CN108864152B - Preparation method and application of benzo-bis-thiazole azo compound - Google Patents

Preparation method and application of benzo-bis-thiazole azo compound Download PDF

Info

Publication number
CN108864152B
CN108864152B CN201811072857.9A CN201811072857A CN108864152B CN 108864152 B CN108864152 B CN 108864152B CN 201811072857 A CN201811072857 A CN 201811072857A CN 108864152 B CN108864152 B CN 108864152B
Authority
CN
China
Prior art keywords
compound
formula
water
benzo
ethanol
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.)
Active
Application number
CN201811072857.9A
Other languages
Chinese (zh)
Other versions
CN108864152A (en
Inventor
王科伟
贾治芳
刘慧君
郭英
郭永
冯锋
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 CN201811072857.9A priority Critical patent/CN108864152B/en
Publication of CN108864152A publication Critical patent/CN108864152A/en
Application granted granted Critical
Publication of CN108864152B publication Critical patent/CN108864152B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
    • C07D513/04—Ortho-condensed systems
    • 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
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Biochemistry (AREA)
  • Analytical Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)

Abstract

The invention provides a preparation method and application of a benzo-bis-thiazole azo compound. The preparation method comprises the following steps: process for preparing 2, 6-diaminobenzo (1, 2-d; 4,5-d) bisthiazolesPreparing; and 2, 2' - [ benzo (1, 2-d; 4,5-d) dithiazolyl hydrazone group]Preparing the bismalononitrile; hydrazine hydrate is added dropwise to the 2, 2' - [ benzo (1, 2-d; 4,5-d) dithiazolyl hydrazone group]Dissolving the bismalononitrile in the solution of ethanol, refluxing, filtering, precipitating, washing with water and recrystallizing to obtain 2, 6-bis (3, 5-diamino-4-pyrazolylazo) benzo (1, 2-d; 4,5-d) bithiazole serving as a purple brown solid. The invention has the characteristics of simple preparation method of the reagent, easy synthesis and stable reagent. Can be used for Fe in acid medium in the presence of surfactant3+The photometric analysis and detection of (1). Has the effect on Fe3+The detection has the characteristics of good selectivity, high sensitivity and stable test system.

