CN109232397A - It is a kind of to pass through the alkaline accurate pH test paper and its preparation method and application of washing recycling - Google Patents

It is a kind of to pass through the alkaline accurate pH test paper and its preparation method and application of washing recycling Download PDF

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CN109232397A
CN109232397A CN201811094853.0A CN201811094853A CN109232397A CN 109232397 A CN109232397 A CN 109232397A CN 201811094853 A CN201811094853 A CN 201811094853A CN 109232397 A CN109232397 A CN 109232397A
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aqueous solution
terpyridyls
solution
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test paper
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CN109232397B (en
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郝京诚
董川
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Shandong University
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
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    • C07D213/42—Radicals substituted by singly-bound nitrogen atoms having hetero atoms attached to the substituent nitrogen atom
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    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
    • G01N21/80—Indicating pH value

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Abstract

Colorimetric analysis detection technique field can be belonged to by the alkaline accurate pH test paper and its preparation method and application of washing recycling the present invention relates to a kind of, provide I compound represented of formula, 4 '-p- hydroxyazo phenyl -2,2 ': 6 ' 2 "-terpyridyls,The preparation method of I compound represented of formula, 4 '-nitros -2 are first prepared, 2 ': 6 ' 2 "-terpyridyls; 4 '-amino -2 are prepared by it again; 2 ': 6 ' 2 "-terpyridyls, then 4 '-p- hydroxyazo phenyl -2,2 ': 6 ' 2 "-terpyridyls are obtained with phenol reactant; I compound represented of formula is prepared for a kind of pH test paper that alkalinity is accurate as probe molecule, is able to detect within the scope of water phase pH 11-14 and changes.

Description

It is a kind of can by alkaline accurate pH test paper and preparation method thereof of washing recycling and Using
Technical field
The invention belongs to colorimetric analysis detection technique fields, and in particular to a kind of to pass through the alkalinity essence of washing recycling Close pH test paper and its preparation method and application.
Background technique
PH is the important basic concept in electrochemistry, and applies very extensive solution chemistry index.Because in its definition Single ionic activity is contained, and thermodynamics method can only measure mean activity (the i.e. average work of negative ions of electrolyte Degree), thus its be not one being capable of physical quantity measured directly.Weight in solution chemistry, as detection solution acid alkalinity Index is wanted, pH value generally requires a fixed examination criteria and the primary battery electrode based on potentiometry is needed to support.And The appearance of pH test paper then provides a kind of more convenient intuitive thinking for pH detection.The 17th century, Britain chemist Robert Boyle meets the phenomenon that acid reddens from violet petal and takes a hint, and after being tested using various plants, having invented can be met Acid, which reddens, meets the litmus paper that alkali becomes blue, this is also the blank of current pH test paper.In following 300 years, it becomes chemistry Indispensable necessary article in experiment.
In general pH test paper used in now includes methyl red, three kinds of indicator of bromocresol green and thymol blue, It can change color according to certain rule in the solution of different pH ranges.It is although convenient and efficient that test paper method detects pH, but often PH test paper, which still has, to be recycled, and the disadvantages of being influenced by laboratory air atmosphere is easy.
Summary of the invention
For above-mentioned problems of the prior art, the first purpose of the invention is to provide the chemical combination of formula (I) a kind of Object.A kind of novel compound with coloration, formula (I) compound and OH are provided-Effect becomes ion salt and color occurs Variation, and and OH-It can be protonated again under the action of such excess water molecules after effect, production (I) compound.
