CN105399720A - 9,9'-(N-phenyl-N,N-4,4'-diphenyl)bifluorone reagent, and preparation method and application thereof - Google Patents

9,9'-(N-phenyl-N,N-4,4'-diphenyl)bifluorone reagent, and preparation method and application thereof Download PDF

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CN105399720A
CN105399720A CN201511016446.4A CN201511016446A CN105399720A CN 105399720 A CN105399720 A CN 105399720A CN 201511016446 A CN201511016446 A CN 201511016446A CN 105399720 A CN105399720 A CN 105399720A
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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 9,9'-(N-phenyl-N,N-4,4'-diphenyl)bifluorone. According to the invention, triphenylamine with a great conjugation degree and fluorescence characteristics is subjected to formylation so as to prepare 4,4'-diformyl triphenylamine, and 4,4'-diformyl triphenylamine reacts with hydroxyquinol triacetate so as to synthesize a 9,9'-(N-phenyl-N,N-4,4'-diphenyl)bifluorone reagent (9,9'-NNBPBF, for short) with high sensitivity and good selectivity. The reagent can be used for spectrophotometric detection of Zn<2+> in an alkaline medium and fluorescence quenching detection of Cu<2+>.

Description

9,9 '-(N-phenyl-N, N-4,4 '-phenylbenzene) two fluorone reagent and its preparation method and application
Technical field
The invention belongs to the technical field of fluorones compound, be specifically related to a kind of preparation method and application of 9,9 '-(N-phenyl-N, N-4,4 '-phenylbenzene) two fluorone reagent.
Background technology
Fluorone reagent series reagent is a class acid triphenylmethane organic dye reagent, mostly be red solid, be insoluble in water, be soluble in the ethanol after acidifying, tensio-active agent can significantly improve the solubleness of such reagent and the sensitivity with metal ion color reaction under existing.Such reagent is the rigid plane macromolecular agent with the large π key of conjugation, therefore, there is stronger fluorescence property, in addition, due at 2 of pyranoid ring, 3 and 7 have 3 hydroxyls, in hydroxyl, Sauerstoffatom has 2 lone-pair electron, or hydroxyl easily forms negative oxygen ion in alkaline medium, can form coordinate bond [Huang Yingping with the unoccupied orbital of metal ion, Zhang Huali. metallurgical analysis, 1977.17 (4)].Under cats product or nonionogenic tenside exist, in acidic medium or alkaline medium, this reagent can with heavy metal ion generation color reaction, form stable blueness or red complex, be widely used in some metal ion of spectrophotometry [Zhou Mingcheng, Yang Gaoqiang. analytical chemistry, 1987.15 (4): 361], now become light-intensity method and detected one of sensitive reagents of heavy metal ion content.The structural formula of phenyl fluorone (PF) is:
Fluorone reagent series reagent has the advantages such as easy synthesis, testing cost be low, easy to operate, enjoys the concern of people.But its sensitivity and selectivity are to be further improved in addition, and such reagent is usually only for photometric analysis, and the fluoroscopic examination report being used for metal ion as fluorescent reagent is less.According to increase in the conjugated system of organic agent molecule or organic agent molecule introduce substituting group can improve the sensitivity of organic reagent color reaction principle [white birch. the modification of fluorone reagent and the applied research in photometric analysis thereof, Southern Yangtze University .2006 Master's thesis], aromatic ring structure well pushes away electronics owing to having or draws electronic capability, be considered to the potent agent [Abboto designing and synthesize the organic molecule with strong two-photon induction up-conversion fluorescence and two photon absorption cross section, A., Beverina, L., Bozio, R., etal.Orglett..2002.4:1495-1498].