Description

Preparation method and application of benzo-bis-thiazole azo compound
Technical Field
The invention belongs to the technical field of bisazo compound application, and particularly relates to a preparation method and application of a benzo-bis-thiazole azo compound.
Background
The heterocyclic azo reagent is an important branch in azo organic reagents, and the structural formula of the heterocyclic azo reagent can be simply represented as R '-N ═ N-R, wherein R' is heterocyclic radical, and R is coupling component (including heterocyclic component). According to the difference of the structures, the most applied reagents in the analysis and detection are pyridylazo reagents, thiazolylazo reagents and benzothiazolyazo reagents. Thiazole azo reagents are widely concerned by people due to the characteristics of easy synthesis, good selectivity and the like. But its presence is less sensitive (mostly at 10)4Order of magnitude), selectivity is not yet ideal. After the benzene ring is aromatic hydrocarbon and condensed with the thiazole ring, a conjugated system is increased due to the incorporation of the benzene ring, the benzothiazole azo reagent has better selectivity and sensitivity compared with the thiazole azo reagent, the types of interference ions are reduced, the allowable content range is widened, and the sensitivity of the reagent is greatly improved (Megaku institute of Touchai university, Jialidan, Liudajie, 2001, 14 (4): 52-57).
In benzothiazole azo reagents, the coupling component (usually benzene, naphthalene or other heterocyclic derivatives) is also an important factor in determining the performance of the reagent. In the coupling component, the ortho-substituent of the azo group has a great influence on the selectivity of the reagent and also on the sensitivity (Liu, silk, Metallurgical analysis, 2001, 21 (5): 36-42). Amino at the ortho position of the azo group and nitrogen atoms in the benzothiazole heterocyclic ring can be coordinated with metal ions, and the amino and the nitrogen atoms are easy to react with nitrogen-philic metals, so that the azo-containing complex has high selectivity, and therefore, a color developing agent with a large conjugated system and good sensitivity and selectivity is selected, and the azo-containing complex is very important in the aspect of detecting iron ions.
Disclosure of Invention
The invention provides 2, 6-bis (3, 5-diamino-4-pyrazolylazo) benzo (1, 2-d; 4,5-d) bithiazole for solving the problem of the prior art that the sensitivity and the selectivity of a reagent for detecting heavy metal ions are not ideal.
It is a further object of the present invention to provide a process for the preparation of 2, 6-bis (3, 5-diamino-4-pyrazolylazo) benzo (1, 2-d; 4,5-d) bisthiazole and its use.
An object of the present invention is to solve at least the above problems and/or disadvantages and to provide at least the advantages described hereinafter.
The invention takes p-phenylenediamine as raw material, according to the structure-activity relationship of heterocyclic azo compound, 2, 6-di (3, 5-diamino-4-pyrazole azo) benzo (1, 2-d; 4,5-d) bithiazole is synthesized by series reaction, which is characterized in that the benzo bithiazole and two pyrazole heterocycles are connected together by azo group (-N ═ N-) to form a larger conjugated system, which is a color developing agent with good sensitivity and selectivity and is used for the photometric determination of iron ions in an acid medium.
To achieve these objects and other advantages in accordance with the present invention, there is provided a benzobisthiazole azo compound, which is named 2, 6-bis (3, 5-diamino-4-pyrazolylazo) benzo (1, 2-d; 4,5-d) bisthiazole, having the following structural formula (I):
Figure BDA0001800020320000021
a method for preparing 2, 6-di (3, 5-diamino-4-pyrazolazo) benzo (1, 2-d; 4,5-d) bithiazole comprises the following synthetic route:
Figure BDA0001800020320000022
the method specifically comprises the following steps:
step one, weighing p-phenylenediamine and ammonium thiocyanate according to a proportion, adding concentrated hydrochloric acid and removing O2Dissolving the mixed solution to obtain a mixed solution, carrying out reflux reaction on the mixed solution at the temperature of 80-90 ℃, after the reaction is finished, cooling, filtering, washing with hot water, and drying in vacuum to obtain a compound shown in a formula 2, adding glacial acetic acid to dissolve the compound shown in the formula 2, slowly and uniformly adding bromine dissolved in the glacial acetic acid, stirring and reacting at the temperature of 60-70 ℃ to obtain a stirred mixture, pouring the stirred mixture into cold water, adding ammonia water, adjusting the pH to 9-10, cooling, carrying out suction filtration, washing with water to be neutral, drying to obtain a crude product, dissolving the crude product in hot DMF, aging, cooling, filtering, and washing to obtain a compound shown in a formula 3;
