CN106188100B - 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 - Google Patents

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 Download PDF

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CN106188100B
CN106188100B CN201610609623.8A CN201610609623A CN106188100B CN 106188100 B CN106188100 B CN 106188100B CN 201610609623 A CN201610609623 A CN 201610609623A CN 106188100 B CN106188100 B CN 106188100B
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尚建鹏
许琳
刘�文
王尚芝
樊月琴
解海
孟双明
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Shanxi Datong University
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    • 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
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Abstract

The invention belongs to a kind of bis-azo compound field, can solve the problems, such as that the sensitivity for detecting heavy metal ion reagent in the prior art and selectivity are not ideal enough, 2,6 diaminourea benzos are prepared by raw materials such as 4,4 ' p-phenylenediamine, glacial acetic acid and potassium rhodanides first（1,2‑d;4,5‑d）Double thiazole, then pass through NaNO22,2 ' [benzos are prepared Deng raw material（1,2‑d;4,5‑d）Double thiazole hydrazone group] double malononitrile, finally by the ethanol solution reaction of guanidine nitrate and NaOH ethanol solution, and the product of second step reaction, obtain 2,6 two（The pyrimidine azo of 2,4,6 triamido 5）Benzo（1,2‑d;4,5‑d）Double thiazole.The present invention is for Cu2+The detection of concentration has the characteristics of good fast response time, selectivity, high sensitivity, stable test system.

Description

2,6- bis-（2,4,6- triamido -5- pyrimidine azos）Benzo（1, 2-d; 4, 5- d）The preparation method and application of double thiazole
Technical field
The invention belongs to a kind of bis-azo compound field, and in particular to one kind 2,6- bis-（2,4,6- triamidos -5- Pyrimidine azo）Benzo（1, 2-d; 4, 5-d）The preparation method and applications of double thiazole.
Background technology
Heterocylic azo dyes are an important branch in azo organic reagent, and its structural formula can simply be expressed as R '-N=N-R, wherein R ' are heterocyclic radical, and R is coupling component（Including heterocycle component）., should in analysis detection according to the difference of structure With it is most be pyridylazo class, thiazolylazo class, benzothiazole azo class reagent.This three classes reagent is widely used to metal Ion Ni2+、Co2+、Zn2+、Pd2+、Hg2+、Ag+、Cu2+Photometric analysis Deng metal ion detects（Theory testing-chemistry fascicle, Zhang Hanpeng, 1996,32（1）：53-58）.Thiazoles azo agents are because it is easily-synthesized, has the features such as preferable selective, by people Extensive concern.But it is relatively low sensitivity to be present in it（Majority is 104The order of magnitude）, selectivity it is preferable not enough the shortcomings that.Phenyl ring It is aromatic hydrocarbon, after being condensed with thiazole ring, due to being incorporated to for phenyl ring, conjugated system increase, benzothiazole azo class reagent is compared with thiazole Azo-reagents have preferable selectivity and sensitivity, and interfering ion species reduces and allows content range to broaden, the spirit of reagent Sensitivity also greatly improves（Tiaocheng Teacher-Training College's journal, Jia Liping, Liu Daojie, 2001,14（4）：52-57）.
In benzothiazolylazo reagents, coupling component（Typically benzene, naphthalene or other Hete rocyclic derivatives）And determine reagent An important factor for performance.In coupling component, azo group ortho-substituent is influenceed greatly, to sensitivity on the selectivity of reagent Have an impact（Liu Bin, Sun Jiajuan, metallurgical analysis, 2001,21（5）：36-44）.The amino and benzothiazole heterocycle at azo group ortho position In nitrogen-atoms, can be with metallic ion coordination, they easily react with close nitrogen metal ion, thus have higher selectivity, It is considered as design high selectivity, the effective way of high sensitivity reagent.The present invention is using p-phenylenediamine as raw material, according to heterocycle The structure-activity relationship of azo-compound, 2,6- bis- is synthesized by serial reaction（2,4,6- triamido -5- pyrimidine azos）Benzo （1, 2-d; 4, 5-d）Double thiazole, it is characterized in passing through azo group（-N=N-）Benzo double thiazole and two pyrimidine heterocyclics are connected It is connected together to form bigger conjugated system, is sensitivity, selective good developer, copper ion is used in acid medium Photometry measure.