Summary of the invention
The present invention aims to provide a kind of 9; 9 '-(N-phenyl-N; N-4; 4 '-phenylbenzene) preparation method of two fluorone reagent and application; solve in prior art the reagent sensitivity and the dissatisfactory problem of selectivity that exist and detect heavy metal ion; to there is the triphenylamine of larger conjugated degree and fluorescent characteristic by formylation reaction obtained 4; 4 '-diformyl triphenylamine; again, selectivity highly sensitive with inclined triphenol triacetate Reactive Synthesis good 9; 9 '-(N-phenyl-N; N-4,4 '-phenylbenzene) two fluorone reagent (being called for short 9,9 '-NNBPBF).This reagent can for light-intensity method Zn in alkaline medium 2+detection, also can be used for Cu 2+quenching of fluorescence detect.
The present invention is achieved by the following technical solutions:
The invention provides a kind of 9,9 '-(N-phenyl-N, N-4,4 '-phenylbenzene) two fluorone (being called for short 9,9 '-NNBPBF), its structural formula is:
The invention provides a kind of preparation method of 9,9 '-(N-phenyl-N, N-4,4 '-phenylbenzene) two fluorone, comprise the following steps:
Comprise the following steps:
(1) synthesis of para benzoquinone:
Then etc. Resorcinol is dissolved in 50 DEG C of hot water, when being cooled to 20 DEG C, slowly drips dense H 2sO 4, control temperature of reaction at 20 ~ 30 DEG C with trash ice, then slowly drip K with constant pressure funnel 2cr 2o 7solution; React rear suction filtration and obtained para benzoquinone crude product, obtain yellow para benzoquinone with cold water washing drying;
Described Resorcinol and K 2cr 2o 7quality proportioning be: 1:1.64; Every 1g Resorcinol needs to use the dense H of 1mL 2sO 4;
(2) synthesis of inclined triphenol triacetate:
To in diacetyl oxide and vitriol oil mixed solution, add para benzoquinone with vigorous stirring, in whole process, temperature of reaction controls at 40 ~ 50 DEG C in batches; Continue to stir cool to room temperature, be then poured into and fill in the beaker of frozen water, have a large amount of white precipitates to separate out immediately, leave standstill suction filtration, ethyl alcohol recrystallization obtains the inclined triphenol triacetate of white product;
The volume ratio of described diacetyl oxide and the vitriol oil is 20:1, and the quality proportioning of diacetyl oxide and para benzoquinone is: 4.55:1;
(3) 4, the synthesis of 4 '-diformyl triphenylamine (FTA) and purifying:
At 0 DEG C, in DMF, dropwise add POCl 3, drip while stir, stir 1 hour at 0 DEG C after mixing, more at room temperature stir 1 hour, then add and be dissolved in CH 2cl 2in triphenylamine, under oil bath reflux 48 hours, cool after question response, normal temperature leaves standstill 15min and pours in frozen water, and being adjusted to pH with the NaOH of 2mol/L is 7, uses CH 2cl 2extract and take off a layer liquid 3 times, add Na 2sO 4drying, then obtains yellow solid with Rotary Evaporators evaporate to dryness, uses CH 2cl 2dissolve, crude product is separated to obtain sterling 4,4 '-diformyl triphenylamine through silica gel chromatographic column (ethyl acetate: sherwood oil=1:10);
DMF and POCl 3volume proportion be 1.66:1, CH 2cl 2with the proportioning of triphenylamine be: every 4mLCH 2cl 2dissolve 1g triphenylamine;
The synthesis of (4) 9,9 '-(N-phenyl-N, N-4,4 '-phenylbenzene) two fluorone:
Get the ethanol of inclined triphenol triacetate and 60%, add the vitriol oil with vigorous stirring, heating in water bath makes it dissolve, and then adds 4,4 '-diformyl triphenylamine, heating in water bath makes it dissolve, and after cooling, oil bath refluxes 48 hours, leaves standstill cooling after completion of the reaction, suction filtration obtains dark green solid crude product 9,9 '-(N-phenyl-N, N-4,4 '-phenylbenzene) two fluorone;
Inclined triphenol triacetate and 4, the quality proportioning of 4 '-diformyl triphenylamine is: 2.83:1;
By crude product 9,9 '-NNBPBF, ethyl acetate, the vitriol oil shake up rear stirring, suction strainer must precipitate, by ethyl acetate washing several (cumulative volume is 100mL), add water precipitation after suction filtration stirring, and water-bath is heated one hour, and after cooling, suction strainer goes out precipitation, wash dry sterling 9,9 '-NNBPBF with water; The volume proportion of described ethyl acetate, the vitriol oil is: 10:3.