step two, dissolving the compound of the formula 3 obtained in the step one in DMSO, dropwise adding the solution into a nitroso-sulfuric acid solution (stored at-5 ℃) under the conditions of ice water bath and continuous stirring, stirring at 0-5 ℃ to obtain a compound of the formula 4, and storing at low temperature for later use; dissolving malononitrile in ethanol, dissolving NaAc in distilled water, mixing the solutions, cooling to 0-5 ℃, dropwise adding the mixture to the compound of formula 4 while stirring, continuously stirring the reaction solution in an ice bath, separating out a precipitate, filtering, washing with water, and recrystallizing with ethanol to obtain the compound of formula 5;
and step three, dissolving the compound of the formula 5 obtained in the step two in ethanol, adding hydrazine hydrate dissolved in the ethanol into the solution for reflux reaction, and after the reaction is finished, filtering, washing with water and recrystallizing to obtain a compound (I).
The preparation method of the nitroso-sulfuric acid solution comprises the following steps: under the condition of continuous stirring, adding NaNO powder2Slowly add to concentrated H2SO4And H2And (3) keeping the temperature of the mixed solution of O not more than 10 ℃, and cooling the obtained nitroso-sulfuric acid solution to-5 ℃ by using an ice water bath for later use.
The compound shown in the formula 2 is p-dithiobiurea, the compound shown in the formula 3 is 2, 6-diaminobenzo (1, 2-d; 4,5-d) bithiazole, the compound shown in the formula 4 is a diazonium salt, and the compound shown in the formula 5 is 2, 2' - [ benzo (1, 2-d; 4,5-d) bithiazolylhydrazone ] bismalononitrile.
Preferably, in the step one, the amount ratio of the p-phenylenediamine and the ammonium thiocyanate is 1:2, and the amount ratio of the compound of the formula 2 and the substances of the p-phenylenediamine and the ammonium thiocyanate is 1:2: 4.
Preferably, in the step one, 0.2moL of p-phenylenediamine, 0.4moL of ammonium thiocyanate and 0.1moL of the compound of the formula 2 are added.
Preferably, wherein, in the second step, 0.07moL of the compound of formula 3 is dissolved in DMSO; and 0.14moL of malononitrile was dissolved in ethanol.
Preferably, in the third step, 0.03moL of the compound of formula 5 is dissolved in ethanol, 0.6moL of hydrazine hydrate dissolved in ethanol is added to the solution to carry out reflux reaction, and after the reaction is finished, the compound is filtered, washed with water and recrystallized to obtain the compound (I).
2, 6-di (3, 5-diamino-4-pyrazolylazo) benzo (1, 2-d; 4,5-d) bithiazole, wherein the compound is applied to photometry for determining Fe in various samples3+。
The invention has the beneficial effects that:
1.2, 6-bis (3, 5-diamino-4-pyrazolazo) benzo (1, 2-d; 4,5-d) bithiazole is a bis-benzothiazolylazo reagent, has a bidentate heterocyclic nitrogen atom and a bidentate functional group (-N ═ N-), and further enhances the coordination capacity of the reagent and metal ions, so that the reagent has higher sensitivity.
2. In 2, 6-di (3, 5-diamino-4-pyrazolazo) benzo (1, 2-d; 4,5-d) bithiazole molecule, four amino (-NH) groups are introduced on pyrazole ring2) Auxochromes, conjugated systems in the reagent molecule due to the p-pi conjugation effectThe activity of the pi electron is enhanced, and the fluidity is increased; in addition, the reagent molecule contains two benzothiazole azo pyrazole structural units, has a larger conjugated system compared with a single benzothiazole azo reagent, and has an iron-measuring molar absorption coefficient of 1.85 multiplied by 105。
3. In heterocyclic azo reagent systems, the coupling component is often an important factor in determining the performance of the reagent. In the reagent 2, 6-bis (3, 5-diamino-4-pyrazolylazo) benzo (1, 2-d; 4,5-d) bithiazole, the coordination sites participating in the coordination of the metal ions are two nitrogen atoms (benzothiazole nitrogen and azo nitrogen), and the coupling component is an amino group (-NH) ortho to the azo group on the pyrazole ring2) Also participate in coordination. Thus, the reagent 2, 6-bis (3, 5-diamino-4-pyrazolylazo) benzo (1, 2-d; 4,5-d) bisthiazole is generally only reactive with the nitrogenophilic metal ion and reacts with Fe in an acidic medium3+The reaction is obvious and is a photometric analysis reagent with good selectivity (see table 3).
4. The invention has the characteristics of simple preparation method of the reagent, easy synthesis and stable reagent. Can be used for Fe in acid medium in the presence of surfactant3+The photometric analysis and detection of (1). For Fe3+The detection has the characteristics of high response speed, good selectivity, high sensitivity and stable test system.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of Compound (I) in an example of the present invention;
FIG. 2 is an infrared spectrum of Compound (I) in the example of the present invention.
Detailed Description
The present invention is further described in detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description text.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Example 1