In order to solve the above technical problems, the technical solution of the present invention is as follows:
A kind of compound of formula I, 4 '-p- hydroxyazo phenyl -2,2 ': 6 ' 2 "-terpyridyls, structural formula are as follows:
A second object of the present invention is to provide the preparation method of compound shown in above-mentioned formula (I), specific steps are as follows:
1) 4 '-nitro -2,2 ': the synthesis of 6 ' 2 "-terpyridyls
2- acetylpyridine and 4- nitrobenzaldehyde are mixed into solution A, and potassium hydroxide aqueous solution and concentrated ammonia liquor reaction is added The solid obtained afterwards washed, extracted, being dried, being rotated, being recrystallized, being filtered, is dried and is obtained 4 '-nitros -2,2 ': 6 ' 2 "-three Bipyridyl；
2) 4 '-amino -2,2 ': the synthesis of 6 ' 2 "-terpyridyls
The 4 '-nitros -2,2 ' that step 1) is obtained: 6 ' 2 "-terpyridyls and stannous chloride are suspended in concentrated hydrochloric acid and heat Reaction, it is cooling, sodium bicarbonate aqueous solution is added, solid is obtained by filtration by column Chromatographic purification and obtains 4 '-amino -2,2 ': 6 ' 2 " - Terpyridyl；
3) 4 '-p- hydroxyazo phenyl -2,2 ': the synthesis of 6 ' 2 "-terpyridyls
4 '-amino -2 that step 2) is obtained, 2 ': 6 ' 2 "-terpyridyls are dissolved in concentrated hydrochloric acid, are placed in ice bath, drop Enter sodium nitrite in aqueous solution, the mixed aqueous solution B of sodium hydroxide and phenol is added, filters, washs, drying obtains 4 '-p- hydroxyls Azobenzene -2,2 ': 6 ' 2 "-terpyridyls.
Preferably, the solvent of solution A is methanol in step 1)；The process of 2- acetylpyridine and the mixing of 4- nitrobenzaldehyde In be vigorously stirred, solution A and potassium hydroxide, ammonium hydroxide reaction condition are room temperature, time 2-4d, preferably 3d；Preferably, step 1) washing process is to be washed respectively with distilled water and cold methanol in；Preferably, the process extracted in step 1) is that will wash Solid afterwards is first dissolved in ethyl acetate, adds sodium bicarbonate aqueous solution；Preferably, it is carried out in step 1) using anhydrous sodium sulfate It is dry.
Preferably, 4 '-nitro -2 in step 2), the temperature that 2 ': 6 ' 2 "-terpyridyls and stannous chloride react in concentrated hydrochloric acid Degree is 70-90 DEG C, is cooled to room temperature after reaction, and the temperature preferably reacted is 80 DEG C；Preferably, solid powder is added in step 2) After into sodium bicarbonate solution, pH to 12-13 is adjusted；Preferably, filtered solid passes through alkali alumina column in step 2) Chromatography is carried out, eluent is the mixture of ethyl acetate and petroleum ether；It is further preferred that in step 2) in eluent Ethyl acetate and petroleum ether ratio are 1:1-2:1, preferably 1:1.
Preferably, 4 '-amino -2 in step 3), progress ultrasound is stirred during 2 ': 6 ' 2 "-terpyridyls are dissolved in concentrated hydrochloric acid It mixes；Preferably, 0.9-1.2h, preferably 1h are reacted in ice bath after instilling sodium nitrite in aqueous solution in step 3)；Preferably, it walks It is rapid 3) in be added dropwise mixed aqueous solution B, be added after mixed aqueous solution B after reacting 0.9-1.2h in ice bath, at room temperature instead 11-13h is answered, after reacting 1h preferably in ice bath, reacts 12h at room temperature.
Preferably, the mass fraction of KOH aqueous solution is 15% in step 1), and the concentration of concentrated ammonia liquor is 25%-28%；It is preferred that , 2- acetylpyridine in step 1), 4- nitrobenzaldehyde, potassium hydroxide aqueous solution, concentrated ammonia liquor, methanol ratio be 1g:0.6- 0.7g:2-4mL:32-36mL:30-38mL, preferably 1g:0.634g:3mL:34mL:34mL；Preferably, in step 1) NaHCO3The mass concentration of aqueous solution is 1%.
Preferably, 4 '-nitro -2 in step 2), 2 ': 6 ' 2 "-terpyridyls, SnCl2, dense HCl ratio be 1g:3-4g: 24-28mL, preferably 1g:3.3g:26mL；Preferably, 4 '-nitro -2 in step 2), 2 ': 6 ' 2 "-terpyridyls and protochloride The temperature that tin reacts in concentrated hydrochloric acid is 70-90 DEG C, time 7-9h, and the temperature preferably reacted is 80 DEG C, time 8h；Preferably, NaHCO is added in step 2)3Adjust pH to 12-13.
Preferably, 4 '-amino -2 in step 3), 2 ': 6 ' 2 "-terpyridyls, concentrated hydrochloric acid, NaNO2, distilled water: NaOH: benzene The ratio of phenol is 380-420mg:1mL:85-87mg:4mL:320-360mg:110-120mg, preferably 400mg:1mL: 85.18mg:4mL:340mg:116.2mg；Preferably, the mass concentration of mixed aqueous solution B be NaOH:16-18mg/ml, phenol: 5.6-6.0ml/ml preferably 17mg/ml:5.81mg/ml.
Third object of the present invention is to provide above-mentioned 4 '-p- hydroxyazo phenyl -2,2 ': 6 ' 2 "-terpyridyl conducts Application of the probe molecule in pH test paper.
Fourth object of the present invention is to provide a kind of alkaline accurate pH test paper that can be reused by washing, by above-mentioned 4 '-p- hydroxyazo phenyl -2, for 2 ': 6 ' 2 "-terpyridyls as probe molecule, probe molecule loads to qualitative filter paper at a slow speed On obtain alkaline accurate pH test paper.
The test paper of the application preparation is a kind of for detecting the accurate pH test paper changed within the scope of water phase pH 11-14, the examination Paper can be reused by washing drying, have very strong tolerance, comparative, favorable reproducibility, colour developing to environment variation It is uniformly obvious.It can effectively solve the problem that the shortcomings that existing pH test paper can not be reused and be there are certain requirements to use environment temperature, It assigns pH and detects higher stability and convenience.
Above-mentioned one kind can pass through the preparation method of the alkaline accurate pH test paper of washing recycling, the specific steps are as follows:
By 4 '-p- hydroxyazo phenyl -2,2 ': 6 ' 2 "-terpyridyl probe molecules, which are dissolved in organic solvent, to be mixed Solution C is put into qualitative filter paper, and drying obtains alkaline accurate pH test paper.
Preferably, the concentration of mixed solution C is 0.015-0.020mol/L；Preferably, organic solvent is dimethyl sulfoxide (DMSO) or N,N-dimethylformamide；Preferably, it is 15-30min that qualitative filter paper, which is put into time for impregnating in mixed solution C, Temperature is 20-30 DEG C.
Beneficial effects of the present invention:
1) the p- hydroxyazo phenyl -2,2 ' in of the invention 4 ' -: the phenolic groups of 6 ' 2 "-terpyridyl terminal sites can With the OH in solution-Interact deprotonation, develops the color；The probe molecule of ion like can proton again in excessive water Change, restores coloration ability.
2) probe molecule that will be disengaged from liquid environment is carried on qualitative filter paper, and 4 '-as test paper (faint yellow) are p- Hydroxyazo phenyl -2,2 ': 6 ' 2 "-terpyridyl molecules still are able to and OH in solution-Color change occurs for interaction, from And response is generated to the aqueous solution within the scope of pH11-14, test effect is intuitive and reliable；
3) pH method for preparing test paper of the invention is simple, produce it is low in cost, measurement method it is convenient effectively, anti-interference ability By force.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present application, and the application's shows Meaning property embodiment and its explanation are not constituted an undue limitation on the present application for explaining the application.
Fig. 1 is 4 '-p- hydroxyazo phenyl -2,2 ' in embodiment 1: 6 ' 2 "-terpyridyl probe molecules and hydroxyl from The nuclear-magnetism and mass spectral characteristi of sub- binding mode figure and probe molecule itself.
Fig. 2 is ultraviolet-ray visible absorbing of the organic solution to different pH aqueous solution responding abilities of 1 middle probe molecule of embodiment Spectrum and colour developing photo.
Fig. 3 is the ultraviolet-visible that the organic solution of 1 middle probe molecule of embodiment responds different Brewster alkali salt solution Absorption spectrum and colour developing photo.
Fig. 4 be uv-visible absorption spectra of the 1 middle probe molecule of embodiment in different solvents system and colour developing photo, And table statistics are carried out to spectral data.
Fig. 5 be embodiment 1 in loaded development criteria paper jam of the test paper of probe molecule under different pH solution effects with And the photo of the cycle detection difference pH standard solution after being rinsed by water.
Fig. 6 is the seamless writing made in embodiment 1 using the coloration ability of probe molecule and inkless writing paper photo.
Specific embodiment
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singular Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.
Below with reference to embodiment, the present invention is further described
Embodiment 1
4 '-p- hydroxyazo phenyl -2,2 ': 6 ' 2 "-terpyridyls, to 170ml CH are synthesized first35g is added in OH 15% KOH aqueous solution 15ml and 160ml is added in 2- acetylpyridine and 3.17g paranitrobenzaldehyde thereto while stirring NH4Reaction 3 days is stirred at room temperature in OH, system.Suction filtration obtains dark red precipitate, is respectively rinsed three times with distilled water and cold methanol respectively. The solid filtered is dissolved in ethyl acetate, with 1%NaHCO3After aqueous solution two-phase extraction 1 time, obtained organic phase is with anhydrous NaSO4It is dry, CH3CH2OH is recrystallized to give 4 '-nitro -2,2 ': 6 ' 2 "-terpyridyl molecules, yield 34%.
By 4 '-nitros -2,2 ' of above-mentioned synthesis: 6 ' 2 "-terpyridyl 0.46g and SnCl21.536g it is dense to be added to 12ml In HCl, 80 DEG C are heated 8 hours.After being cooled to room temperature, suction filtration obtains residual solids powder, is dissolved in ice water, utilizes NaHCO3It adjusts Save pH to 12-13.The solid of precipitation is obtained by filtration, using alkali alumina chromatographic column separating-purifying target molecule, eluent is matched Than for ethyl acetate: petroleum ether 1:1 obtains 4 '-amino -2,2 ': 6 ' 2 "-terpyridyl molecule yields 62%.
By above-mentioned 4 '-amino -2,2 ': 6 ' 2 "-terpyridyl molecule 200mg are dissolved in the dense HCl of 0.5ml, and ultrasonic agitation helps It is molten.Solution is vigorously stirred as in 0 DEG C of ice bath until completely dissolved.By NaNO242.59mg is added in 2ml distilled water, It is slowly dropped into above-mentioned solution system, whole process is controlled by starch KI test paper.After system becomes clarification, ice bath is kept to continue to stir Mix reaction 1 hour.Then by 170mg NaOH, the mixed aqueous solution of 58.1mg phenol is added dropwise to dropwise in above-mentioned system, acutely It is stirred to react recession deicing bath in 1 hour room temperature reaction 12 hours.Suction filtration obtains residual solids, is rinsed respectively with brine ice and ice water Three times, drying obtains 4 '-p- hydroxyazo phenyl -2,2 ': 6 ' 2 "-terpyridyl molecules, yield 81%.
H is carried out to obtained molecule1Nuclear-magnetism and Mass Spectrometer Method, as shown in Figure 1,1a is the action principle of probe molecule, 1b For the nuclear magnetic spectrogram of probe molecule, 1c is mass spectrogram, and probe molecule end group is phenolic hydroxyl group, corresponds to the width at nuclear-magnetism 10.5ppm It peak can be with the OH in solution in organic-water mixed system-Have an effect, dissociate hydrogen ion, make molecule formed from Alite.The probe molecule of ion salt form can interact again with excessive water, and protonation becomes molecular state again.
Embodiment 2
Probe changes the colour developing of alkalinity.
Weigh the p- hydroxyazo phenyl -2,2 ' in 4 '-synthesized in embodiment 1: 6 ' 2 "-terpyridyl 10.84mg are dissolved in In 20ml DMSO, after solution stable homogeneous, pipettes above-mentioned solution 1ml and be diluted to 50ml, obtain faint yellow probe mother liquor.
The NaOH aqueous solution of 250ml 0.1mol/L is configured, successive dilution simultaneously configures pH 7-13 by pH meter accurate quantification Standard NaOH aqueous solution, pipette 4ml probe mother liquor respectively into multiple vials, pipette the titer 67ul of different pH with The mixing of probe mother liquor measures the ultravioletvisible absorption curve of the different lower detection liquid of pH effect and to the color change in different bottles It photographs to record.
From Fig. 2 a ultravioletvisible absorption curve, it can be seen that and OH-The probe molecule of interaction, absorption peak have occurred from The red shift of 372nm to 523nm, respectively corresponds probe molecule and OH-The binary states variation of effect front and back, as pH value of solution increases, Absorption peak absorbance at its 523nm gradually increases, and the absorption peak absorbance of original molecule gradually weakens at 372nm, system color Be peony from light yellow, as shown in Figure 2 b, be from 7 color of pH it is transparent light yellow, pH8-9, color is gradually deepened, Color is yellow, and pH10.5 can see light red slightly, and pH11 can see apparent light red, pH12-14 color by Light red gradually becomes peony.
Embodiment 3
The preparation process of probe mother liquor is same as Example 2.
The NaBr, NaF, NaCl, NaH that concentration is 0.012mol/L is respectively configured2PO4, Na2HPO4, Na3PO4, Na2SO4Water Solution pipettes various salts 67ul and mixes with mother liquor, measures the ultravioletvisible absorption curve of different detection liquid and to different small Color change in bottle photographs to record.
From the ultravioletvisible absorption curve of Fig. 3 a, it can be seen that for the different Bu Lu that can dissociate hydroxide ion This special aqueous alkali, probe molecule can also respond, and make the absorption peak of molecule that the red shift from 372nm to 523nm occur.It can It is related depending on the pH of the dissociation constant also ie in solution of the depth and the salting liquid of color change in range, wherein pka3Biggish Na3PO4 Solution alkaline is most strong, and the color change of solution is most obvious.And other several alkaline salt solutions such as Na2HPO4, NaF, Na2SO4Deng It can make probe solution that different degrees of discoloration occur, as shown in Figure 3b.NaBr,NaCl,NaH2PO4Color change is unobvious, is Blank group is similar light yellow, NaF, Na2SO4、NaH2PO4Aobvious light red, Na3PO4Aobvious peony.
Embodiment 4
Prepare the screening of the organic solvent of test paper
The preparation process of probe mother liquor is same as Example 2.
4 '-p- hydroxyazo phenyl -2,2 ' prepared by embodiment 1: 6 ' 2 "-terpyridyl 10.84mg are dissolved separately in 20ml 1,3-Dimethyl-2-imidazolidinone (DMI), tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), N, N- dimethyl formyl Amine (DMF) in acetonitrile and acetone, after solution stable homogeneous, pipettes the above-mentioned solution of 1ml and is diluted to 50ml, obtain different solvents Probe mother liquor.
Configure the Na of 0.012mol/L3PO4Aqueous solution pipettes 67ul and is added in above-mentioned different probe mother liquor, respectively after colour developing The ultraviolet-ray visible absorbing curve of measurement detection liquid, takes off H to different solvents middle probe molecule+The peak red shift range of front and back carries out Table statistics.
That indicate in the sterogram of upper right in Fig. 4 is the Na that probe mother liquor is not added and probe mother liquor is added3PO4It is water-soluble The colour developing of liquid is as a result, two vials discoloration of DMI is unobvious；Light red is shown on the right side of two vials of DMF, left side does not become Color；Two vials discoloration of THF is unobvious；Light red is shown on the right side of two vials of DMSO, left side does not change colour；The two of acetonitrile Displaing yellow on the right side of a vial, left side do not change colour；Displaing yellow on the right side of two vials of acetone, left side do not change colour.
The a of Fig. 4 upper left represents DMI, and b represents THF, and c represents acetonitrile, and d represents DMF, and e represents DMSO；It is limited to visit The dissolubility of needle molecule, there is no apparent peak positions to change for DMI and THF middle probe molecule.And it is organic at remaining four kinds In solvent, with the increase of solvent polarity, the red shift range of molecule absorption is gradually increased, this is the π π transition of intramolecular chromophore It is caused.Wherein the red shift range of DMSO and DMF middle probe molecule is maximum, and color developing effect is also most obvious.
Embodiment 5
4 '-p- hydroxyazo phenyl -2 that embodiment 1 is synthesized, 2 ': 6 ' 2 "-terpyridyl probes are dissolved in DMSO, match It sets to obtain the faint yellow precursor solution of 0.015mol/L, then qualitative filter paper at a slow speed is soaked into the precursor solution of preparation, to After filter paper is totally submerged, coloring 15 minutes are stood, drying is taken out, obtains the faint yellow pH test paper of uniform coloring.It then will be made Standby obtained pH test paper is cut into the rectangle fragment of consolidation size, and the NaOH standard aqueous solution of pH 7-14 is added dropwise in test paper Above.It is finished to test paper quick colour-developing, photographs to record color change, as standard color comparison card, as shown in Figure 5 a.It is then sharp respectively It is repeatedly detected the standard solution that pH is 12,12.5,13,13.5,14 with same test paper, is rinsed with water examination after the completion of colour developing every time Paper makes it reply primary colors, and record test paper tests the color change of front and back and comparison of taking pictures repeatedly, as shown in Figure 5 b.
It is the faint yellow pH test paper of uniform coloring on the left of Fig. 5 a, right side is that the NaOH standard aqueous solution of pH 7-14 is added dropwise Chromogenic reaction after above the test paper, from left to right color is successively deepened, be by pH=7 it is light yellow, pH 8-11 color gradually adds Deep, pH=11 color becomes buff, and pH 11.4-13 color is gradually deepened, and pH 13.5-14 color becomes dark brown, by a left side Gradually deepen to the right side.
Fig. 5 b is substituted by the left-to-right colour developing (dark brown) responded for test paper primary colors (yellow), difference pH, as pH increases, Colour developing is gradually deepened, until most deep when pH14.
By comparing with standard paper jam, test paper can retain accurate measurement capability under the premise of washing recycling, In entire detection process, under the premise of not considering that test paper itself is damaged, color speed and levels of precision be not substantially by cycle-index It influences.
Embodiment 6
The preparation process of probe mother liquor is same as Example 3.
Test paper itself can be used as special paper and carry out seamless and inkless writing, the titer configuration mode of pH 13 and Embodiment 5 is identical.Using the standard aqueous solution of pH 13 as ink, text is write on filter paper.After standing for a period of time Completely to solvent volatilization, it then will impregnate with the filter paper of text as in probe mother liquor, photographed to record color sample variation.Simultaneously It can be using the test paper after dyeing as substrate, using the standard aqueous solution of pH 13 as ink, book of drawing repeatedly on test paper It writes, rinses test paper followed by water, photograph to record the color change of entire cyclic process.
As shown in fig. 6, being the filter paper of white on the right side of Fig. 6 a, centre is the filter paper before writing, and right side is the filter after writing Paper is put into flaxen probe mother liquor, and colour developing font is dark brown；Fig. 6 b is respectively that probe is female by first to last one The replacement of probe mother liquor filter paper after the filter paper of liquid, writing, the filter paper after writing carry out water and rinse to obtain new filter paper, colour developing figure Case is dark brown.
As shown in fig. 6, the probe molecule can be as the color developing agent of seamless writing and the paper of inkless writing, written word Mark can be removed by washing, be recycled, and have good reproducibility.
The foregoing is merely preferred embodiment of the present application, are not intended to limit this application, for the skill of this field For art personnel, various changes and changes are possible in this application.Within the spirit and principles of this application, made any to repair Change, equivalent replacement, improvement etc., should be included within the scope of protection of this application.

Claims (10)

1. a kind of I compound represented of formula, it is characterised in that: structural formula are as follows:
2. a kind of preparation method of type I compound described in claim 1, it is characterised in that:
1) 4 '-nitro -2,2 ': the synthesis of 6 ' 2 "-terpyridyls
2- acetylpyridine and 4- nitrobenzaldehyde are mixed into solution A, obtain after potassium hydroxide aqueous solution and concentrated ammonia liquor reaction is added To solid washed, extracted, dried, rotated, recrystallized, filtered, dry and obtain 4 '-nitros -2,2 ': 6 ' 2 "-three connection pyrroles Pyridine；
2) 4 '-amino -2,2 ': the synthesis of 6 ' 2 "-terpyridyls
4 '-nitro -2 that step 1) is obtained, 2 ': 6 ' 2 "-terpyridyls and stannous chloride are suspended in concentrated hydrochloric acid and react, cold But, sodium bicarbonate aqueous solution is added, solid is obtained by filtration by column Chromatographic purification and obtains 4 '-amino -2,2 ': 6 ' 2 "-three connection pyrroles Pyridine；
3) 4 '-p- hydroxyazo phenyl -2,2 ': the synthesis of 6 ' 2 "-terpyridyls
4 '-amino -2 that step 2) is obtained, 2 ': 6 ' 2 "-terpyridyls are dissolved in concentrated hydrochloric acid, are placed in ice bath, instill sub- The mixed aqueous solution B of sodium hydroxide and phenol is added in sodium nitrate aqueous solution, filters, washs, drying obtains 4 '-p- hydroxyazos Phenyl -2,2 ': 6 ' 2 "-terpyridyls；
Preferably, the solvent of solution A is methanol in step 1)；2- acetylpyridine and 4- nitrobenzaldehyde are acute during mixing Strong stirring, solution A and potassium hydroxide, ammonium hydroxide reaction condition are room temperature, time 3d；Preferably, washing process is in step 1) It is washed respectively with distilled water and cold methanol；Preferably, the process extracted in step 1) is to be first dissolved in the solid after washing Ethyl acetate adds sodium bicarbonate aqueous solution；Preferably, it is dried in step 1) using anhydrous sodium sulfate.
3. preparation method according to claim 2, it is characterised in that: 4 ' in step 2) -2,2 ': 6 ' 2 "-three connection pyrrole of nitro - The temperature that pyridine and stannous chloride react in concentrated hydrochloric acid is 70-90 DEG C, is cooled to room temperature after reaction, and the temperature preferably reacted is 80 ℃；
After solid powder is added in sodium bicarbonate solution in step 2), pH to 12-13 is adjusted；
Filtered solid carries out column chromatography by alkali alumina in step 2), and eluent is the mixed of ethyl acetate and petroleum ether Close object；
Preferably, the ethyl acetate in step 2) in eluent and petroleum ether ratio are 1:1-2:1, preferably 1:1.
4. preparation method according to claim 2, it is characterised in that: 4 ' in step 3) -2,2 ': 6 ' 2 "-three connection pyrrole of amino - Pyridine is stirred by ultrasonic during being dissolved in concentrated hydrochloric acid；
0.9-1.2h, preferably 1h are reacted in ice bath after instilling sodium nitrite in aqueous solution in step 3)；
Mixed aqueous solution B is added dropwise in step 3), is added after mixed aqueous solution B after reacting 0.9-1.2h in ice bath, in room Temperature is lower to react 11-13h, after reacting 1h preferably in ice bath, reacts 12h at room temperature.
5. preparation method according to claim 2, it is characterised in that: the mass fraction of KOH aqueous solution is in step 1) 15%, the concentration of concentrated ammonia liquor is 25%-28%；
2- acetylpyridine in step 1), 4- nitrobenzaldehyde, potassium hydroxide aqueous solution, concentrated ammonia liquor, methanol ratio be 1g:0.6- 0.7g:2-4mL:32-36mL:30-38mL, preferably 1g:0.634g:3mL:34mL:34mL；Preferably, in step 1) NaHCO3The mass concentration of aqueous solution is 1%.
6. preparation method according to claim 2, it is characterised in that: 4 ' in step 2) -2,2 ': 6 ' 2 "-three connection pyrrole of nitro - Pyridine, SnCl2, dense HCl ratio be 1g:3-4g:24-28mL, preferably 1g:3.3g:26mL；
4 ' in step 2)-and nitro -2,2 ': the temperature that 6 ' 2 "-terpyridyls and stannous chloride react in concentrated hydrochloric acid is 70-90 DEG C, time 7-9h, the temperature preferably reacted is 80 DEG C, time 8h；
NaHCO is added in step 2)3Adjust pH to 12-13.
7. preparation method according to claim 2, it is characterised in that: 4 ' in step 3) -2,2 ': 6 ' 2 "-three connection pyrrole of amino - Pyridine, concentrated hydrochloric acid, NaNO2, distilled water: NaOH: the ratio of phenol be 380-420mg:1mL:85-87mg:4mL:320-360mg: 110-120mg, preferably 400g:1mL:85.18mg:4mL:340mg:116.2mg；Preferably, the concentration of mixed aqueous solution B is NaOH:16-18ml/ml, phenol: 5.6-6.0ml/ml, preferably 17mg/ml:5.81mg/ml.
8. 4 '-p- hydroxyazo phenyl -2,2 ' described in claim 1: 6 ' 2 "-terpyridyls are tried as probe molecule in pH Application in paper.
9. one kind can pass through the alkaline accurate pH test paper of washing recycling, it is characterised in that: by described in claim 14 '- P- hydroxyazo phenyl -2, for 2 ': 6 ' 2 "-terpyridyls as probe molecule, probe molecule, which loads to, obtains alkali on qualitative filter paper Property accurate pH test paper.
10. the preparation method of alkalinity accurate pH test paper as claimed in claim 9, it is characterised in that: by 4 '-p- hydroxyazobenzenes 2,2 ': 6 ' 2 "-terpyridyl probe molecule of base-, which is dissolved in organic solvent, obtains mixed solution C, is put into qualitative filter paper, and drying obtains To alkaline accurate pH test paper；
Preferably, the concentration of mixed solution C is 0.015-0.020mol/L；
Preferably, organic solvent is dimethyl sulfoxide or n,N-Dimethylformamide；
Preferably, it is 15-30min that qualitative filter paper, which is put into time for impregnating in mixed solution C, and temperature is 20-30 DEG C.
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