- dihydroxy -4,4'- diphenyl ether bases) double fluorones are to Co in alkaline medium2+Light
Degree analysis detection.
Accurately pipette≤20 μ g Co2+In 25 mL volumetric flasks, pH9.0 2.0mL boraxs-hydrogen-oxygen is then sequentially added
Change sodium cushioning liquid, 10 g/L bromide sixteen alkyls pyridines（CPB）Microemulsion（CPB：N-butanol：Normal heptane：Water=1.0：1.0：
1.0：97）Then 3.0 mL, 0.2 g/L 9, the mL of 9'-DHDPDF 1.0 be diluted to scale with redistilled water, shake up standing
10 min, using 1 cm cuvette, at 660 nm, the absorbance that reference determines complex compound is made with reagent blank.
Sample analysis：By document [Pharmaceutical Analysis magazine, the 4th phase 261-264. Wei Qin of volume 77 in 1997, Du Bin, Zhang Xu
Hardwood], pipette vitamin B12The mL of sample 1.0 adds 8 mol/L nitric acid and carries out nitre solution in 50 mL beakers, plus 5 mL concentration are
2 % hydrogen peroxide is steamed near dry, adds the mL of 1 ︰, 1 hydrochloric acid 3 and suitable quantity of water dissolving soluble-salt, molten with 30% sodium hydroxide
Liquid adjustment pH value is about 7,50 mL is diluted with water to, with 6 mL/min flow velocitys by SDG adsorption columns, then with 0.1 mol/L salt
2 mL of acid are eluted, and eluent is neutralized to be contained in 25 mL volumetric flasks when pH is 7 with NaOH solution uses water constant volume, below empirically
Method is measured, and the results are shown in Table 1.
By document, [azoxy arsine Decoloring Spectrophotometric Determination trace cobalt, institute of East China Institute Of Technology reports, George's loyalty etc., 2005
Year 28（1）], 2g honey is weighed in 10 mL beakers, adds 8 mL HNO3-HClO4(9+3) clears up, and steams near dry.Plus 6mL
2% H2O2And 6 mL water steam near dry, same vitamin B is handled below12, then empirically method is determined.It the results are shown in Table 1.
Co in the sample of table 12+The measure of content（n=6）
| Sample | This law measured value | AAS method measured values | RSD（%） |
| Vitamin B12 | 4.32 (µg/mL) | 4.24 (µg/mL) | 2.6 |
| Honey | 0.21 (µg/g) | 0.20 (µg/g) | 3.2 |
The present invention relatively the results are shown in Table 2 with available reagent to the sensitivity of cobalt to the remolding sensitivity of cobalt, as a result show the present invention
The detection sensitivity that the compound is used for cobalt ions is high.
Several fluorone reagents of table 2 determine the sensitivity of cobalt
Experimental example 2：9,9'- (3,3'- dihydroxy -4,4'- diphenyl ether bases) double fluorone Fluorimetric Quenching Method for Determination nickel.
≤ 0.005 μ g nickel is accurately weighed in 25ml volumetric flasks, 3 % the Tritonx-100 aqueous solution 2 mL, pH is sequentially added
9.4 borax-hydrochloric acid buffer solution 3.0 mL, 2 × 10-5The mol/L mL of 9,9'-DHDPDF ethanol solutions 2.0, with water constant volume,
Place 10 min.Using 1cm quartz colorimetric utensils, in excitation wavelength (λex) 465 nm, launch wavelength (λem) network is determined at 586 nm
The fluorescence intensity F of compound, while determining the fluorescence absorbance F of the reagent blank condition, calculates fluorescence quenching value Δ F (Δ F=F0-
F)。
Sample is determined：The g of solid sample 1.0000 is weighed, by document [Food Science, the 12nd phase 204- of volume 32 in 2011
Page 208, Zhao Lijie etc.] micro-wave digestion is carried out to sample, then by document [Journal of Analytical Science, the 2nd phase of volume 21 in 2005
158-160 pages, Wei Qin] separation and concentration is carried out to nickel, it the results are shown in Table 3.9,9'-DHDPDF Fluorimetric Quenching Methods detection nickel of the present invention
Detection limit detects that the comparative result of the detection limit of nickel is shown in Table 4 to Fluorimetric Quenching Method with available reagent, as a result shows the inspection of the present invention
Rising limit is quenched the detection limit that method surveys nickel less than other reagents.
Table 3：Ni in sample2+Content 9,9'-DHDPDF Fluorimetric Quenching Method for Determination results
The detection limit of the Fluorimetric Quenching Method of table 4 detection nickel compares
Experimental example 3：The double fluorone catalytic decolourization AASs of 9,9'- (3,3'- dihydroxy -4,4'- diphenyl ether bases) are surveyed
Determine cobalt.