The invention provides 9,9 '-(N-phenyl-N, N-4,4 '-phenylbenzene) two fluorone Zn in the presence of surfactants 2+the application of the spectrophotometry aspect of ion:
The invention provides 9,9 '-(N-phenyl-N, N-4,4 '-phenylbenzene) two fluorone is at fluorescence quenching method Cu 2+application in detection:
Beneficial effect of the present invention:
(1) phenyl fluorone reagent is made up of phenyl and pyranose ring structure unit, because hydroxyl and ketone carbonyl exist in pyranose ring structure unit, can with metallic ion coordination, therefore, such reagent be measure molybdenum, tungsten, titanium, tin, germanium, iron, aluminium, the isoionic highly sensitive developer of niobium.Reagent 9, introduce the structural unit of two pyranoid rings in 9 '-NNBPBF molecule, increase with the hapto of metal ion, enhance the coordination ability of reagent and metal ion, therefore, reagent 9,9 '-NNBPBF has higher sensitivity.
(2) reagent 9,9 '-NNBPBF is by N, N-4, two pyranose ring structure unit link together by 4 '-phenylbenzene, form larger conjugated system, and molecular cross sectional area increases, in conjugated system, π-electron mobility strengthens, and the sensitivity of reagent and metal ion color reaction is higher.
(3) reagent 9,9 '-NNBPBF will have the N of fluorescent characteristic, N-4,4 '-phenylbenzene is connected with two pyranose ring structure unit, generates larger conjugated system, thus the energy level of transition of electron is reduced, fluorescence quantum yield increases, and is highly sensitive new fluorometric analysis reagent.
(4) preparation method of reagent thereof of the present invention is simple, with low cost.
Embodiment
Further illustrate the present invention below by embodiment, but be not limited to following examples.
Embodiment 1: a kind of 9,9 '-(N-phenyl-N, N-4,4 '-phenylbenzene) two fluorone preparation method
Reaction formula is as follows:
A kind of 9,9 '-(N-phenyl-N, N-4,4 '-phenylbenzene) two fluorone preparation method, comprises the following steps:
(1) synthesis of para benzoquinone
Then etc. what 20.0g Resorcinol is dissolved in 1000mL fills in the Kjeldahl flask of 333mL50 DEG C of hot water, slowly drips 20mL dense H when being cooled to 20 DEG C 2sO 4, strictly control temperature of reaction at 20 ~ 30 DEG C with trash ice, then slowly drip 266.6mLK with constant pressure funnel 2cr 2o 7solution is (containing K 2cr 2o 732.79g).Reacted rear suction filtration and obtained para benzoquinone crude product, obtained yellow para benzoquinone 9.5g with cold water washing drying, productive rate is 48.3%.
(2) synthesis of inclined triphenol triacetate
In 100mL round-bottomed flask, add 40.0mL diacetyl oxide and the 2.0mL vitriol oil successively, add 9.5g para benzoquinone under vigorous stirring in batches, in whole process, temperature of reaction is between 40 ~ 50 DEG C.Continue to stir cool to room temperature, be then poured in the beaker filling 150mL frozen water, have a large amount of white precipitates to separate out immediately, leave standstill suction filtration, ethyl alcohol recrystallization obtains white product 14.3g, productive rate 64.4%.
(3) 4, the synthesis of 4 '-diformyl triphenylamine (FTA) and purifying
In 250mL round-bottomed flask, add 38.7mLDMF, at 0 DEG C, dropwise add 23.3mLPOCl 3, drip while stir, stir 1 hour at 0 DEG C after mixing, more at room temperature stir 1 hour, then add and be dissolved in 20mLCH 2cl 2in 5g triphenylamine, under oil bath (80 DEG C) reflux 48 hours, cool after question response, normal temperature leaves standstill 15min and pours in frozen water, and being adjusted to pH with the NaOH of 2mol/L is 7, uses CH 2cl 2extract and take off a layer liquid 3 times, add Na 2sO 4drying, then obtains yellow solid with Rotary Evaporators evaporate to dryness, uses CH 2cl 2dissolve, crude product is separated to obtain sterling through silica gel chromatographic column (ethyl acetate: sherwood oil=1:10).
The synthesis of (4) 9,9 '-(N-phenyl-N, N-4,4 '-phenylbenzene) two fluorone
The ethanol 105mL of the inclined triphenol triacetate of 3.4g and 60% is added in 250mL round-bottomed flask; add vitriol oil 5.0mL with vigorous stirring; heating in water bath makes it dissolve; add 1.2g4 to it, 4 '-diformyl triphenylamine, heating in water bath dissolves; oil bath (100 DEG C) backflow 48 hours after cooling; leave standstill cooling after completion of the reaction, suction filtration obtains dark green solid crude product 9,9 '-NNBPBF.
Crude product 9 is added successively in 250mL beaker, 9 '-NNBPBF, ethyl acetate 50mL, vitriol oil 15mL, shake up rear stirring, suction strainer must precipitate, by ethyl acetate washing several (cumulative volume is about 100mL), after suction filtration, precipitation is proceeded in beaker, add water stirring, and water-bath is heated one hour, and after cooling, suction strainer goes out precipitation, wash dry sterling 9,9 '-NNBPBF with water.
Characterize products obtained therefrom, Product checking data are as follows:
The theoretical value (w%) calculating each element by the molecular formula of synthetic product conforms to (being theoretical value in bracket) substantially with measured value (w%).C72.11(72.43)；N1.94(1.92)；O21.80(21.95)；H3.67(3.70)。
9, infrared absorption spectrum and the parsing of 9 '-N, NBPBF are as follows:
1597cm -1, 1550cm -1, 1505cm -1, 1451cm -1be C=C skeleton stretching vibration absorption peak on phenyl ring, illustrate in molecule to there is phenyl ring; 3391cm -1be that hydroxyl O-H stretching vibration absorbs, illustrate to there is hydroxyl; 1631cm -1be the stretching vibration of C=O key, illustrate to there is C=O key; 1628cm -1be the stretching vibration of C=C key, illustrate to there is C=C key; 1177cm -1be the stretching vibration of C-O-C key, illustrate to there is C-O-C key; 1283cm -1be the C-N stretching vibration of tertiary aromatic amine, illustrate to there is substituted amido.In conjunction with building-up process, the reagent of known synthesis and target product 9,9 '-NNBPBF is consistent.
Embodiment 2:9,9 '-(N-phenyl-N, N-4,4 '-phenylbenzene) two fluorone reagent light-intensity method is to Zn 2+the analyzing and testing of ion
In 25mL volumetric flask, accurately pipette the Zn of no more than 15 μ g 2+, add the borax-NaOH buffered soln of 2.0mLpH10.6 successively, 1.5mLCPB (bromide sixteen alkyls pyridine)-OP microemulsion (CPB:OP: propyl carbinol: normal heptane: H 2the mass ratio of O is 1:5:3.5:0.8:89), 9, the 9 '-NNBPBF ethanolic soln of 2.0mL0.3g/L, then scale is diluted to redistilled water, shake up standing 15min, with 1cm cuvette in 620nm place, make with reagent blank the absorbancy that reference measures system.
By document [analytical chemistry, Wei Qin etc., 32 volume 11 phase 1509-1512 in 2004] accurately take 5g sample and be placed in muffle furnace at 600 DEG C of ashing 4h, add a small amount of hydrochloric acid (1+1) dissolved residue, add 4mL nitric acid and 1mL perchloric acid again, be placed in heating evaporation on hot plate to do near, add suitable quantity of water after cooling and heating for dissolving resistates, the hydrochloric acid and the 5mL concentration that add 10mLpH=4.5 are 20g/L ascorbic acid solution.By sample solution through SDG adsorption column, flow rate control is at 5mL/min separation and concentration Zn 2+after, be finally the hydrochloric acid wash-out of 0.5mol/L by 3mL concentration, now cadmium is eluted, and discards this elutriant.Use the hydrochloric acid 3mL of 1mol/L by Zn again 2+wash-out, in 10mL volumetric flask, adjusts pH value of solution weakly acidic pH, then uses water constant volume.Pipette appropriate test solution in 25mL volumetric flask, empirically method measures, and the results are shown in Table 1.
Direct spectrophotometry result (n=5) in table 1 sample
The comparison of zinc sensitivity surveyed by the different fluorone reagent of table 2
Embodiment 3:9,9 '-(N-phenyl-N, N-4,4 '-phenylbenzene) two fluorone reagent fluorescence sudden come method to Cu 2+the analyzing and testing of ion
In 25mL volumetric flask, add the Cu of no more than 5 μ g 2+, add 2.0mL1.0 × 10 successively -49, the 9 '-NNBPBF ethanolic soln of mol/L, the trolamine-hydrochloric acid buffer solution of 3.0mLpH=8.0,3.0mL dehydrated alcohol, 4.0mL0.5% cetrimonium bromide (CTMAB) solution, then be diluted with water to scale, shake up.Blank with same method reagent preparation.Place 10min.In λ on spectrophotofluorometer ex=556nm, λ em=596nm place measures test solution and blank fluorescence intensity F, F respectively 0, calculate quenching of fluorescence value Δ F=F 0-F.
Accurately take a clean sample 1g in small beaker by document [analytical chemistry, 2004,32 (6): 838], add 10mLHNO 3, low-temperature heat digestion is most to Brown gas ease, and solution is faint yellow, drips 1mLH 2o 2, continuation digestion is to bright, and heating evaporation, to dry, after adding 5mL (1+2) HCl leaching cooling, add appropriate xitix, shakes up.Accurately take tealeaves sample 2g that is clean, that dry, pulverize, add 15mLHNO 3, 5mLH 2sO 4slowly be heated to the white cigarette of sulfuric acid emit to the greatest extent, add 5mL (1+2) HCl and leach, after cooling, add appropriate xitix.
Regulate pH to be 3.0 ~ 4.0 respectively on sample good for above-mentioned dissolving, with the speed of 4.0 ~ 5.0mL/min by Sulfhydryl Cotton post, wash 1 time with 0.4mol/LHCl2.0mL, finally use the Cu of 3mol/LHCl3.0mL wash-out enrichment 2+, collect elutriant in volumetric flask, be settled to graticule and shake up.Get the above-mentioned sample solution 2 ~ 5mL prepared in 25mL volumetric flask, empirically method replicate(determination) 6 times, measurement result is in table 3.