The preparation method of 2, 6-di (3, 5-diamino-4-pyrazolazo) benzo (1, 2-d; 4,5-d) bithiazole includes the following steps:
(1) preparation of 2, 6-diaminobenzo (1, 2-d; 4,5-d) bisthiazole (the compound of formula 3)
Into a 500mL three-necked flask equipped with a reflux condenser and a dropping funnel were charged 21.6g (0.2moL) of p-phenylenediamine and 120mL of a solution from which O was removed228.0mL of concentrated hydrochloric acid and 30.4g (0.4moL) of ammonium thiocyanate, the above mixture was refluxed at 80-90 ℃ for 24 hours, and after cooling, the precipitate was collected by filtration, then washed three times with hot water and dried in vacuum to obtain 36.0g of p-dithiothiourea (the compound of formula 2) as a pale yellow solid. Adding 22.6g (0.1moL) of p-benzenedithiothiourea (the compound shown in the formula 2) and 180mL of glacial acetic acid into a 500mL three-necked bottle, measuring 10mL of a solution of bromine dissolved in 120mL of glacial acetic acid, slowly (about 60min is needed) dropwise adding the solution into the reaction mixture, keeping the reaction temperature at 60-70 ℃, stirring for reaction for 16h, pouring the mixture into cold water, adding ammonia water into the mixture under vigorous stirring, adjusting the pH value to 9-10, standing, cooling the solution, performing suction filtration, washing with water to be neutral, and drying to obtain a crude product. The crude product was dissolved in hot DMF and aged for 30min, cooled and filtered, and washed with acetone to give 17.00g of yellow needle-like crystals of 2, 6-diaminobenzo (1, 2-d; 4,5-d) dithiazole (the compound of formula 3).
(2) Preparation of 2, 2' - [ benzo (1, 2-d; 4,5-d) dithiazolylhydrazone ] bismalononitrile (said 5 compound)
10.35g (0.15moL) of NaNO in powder form are added with stirring2Slowly add to 90mL of concentrated H2SO4And 70mL H2In the mixed solution of O, the temperature is kept to be not more than 10 ℃, and the obtained nitroso-sulfuric acid solution is cooled to-5 ℃ by using an ice water bath. 15.56g (0.07moL) of 2, 6-diaminobenzo (1, 2-d; 4,5-d) bithiazole (the compound of formula 3) is dissolved in 170ml of DMSO, the solution is added dropwise to the above nitroso sulfuric acid solution under cooling in an ice-water bath and continuous stirring, and after the dropwise addition is finished, the solution is stirred for 2.5 hours at 0-5 ℃ to obtain a dark brown diazonium salt (the compound of formula 4), and the diazonium salt is stored at low temperature for later use.
9.24g (0.14moL) of malononitrile were dissolved in 320mL of ethanol and 100.00g of NaAc were dissolved in 150mL of distilled water. And then mixing the solutions, cooling to 0-5 ℃, dropwise adding the diazonium salt (the compound shown in the formula 4) solution while stirring, continuously stirring the reaction solution in an ice bath for 4 hours, filtering, separating out a precipitate, washing with water, and recrystallizing with ethanol to obtain 18.00g of red crystal 2, 2' - [ benzo (1, 2-d; 4,5-d) dithiazolyl hydrazone ] malononitrile (the compound shown in the formula 5).
(3) Preparation of 2, 6-bis (3, 5-diamino-4-pyrazolylazo) benzo (1, 2-d; 4,5-d) bisthiazole
30.00g (0.6moL) of hydrazine hydrate is dissolved in 100mL of ethanol, and then added dropwise to a solution of 11.29g (0.03moL) of 2, 2' - [ benzo (1, 2-d; 4,5-d) dithiazolylhydrazone ] bismalononitrile dissolved in 300mL of ethanol, the mixture is refluxed for 10 hours and left overnight at room temperature. The precipitate separated out was filtered, washed with water, and recrystallized from a mixture of DMF and ethanol (2:1) to give 11.00g of 2, 6-bis (3, 5-diamino-4-pyrazolylazo) benzo (1, 2-d; 4,5-d) dithiazole as a tan solid, i.e., 11.00g of the compound (I).
The compound (I) is subjected to elemental analysis, infrared spectrum detection and nuclear magnetic resonance hydrogen spectrum analysis, and the results are as follows:
elemental analysis results: the theoretical contents of the elements are calculated according to the molecular formula of the synthesized product, and compared with the measured value, the two values are consistent (the theoretical value is in parentheses):
C：38.86％(38.18％)；
N：44.20％(44.52％)；
S：14.08％(14.56％)；
H：2.78％(2.75％)。
infrared spectrum data: (KBr pellet) 3430, 3320cm-1Two peaks are ArNH2middle-NH2A stretching vibration absorption peak; 3050cm-1Is an Ar-H stretching vibration absorption peak; 1590, 1496, 1450cm-1Is a vibration absorption peak of an aromatic ring skeleton; 1578cm-1is-N ═ N-vibration absorption peak, 1640cm-1Is C ═ N bond absorption peak.
Nuclear magnetic resonance data analysis: nuclear magnetism1H NMR(400MHz,CDCl3)＝12.67(s,2H),7.77(s,2H),6.70(s,2H)；Nuclear magnetism13C NMR(101MHz,CDCl3)＝165.87,151.36,140.21,131.11,122.08,76.48。
In summary, the synthesized product was matched with the target product by elemental analysis, infrared spectroscopy and nuclear magnetic resonance data.
2, 6-di (3, 5-diamino-4-pyrazolazo) benzo (1, 2-d; 4,5-d) bithiazole is used as a display agent, and the content of iron ions in food is measured by a photometry method, wherein the test method comprises the following steps:
the experimental method comprises the following steps: measuring Fe not more than 16 mu g3+1.0mL of 100. mu.g/mL ascorbic acid solution is added into a 25mL volumetric flask, the mixture is shaken and placed for 3min, then 2mL of 8.0g/L Triton X-100 solution, 3mL of HAc-NaAc buffer solution with the pH value of 6, 2 mL0.2g/L2, 6-bis (3, 5-diamino-4-pyrazolazo) benzo (1, 2-d; 4,5-d) dithiazole ethanol solution are added, the mixture is diluted with water to scale and shaken evenly, and after 5min, the absorbance of the complex is measured by using a 1cm cuvette at 620nm and taking a reagent blank as a reference.
And (3) sample analysis: according to the method of literature (food science-analytical inspection, Houming, 2000, 21 (7): 38-40), 1.0000g of cleaned and dried sample is accurately weighed, put into a 30mL porcelain crucible, carbonized on a low-temperature electric furnace, transferred into a muffle furnace, ashed at 800 ℃ for 4 hours, taken out of the crucible to be cooled, and added with 5.0mL of 2mol/L HNO3Heating and leaching the solution, cooling, transferring the solution into a 50mL volumetric flask, adjusting the acidity of the solution to be neutral, diluting the solution to the degree by using water, shaking the solution uniformly for later use, and meanwhile, making a reagent blank. The results, determined by experimental methods, are detailed in table 1:
table 1 trace Fe in sample3+Measurement result of (n ═ 5)
Figure BDA0001800020320000071
The measurement results of the compound provided by the invention as a reagent for detecting iron ions in two detection methods are almost the same, which is a strong evidence for the stability and reliability of the compound.
The invention carries out a comparative test on several heterocyclic azo reagents and the compound provided by the invention, wherein the detection is carried outTo Fe3+The sensitivity data results are shown in table 2:
TABLE 2 measurement of Fe by the use of the heterocyclic azo reagent photometrically3+Sensitivity contrast
Figure BDA0001800020320000081
Since, in the reagent 2, 6-bis (3, 5-diamino-4-pyrazolylazo) benzo (1, 2-d; 4,5-d) bithiazole, the coordination sites involved in coordination of the metal ions are two nitrogen atoms (benzothiazole nitrogen and azo nitrogen), the coupling component is an amino group (-NH-) ortho to the azo group on the pyrazole ring2) Also participate in coordination. Thus, the reagent 2, 6-bis (3, 5-diamino-4-pyrazolylazo) benzo (1, 2-d; 4,5-d) bisthiazole is generally only reactive with the nitrogenophilic metal ion and reacts with Fe in an acidic medium3+Obvious reaction occurs, and the reagent is a photometric analysis reagent with good selectivity;
as shown in Table 2, the compounds of the present invention have higher sensitivity of color reaction because of higher molar absorption coefficient for detecting iron ions as compared with the above heterocyclic azo reagents.
In addition, the invention determines Fe for several heterocyclic azo compounds through a photometric test3+The selectivities (5. mu.g/25 ml) were compared and the results are shown in Table 3:
TABLE 3 measurement of Fe by the photometric method with heterocyclic azo reagents3+Selective comparison (relative error. + -. 5%)
Figure BDA0001800020320000091
Note: CTZAN: 2- (5-carboxy-1, 3, 4-triazoleazo) -5-diethylaminoaniline;
CTZDBA: 2- (5-carboxy-1, 3, 4-triazoleazo) -5-diethylaminobenzoic acid;
BTACAPCA: 2-benzothiazolylazo-7- (4-carboxyphenylazo) -1, 8-dihydroxynaphthalene-3, 6-disulfonic acid;
IZAPN: 2- (2-imidazolazo) -5-diethylaminophenol;
BTMB (branch block) is as follows: 2- (2-benzothiazolylazo) -5-dimethylaminobenzoic acid;
DMPZDT: 2, 6-bis (3, 5-diamino-4-pyrazolylazo) benzo (1, 2-d; 4,5-d) bisthiazole (present invention).
As can be seen from Table 3, the concentration of copper ions is large, and the detection of the concentration of iron ions is not influenced, so that the compound provided by the invention is sensitive to the induction of iron and is not sensitive to copper;
in addition, in the invention, compared with some reported reagents, the selectivity of the reagent on iron ions is best through the measurement of interference of some common ions and comparison with the literature.
In conclusion, the invention has the characteristics of simple reagent preparation method, easy synthesis and stable reagent. Can be used for Fe in acid medium in the presence of surfactant3+The photometric analysis and detection of (1). Has the effect on Fe3+The detection has the characteristics of good selectivity, high sensitivity and stable test system.
While embodiments of the invention have been disclosed above, it is not intended to be limited to the uses set forth in the specification and examples. It can be applied to all kinds of fields suitable for the present invention. Additional modifications will readily occur to those skilled in the art. It is therefore intended that the invention not be limited to the exact details and illustrations described and illustrated herein, but fall within the scope of the appended claims and equivalents thereof.