The content of the invention
The present invention is dissatisfactory in order to solve the sensitivity for detecting heavy metal ion reagent in the prior art and selectivity Problem, there is provided one kind 2,6- bis-（2,4,6- triamido -5- pyrimidine azos）Benzo（1, 2-d; 4, 5-d）The system of double thiazole Preparation Method and application.
The present invention adopts the following technical scheme that realization：
A kind of 2,6- bis-（2,4,6- triamido -5- pyrimidine azos）Benzo（1, 2-d; 4, 5-d）Double thiazole （DTAPABDP）, its molecular structural formula is：
。
Above-mentioned 2,6- bis-（2,4,6- triamido -5- pyrimidine azos）Benzo（1, 2-d; 4, 5-d）Double thiazole preparation side Method, comprise the following steps：
（1）2,6- diaminourea benzos（1,2-d; 4,5-d）The preparation of double thiazole
In there-necked flask, 4 are sequentially added, 4 '-p-phenylenediamine, glacial acetic acid and potassium rhodanide, stirs, then measures at room temperature Bromine is dissolved in glacial acetic acid, is added dropwise in the reactive mixture, and it is 45-55 DEG C to keep reaction temperature, will be mixed after continuing stirring reaction Compound is poured into cold water, adds ammoniacal liquor into mixture under agitation, and regulation pH is 8-9, is stood, and after solution cooling, is filtered, It is washed with water to neutrality, dries, obtain crude product, crude product is dissolved in the DMF of heat and is aged, cooled and filtered, washed, obtained yellow with acetone Color acicular crystal 2,6- diaminourea benzos（1,2-d; 4,5-d）Double thiazole；
（2）2,2 '-[benzo（1,2-d; 4,5-d）Double thiazole hydrazone group] it is prepared by double malononitrile
Under agitation, by powdered NaNO2It is added to dense H2SO4And H2In O mixed liquor, keeping temperature≤10 DEG C, gained Nitrosylsulfuric acid solution be cooled to -5 DEG C with ice-water bath；By 2,6- diaminourea benzos（1,2-d; 4,5-d）Double thiazole is dissolved in In DMSO, under cooling and stirring, this solution is added drop-wise in above-mentioned nitrosylsulfuric acid solution, is added dropwise, in 0-5 DEG C of continuation Stirring, obtains dark-brown diazol, standby in Cord blood；
Malononitrile is dissolved in ethanol, NaAc is dissolved in distilled water, is then mixed above-mentioned solution, is cooled to 0-5 DEG C, Above-mentioned diazonium salt solution is added drop-wise under stirring, reaction solution continues to stir in ice bath, separates out precipitation, filters, and washing, ethanol is tied again Crystalline substance, obtain 2,2 '-[benzo of red crystals（1,2-d; 4,5-d）Double thiazole hydrazone group] double malononitrile；
（3）2,6- bis-（2,4,6- triamido -5- pyrimidine azos）Benzo（1, 2-d; 4, 5-d）The preparation of double thiazole
Guanidine nitrate and NaOH are dissolved in ethanol, then, are added drop-wise to 2,2 '-[benzo（1,2-d; 4,5-d）Double thiazole Hydrazone group] double malononitrile are dissolved in the solution in ethanol, mixed-liquor return reaction, room temperature left overnight, the precipitation of precipitation is filtered, Washing, is recrystallized with DMF, obtains puce solid 2,6- bis-（2,4,6- triamido -5- pyrimidine azos）Benzo（1, 2-d; 4, 5-d）Double thiazole.
2,6- bis- to illustrate the invention（2,4,6- triamido -5- pyrimidine azos）Benzo（1, 2-d; 4, 5-d）It is double The chemical constitution of thiazole, is further characterized.
Elementary analysis result：The theoretical content of each element is calculated by the molecular formula of synthetic product（wt %）, and and measured value （wt%）Compare, two values are consistent（It is theoretical value in bracket）：
C：38.63（38.86）；N：45.54（45.32）；S：13.12（12.97）；H：2.71（2.85）.
Ir data（KBr tablettings）：3400,3340cm-1Two peaks are ArNH2In-NH2Stretching vibration absworption peak； 3020cm-1For Ar-H stretching vibration absworption peaks；1593,1495,1440cm-1For aromatic ring frame vibration absorption peak；1575 cm-1 For-N=N- vibration absorption peaks, 1630 cm-1For C=N key absworption peaks.
In summary, it is consistent by elementary analysis and infrared spectrum test, synthetic product with target product.
Advantages of the present invention and good effect：
（1）Benzothiazole azo class reagent（R '-N=N-R is represented simply as, wherein R ' is benzothiazolyl, and R is another idol Join component, usually benzene, naphthalene, phenanthrene, quinoline etc.）It is photometry measure Ni2+、Co2+、Fe3+、Cu2+The highly sensitive colour developing examination of plasma Agent.Document（Analytical chemistry, Shen Hanxi, 1989,17（3）：279-288）Point out：" in thiazolylazo class reagent, due to heterocycle Nitrogen-atoms participate in the coordination of metal ion so that this kind of reagent can produce stable complex with metal ion ".2,6- bis- （2,4,6- triamido -5- pyrimidine azos）Benzo（1, 2-d; 4, 5-d）Double thiazole is double benzothiazole azo class reagents, With double coordination heterocyclic nitrogen atoms and double coordination functional groups（-N=N-）, further enhancing the configurational energy of reagent and metal ion Power, therefore, reagent have higher sensitivity.
（2）Reagent 2,6- bis-（2,4,6- triamido -5- pyrimidine azos）Benzo（1, 2-d; 4, 5-d）Double thiazole point In son, six amino are introduced on pyrimidine ring（-NH2）Auxochromes, due to the pi-conjugated effects of p-, the π of conjugated system is electric in reagent molecule Sub- increased activity, mobility increase；In addition, reagent molecule contains two benzothiazole azo pyrimidine structure units, with single benzo thiophene Azoles azo agents are compared, and have bigger conjugated system, thus the reagent is the highly sensitive developer of photometric analysis, and it is surveyed copper and rubbed Your absorptivity is up to 1.64 × 105。
（3）In heterocylic azo dyes system, coupling component is often an important factor for determining reagent performance.In reagent 2, 6- bis-（2,4,6- triamido -5- pyrimidine azos）Benzo（1, 2-d; 4, 5-d）In double thiazole, metallic ion coordination is participated in Coordination site be two nitrogen-atoms（Benzothiazole nitrogen and azo nitrogen）, the amino at azo group ortho position on coupling component pyrimidine ring（- NH2）Also assist in coordination.Therefore, reagent 2,6- bis-（2,4,6- triamido -5- pyrimidine azos）Benzo（1, 2-d; 4, 5- d）Double thiazole generally only with close nitrogen metal ion react, in acid medium only and Pd2+、Hg2+、Cu2+Deng occur significant reaction, It is the good photometric analysis reagent of selectivity（It is shown in Table 3）.
（4）The present invention has the characteristics of preparation method of reagent thereof is simple, be easily-synthesized, stable reagent.Exist in surfactant Under, available for the Cu in acid medium2+Photometric analysis detection.For Cu2+Detection have fast response time, selectivity it is good, The characteristics of high sensitivity, test system are stable.
2,6- bis-（2,4,6- triamido -5- pyrimidine azos）Benzo（1, 2-d; 4, 5-d）Double thiazole photometry is surveyed Determine the content of copper ions in food.
Experimental method, measure not more than 15 μ g Cu2+In 25mL volumetric flasks, add the HAc-NaAc that 3mLpH is 3 and buffer Solution, 3mL8.0g/L Triton X-100 solution, 2mL1.0g/L2,6- bis-（2,4,6- triamido -5- pyrimidine azos） Benzo（1, 2-d; 4, 5-d）Double thiazole solution, it is diluted with water to scale and shakes up, 5min uses 1cm cuvettes at 680nm, Using reagent blank as reference, the absorbance of complex compound is determined.
Sample analysis, by document（Micro- table and health research, Lv Wenying, 2000,17（4）：46-47）Method, it is accurate Dried sample 2g is really weighed, is put into 250mL beakers, enriching nitric acid 25mL, is shaken up, is put about 200 on electric hot plateoC, which disappears, to be boiled 30min is removed, and after cooling, adds HNO3-HClO4（3+1）Mixed acid 15mL, continue to heat and step up temperature, treat that digest is residual Stay less, when digestive juice is white transparent, then raises temperature and make HClO4Decompose.When it is surplus have solution about 2mL when untill.After cooling 25mL volumetric flasks are all washed with distilled water, after tune pH is 7 or so, add 2mL10% NH4F solution, it is fixed molten with distilled water, by reality Proved recipe method determines, as a result as shown in table 1.
Table 2 is that Study of Heterocyclic Azo Reagents photometry surveys Cu2+Sensitivity comparative result.
Table 3 is that Study of Heterocyclic Azo Reagents photometry surveys Cu2+（5μg/25ml）Selectivity ratios compared with（Relative error ± 5%）.
Micro Cu in the sample of table 12+Measurement result（n=5）
The Study of Heterocyclic Azo Reagents photometry of table 2 surveys Cu2+Remolding sensitivity compared with
The Study of Heterocyclic Azo Reagents photometry of table 3 surveys Cu2+（5μg/25ml）Selectivity ratios compared with（Relative error ± 5%）
Note：m-CPAQ：5-（3- carboxyl benzeneazos）- 8- aminoquinolines；
5-NO2-PAMB：2-（5- nitro -2- pyridylazos）- 5- dimethylaminobenzoic acids；
QADMAA：2-（2- quinoline azos）- 5- dimethylaminobenzoic acids；
ANN：1-（4- antipyrine azos）- beta naphthal；
CPBSQ：5-（4- chlorphenyl azos）- 8- phenylsulfonyl-amido quinoline；
DTAPABDP：2,6- bis- (2,4,6- triamido -5- pyrimidines azo) benzo（1,2-d；4,5-d）Double thiazole（This hair It is bright）.
Brief description of the drawings：
Fig. 1 is synthetic route flow chart of the present invention.
Embodiment：
Embodiment 1, a kind of 2,6- bis-（2,4,6- triamido -5- pyrimidine azos）Benzo（1, 2-d; 4, 5-d）It is double Thiazole（DTAPABDP）, its molecular structural formula is：
。
2,6- bis- (2,4,6- triamido -5- pyrimidines azo) benzo（1,2-d; 4,5-d）Double thiazole preparation method walks as follows Suddenly：
（1）2,6- diaminourea benzos（1,2-d; 4,5-d）The preparation of double thiazole
The dry reflux condensing tube for being provided with drying tube, dropping funel 500mL there-necked flasks in, sequentially add 4,4 The g of '-p-phenylenediamine 10.81（0.1mol）, glacial acetic acid 150mL and potassium rhodanide 70g, stir 20min at room temperature, then measure 10mL bromines are dissolved in 130mL glacial acetic acids, are added in the reactive mixture, and it is 45-55 DEG C to keep reaction temperature, continues stirring reaction After 24h, pour the mixture into cold water, add ammoniacal liquor into mixture under agitation, regulation pH is 8-9, stands, treats that solution is cold But after, filtering, be washed with water to neutrality, dry, obtain crude product, crude product, which is dissolved in the DMF of heat, is aged 30min, cooled and filtered, Washed with acetone, obtain yellow needle-like crystals 2,6- diaminourea benzos（1,2-d; 4,5-d）Double thiazole 15g；
（2）2,2 '-[benzo（1,2-d; 4,5-d）Double thiazole hydrazone group] it is prepared by double malononitrile
Under conditions of stirring, by 9.66g（0.14mol）Powdered NaNO2It is added to the dense H of 90mL2SO4And 50mLH2O's In mixed liquor, keeping temperature≤10oC, the nitrosylsulfuric acid solution of gained is cooled to -5 DEG C with ice-water bath, by 15.56 g （0.07mol）2,6- diaminourea benzos（1,2-d; 4,5-d）Double thiazole is dissolved in 160mLDMSO, is being cooled down and is being stirred continuously Under, this solution is added drop-wise in above-mentioned nitrosylsulfuric acid solution, is added dropwise, continues to stir 1.5h at 0-5 DEG C, obtains dark-brown Diazol, it is standby in Cord blood；
By 9.24g（0.14 mol）Malononitrile is dissolved in 300mL ethanol, and 120gNaAc is dissolved in 150mL distilled water.So Above-mentioned solution is mixed afterwards, is cooled to 0-5 DEG C, above-mentioned diazonium salt solution is added drop-wise under stirring, reaction solution continues to stir in ice bath 2h is mixed, separates out precipitation, is filtered, washing, ethyl alcohol recrystallization, obtains 2,2 '-[benzo of red crystals（1,2-d; 4,5-d）Double thiazole hydrazone Base] double g of malononitrile 15；
（3）2,6- bis-（2,4,6- triamido -5- pyrimidine azos）Benzo（1, 2-d; 4, 5-d）The preparation of double thiazole
By 7.32 g（0.06mol）Guanidine nitrate and 12gNaOH are dissolved in 400mL ethanol, then, are added drop-wise to 11.29 g （0.03mol）2,2 '-[benzo（1,2-d; 4,5-d）Double thiazole hydrazone group] double malononitrile are dissolved in the solution in 150mL ethanol, Mixed-liquor return reacts 10h, room temperature left overnight.The precipitation separated out is filtered, washing, is recrystallized with DMF, obtains puce solid 2,6- bis-（2,4,6- triamido -5- pyrimidine azos）Benzo（1, 2-d; 4, 5-d）Double thiazole 8g.

Claims (4)

  1. A kind of 1. 2,6- bis-（2,4,6- triamido -5- pyrimidine azos）Benzo（1, 2-d; 4, 5-d）Double thiazole, its feature It is：Its molecular structural formula is：
    。
  2. A kind of 2. 2,6- bis-（2,4,6- triamido -5- pyrimidine azos）Benzo（1, 2-d; 4, 5-d）The preparation of double thiazole Method, it is characterised in that：Comprise the following steps：
    （1）2,6- diaminourea benzos（1,2-d; 4,5-d）The preparation of double thiazole
    In there-necked flask, 4 are sequentially added, 4 '-p-phenylenediamine, glacial acetic acid and potassium rhodanide stir at room temperature, and it is molten then to measure bromine Solution is added dropwise in the reactive mixture in glacial acetic acid, and it is 45-55 DEG C to keep reaction temperature, after continuing stirring reaction, by mixture Pour into cold water, add ammoniacal liquor into mixture under agitation, regulation pH is 8-9, is stood, and after solution cooling, filters, uses water Neutrality is washed till, is dried, obtains crude product, crude product is dissolved in the DMF of heat and is aged, cooled and filtered, washed with acetone, obtain yellow pin Shape crystal 2,6- diaminourea benzos（1,2-d; 4,5-d）Double thiazole；
    （2）2,2 '-[benzo（1,2-d; 4,5-d）Double thiazole hydrazone group] it is prepared by double malononitrile
    Under agitation, by powdered NaNO2It is added to dense H2SO4And H2In O mixed liquor, keeping temperature≤10 DEG C, the Asia of gained Nitro sulfuric acid solution is cooled to -5 DEG C with ice-water bath；By 2,6- diaminourea benzos（1,2-d; 4,5-d）Double thiazole is dissolved in DMSO In, under cooling and stirring, this solution is added drop-wise in above-mentioned nitrosylsulfuric acid solution, is added dropwise, continue to stir at 0-5 DEG C Mix, obtain dark-brown diazol, it is standby in Cord blood；
    Malononitrile is dissolved in ethanol, NaAc is dissolved in distilled water, then mixes above-mentioned solution, is cooled to 0-5 DEG C, stirring Under be added drop-wise to above-mentioned diazonium salt solution, reaction solution continues to stir in ice bath, separate out precipitation, filter, washing, ethyl alcohol recrystallization, Obtain red crystals 2,2 '-[benzo（1,2-d; 4,5-d）Double thiazole hydrazone group] double malononitrile；
    （3）2,6- bis-（2,4,6- triamido -5- pyrimidine azos）Benzo（1, 2-d; 4, 5-d）The preparation of double thiazole
    Guanidine nitrate and NaOH are dissolved in ethanol, then, are added drop-wise to 2,2 '-[benzo（1,2-d; 4,5-d）Double thiazole hydrazone group] Double malononitrile are dissolved in the solution in ethanol, mixed-liquor return reaction, room temperature left overnight, are filtered the precipitation of precipitation, are washed, Recrystallized with DMF, obtain puce solid 2,6- bis-（2,4,6- triamido -5- pyrimidine azos）Benzo（1, 2-d; 4, 5- d）Double thiazole.
  3. 3. 2,6- bis- as claimed in claim 2（2,4,6- triamido -5- pyrimidine azos）Benzo（1, 2-d; 4, 5-d） The preparation method of double thiazole, it is characterised in that：Comprise the following steps：
    （1）2,6- diaminourea benzos（1,2-d; 4,5-d）The preparation of double thiazole
    In there-necked flask, 4 are sequentially added, 4 '-p-phenylenediamine 10.81g, glacial acetic acid 150mL and potassium rhodanide 70g, is stirred at room temperature 20min is mixed, 10mL bromines is then measured and is dissolved in 130mL glacial acetic acids, is added dropwise in the reactive mixture, holding reaction temperature is 45-55 DEG C, after continuing stirring reaction 24h, pour the mixture into cold water, add ammoniacal liquor into mixture under agitation, adjust PH is 8-9, is stood, and after solution cooling, is filtered, and is washed with water to neutrality, dries, and obtains crude product, and crude product is dissolved in the DMF of heat 30min is aged, cooled and filtered, is washed with acetone, obtains yellow needle-like crystals 2,6- diaminourea benzos（1,2-d; 4,5-d）It is double Thiazole 15g；
    （2）2,2 '-[benzo（1,2-d; 4,5-d）Double thiazole hydrazone group] it is prepared by double malononitrile
    Under conditions of stirring, by the powdered NaNO of 9.66g2It is added to the dense H of 90mL2SO4And 50mLH2In O mixed liquor, keep Temperature≤10 DEG C, the nitrosylsulfuric acid solution of gained are cooled to -5 DEG C with ice-water bath, by 15.56g 2,6- diaminourea benzos（1, 2-d; 4,5-d）Double thiazole is dissolved in 160mLDMSO, and under cooling and stirring, this solution is added drop-wise into above-mentioned nitrosylsulfuric acid In solution, it is added dropwise, continues to stir 1.5h at 0-5 DEG C, obtain dark-brown diazol, it is standby in Cord blood,
    9.24g malononitrile is dissolved in 300mL ethanol, 120gNaAc is dissolved in 150mL distilled water, then mixes above-mentioned solution Closing, be cooled to 0-5 DEG C, above-mentioned diazonium salt solution is added drop-wise under stirring, reaction solution continues to stir 2h in ice bath, separates out precipitation, Filtering, washing, ethyl alcohol recrystallization, obtains 2,2 '-[benzo of red crystals（1,2-d; 4,5-d）Double thiazole hydrazone group] double malononitrile 15g；
    （3）2,6- bis-（2,4,6- triamido -5- pyrimidine azos）Benzo（1, 2-d; 4, 5-d）The preparation of double thiazole
    7.32g guanidine nitrates and 12gNaOH are dissolved in 400mL ethanol, then, are added drop-wise to 2,2 '-[benzos of 11.29g（1,2- d; 4,5-d）Double thiazole hydrazone group] double malononitrile are dissolved in the solution in 150mL ethanol, mixed-liquor return reaction 10h, at room temperature Stand overnight, filter the precipitation of precipitation, wash, recrystallized with DMF, obtain puce solid 2,6- bis-（2,4,6- triamidos- 5- pyrimidine azos）Benzo（1, 2-d; 4, 5-d）Double thiazole 8g.
  4. A kind of 4. 2,6- bis-（2,4,6- triamido -5- pyrimidine azos）Benzo（1, 2-d; 4, 5-d）Double thiazole is applied to Cu in food2+The detection of concentration.
CN201610609623.8A 2016-07-29 2016-07-29 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 Expired - Fee Related CN106188100B (en)

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