Take two 10 mL colorimetric cylinders, an addition Co（Ⅱ）Standard liquid（Catalyst system and catalyzing）, another is not added with Co（Ⅱ）Mark
Quasi- solution（Uncatalyzed Systems）, sequentially add 1 × 10-4Mol/L 9,9'-DHDPDF ethanol solutions 1.0 mL, 1 mol/L
NaOH solution 2 mL, 0.1 mol/L H2O2The mL of the aqueous solution 2, is shaken up, and 10 min are placed at room temperature, 0.15 is added immediately
The bad mL terminating reactions of hematic acid solution 1.5 of mol/L antioxygens, with distilled water diluting to scale, shake up.With distilled water reference, use
1cm quartz colorimetric utensils, determine the absorbance A of catalytic reaction and the absorbance of uncatalyzed reaction respectively at the nm of excitation wavelength 525
Ao, and calculate log (Ao/A)。
Sample is determined：Handled by document [assay office, the 4th phase of volume 13 in 1994, Fang Guochun, Wang Hongxiang etc.] method
Water sample, 9,9'-DHDPDF Catalytic Discoloring Spectrophotometries determine sewage sample and the results are shown in Table 5.As a result show that Catalytic Photometry surveys the inspection of cobalt
Rising limit, less than other class fluorone reagents.
The measurement result of cobalt in the water sample of table 5（N=6, ng/mL）
Claims (3)
1. one kind 9,9'- (3,3'- dihydroxy -4,4'- diphenyl ether base) double fluorone reagents, referred to as 9,9'-DHDPDF, it is special
Levy and be：Its molecular structural formula is：
。
2. prepare a kind of side of 9,9'- (3,3'- dihydroxy -4,4'- diphenyl ether bases) double fluorone reagents described in claim 1
Method, it is characterised in that：Comprise the following steps：
(1) synthesis of triphenol triacetate partially：28mL acetic anhydrides and the dense H of 1mL2SO411g pairs is added under stirring mixing, stirring condition
Benzoquinones, 40 DEG C of -50 DEG C of reaction 1.5h, is poured into 100mL cold water under stirring, separates out white precipitate, suction filtration obtains crude product, second
Alcohol recrystallizes to obtain the inclined triphenol triacetate of sterling；
(2) preparation of 3,3'- dihydroxy -4,4'- diphenyl ether base dicarbaldehydes：Sequentially added in the flask equipped with reflux condensing tube
50mmol 3,3'- dihydroxy diphenyl ethers, 120mL absolute ethyl alcohols, 0.7mol sodium hydroxides, 57.55mmol triethylamines,
8h is reacted under 0.0248mol pyridines, 0.09952mol chloroforms, 85 DEG C of return stirrings, is cooled to room temperature, 1mol/L is added
Hydrochloric acid is neutralized, and modulation is neutral, suction filtration, and absolute ethyl alcohol is washed three times, is dried, is obtained 3,3'- dihydroxy -4,4'- diphenyl ether base diformazans
Aldehyde；
(3) preparation of 9,9'- (3,3'- dihydroxy -4,4'- diphenyl ether bases) double fluorones：Step（1）The sterling inclined three of acquisition
Phenol triacetate is dissolved in the ethanol that concentration is 50%, and dense H is added dropwise thereto2SO4, after mixture is completely dissolved, it is slowly added to 5g
Step（2）3,3'- dihydroxy -4, the 4'- diphenyl ether base dicarbaldehydes obtained, stirring, 75-85 DEG C of back flow reaction 16h is cooled to room
Wen Hou, adds 6g natrium nitrosums, stands 4d, separates out suction filtration after precipitation, obtains crude product, crude product is placed in 70ml ethyl acetate and 10ml is dense
Spend in the sulfuric acid solution for 1mol/L, then 55-65 DEG C of heating 1h stand 4h, separate out sediment suction filtration, washed with ethyl acetate
Moved to after 3 times in beaker, add 70mL water, 75-85 DEG C of heating 0.5h, cooling, suction filtration is washed 3 times；Precipitation after washing is turned
Move in 70mL absolute ethyl alcohols and dissolve by heating, stand, separate out crystallization, repetition 70mL absolute ethyl alcohols, which are dissolved by heating, separates out crystallization process
2 times, dry, obtain sterling 9,9'- (3,3'- dihydroxy -4,4'- diphenyl ether base) double fluorones.
3. a kind of 9,9'- (3,3'- dihydroxy -4,4'- diphenyl ether bases) double fluorone reagents described in claim 1 are to cobalt
（Ⅱ）AAS, the detection of Catalytic Discoloring Spectrophotometry and to nickel（Ⅱ）Fluorescence quenching method detection in application.
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