Claims (7)

1. A benzo-bis-thiazole azo compound, which is named as 2, 6-bis (3, 5-diamino-4-pyrazolazo) benzo (1, 2-d; 4,5-d) bis-thiazole, and has the following structural formula (I):
Figure FDA0002570306410000011
。
2. a process for the preparation of a compound according to claim 1, which is prepared by the following synthetic route:
Figure FDA0002570306410000012
the method specifically comprises the following steps:
step one, weighing p-phenylenediamine and ammonium thiocyanate according to a proportion, adding concentrated hydrochloric acid and removing O2Dissolving the obtained product in water to obtain a mixed solution, carrying out reflux reaction on the mixed solution at the temperature of 80-90 ℃, after the reaction is finished, cooling, filtering, washing with hot water, and drying in vacuum to obtain a compound shown in a formula 2, adding glacial acetic acid to dissolve the compound shown in the formula 2, slowly and uniformly adding bromine dissolved in the glacial acetic acid, stirring and reacting at the temperature of 60-70 ℃ to obtain a stirred mixture, pouring the stirred mixture into cold water, adding ammonia water, adjusting the pH to 9-10, cooling, carrying out suction filtration, washing with water to be neutral, drying to obtain a crude product, dissolving the crude product in hot DMF, aging, cooling, filtering, and washing to obtain a compound shown in a formula 3;
step two, dissolving the compound of the formula 3 obtained in the step one in DMSO, dropwise adding the solution into a nitroso-sulfuric acid solution (stored at-5 ℃) under the conditions of ice water bath and continuous stirring, stirring at 0-5 ℃ to obtain a compound of the formula 4, and storing at low temperature for later use; dissolving malononitrile in ethanol, dissolving NaAc in distilled water, mixing the solutions, cooling to 0-5 ℃, dropwise adding the mixture to the compound of formula 4 while stirring, continuously stirring the reaction solution in an ice bath, separating out a precipitate, filtering, washing with water, and recrystallizing with ethanol to obtain the compound of formula 5;
and step three, dissolving the compound of the formula 5 obtained in the step two in ethanol, adding hydrazine hydrate dissolved in the ethanol into the solution for reflux reaction, and after the reaction is finished, filtering, washing with water and recrystallizing to obtain a compound (I).
3. The method of claim 2, wherein in step one, the amount of p-phenylenediamine and ammonium thiocyanate is in a ratio of 1:2, and the amount of the compound of formula 2 and p-phenylenediamine and ammonium thiocyanate is in a ratio of 1:2: 4.
4. The process of claim 3, wherein in step one, 0.2moL of p-phenylenediamine, 0.4moL of ammonium thiocyanate, and 0.1moL of the compound of formula 2 are added.
5. The method of claim 2, wherein in step two, 0.07moL of the compound of formula 3 is dissolved in DMSO; and 0.14moL of malononitrile was dissolved in ethanol.
6. The method of claim 2, wherein in step three, 0.03moL of the compound of formula 5 is dissolved in ethanol, 0.6moL of hydrazine hydrate dissolved in ethanol is added to the solution for reflux reaction, and after the reaction is finished, the compound (I) is obtained by filtration, water washing and recrystallization.
7. Use of the compound of claim 1 for photometric determination of Fe in various samples3+。
CN201811072857.9A 2018-09-14 2018-09-14 Preparation method and application of benzo-bis-thiazole azo compound Active CN108864152B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811072857.9A CN108864152B (en) 2018-09-14 2018-09-14 Preparation method and application of benzo-bis-thiazole azo compound

