CN105399720B - 9,9 ' (N phenyl N, N 4,4 ' diphenyl) double fluorone reagents and its preparation method and application - Google Patents

9,9 ' (N phenyl N, N 4,4 ' diphenyl) double fluorone reagents and its preparation method and application Download PDF

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CN105399720B
CN105399720B CN201511016446.4A CN201511016446A CN105399720B CN 105399720 B CN105399720 B CN 105399720B CN 201511016446 A CN201511016446 A CN 201511016446A CN 105399720 B CN105399720 B CN 105399720B
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吕存琴
刘建红
郭永
晋春
费鹏
张进
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Shanxi Datong University
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Abstract

The invention discloses a kind of 9; 9 ' (N phenyl N; N 4; 4 ' diphenyl) double fluorones, the triphenylamine with larger conjugated degree and fluorescent characteristic is obtained 4,4 ' diformyl triphenylamines by formylation reaction; it is synthesized that sensitivity is high, selectivity good 9 with inclined triphenol triacetate again; 9 ' (diphenyl of N phenyl N, N 4,4 ') double fluorone reagents（Referred to as 9,9 ' NNBPBF）.The reagent can be used for photometry Zn in alkaline medium2+Detection, it can also be used to Cu2+Fluorescent quenching detection.

Description

9,9 '-(N- phenyl-N, N-4,4 '-diphenyl) double fluorone reagents and its preparation side Method and application
Technical field
The invention belongs to the technical field of fluorones compound, and in particular to a kind of 9,9 '-(N- phenyl-N, N-4,4 '- Diphenyl) double fluorone reagents preparation method and application.
Background technology
Fluorone reagent series reagent is class acidity triphenylmethane organic dyestuff reagent, mostly red solid, is insoluble in Water, is soluble in the ethanol after acidifying, and the solubility and and metal ion of such reagent can be significantly improved in the presence of surfactant The sensitivity of chromogenic reaction.Such reagent is the rigid plane macromolecular agent with the big π keys of conjugation, therefore, with stronger Fluorescence property, further, since 2,3 and 7 in pyranoid ring have 3 hydroxyls, oxygen atom has 2 lone pair electrons in hydroxyl, or Hydroxyl easily forms negative oxygen ion in alkaline medium, can form coordinate bond [Huang Yingping, Zhang Huali smeltings with the unoccupied orbital of metal ion Gold analysis, 1977.17 (4)].In the presence of cationic surfactant or nonionic surfactant, in acid medium or alkali Property medium in, the reagent can with heavy metal ion occur chromogenic reaction, formed stabilization blueness or red complex, extensively use In spectrophotometry some metal ion [Zhou Mingcheng, Yang Gaoqiang analytical chemistry, 1987.15 (4):361], turned into One of sensitive reagents of photometry detection heavy metal ion content.The structural formula of phenylfluorone (PF) is：
Fluorone reagent series reagent has the advantages that to be easily-synthesized, testing cost is low, easy to operate, enjoys the concern of people. But its sensitivity and selectivity are also to be further improved, and such reagent is generally only used for photometric analysis, are tried as fluorescence The fluoroscopic examination report that agent is used for metal ion is less.According to the conjugated system or organic agent molecule of increase organic agent molecule It is middle introduce substitution base can improve organic reagent chromogenic reaction sensitivity principle [white birch fluorone reagents modified and its Application study in photometric analysis, Southern Yangtze University .2006 Master's thesis], aromatic ring structure due to well push away electronics or Draw electronic capability, it is considered to be design and synthesis induce the organic of up-conversion fluorescence and two photon absorption cross section with strong two-photon Potent agent [Abboto, A., Beverina, L., Bozio, R., the et al.Orglett..2002.4 of molecule:1495- 1498]。
The content of the invention
The present invention is intended to provide a kind of preparation method of 9,9 '-(N- phenyl-N, N-4,4 '-diphenyl) double fluorone reagents And application, solve there are problems that the reagent sensitivity for detecting heavy metal ion and selectivity are dissatisfactory in the prior art, will Triphenylamine with larger conjugated degree and fluorescent characteristic by formylation reaction be obtained 4,4 '-diformyl triphenylamine, then with Inclined triphenol triacetate is synthesized 9,9 '-(N- phenyl-N, N-4,4 '-diphenyl) double fluorescence that sensitivity is high, selectivity is good Ketone reagent (referred to as 9,9 '-NNBPBF).The reagent can be used for photometry Zn in alkaline medium2+Detection, it can also be used to Cu2+ Fluorescent quenching detection.
The present invention is achieved by the following technical solutions：
The invention provides a kind of 9,9 '-(N- phenyl-N, N-4,4 '-diphenyl) double fluorones (referred to as 9,9 '- NNBPBF), its structural formula is：
The invention provides a kind of preparation method of 9,9 '-(N- phenyl-N, N-4,4 '-diphenyl) double fluorones, including Following steps：
Comprise the following steps：
(1) synthesis of 1,4-benzoquinone：
Then etc. hydroquinones is dissolved in 50 DEG C of hot water, dense H is slowly added dropwise when being cooled to 20 DEG C2SO4, use trash ice control Then reaction temperature processed is slowly added dropwise K at 20~30 DEG C with constant pressure funnel2Cr2O7Solution；Having reacted rear suction filtration must be to benzene Quinone crude product, is washed with cold water and is dried to obtain yellow 1,4-benzoquinone；
The hydroquinones and K2Cr2O7Quality proportioning be：1:1.64；Need to use 1mL dense per 1g hydroquinones H2SO4；
(2) synthesis of triphenol triacetate partially：
In to acetic anhydride and concentrated sulfuric acid mixed liquor, 1,4-benzoquinone is dividedly in some parts with vigorous stirring, temperature is reacted in whole process Degree control is at 40~50 DEG C；Continue stirring and be cooled to room temperature, be then poured into the beaker for filling frozen water, there is substantial amounts of immediately White precipitate is separated out, and stands suction filtration, and ethyl alcohol recrystallization obtains the inclined triphenol triacetate of white product；
The volume ratio of the acetic anhydride and the concentrated sulfuric acid is 20:1, the quality proportioning of acetic anhydride and 1,4-benzoquinone is：4.55:1；
The synthesis and purifying of (3) 4,4 '-diformyl triphenylamines (FTA)：
At 0 DEG C, to being added dropwise over POCl in DMF3, stirred in drop, stirred 1 hour at 0 DEG C after mixing, then in room The lower stirring of temperature 1 hour, is subsequently adding and is dissolved in CH2Cl2In triphenylamine, under oil bath flow back 48 hours, question response finishes rear cold But, normal temperature stands 15min and pours into frozen water, and it is 7 to be adjusted to pH with the NaOH of 2mol/L, uses CH2Cl2Extraction takes subnatant 3 times Body, plus Na2SO4Dry, be then evaporated to obtain yellow solid with Rotary Evaporators, use CH2Cl2Dissolving, crude product is through silica gel chromatographic column (ethyl acetate:Petroleum ether=1:10) sterling 4,4 '-diformyl triphenylamine is separated to obtain；
DMF and POCl3Volume proportion be 1.66:1, CH2Cl2Proportioning with triphenylamine is：Per 4mLCH2Cl2Dissolving 1g tri- Aniline；
The synthesis of (4) 9,9 '-(N- phenyl-N, N-4,4 '-diphenyl) double fluorones：
Inclined triphenol triacetate and 60% ethanol are taken, add the concentrated sulfuric acid, heating water bath to dissolve it with vigorous stirring, 4 are subsequently adding, 4 '-diformyl triphenylamine, heating water bath dissolves it, oil bath flows back 48 hours after cooling, after completion of the reaction Cooling is stood, suction filtration obtains dark green solid crude product 9,9 '-(N- phenyl-N, N-4,4 '-diphenyl) double fluorones；
The quality proportioning of inclined triphenol triacetate and 4,4 '-diformyl triphenylamine is：2.83:1；
By crude product 9,9 '-NNBPBF, ethyl acetate, the concentrated sulfuric acid are stirred after shaking up, and suction strainer must be precipitated, washed with ethyl acetate For several times (cumulative volume is 100mL), precipitation is added water stirring after suction filtration, is heated one hour in water-bath, suction strainer goes out precipitation after cooling, Wash the dry-NNBPBF of sterling 9,9 ' with water；The ethyl acetate, the volume proportion of the concentrated sulfuric acid are：10:3.
The invention provides 9,9 '-(N- phenyl-N, N-4,4 '-diphenyl) double fluorones are in the presence of surfactants Zn2+Application in terms of the spectrophotometry of ion：
The invention provides 9,9 '-(N- phenyl-N, N-4,4 '-diphenyl) double fluorones in fluorescence quenching method Cu2+Detection In application：
Beneficial effects of the present invention：
(1) phenylfluorone reagent is made up of phenyl and pyranose ring structure unit, due to hydroxyl in pyranose ring structure unit Base and ketone carbonyl are present, can with metallic ion coordination, therefore, such reagent is to determine molybdenum, tungsten, titanium, tin, germanium, iron, aluminium, niobium etc. The highly sensitive developer of ion.Two construction units of pyranoid ring are introduced in-NNBPBF the molecules of reagent 9,9 ', with metal ion Coordination site increases, and enhances the coordination ability of reagent and metal ion, therefore, reagent 9,9 '-NNBPBF have sensitivity higher.
(2) reagent 9,9 '-NNBPBF are linked together two pyranose ring structure units by N, N-4,4 '-diphenyl, Bigger conjugated system is formed, molecular cross sectional area increase, pi-electron mobility enhancing in conjugated system, reagent shows with metal ion The sensitivity of colour response is higher.
(3)-the NNBPBF of reagent 9,9 ' is by the N with fluorescent characteristic, N-4,4 '-diphenyl and two pyranose ring structure units Connection, generates bigger conjugated system, so that the energy level reduction of electron transition, fluorescence quantum yield increases, and is sensitivity high New fluorescence analysis reagent.
(4) preparation method of reagent thereof of the invention is simple, with low cost.
Specific embodiment
The present invention is further illustrated below by embodiment, but is not limited to following examples.
Embodiment 1：A kind of 9,9 '-(N- phenyl-N, N-4,4 '-diphenyl) double fluorone preparation methods
Reaction equation is as follows：
A kind of 9,9 '-(N- phenyl-N, N-4,4 '-diphenyl) double fluorone preparation methods, comprise the following steps：
(1) synthesis of 1,4-benzoquinone
50 DEG C of kieldahl flasks of hot water of 333mL are filled by what 20.0g hydroquinones was dissolved in 1000mL, it is then etc. cold 20mL dense H are slowly added dropwise when but to 20 DEG C2SO4, with the strict controlling reaction temperature of trash ice at 20~30 DEG C, then use constant pressure addition Funnel is slowly added dropwise 266.6mL K2Cr2O7Solution (contains K2Cr2O732.79g).Rear suction filtration is reacted and has obtained 1,4-benzoquinone crude product, used Cold water washing is dried to obtain yellow 1,4-benzoquinone 9.5g, and yield is 48.3%.
(2) synthesis of triphenol triacetate partially
In 100mL round-bottomed flasks, 40.0mL acetic anhydrides and the 2.0mL concentrated sulfuric acids are sequentially added, be stirred vigorously down and add in batches Enter 9.5g 1,4-benzoquinone, reaction temperature is between 40~50 DEG C in whole process.Continue stirring and be cooled to room temperature, be then poured into Fill in the beaker of 150mL frozen water, there is substantial amounts of white precipitate to separate out immediately, stand suction filtration, ethyl alcohol recrystallization obtains white product 14.3g, yield 64.4%.
The synthesis and purifying of (3) 4,4 '-diformyl triphenylamines (FTA)
To 38.7mL DMF are added in 250mL round-bottomed flasks, at 0 DEG C, 23.3mL POCl are added dropwise over3, stirred in drop Mix, stirred 1 hour at 0 DEG C after mixing, then be stirred at room temperature 1 hour, be subsequently adding and be dissolved in 20mL CH2Cl2In 5g Triphenylamine, is flowed back 48 hours under oil bath (80 DEG C), and question response is cooled down after finishing, and normal temperature stands 15min and pours into frozen water, is used The NaOH regulations of 2mol/L are 7 to pH, use CH2Cl2Extraction removes a layer liquid, plus Na 3 times2SO4Dry, then use rotary evaporation Instrument is evaporated to obtain yellow solid, uses CH2Cl2Dissolving, crude product is through silica gel chromatographic column (ethyl acetate:Petroleum ether=1:10) separate pure Product.
The synthesis of (4) 9,9 '-(N- phenyl-N, N-4,4 '-diphenyl) double fluorones
To the inclined triphenol triacetates of 3.4g and 60% ethanol 105mL is added in 250mL round-bottomed flasks, with vigorous stirring Adding concentrated sulfuric acid 5.0mL, heating water bath dissolves it, and 1.2g 4 is added to it, and 4 '-diformyl triphenylamine, heating water bath is molten Solution, (100 DEG C) of oil bath flows back 48 hours after cooling, stands cooling after completion of the reaction, suction filtration obtain dark green solid crude product 9,9 '- NNBPBF。
Crude product 9 is sequentially added in 250mL beakers, 9 '-NNBPBF, ethyl acetate 50mL, concentrated sulfuric acid 15mL are stirred after shaking up Mix, suction strainer must be precipitated, (cumulative volume about 100mL) for several times is washed with ethyl acetate, precipitation is transferred in beaker after suction filtration, add water and stir Mix, heated one hour in water-bath, suction strainer goes out precipitation after cooling, wash dry sterling 9,9 '-NNBPBF with water.
Products obtained therefrom is characterized, Product checking data are as follows：
The theoretical value (w%) for calculating each element by the molecular formula of synthetic product is consistent (in bracket substantially with measured value (w%) It is theoretical value).C 72.11(72.43)；N 1.94(1.92)；O 21.80(21.95)；H 3.67(3.70).
The infrared absorption spectroscopy of 9,9 '-N, NBPBF and parsing are as follows：
1597cm-1、1550cm-1、1505cm-1、1451cm-1It is C=C skeletons stretching vibration absworption peak on phenyl ring, illustrates point There is phenyl ring in son；3391cm-1It is that hydroxyl O-H stretching vibrations absorb, illustrates there is hydroxyl；1631cm-1It is that C=O keys are flexible to shake It is dynamic, illustrate there is C=O keys；1628cm-1It is C=C key stretching vibrations, illustrates there is C=C keys；1177cm-1It is C-O-C keys Stretching vibration, illustrates there is C-O-C keys；1283cm-1It is the C-N stretching vibrations of tertiary aromatic amine, illustrates there is substituted amido.With reference to conjunction Into process, it is known that the reagent of synthesis and target product 9,9 '-NNBPBF are consistent.
Embodiment 2：9,9 '-(N- phenyl-N, N-4,4 '-diphenyl) double fluorone reagent photometries are to Zn2+Ion point Analysis detection
In 25mL volumetric flasks, the Zn of not more than 15 μ g is accurately pipetted2+, sequentially add the borax of 2.0mL pH 10.6- NaOH cushioning liquid, 1.5mL CPB (bromide sixteen alkyls pyridine)-OP microemulsions (CPB:OP:N-butanol:Normal heptane:H2O's Mass ratio is 1:5:3.5:0.8:89), the 9 of 2.0mL 0.3g/L, 9 '-NNBPBF ethanol solutions are then dilute with redistilled water Scale is released, standing 15min is shaken up, with 1cm cuvettes at 620nm, the absorbance that reference determines system is made with reagent blank.
By document [analytical chemistry, Wei Qin etc., 11 phase 1509-1512 of volume 32 in 2004], accurately weighing 5g samples is placed in Ma Fu 4h, plus a small amount of hydrochloric acid (1+1) dissolved residue are ashed in stove at 600 DEG C, 4mL nitric acid and 1mL perchloric acid is added, electric hot plate is placed in Upper heating evaporation adds suitable quantity of water and heating for dissolving residue near dry after cooling, add the hydrochloric acid and 5mL of 10mL pH=4.5 Concentration is 20g/L ascorbic acid solutions.By sample solution through SDG adsorption columns, flow control is in 5mL/min separation and concentrations Zn2+Afterwards, Finally eluted with the hydrochloric acid that 3mL concentration is 0.5mol/L, now cadmium is eluted, and discards the eluent.Again with 1mol/L's Hydrochloric acid 3mL is by Zn2+Elute in 10mL volumetric flasks, adjust pH value of solution weakly acidic pH, then use water constant volume.Appropriate test solution is pipetted in 25mL In volumetric flask, empirically method is determined, and the results are shown in Table 1.
Direct spectrophotometry result (n=5) in the sample of table 1
The different fluorone reagents of table 2 survey the comparing of zinc sensitivity
Embodiment 3：9,9 '-(N- phenyl-N, N-4,4 '-diphenyl) double fluorone reagent fluorescence it is sudden come method to Cu2+Ion Analysis detection
In 25mL volumetric flasks, the Cu for being not more than 5 μ g is added2+, sequentially add 2.0mL 1.0 × 10-4The 9,9 ' of mol/L- NNBPBF ethanol solutions, the triethanolamine-hydrochloric acid buffer solution of 3.0mL pH=8.0,3.0mL absolute ethyl alcohols, 4.0mL0.5% Cetrimonium bromide (CTMAB) solution, then scale is diluted with water to, shake up.With same method reagent preparation blank. Place 10min.In λ on sepectrophotofluorometerex=556nm, λemThe fluorescence of test solution and blank is determined at=596nm respectively Intensity F, F0, calculate fluorescence quenching value Δ F=F0- F.
By document [analytical chemistry, 2004,32 (6):838] the accurate hair sample 1g for weighing cleaning is added in small beaker 10mL HNO3, low-temperature heat is digested to Brown gas escapes to the greatest extent, and solution is added dropwise 1mL H in faint yellow2O2, continue to digest to bright, Heating evaporation is to dry, plus after 5mL (1+2) HCl leaching coolings, adds appropriate ascorbic acid, shakes up.Accurately weigh clean, baking Tealeaves sample 2g that is dry, crushing, adds 15mL HNO3, 5mL H2SO4Sulfuric acid white cigarette is slowly heated to emit to the greatest extent, plus 5mL (1+2) HCl is leached, and appropriate ascorbic acid is added after cooling.
It is 3.0~4.0 that the good sample of above-mentioned dissolving is adjusted into pH respectively, and sulfydryl is passed through with the speed of 4.0~5.0mL/min Cotton post, is washed 1 time with 0.4mol/L HCl 2.0mL, and the Cu of enrichment is finally eluted with 3mol/L HCl3.0mL2+, collect eluent In volumetric flask, it is settled to graticule and shakes up.Take the above-mentioned 2~5mL of sample solution for preparing in 25mL volumetric flasks, empirically just Method parallel determination 6 times, measurement result is shown in Table 3.
Copper (n=6) in the fluorescence quenching method determination sample of table 3
Several fluorone reagent fluorescence quenching methods of table 4 are surveyed copper detection limit and are compared

Claims (5)

1. one kind 9,9 '-(N- phenyl-N, N-4,4 '-diphenyl) double fluorones, it is characterised in that：Structural formula is：
2. 9 described in a kind of claim 1, the preparation method of 9 '-(N- phenyl-N, N-4,4 '-diphenyl) double fluorones, it is special Levy and be：Comprise the following steps：
(1) synthesis of 1,4-benzoquinone：
Then etc. hydroquinones is dissolved in 50 DEG C of hot water, dense H is slowly added dropwise when being cooled to 20 DEG C2SO4, controlled with trash ice anti- Answer temperature at 20~30 DEG C, be then slowly added dropwise K with constant pressure funnel2Cr2O7Solution；Having reacted rear suction filtration, to obtain 1,4-benzoquinone thick Product, are washed with cold water and are dried to obtain yellow 1,4-benzoquinone；
The hydroquinones and K2Cr2O7Quality proportioning be：1:1.64；The dense H of 1mL are needed to use per 1g hydroquinones2SO4；
(2) synthesis of triphenol triacetate partially：
In to acetic anhydride and concentrated sulfuric acid mixed liquor, 1,4-benzoquinone is dividedly in some parts with vigorous stirring, reaction temperature control in whole process System is at 40~50 DEG C；Continue stirring and be cooled to room temperature, be then poured into the beaker for filling frozen water, there is substantial amounts of white immediately Precipitation, stands suction filtration, and ethyl alcohol recrystallization obtains the inclined triphenol triacetate of white product；
The volume ratio of the acetic anhydride and the concentrated sulfuric acid is 20:1, the quality proportioning of acetic anhydride and 1,4-benzoquinone is：4.55:1；
The synthesis and purifying of (3) 4,4 '-diformyl triphenylamine FTA：
At 0 DEG C, to being added dropwise over POCl in DMF3, stirred in drop, stirred 1 hour at 0 DEG C after mixing, then at room temperature Stirring 1 hour, is subsequently adding and is dissolved in CH2Cl2In triphenylamine, under oil bath flow back 48 hours, question response finish after cool down, Normal temperature stands 15min and pours into frozen water, and it is 7 to be adjusted to pH with the NaOH of 2mol/L, uses CH2Cl2Extraction removes a layer liquid 3 times, plus Na2SO4Dry, be then evaporated to obtain yellow solid with Rotary Evaporators, use CH2Cl2Dissolving, crude product is obtained through silica gel chromatograph post separation Sterling 4,4 '-diformyl triphenylamine, the solvent of silica gel chromatographic column is：Ethyl acetate:Petroleum ether=1:10；
DMF and POCl3Volume proportion be 1.66:1, CH2Cl2Proportioning with triphenylamine is：Per 4mLCH2Cl2Dissolving 1g triphens Amine；
The synthesis of (4) 9,9 '-(N- phenyl-N, N-4,4 '-diphenyl) double fluorones：
Inclined triphenol triacetate and 60% ethanol are taken, adds the concentrated sulfuric acid, heating water bath to dissolve it with vigorous stirring, then 4 are added, 4 '-diformyl triphenylamine, heating water bath dissolves it, oil bath flows back 48 hours after cooling, stands after completion of the reaction Cooling, suction filtration obtains dark green solid crude product 9,9 '-(N- phenyl-N, N-4,4 '-diphenyl) double fluorones；
The quality proportioning of inclined triphenol triacetate and 4,4 '-diformyl triphenylamine is：2.83:1；
Stirred after crude product 9,9 '-(N- phenyl-N, N-4,4 '-diphenyl) double fluorones, ethyl acetate, the concentrated sulfuric acid are shaken up, inhaled Filtering to be precipitated, and washed with ethyl acetate for several times, and cumulative volume is 100mL, and precipitation adds water stirring after suction filtration, and one is heated in water-bath Hour, suction strainer goes out precipitation after cooling, washes dry sterling 9,9 '-(N- phenyl-N, N-4,4 '-diphenyl) double fluorescence with water Ketone；The ethyl acetate, the volume proportion of the concentrated sulfuric acid are：10:3.
3. the preparation method of according to claim 29,9 '-(N- phenyl-N, N-4,4 '-diphenyl) double fluorones, it is special Levy and be：Comprise the following steps：
(1) synthesis of 1,4-benzoquinone
Then etc. 20.0g hydroquinones is dissolved in filling 50 DEG C of kieldahl flasks of hot water of 333mL, is cooled to slow at 20 DEG C It is slow that the dense H of 20mL are added dropwise2SO4, with the strict controlling reaction temperature of trash ice at 20~30 DEG C, then it is slowly added dropwise with constant pressure funnel 266.6mL K2Cr2O7Solution, contains K2Cr2O732.79g；Rear suction filtration is reacted and has obtained 1,4-benzoquinone crude product, drying has been washed with cold water Yellow 1,4-benzoquinone 9.5g is obtained, yield is 48.3%；
(2) synthesis of triphenol triacetate partially
In 100mL round-bottomed flasks, 40.0mL acetic anhydrides and the 2.0mL concentrated sulfuric acids are sequentially added, be stirred vigorously down and be dividedly in some parts 9.5g 1,4-benzoquinone, reaction temperature is between 40~50 DEG C in whole process；Continue stirring and be cooled to room temperature, be then poured into Sheng Have in the beaker of 150mL frozen water, there is substantial amounts of white precipitate to separate out immediately, stand suction filtration, ethyl alcohol recrystallization obtains white product 14.3g, yield 64.4%；
The synthesis and purifying of (3) 4,4 '-diformyl triphenylamine FTA
To 38.7mL DMF are added in 250mL round-bottomed flasks, at 0 DEG C, 23.3mL POCl are added dropwise over3, stirred in drop, mix Stirred 1 hour at 0 DEG C after even, then be stirred at room temperature 1 hour, be subsequently adding and be dissolved in 20mL CH2Cl2In 5g triphens Amine, is flowed back 48 hours at 80 DEG C of oil bath, and question response is cooled down after finishing, and normal temperature stands 15min and pours into frozen water, with 2mol/L's NaOH regulations are 7 to pH, use CH2Cl2Extraction removes a layer liquid, plus Na 3 times2SO4Dry, be then evaporated with Rotary Evaporators Yellow solid, uses CH2Cl2Dissolving, crude product obtains sterling through silica gel chromatograph post separation, and solvent is ethyl acetate:Petroleum ether=1: 10；
The synthesis of (4) 9,9 '-(N- phenyl-N, N-4,4 '-diphenyl) double fluorones
To the inclined triphenol triacetates of 3.4g and 60% ethanol 105mL is added in 250mL round-bottomed flasks, add with vigorous stirring Concentrated sulfuric acid 5.0mL, heating water bath dissolves it, and 1.2g 4 is added to it, and 4 '-diformyl triphenylamine, heating water bath dissolving is cold But 100 DEG C of oil bath flows back 48 hours after, stands cooling after completion of the reaction, suction filtration obtain dark green solid crude product 9,9 '-(N- phenyl- N, N-4,4 '-diphenyl) double fluorones；
Crude product 9,9 '-(N- phenyl-N, N-4,4 '-diphenyl) double fluorones, ethyl acetate are sequentially added in 250mL beakers 50mL, concentrated sulfuric acid 15mL, are stirred after shaking up, and suction strainer must be precipitated, washed with ethyl acetate for several times, and cumulative volume is 100mL, after suction filtration Precipitation is transferred in beaker, add water stirring, is heated one hour in water-bath, suction strainer goes out precipitation after cooling, washed with water dry Sterling 9,9 '-(N- phenyl-N, N-4,4 '-diphenyl) double fluorones.
4. according to claim 19,9 '-(N- phenyl-N, N-4,4 '-diphenyl) double fluorones, it is characterised in that：Should Compound is applied to Zn in the presence of surfactants2+The spectrophotometry of ion.
5. according to claim 19,9 '-(N- phenyl-N, N-4,4 '-diphenyl) double fluorones, it is characterised in that：Should Compound is applied to the Cu in fluorescence quenching method2+Detection.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104910124A (en) * 2015-04-17 2015-09-16 山西大同大学 Preparation method and application of 9,9'-(4,4'-biphenyl)bisfluorone bromination reagent

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Fluorone-Reagentien fut die photometrische Analyse;E.Asmus,et al;《Fresenius Z. Anal. Chem.》;19791231;第298卷;全文 *
新苯基荧光酮试剂合成及在食品分析中的应用;李在均;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20050315(第1期);全文 *

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