Copper (n=6) in table 3 fluorescence quenching method working sample
Several fluorone reagent of table 4 fluorescence quenching method is surveyed copper detection limit and is compared

Claims (5)

1. one kind 9,9 '-(N-phenyl-N, N-4,4 '-phenylbenzene) two fluorone, is characterized in that: structural formula is:
2. one kind according to claim 19, the preparation method of 9 '-(N-phenyl-N, N-4,4 '-phenylbenzene) two fluorone, is characterized in that: comprise the following steps:
(1) synthesis of para benzoquinone:
Then etc. Resorcinol is dissolved in 50 DEG C of hot water, when being cooled to 20 DEG C, slowly drips dense H 2sO 4, control temperature of reaction at 20 ~ 30 DEG C with trash ice, then slowly drip K with constant pressure funnel 2cr 2o 7solution; React rear suction filtration and obtained para benzoquinone crude product, obtain yellow para benzoquinone with cold water washing drying;
Described Resorcinol and K 2cr 2o 7quality proportioning be: 1:1.64; Every 1g Resorcinol needs to use the dense H of 1mL 2sO 4;
(2) synthesis of inclined triphenol triacetate:
To in diacetyl oxide and vitriol oil mixed solution, add para benzoquinone with vigorous stirring, in whole process, temperature of reaction controls at 40 ~ 50 DEG C in batches; Continue to stir cool to room temperature, be then poured into and fill in the beaker of frozen water, have a large amount of white precipitates to separate out immediately, leave standstill suction filtration, ethyl alcohol recrystallization obtains the inclined triphenol triacetate of white product;
The volume ratio of described diacetyl oxide and the vitriol oil is 20:1, and the quality proportioning of diacetyl oxide and para benzoquinone is: 4.55:1;
(3) 4, the synthesis of 4 '-diformyl triphenylamine FTA and purifying:
At 0 DEG C, in DMF, dropwise add POCl 3, drip while stir, stir 1 hour at 0 DEG C after mixing, more at room temperature stir 1 hour, then add and be dissolved in CH 2cl 2in triphenylamine, under oil bath reflux 48 hours, cool after question response, normal temperature leaves standstill 15min and pours in frozen water, and being adjusted to pH with the NaOH of 2mol/L is 7, uses CH 2cl 2extract and take off a layer liquid 3 times, add Na 2sO 4drying, then obtains yellow solid with Rotary Evaporators evaporate to dryness, uses CH 2cl 2dissolve, crude product is separated to obtain sterling 4,4 '-diformyl triphenylamine through silica gel chromatographic column (ethyl acetate: sherwood oil=1:10);
DMF and POCl 3volume proportion be 1.66:1, CH 2cl 2with the proportioning of triphenylamine be: every 4mLCH 2cl 2dissolve 1g triphenylamine;
The synthesis of (4) 9,9 '-(N-phenyl-N, N-4,4 '-phenylbenzene) two fluorone:
Get the ethanol of inclined triphenol triacetate and 60%, add the vitriol oil with vigorous stirring, heating in water bath makes it dissolve, and then adds 4,4 '-diformyl triphenylamine, heating in water bath makes it dissolve, and after cooling, oil bath refluxes 48 hours, leaves standstill cooling after completion of the reaction, suction filtration obtains dark green solid crude product 9,9 '-(N-phenyl-N, N-4,4 '-phenylbenzene) two fluorone;
Inclined triphenol triacetate and 4, the quality proportioning of 4 '-diformyl triphenylamine is: 2.83:1;
By crude product 9,9 '-NNBPBF, ethyl acetate, the vitriol oil shake up rear stirring, suction strainer must precipitate, with ethyl acetate washing several, cumulative volume is 100mL, and add water precipitation after suction filtration stirring, water-bath is heated one hour, after cooling, suction strainer goes out precipitation, washes dry sterling 9,9 '-NNBPBF with water; The volume proportion of described ethyl acetate, the vitriol oil is: 10:3.
3. the preparation method of according to claim 29,9 '-(N-phenyl-N, N-4,4 '-phenylbenzene) two fluorone, is characterized in that: comprise the following steps:
(1) synthesis of para benzoquinone
Then etc. 20.0g Resorcinol is dissolved in the Kjeldahl flask filling 333mL50 DEG C of hot water, when being cooled to 20 DEG C, slowly drips the dense H of 20mL 2sO 4, strictly control temperature of reaction at 20 ~ 30 DEG C with trash ice, then slowly drip 266.6mLK with constant pressure funnel 2cr 2o 7solution, containing K 2cr 2o 732.79g; Reacted rear suction filtration and obtained para benzoquinone crude product, obtained yellow para benzoquinone 9.5g with cold water washing drying, productive rate is 48.3%;
(2) synthesis of inclined triphenol triacetate
In 100mL round-bottomed flask, add 40.0mL diacetyl oxide and the 2.0mL vitriol oil successively, add 9.5g para benzoquinone under vigorous stirring in batches, in whole process, temperature of reaction is between 40 ~ 50 DEG C; Continue to stir cool to room temperature, be then poured in the beaker filling 150mL frozen water, have a large amount of white precipitates to separate out immediately, leave standstill suction filtration, ethyl alcohol recrystallization obtains white product 14.3g, productive rate 64.4%;
(3) 4, the synthesis of 4 '-diformyl triphenylamine FTA and purifying
In 250mL round-bottomed flask, add 38.7mLDMF, at 0 DEG C, dropwise add 23.3mLPOCl 3, drip while stir, stir 1 hour at 0 DEG C after mixing, more at room temperature stir 1 hour, then add and be dissolved in 20mLCH 2cl 2in 5g triphenylamine, at oil bath 80 DEG C reflux 48 hours, cool after question response, normal temperature leaves standstill 15min and pours in frozen water, and being adjusted to pH with the NaOH of 2mol/L is 7, uses CH 2cl 2extract and take off a layer liquid 3 times, add Na 2sO 4drying, then obtains yellow solid with Rotary Evaporators evaporate to dryness, uses CH 2cl 2dissolve, crude product is separated to obtain sterling through silica gel chromatographic column, and developping agent is ethyl acetate: sherwood oil=1:10;
The synthesis of (4) 9,9 '-(N-phenyl-N, N-4,4 '-phenylbenzene) two fluorone
The ethanol 105mL of the inclined triphenol triacetate of 3.4g and 60% is added in 250mL round-bottomed flask, add vitriol oil 5.0mL with vigorous stirring, heating in water bath makes it dissolve, add 1.2g4 to it, 4 '-diformyl triphenylamine, heating in water bath dissolves, oil bath 100 DEG C backflow 48 hours after cooling, leave standstill cooling after completion of the reaction, suction filtration obtains dark green solid crude product 9,9 '-NNBPBF;
Crude product 9 is added successively in 250mL beaker, 9 '-NNBPBF, ethyl acetate 50mL, vitriol oil 15mL, shake up rear stirring, and suction strainer must precipitate, with ethyl acetate washing several, cumulative volume is 100mL, proceeds in beaker after suction filtration by precipitation, and add water stirring, water-bath is heated one hour, after cooling, suction strainer goes out precipitation, washes dry sterling 9,9 '-NNBPBF with water.
4. one kind according to claim 19,9 '-(N-phenyl-N, N-4,4 '-phenylbenzene) two fluorone Zn in the presence of surfactants 2+application in the spectrophotometry of ion.
5. one kind according to claim 19,9 '-(N-phenyl-N, N-4,4 '-phenylbenzene) two fluorone is at fluorescence quenching method Cu 2+application in detection.
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CN105777607A (en) * 2016-04-22 2016-07-20 山西大学 Triphenylamine bis-indolyl iodised salt as well as synthesis method and application thereof
CN108558739A (en) * 2018-04-30 2018-09-21 华南理工大学 Small molecule material and preparation method thereof of the one kind based on the high two-photon absorption of naphtho- indenes fluorenes

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CN105733561A (en) * 2016-03-21 2016-07-06 山西大同大学 9,9'-(3,3'-Dihydroxy-4,4'-diphenylether)bifluorone reagent and preparation method and application thereof
CN105777607A (en) * 2016-04-22 2016-07-20 山西大学 Triphenylamine bis-indolyl iodised salt as well as synthesis method and application thereof
CN105777607B (en) * 2016-04-22 2019-04-02 山西大学 A kind of double indoles salt compounded of iodine of triphenylamine and its synthetic method and application
CN108558739A (en) * 2018-04-30 2018-09-21 华南理工大学 Small molecule material and preparation method thereof of the one kind based on the high two-photon absorption of naphtho- indenes fluorenes
CN108558739B (en) * 2018-04-30 2020-05-22 华南理工大学 Small molecule material based on naphthoindene fluorene high two-photon absorption and preparation method thereof

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