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811072857.9A CN108864152B (en) 2018-09-14 2018-09-14 Preparation method and application of benzo-bis-thiazole azo compound

Publications (2)

Publication Number Publication Date
CN108864152A CN108864152A (en) 2018-11-23
CN108864152B true CN108864152B (en) 2020-10-27

Family

ID=64323988

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811072857.9A Active CN108864152B (en) 2018-09-14 2018-09-14 Preparation method and application of benzo-bis-thiazole azo compound

Country Status (1)

Country Link
CN (1) CN108864152B (en)

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103980227B (en) * 2014-05-07 2016-04-20 山西大同大学 Two (2-carboxyl-5-methyl-4-hydroxybenzene azo)-6, the 6`-biphenyl of 2,2`-double thiazole and its preparation method and application

Also Published As

Publication number Publication date
CN108864152A (en) 2018-11-23

Similar Documents

Publication Publication Date Title
Vincent et al. Preparation and physical properties of trinuclear oxo-centered manganese complexes of general formulation [Mn3O (O2CR) 6L3] 0,+(R= methyl or phenyl; L= a neutral donor group) and the crystal structures of [Mn3O (O2CMe) 6 (pyr) 3](pyr) and [Mn3O (O2CPh) 6 (pyr) 2 (H2O)]. cntdot. 0.5 MeCN
CN105694866B (en) Symmetric form phenanthro- imidazoles Fe3+ fluorescence probes of double-Schiff base link and preparation method thereof
CN107629008B (en) Phenanthroimidazole micromolecule Fe3+Fluorescent probe and synthetic method thereof
CN106632064B (en) Reversible dihydroxy phenanthroimidazole Hg2+Fluorescent probe synthesis and methods of use
Gup et al. Metal complexes and solvent extraction properties of isonitrosoacetophenone 2-aminobenzoylhydrazone
CN109503422A (en) A kind of synthesis and application of schiff bases aluminium ion probe compound
CN106117230A (en) Replace rhodamine B amide groups Thiourea fluorescent probe compounds and its preparation method and application
CN110028471B (en) Coumarin Schiff base Cu2+Fluorescent probe and preparation method and application thereof
Qin et al. Ratiometric fluorescent probe for Al 3+ based on coumarin derivative in aqueous media
CN108864152B (en) Preparation method and application of benzo-bis-thiazole azo compound
Çelik et al. The new water-soluble Schiff base derivative fluorometric chemosensor with highly selective and instantly sensitivity for Fe3+ ion detection in aqueous media
CN106187874B (en) 3,5- dinitros -2,6- two（4,4 '-sulfonic group azo benzeneazo amino）Pyridine and preparation method and application
CN102532017B (en) 3,3'-diethoxy-4,4'-di(8-hydroxy-5-quinoline ammonia azo)azobenzene and preparation method and application thereof
CN109134454B (en) Preparation method and application of bithiazole azo compound
CN114409591B (en) Bishydrazide viologen derivative, preparation method thereof and humidity sensing application
CN102127035B (en) Compound azo salicyl aldehyde semicarbazone mercaptothiodiazole and preparation and application thereof
CN103980227B (en) Two (2-carboxyl-5-methyl-4-hydroxybenzene azo)-6, the 6`-biphenyl of 2,2`-double thiazole and its preparation method and application
CN108191809B (en) Rhodamine derivative and synthesis method and application thereof
CN102584857B (en) 2,6-bis-(1,1'-naphthalene amino azo)benzo(1,2-d;4,5-d') dithiazole, and preparation method and application thereof
CN106188100B (en) 2,6 2（The pyrimidine azo of 2,4,6 triamido 5）Benzo（1, 2‑d; 4, 5‑d）The preparation method and application of double thiazole
CN105384701B (en) A kind of benzotriazole benzaldehyde-p-phenylenediamine bi-schiff base and preparation method thereof
Li et al. NIR squaraine dyes for dual colorimetric and fluorescent determination of Fe 3+, Cu 2+, and Hg 2+ ions
Mohanan et al. Synthesis, spectroscopic characterization and thermal studies of some lanthanide (III) nitrate complexes with a hydrazo derivative of 4-aminoantipyrine
CN113651828A (en) Near-infrared fluorescent probe for detecting chromium ions and aluminum ions as well as preparation method and application of near-infrared fluorescent probe
CN108276423B (en) Calcium ion and zinc ion dual-channel rhodamine fluorescent probe and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant