CN106187874B - 3,5- dinitros -2,6- two（4,4 '-sulfonic group azo benzeneazo amino）Pyridine and preparation method and application - Google Patents

3,5- dinitros -2,6- two（4,4 '-sulfonic group azo benzeneazo amino）Pyridine and preparation method and application Download PDF

Info

Publication number
CN106187874B
CN106187874B CN201610530941.5A CN201610530941A CN106187874B CN 106187874 B CN106187874 B CN 106187874B CN 201610530941 A CN201610530941 A CN 201610530941A CN 106187874 B CN106187874 B CN 106187874B
Authority
CN
China
Prior art keywords
added
solution
amino
dinitros
sulfonic group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201610530941.5A
Other languages
Chinese (zh)
Other versions
CN106187874A (en
Inventor
解海
许琳
赵强
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanxi Datong University
Original Assignee
Shanxi Datong University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanxi Datong University filed Critical Shanxi Datong University
Priority to CN201610530941.5A priority Critical patent/CN106187874B/en
Publication of CN106187874A publication Critical patent/CN106187874A/en
Application granted granted Critical
Publication of CN106187874B publication Critical patent/CN106187874B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C07D213/60—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/76—Nitrogen atoms to which a second hetero atom is attached
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Plasma & Fusion (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Pyridine Compounds (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
  • Cosmetics (AREA)

Abstract

The invention belongs to double tri azene compound fields, the present invention can solve the problems, such as that Triazenes Reagent detection heavy metal ion sensitivity is not high in the prior art and selectivity is not ideal enough, use NaHSO first3, formaldehyde and aniline aminopropyltriethoxysilane sodium sulfonate clear solution is made, diazonium salt solution is made with p-aminobenzene sulfonic acid, 4 amino, 4 ' sulfonic group azobenzene is made in two kinds of solution mixing；Second step is again with 2,6 diamino-pyridines, KNO33,5 dinitro, 2,6 diamino-pyridine is made in solid and fuming nitric aicd；Finally solution is made in two kinds of substances made from first two steps by third step, and products therefrom carries out column chromatography for separation after reaction, obtains 3,5 dinitros 2,6 two（4,4 ' sulfonic group azo benzeneazo amino）Pyridine.Pyridine prepared by the present invention is the highly sensitive color developing agent that photometry surveys cadmium, and the selectivity for surveying cadmium is good.

Description

3,5- dinitros -2,6- two（4,4’Sulfonic group azo benzeneazo amino）Pyridine and system Preparation Method and application
Technical field
The invention belongs to double tri azene compound fields, and in particular to 3,5- of one kind dinitros -2,6- bis-（4, 4,Sulfonic acid Base azo benzeneazo amino）Pyridine and preparation method and application.
Background technology
Triazene Reagents are a kind of highly sensitive photometric analysis color developing agents, and general formula is Ar-N=N-NH-Ar ', wherein Ar, Ar ' are aryl or aromatic heterocyclic.In the presence of surfactants, Triazene Reagents are matched with IB, Group IIB metal ion Position, generates stable complex, and therefore, such reagent is commonly used in Cd2+、Hg2+、Cu2+、Ni2+And Ag+The light of equal metal ions Degree method measures（Feng Yonglan, Liu Zhi virtue metallurgical analysis, 2008,26 (4): 65-67）.Such reagent have high sensitivity, Synthesis is simple, the advantages that being easy to purification, is of low cost, and therefore, the photometry for being widely used in metal ion in actual sample is surveyed It is fixed, in order to further improve the analytical performance of such reagent, according to triazenes mother nucleus structure, substituent group type and increase-NH- Acidity can change the principle of its sensitivity and selectivity（Liu Yu, Zhang Huashan chemical reagent, 1990,12 (2): 65-70； Gong Churu Hainan Teachers Colleges journal, 2001,14 (1): 71-76）, distinct fragrance heterocyclic amine is selected to be respectively synthesized pyridine Class, thiazoles, the double Triazene Reagents of three kinds of aromatic hydrocarbons, experiment show 3,5- dinitros -2,6- bis-（4, 4,Sulfonic group azo Benzeneazo amino）Pyridine is that the best reagent of cadmium sensitivity highest, selectivity is surveyed in this three classes reagent, which is used for practical sample Product measure, easy to operate, of low cost, result satisfaction.
Invention content
The present invention is not high and selective in order to solve Triazenes Reagent detection heavy metal ion sensitivity in the prior art Not ideal enough problem and a kind of 3,5- dinitros -2,6- two is provided（4, 4,Sulfonic group azo phenylamino azo group）Pyridine and Preparation method and application.
The present invention adopts the following technical scheme that realization：
A kind of 3,5- dinitros -2,6- two（4, 4,Sulfonic group azo benzeneazo amino）Pyridine（Abbreviation DNDSZBZAB）, Its molecular structural formula is shown below：
。
Above-mentioned 3,5- dinitros -2,6- two（4, 4,Sulfonic group azo benzeneazo amino）The preparation method of pyridine, including Following steps：
（1）The preparation of 4- amino -4 '-sulfonic group azobenzene
In beaker, NaHSO is added3, water and formaldehyde is then added, after being stirred under water-bath, aniline is added, reacts light Yellow aminopropyltriethoxysilane sodium sulfonate clear solution；Separately p-aminobenzene sulfonic acid is dissolved in sodium carbonate liquor, under ice water cooling, is added Enter sodium nitrite solution；Under stiring, be added concentrated hydrochloric acid, after place, it is spare to obtain diazonium salt solution；
Ice-water bath cooling under, this diazonium salt solution is added in above-mentioned aminopropyltriethoxysilane sodium sulfonate solution, at the same with satisfy PH to 5 ~ 6 is adjusted with sodium carbonate liquor, after reaction, sodium hydroxide heating hydrolysis is added, stands overnight, washes, recrystallization obtains 4- Amino -4 '-sulfonic group azobenzene；
(2) preparation of 3,5- dinitros -2,6- diamino-pyridines
The concentrated sulfuric acid is added in three-necked flask, 10 ~ 15 DEG C are reduced the temperature on low temperature thermostat bath；2,6- diamino is added Pyridine after adding, maintains thermotonus, KNO is added3Solid maintains 10 ~ 15 DEG C of reactions after adding, then reduce the temperature to- 10 ~ -5 DEG C, fuming nitric aicd is added, after adding, reaction temperature is raised to 30 DEG C, reaction is sudden cold after the completion of reaction, filters, dry Crude product；Crude product is dissolved in dimethyl sulfoxide, distilled water is added, yellow 3 is precipitated, 5- dinitros -2,6-diaminopyridine is brilliant Body, filtering, vacuum freeze drying obtain product；
（3）3,5- dinitros -2,6- two（4, 4,Sulfonic group azo benzeneazo amino）The preparation of pyridine
It weighs 4- amino -4 '-sulfonic group azobenzene to be added in the concentrated sulfuric acid, stir, ice water cooling is solution A, will be sub- Sodium nitrate is added in the concentrated sulfuric acid, and heating makes sodium nitrite dissolve, and ice water cooling is B solution；Under stiring, solution B is added to molten In liquid A, diazonium salt solution is stirred to obtain in ice-water bath；3,5- dinitros -2,6-diaminopyridine is dissolved in ethyl alcohol, is then added Into above-mentioned diazonium salt solution, after stirring, pH to 5 is adjusted with saturated sodium carbonate solution, after reaction, pH to 7 is then adjusted, is warming up to It 10 ~ 15 DEG C, places, is then poured into ice water, tan precipitate is precipitated, filters to obtain crude product, crude product is completely dissolved in DMF In, it is diluted with water precipitation precipitation, handles repeatedly three times, obtains Tan solid product；With acetone and ethanol as solvent, acetic acid second Ester and petroleum ether make eluant, eluent and carry out column chromatography for separation, obtain sterling.
3,5- dinitros -2,6- two to illustrate the invention（4, 4,Sulfonic group azo benzeneazo amino）The chemistry knot of pyridine Structure further characterizes：
Elemental 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 44.70（44.90）, H 2.67（2.71）, N 23.57（23.48）, O 20.75（20.65）.
The IR modal datas (KBr tablettings) of reagent：3412cm-1There is the characteristic absorption peak of-NH- at place;1605cm-1, 1520cm-1,1455cm-1There is the characteristic absorption peak of phenyl ring skeleton at place;3020cm-1There is the characteristic absorption peak of Ar-H at place; 1642cm-1 There is the characteristic absorption peak of N=N at place;638cm-1There are S-O characteristic absorption peaks at place；1035cm-1There are S=O characteristic absorption peaks at place；1535cm-1 With 1355 cm-1There is-NO at place2Characteristic absorption peak.Through elemental analysis and infrared spectrum test synthetic product and target molecular structure It is consistent.
Compared with prior art, the present invention has the advantages that：
（1）The organicvisualization reagent that photometry surveys cadmium mainly has dithizone class, porphyrin, Triazenes Reagent.Dithizone tries Agent sensitivity（ε majorities are 104The order of magnitude）It is bad with selectivity, though plain quinoline class reagent high sensitivity（ε some is up to 106Quantity Grade）, but poor selectivity, while reagent prepares difficulty.Triazene Reagents are the excellent color developing agents for surveying cadmium.Currently, Triazene Reagents Containing only there are one coordination functional groups（- N=N-NH-）Belong to single triazenes.3,5- dinitros -2,6- bis-（4, 4,Sulfonic group is even Pyridine amino azo group）Containing there are two coordination functional groups in Pyridine Molecules（- N=N-NH-）, to increase reagent and gold Belong to the coordination ability of ion, therefore, sensitivity is usually higher than single Triazene Reagents.In addition, reagent is due to nitro and dual-functional group （- N=N-NH-）The conjugated system of introducing reagent molecule further increase, while the acidity of-NH- is increased, to increase Add reagent electron supplying capacity and coordination ability, improves the sensitivity that reagent surveys cadmium, molar absorption coefficient is up to 2.86 × 105 L·mol-1·cm-1, it is the highly sensitive color developing agent that photometry surveys cadmium；
（2）Parent nucleus in DNDSZBZAB reagent molecules is pyridine ring, the nitrogen on pyridine ring and triazenes function base（- N= N-NH-）In nitrogen participate in metallic ion coordination, since coordination atom is nitrogen, the reagent only ion complexation with close nitrogen improves The reaction selectivity of reagent and metal ion, the reagent photometry measure 5 μ g Cd2+When in addition to nickel, mercury have severe jamming, His common metal ion allowance reacted with Triazene Reagents is more than 50 μ g, it is seen then that the selectivity that reagent surveys cadmium is good；
（3）Two sulfonic groups are introduced in DNDSZBZAB reagent molecules, since the group is hydrophilic group, increase examination The water solubility and water phase color development of agent.Increase reagent and the stability of cadmium ion complex in aqueous solution；
（4）DNDSZBZAB reagent preparation conditions are mild, of low cost, and solid reagent and reagent solution stability are good, are convenient for Storage.
3,5- dinitros -2,6- two（4, 4,Sulfonic group azo benzeneazo amino）Pyridine to Cd in biological sample (II) from The detection of sub- concentration：
The first step takes 1.0 g of biological sample in polytetrafluoroethylene (PTFE) microwave digestion bottle, and 5 mL concentrated nitric acids and 10 mL are added 30% hydrogen peroxide clears up 15 min in microwave digestion bottle, is done to close in heating evaporation on electric jacket after resolution, adds 5 The sodium chloride solution of 2.0 mol/L of hydrochloric acid (1+1) and 20 mL of mL dissolves by heating salt, and document [Zhang Xin, Zhu Hui are pressed after cooling It is virtuous etc., Yuxi Normal College's journal 2004,20（12）] method to cadmium ion carry out Solid phase extraction separation enrichment；
Second step sequentially adds the Cd of not more than 16 μ g in 25mL volumetric flasks2+, 1.0 mL 2%（V/V）'s Triton X-100 solution, the ethanol solution of 2.0 mL 0.2g/L DNDSZBZAB, the Na of 3.0 mL pH 8.82B4O7-NaOH Buffer solution is settled to 25 mL with water, shakes up, and after 10 min, using blank reagent as reference, 526 are placed in 1 cm cuvettes Complex compound absorbance is surveyed at nm.Measure that the results are shown in Table 1.
The measurement result (μ g/g) of Cd (II) in 1. biological sample of table
Sample This law measured value Sampling Graphite Furnace Atomic Absorption measured value
Human hair 0.85 0.82
Peanut 0.14 0.12
Seaweed 0.42 0.39
2 several Triazene Reagents of table survey Cd (II) remolding sensitivities compared with
Reagent name Molar absorption coefficient (Lmol-1·cm-1)
1- azobenzenes -3- (5- nitro -2- pyridines)-triazenes 2.07×105
4,4 '-dinitrophenyl diazoaminoazobenzenes 1.66×105
1- pyridines -3- (4- phenylazos) phenyl triazenes 1.72×105
Bis- chloro- 4- aminosulfonylphenyls diazoaminoazobenzenes of 2,6- 1.85×105
1- (4- nitrobenzophenones) -3- (- 1,2,4 triazole of 5,6- dimethyl) triazenes 1.34×105
1- (4- antipyrines) -3- (4- nitrobenzenes) triazenes 2.32×105
1- (bis- bromo- 8- quinoline of 5,7-) -3- (azobenzene) triazenes 2.10×105
Reagent of the present invention 2.86×105
Description of the drawings
Fig. 1 is synthetic route flow chart of the present invention.
Specific implementation mode
A kind of 3,5- dinitros -2,6- two（4, 4,Sulfonic group azo benzeneazo amino）Pyridine（Abbreviation DNDSZBZAB）, Its molecular structural formula is：
。
3,5- dinitros -2,6- two（4, 4,Sulfonic group azo benzeneazo amino）The preparation method of pyridine, including it is as follows Step, as shown in Figure 1：
（1）The preparation of 4- amino -4 '-sulfonic group azobenzene
In beaker, 10.4 g are added（0.1 mol）NaHSO3, 38 mL water and 8 mL volume fractions 40% are then added （0.1 mol）After stirring 40min under 60-66 DEG C of water-bath, 7.2 g are added in formaldehyde（0.08 mol）Aniline, reaction 2h obtain yellowish Color aminopropyltriethoxysilane sodium sulfonate clear solution；13.8g (0.08 mol) p-aminobenzene sulfonic acid is separately dissolved in the carbonic acid of 140 mL 3% In sodium solution, under ice water cooling, the sodium nitrite solution that 5.6 g sodium nitrites are dissolved in 30 mL water is added；Under stiring, add Enter 210 mL concentrated hydrochloric acids, process control is added dropwise in 20 min, finishes and places 15 min, it is spare to obtain diazonium salt solution；
Under ice-water bath cooling, this diazonium salt solution is added in above-mentioned aminopropyltriethoxysilane sodium sulfonate, while using saturated carbon Acid sodium solution adjusts pH 5 ~ 6, and after reacting 2h, 200 g sodium hydroxides of addition are heated to 80 ~ 85 DEG C and hydrolyze 1 hour, stand Night, washing with 95% ethyl alcohol recrystallization, obtain 4- amino -4 ' -13 g of sulfonic group azobenzene；
(2) preparation of 3,5- dinitros -2,6- diamino-pyridines
The 100 mL concentrated sulfuric acids are added in the three-necked flask equipped with stirring, thermometer, drop temperature on low temperature thermostat bath To 10 DEG C, 10 ~ 15 DEG C are maintained；22 g 2,6-diaminopyridine are added with stirring, after adding, maintain temperature anti-at 10 ~ 15 DEG C 1.5h is answered, 10 g KNO are added3Solid maintains 10 ~ 15 DEG C of reaction 1h, then reduces the temperature to -10 ~ -5 DEG C, add after adding Enter 13 mL fuming nitric aicds, after adding, reaction temperature is raised to 30 DEG C, reacts 150 min, it is sudden cold after the completion of reaction, it filters, does Dry crude product；Crude product is dissolved in dimethyl sulfoxide, distilled water is added, yellow 3,5- dinitros -2,6-diaminopyridine is precipitated Crystal, filtering, vacuum freeze drying obtain 32 g of product that purity is 95%；
（3）3,5- dinitros -2,6- two（4, 4,Sulfonic group azo benzeneazo amino）The preparation of pyridine
Weigh 5.6 g（0.02 mol）4- amino -4 '-sulfonic group azobenzene is added in the 8.0 mL concentrated sulfuric acids, stirring, It is solution A that ice water, which is cooled to 5 DEG C or less, by 1.4 g（0.02 mol）Sodium nitrite is added in the 10 mL concentrated sulfuric acids, and heating makes Asia Sodium nitrate dissolves, and it is B solution that ice water, which is cooled to 5 DEG C or less,；Under stiring, solution B is added in solution A, is stirred in ice-water bath It mixes 80 min and obtains diazonium salt solution；By 2.0g（0.01 mol）3,5- dinitro -2,6- diamino-pyridines are dissolved in 60 mL ethyl alcohol In, it is then added in above-mentioned diazonium salt solution, after stirring 30 min, pH to 5, reaction 60 is adjusted with saturated sodium carbonate solution After min, pH to 7 is then adjusted, is warming up to 10 ~ 15 DEG C, 120 min is placed, is then poured into 100 mL ice water, is precipitated brown Color precipitates, and filters to obtain crude product, and crude product is completely dissolved in DMF, is diluted with water precipitation precipitation, handles repeatedly three times, obtain Huang Brown solid product；With acetone and ethyl alcohol（1+1, volume ratio）Make solvent, ethyl acetate and petroleum ether（1：4, V/V）Make eluant, eluent Column chromatography for separation is carried out, sterling is obtained；m.p196~198℃.

Claims (4)

1. a kind of 3,5- dinitros -2,6- two（4, 4,Sulfonic group azo benzeneazo amino）Pyridine, it is characterised in that：Its molecule Structural formula is：
。
2. a kind of 3,5- dinitros -2,6- two（4, 4,Sulfonic group azo benzeneazo amino）The preparation method of pyridine, feature exist In：Include the following steps：
（1）The preparation of 4- amino -4 '-sulfonic group azobenzene
In beaker, NaHSO is added3, water and formaldehyde is then added, after being stirred under water-bath, aniline is added, reacts faint yellow Aminopropyltriethoxysilane sodium sulfonate clear solution；Separately p-aminobenzene sulfonic acid is dissolved in sodium carbonate liquor, under ice water cooling, is added sub- Sodium nitrate solution；Under stiring, be added concentrated hydrochloric acid, after place, it is spare to obtain diazonium salt solution；
Under ice-water bath cooling, this diazonium salt solution is added in above-mentioned aminopropyltriethoxysilane sodium sulfonate solution, while using saturated carbon Acid sodium solution adjusts pH to 5 ~ 6, after reaction, sodium hydroxide heating hydrolysis is added, stands overnight, washes, recrystallization obtains 4- ammonia Base -4 '-sulfonic group azobenzene；
(2) preparation of 3,5- dinitros -2,6- diamino-pyridines
The concentrated sulfuric acid is added in three-necked flask, 10 ~ 15 DEG C are reduced the temperature on low temperature thermostat bath；2,6- diamino pyrroles are added Pyridine after adding, maintains thermotonus, KNO is added3Solid maintains 10 ~ 15 DEG C of reactions, then reduces the temperature to -10 after adding ~ -5 DEG C, fuming nitric aicd is added, after adding, reaction temperature is raised to 30 DEG C of reactions, it is sudden cold after the completion of reaction, it filters, dry is thick Product；Crude product is dissolved in dimethyl sulfoxide, distilled water is added, yellow 3,5- dinitros -2,6-diaminopyridine crystal, mistake is precipitated Filter, vacuum freeze drying obtain product；
（3）3,5- dinitros -2,6- two（4, 4,Sulfonic group azo benzeneazo amino）The preparation of pyridine
It weighs 4- amino -4 '-sulfonic group azobenzene to be added in the concentrated sulfuric acid, stir, ice water cooling, is solution A, by nitrous acid Sodium is added in the concentrated sulfuric acid, and heating makes sodium nitrite dissolve, and ice water cooling is B solution；Under stiring, solution B is added to solution A In, diazonium salt solution is stirred to obtain in ice-water bath；3,5- dinitros -2,6-diaminopyridine is dissolved in ethyl alcohol, is then added to In above-mentioned diazonium salt solution, after stirring, pH to 5 is adjusted with saturated sodium carbonate solution, after reaction, pH to 7 is then adjusted, is warming up to 10 It ~ 15 DEG C, places, is then poured into ice water, tan precipitate is precipitated, filters to obtain crude product, crude product is completely dissolved in DMF, It is diluted with water precipitation precipitation, handles repeatedly three times, obtains Tan solid product；With acetone and ethanol as solvent, ethyl acetate Make eluant, eluent with petroleum ether and carry out column chromatography for separation, obtains sterling.
3. 3,5- dinitros -2,6- two as claimed in claim 2（4, 4,Sulfonic group azo benzeneazo amino）The preparation of pyridine Method, it is characterised in that：Include the following steps：
（1）The preparation of 4- amino -4 '-sulfonic group azobenzene
In beaker, 10.4 gNaHSO are added3, 40% formaldehyde of 38 mL water and 8 mL volume fractions is then added, in 60-66 DEG C of water After the lower stirring 40min of bath, 7.2 g aniline are added, reaction 2h obtains faint yellow aminopropyltriethoxysilane sodium sulfonate clear solution；Separately will 13.8g p-aminobenzene sulfonic acid is dissolved in the sodium carbonate liquor of 140 mL 3%, and under ice water cooling, it is molten that 5.6 g sodium nitrites are added In the sodium nitrite solution of 30 mL water；Under stiring, 210 mL concentrated hydrochloric acids are added, process control is added dropwise in 20 min, finishes and puts 15 min are set, it is spare to obtain diazonium salt solution；
Under ice-water bath cooling, this diazonium salt solution is added in above-mentioned aminopropyltriethoxysilane sodium sulfonate, while using saturated sodium carbonate Solution adjusts pH 5 ~ 6, and after reacting 2h, 200 g sodium hydroxides of addition are heated to 80 ~ 85 DEG C and hydrolyze 1 hour, stand overnight, water It washes, with 95% ethyl alcohol recrystallization, obtains 4- amino -4 ' -13 g of sulfonic group azobenzene；
(2) preparation of 3,5- dinitros -2,6- diamino-pyridines
The 100 mL concentrated sulfuric acids are added in the three-necked flask equipped with stirring, thermometer, reduce the temperature to 10 on low temperature thermostat bath ~ 15℃；22 g 2,6-diaminopyridine are added with stirring, after adding, temperature is maintained to react 1.5h at 10 ~ 15 DEG C, 10 g is added KNO3Solid maintains 10 ~ 15 DEG C of reaction 1h, then reduces the temperature to -10 ~ -5 DEG C, 13 mL fuming nitric aicds are added after adding, After adding, reaction temperature is raised to 30 DEG C, reacts 150 min, it is sudden cold after the completion of reaction, it filters, dry crude product；Crude product is molten Distilled water is added in dimethyl sulfoxide in solution, and yellow 3,5- dinitros -2,6-diaminopyridine crystal, filtering, vacuum refrigeration is precipitated 32 g of product that dry purity is 95%；
（3）3,5- dinitros -2,6- two（4, 4,Sulfonic group azo benzeneazo amino）The preparation of pyridine
5.6-4 '-sulfonic group azobenzenes of g4- amino are weighed to be added in the 8.0 mL concentrated sulfuric acids, stir, ice water be cooled to 5 DEG C with Down be solution A, 1.4 g sodium nitrites are added in the 10 mL concentrated sulfuric acids, heating so that sodium nitrite is dissolved, ice water be cooled to 5 DEG C with It is B solution down；Under stiring, solution B is added in solution A, 80 min is stirred in ice-water bath and obtain diazonium salt solution；It will 2.0g3,5- dinitro -2,6-diaminopyridine are dissolved in 60 mL ethyl alcohol, are then added in above-mentioned diazonium salt solution, stirring 30 After min, pH to 5 is adjusted with saturated sodium carbonate solution, after reacting 60 min, pH to 7 is then adjusted, is warming up to 10 ~ 15 DEG C, place Then 120 min are poured into 100 mL ice water, tan precipitate is precipitated, filters to obtain crude product, crude product is completely dissolved in DMF In, it is diluted with water precipitation precipitation, handles repeatedly three times, obtains Tan solid product；With acetone and ethanol as solvent, acetic acid second Ester and petroleum ether make eluant, eluent and carry out column chromatography for separation, obtain sterling；m.p196~198℃.
4. a kind of 3,5- dinitros -2,6- two（4, 4,Sulfonic group azo benzeneazo amino）Pyridine is applied to Cd (II) ion The detection of concentration.
CN201610530941.5A 2016-07-07 2016-07-07 3,5- dinitros -2,6- two（4,4 '-sulfonic group azo benzeneazo amino）Pyridine and preparation method and application Expired - Fee Related CN106187874B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610530941.5A CN106187874B (en) 2016-07-07 2016-07-07 3,5- dinitros -2,6- two（4,4 '-sulfonic group azo benzeneazo amino）Pyridine and preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610530941.5A CN106187874B (en) 2016-07-07 2016-07-07 3,5- dinitros -2,6- two（4,4 '-sulfonic group azo benzeneazo amino）Pyridine and preparation method and application

Publications (2)

Publication Number Publication Date
CN106187874A CN106187874A (en) 2016-12-07
CN106187874B true CN106187874B (en) 2018-07-27

Family

ID=57473545

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610530941.5A Expired - Fee Related CN106187874B (en) 2016-07-07 2016-07-07 3,5- dinitros -2,6- two（4,4 '-sulfonic group azo benzeneazo amino）Pyridine and preparation method and application

Country Status (1)

Country Link
CN (1) CN106187874B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106885779B (en) * 2017-04-05 2019-09-17 曲阜师范大学 Synthesis of polydentate ligand containing azo chromophore and colorimetric method for simultaneously detecting trace Ag+And Fe3+Method (2)
CN114149385B (en) * 2021-12-16 2024-02-27 烟台丰鲁精细化工有限责任公司 Synthesis method of 1-pyrrolidinyl- (4- (4' -butylphenylazo)) azobenzene
CN115784944A (en) * 2022-12-27 2023-03-14 宿迁虹光化学工业有限公司 Synthesis method of high-purity environment-friendly acid dye intermediate

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101161637A (en) * 2007-11-26 2008-04-16 山西大同大学 3,5-di-(4-nitrophenylamino diazo) benzoic acid and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101161637A (en) * 2007-11-26 2008-04-16 山西大同大学 3,5-di-(4-nitrophenylamino diazo) benzoic acid and preparation method thereof

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
1-偶氮苯-3-(3-硝基-5-氯-2-吡啶)-三氮烯的合成及其与镉的显色反应;郑云法等;《丽水学院学报》;20061031;第28卷(第5期);39-41、105 *
2-吡啶重氮氨基偶氮苯与镉(II)的显色反应及其应用;汪朝存等;《分析化学研究简报》;19981031;第26卷(第10期);1260-1263 *
Spectrophotometric Determination of Trace Cadmium in Vegetables with 3,5-bis(4-Phenyl azophenylaminodiazo)Benzoic Acid;Shuangming Meng等;《Journal of Analytical Chemistry》;20111231;第66卷(第1期);摘要、第33-35页 *
新三氮烯类试剂的合成及其与金属离子显色反应的研究;刘瑜等;《化学试剂》;19901231;第12卷(第2期);第66页左栏 *
杂环三氮烯试剂的类型和应用及其进展;龚楚儒;《海南师范学院学报《自然科学版》》;20010331;第14卷(第1期);第72页第2点 *

Also Published As

Publication number Publication date
CN106187874A (en) 2016-12-07

Similar Documents

Publication Publication Date Title
Chen et al. A highly selective naked-eye and fluorescent probe for fluoride ion based on 1, 8-naphalimide and benzothizazole
CN106187874B (en) 3,5- dinitros -2,6- two（4,4 '-sulfonic group azo benzeneazo amino）Pyridine and preparation method and application
CN111423423B (en) Application of ratiometric fluorescent probe in detecting peroxynitrite anion
Misra et al. An efficient thiourea-based colorimetric chemosensor for naked-eye recognition of fluoride and acetate anions: UV–vis and 1HNMR studies
Venkateswarulu et al. Sensitive molecular optical material for signaling primary amine vapors
Ghosh et al. Selective sensing of Zn (II) ion by a simple anthracene-based tripodal chemosensor
Gupta et al. A sensitive TICT Probe exhibiting ratiometric fluorescence repose to detect hydrazine in solution and gas phase
Pan et al. Coumarin thiourea-based fluorescent turn-on Hg 2+ probe that can be utilized in a broad pH range 1–11
Yue et al. A novel Schiff-base fluorescent probe based on 1, 8-naphthyridine and naphthalimide for Al3+
CN103965893B (en) Gold ion fluorescent probe based on o-aminopyridine nitrile compound and preparation method thereof
Shu et al. A new peptide-mediated COF nanocatalytic amplification SERS quantitative assay for ultratrace Cu2+
Li et al. A “turn-on” Schiff base fluorescent probe for recognizing Zn2+ and its application in indictor and imaging of zebrafish
CN109490291A (en) Purposes of the 1,8- naphthoyl imide compounds based on electron-withdrawing group substitution as the colour reagent of fluorine ion
CN107235985B (en) A kind of fluorescence probe and the preparation method and application thereof detecting bivalent cupric ion
CN104164229B (en) The heterocycle pH probe of a kind of water-soluble weak acid changeable colour and preparation thereof and application
CN115651006B (en) Hydrogen peroxide ratio type near infrared fluorescent probe with large Stokes displacement and preparation method and application thereof
CN111138373B (en) Fluorescent probe for detecting nitric oxide concentration and synthetic method and application thereof
CN109970634B (en) Pyridine Schiff base structure fluorescent probe for detecting copper ions and preparation method and application thereof
Kumar et al. Synergistic solvent extraction of copper, cobalt, rhodium and iridium into 1, 2-dichloroethane at trace level by newly synthesized 25, 26, 27, 28-tetrahydroxy-5, 11, 17, 23-tetra-[4-(N-hydroxyl-3-phenylprop-2-enimidamido) phenylazo] calix [4] arene
Shruthi et al. Highly selective fluorescent and colorimetric methylphenyl-based sensor towards Zn2+ ion detection: Synthesis, X-ray crystallography and selectivity studies
Zhou et al. Selective detection of HSO3− in living cells using a pyrroloquinoline structure containing turn-on fluorescent probe
CN102584857A (en) 2,6-bis-(1,1'-naphthalene amino azo)benzo(1,2-d;4,5-d') dithiazole, and preparation method and application thereof
CN114621174B (en) Fluorescent probe for detecting peroxynitrite anion and preparation method and application thereof
CN108299396B (en) Organic compound for detecting metal ions in water environment and application thereof
CN109134454B (en) Preparation method and application of bithiazole azo compound

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20180727

Termination date: 20200707

CF01 Termination of patent right due to non-payment of annual fee