CN105777729A - Coumarin amides compound as well as preparation method and application of coumarin amides compound - Google Patents
Coumarin amides compound as well as preparation method and application of coumarin amides compound Download PDFInfo
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Abstract
The invention relates to the field of compound synthesis and in particular relates to a coumarin amides compound as well as a preparation method and application of the coumarin amides compound. The structural formula of the coumarin amides compound is shown as the description, wherein an R radical is phenyl, substituted phenyl or pyridyl. The coumarin amides compound is synthesized by taking acylamino as a bridge group, and has the advantages of convenience for synthesis, moderate reaction conditions and stable product structure; the finally obtained target compound has a relatively strong intramolecular conjugated electron transfer effect, a relatively high molar light absorption coefficient and relatively large Strokes displacement.
Description
Technical field
The present invention relates to compou nd synthesis field, more particularly to a kind of Diarbarone compounds and its preparation method and application.
Background technology
Coumarin and derivant thereof are the organic heterocyclic molecules that a class is important, all contain similar structures, and have multiple biological activity in many natural and synthetic drug molecules.Coumarin and derivant thereof are as the electron transporting compound of conjugation in molecule, there is excellent fluorescence quantum efficiency, high molar absorption coefficient and big Stokes displacement, it is widely used in the high-technology fields such as coloring plastic, color fluorescence coating, the color fluorescence resin of solar collector, sensitive material, light-sensitive material, video disc recording material, it have been reported that coumarin nicotinamide compounds, it is applied mainly as metal ion probe and biostatic agent, its performance in optics of less research.
This kind of coumarin compound with fluorescence is generally made up of three parts: coumarin ring (pi-electron donor), pi-electron bridged group (abbreviation abutment), pi-electron receptor (or donor), pi-electron abutment is generally carbon-carbon double bond (C=C), carbon-to-nitrogen double bon (C=N), and less employing amide groups (CONH) makes abutment.
Summary of the invention
It is an object of the invention to solve the deficiencies in the prior art, it is provided that a kind of be abutment with amide groups Diarbarone compounds and its preparation method and application.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of Diarbarone compounds, its structural formula is as follows:
Described R group is phenyl, substituted-phenyl or pyridine radicals.
Preferably, described substituent group is selected from any one in substituents:
A kind of preparation method of Diarbarone compounds, described preparation method carries out as follows:
(1) with salicylide, cyan-acetic ester, 3,4-AHBA for raw material, one pot process 2-(2-carbonyl-2H-1-.alpha.-5:6-benzopyran-3-base) benzothiazole-5-carboxylic acid；
(2) 2-(2-carbonyl-2H-1-.alpha.-5:6-benzopyran-3-base) benzothiazole-5-carboxylic acid that above-mentioned steps is synthetically derived and chloride reagent carry out acyl chloride reaction and are synthetically derived 2-(2-carbonyl-2H-1-.alpha.-5:6-benzopyran-3-base) benzothiazole-5-formyl chloride；
(3) 2-(2-carbonyl-2H-1-.alpha.-5:6-benzopyran-3-base) benzothiazole-5-formyl chloride that above-mentioned steps obtains reacts with amino-compound and carries out acylation reaction, is synthetically derived Diarbarone compounds.
Preferably, described chloride reagent is oxalyl chloride, thionyl chloride or triphosgene, and described amino-compound is aniline, replacement, aniline or aminopyridine.
More having choosing, described amino-compound is any one in following amino-compound:
Preferably, described preparation method is specific as follows:
(1) in 100mL there-necked flask, salicylide 17mmol, cyan-acetic ester 17mmol, 3,4-AHBA 17mmol, benzoic acid 5.8mmol and n-amyl alcohol 50mL it are sequentially added into, it is heated to reflux 5-12h, it is cooled to room temperature, reactant liquor is poured in 100mL water, precipitate out a large amount of precipitation, sucking filtration, washes with water dried, obtains orange solids 2-(2-carbonyl-2H-1-.alpha.-5:6-benzopyran-3-base) benzothiazole-5-carboxylic acid；
(2) in 50mL there-necked flask, 2-(2-carbonyl-2H-1-.alpha.-5:6-benzopyran-3-base) benzothiazole-5-carboxylic acid 1mmol and solvent 30mL is added, chloride reagent 1.2mmol is dripped under room temperature, add DMF1 and drip as catalyst, solvent and residue chloride reagent are evaporated off after reacting 2-10h at 20-120 DEG C, obtaining khaki solid 2-(2-carbonyl-2H-1-.alpha.-5:6-benzopyran-3-base) benzothiazole-5-formyl chloride, described solvent is dichloromethane or toluene；
(3) in 100mL there-necked flask, it is sequentially added into amino-compound 1mmol, Na2CO31.1mmol and anhydrous CH2Cl220mL, is cooled to 0～5 DEG C, drips 2-(2-carbonyl-2H-1-.alpha.-5:6-benzopyran-3-base) benzothiazole-5-formyl chloride 1mmol and anhydrous CH2Cl2The mixed liquor of 30mL, after reacting 3-106h in-5～10 DEG C, reacts 5-20h, filters under room temperature, filtrate adds saturated NaHCO3Solution 25mL, stratification, the anhydrous CH of water layer2Cl2Extracting, merge organic facies, solvent is evaporated off, column chromatography purifies, and the volume ratio=4:1 of developing solvent petroleum ether and ethyl acetate obtains Diarbarone compounds.
The application of a kind of Diarbarone compounds, as fluorescent pigment application in coating.
The invention has the beneficial effects as follows: the present invention is using amide groups as abutment synthesizing coumarin amides compound, there is the advantage that synthesis is convenient, reaction condition is gentle and product structure is stable, and the target compound finally given has a conjugated electrons transfer effect in stronger molecule, and higher molar absorption coefficient and relatively larger Stokes displacement.
Accompanying drawing explanation
Fig. 1 is target compound uv-visible absorption spectra in dichloromethane；
Fig. 2 is target compound fluorescence emission spectrum in dichloromethane；
Fig. 3 is compound 1a uv-visible absorption spectra in different solvents；
Fig. 4 is compound 1a fluorescence emission spectrum in different solvents；
Fig. 5 is compound 1a fluorescence in different solvents；
In Fig. 5, solvent is followed successively by toluene, dichloromethane, THF, DMF, methanol from left to right.
Detailed description of the invention
Below by specific embodiment, and in conjunction with accompanying drawing, technical scheme is described in further detail.
Embodiment 1:
1.1 reagent and instrument
Instrument: Bruker-500MHz nuclear magnetic resonance spectrometer (AVANCE III type, Bruker company of Germany)；nullShimadzu ultraviolet-visible spectrophotometer (UV-2550 type，Measurement scope: 190-1100nm，Certainty of measurement: 0.01，Shimadzu Corporation of Japan)，Hitachi spectrofluorophotometer instrument (F-2500 type,Wave-length coverage: 220-730nm，HIT)，ThermoFinniganLCQSeries，Agilent6210SeriesTime-of-Flight mass spectrograph (ESI/APCI) (LCQDECAXPPLUS type，Agilent company of the U.S.)，(wave number sweep limits is 350-4000cm-1 to Nicolet6700 Fourier transformation infrared spectrometer，KBr pressed disc method，U.S. thermoelectricity Buddhist nun high-tensile strength company).
Reagent: cyan-acetic ester (AR, Chemical Reagent Co., Ltd., Sinopharm Group)；Salicylide, 3,4-AHBA, oxalyl chloride and substituted aromatic amines etc. (AR, Aladdin biotech inc, Shanghai).
1.2 synthetic routes and method
With salicylide, cyan-acetic ester, 3,4-AHBA for raw material; one pot process 2-(2-carbonyl-2H-1-.alpha.-5:6-benzopyran-3-base) benzothiazole-5-carboxylic acid (I); it is synthesized then through chloride and N-acidylate etc. and obtains 8 target compounds, synthesize as follows in line:
(1) synthesis of 2-(2-carbonyl-2H-1-.alpha.-5:6-benzopyran-3-base) benzothiazole-5-carboxylic acid (I):
It is sequentially added into salicylide (2.076g in 100mL there-necked flask, 17mmol), cyan-acetic ester (7.923g, 17mmol), 3,4-AHBA (2.603g, 17mmol), benzoic acid (0.71g, 5.8mmol) with n-amyl alcohol (50mL), it is heated to reflux 12h, it is cooled to room temperature, reactant liquor is poured in water (100mL), precipitate out a large amount of precipitation, sucking filtration, dried with water (3 × 20mL) washing, obtaining orange solids 3.41g, yield is 65.34%1HNMR (500MHz, DMSO-d6) δ 9.12 (s, 1H, C=CH), 8.35 (s, 1H, Ar-H), 8.10～8.08 (d, 1H, Ar-H), 8.03～8.02 (d, 1H, Ar-H), 7.93～7.91 (d, 1H, Ar-H), 7.80～7.77 (t, 1H, Ar-H), 7.52～7.45 (m, 2H, Ar-H)；
(2) synthesis of 2-(2-carbonyl-2H-1-.alpha.-5:6-benzopyran-3-base) benzothiazole-5-formyl chloride (II):
Compound (I) (0.307g, 1mmol) and anhydrous CH is added in 50mL there-necked flask2Cl2(30mL), under room temperature, drip oxalyl chloride (0.125g, 1.2mmol), add DMF (1) as catalyst, solvent and residue oxalyl chloride are evaporated off after reacting 2h at 20 DEG C, obtain khaki solid 0.305g, yield 93.8%；
(3) synthesis of compound 1a-1h:
Substituted aromatic amines (1mmol), Na it is sequentially added in 100mL there-necked flask2CO3(0.117g, 1.1mmol) and anhydrous CH2Cl2(20mL), it is cooled to 0～5 DEG C, drips compound (II) (0.325g, 1mmol) and anhydrous CH2Cl2(30mL) mixed liquor, after reacting 6h in 0～5 DEG C, reacts 16h, filters at 20 DEG C, filtrate adds saturated NaHCO3Solution (25mL), stratification, the anhydrous CH of water layer2Cl2(3 × 25mL) extracts, and merges organic facies, solvent is evaporated off, and column chromatography purifies, and developing solvent V (petroleum ether): V (ethyl acetate)=4:1 obtains compound 1a-1h, shown in result table 1:
The synthesis of table 1 compound 1a-1h
1.3 target compounds characterize
Compound 1a:IR (KBr, υ/cm-1):3380,3051,2924,1723,1666,1608,1537,1498,1437,1320,1265,1238,1187,1157,1119,1009,900,850,751,687.1HNMR(500MHz,DMSO-d6) δ 10.40 (s, 1H, CO-NH), 9.13 (s, 1H, C=CH), 8.47～8.46 (d, 1H, Ar-H), 8.11～8.09 (dd, 1H, Ar-H), 8.05～8.03 (dd, 1H, Ar-H), 7.98～7.97 (d, 1H, Ar-H), 7.82～7.80 (d, 1H, Ar-H), 7.78～7.76 (m, 2H, Ar-H), 7.53～7.52 (d, 1H, Ar-H), 7.49～7.48 (m, 1H, Ar-H), 7.40～7.37 (t, 2H, Ar-H), 7.15～7.13 (d, 1H, Ar-H)；HR-ESI/MS(m/z)calcdforC23H15N2O4[M+H]+=383.1026, found383.1019.
Compound 1b:IR (KBr, υ/cm-1):3218,3048,2921,2851,1751,1635,1605,1524,1452,1390,1310,1255,1195,1119,968,921,753,685.1HNMR(500MHz,CDCl3) δ 8.85 (s, 1H, C=CH), 8.36 (s, 1H, CO-NH), 8.08～8.03 (m, 2H, Ar-H), 7.78～7.70 (m, 4H, Ar-H), 7.47～7.41 (m, 2H, Ar-H), 7.32～7.30 (d, 1H, Ar-H), 7.28～7.26 (d, 1H, Ar-H), 7.17～7.14 (m, 1H, Ar-H), 2.39 (s, 3H, CH3)；HR-ESI/MS(m/z)calcdforC24H17N2O4[M+H]+=397.1183, found397.1187.
Compound 1c:IR (KBr, υ/cm-1):3274,3094,1742,1646,1611,1527,1440,1314,1250,1182,1066,1002,831,761,645.1HNMR(500MHz,DMSO-d6) δ 10.23 (s, 1H, CO-NH), 9.12 (s, 1H, C=CH), 8.48～8.47 (d, 1H, Ar-H), 8.13～8.12 (dd, 1H, Ar-H), 8.03～8.01 (dd, 1H, Ar-H), 7.98～7.96 (d, 1H, Ar-H), 7.79～7.76 (m, 1H, Ar-H), 7.65～7.64 (dd, 1H, Ar-H), 7.60～7.58 (dd, 1H, Ar-H), 7.52～7.50 (d, 1H, Ar-H), 7.48～7.41 (m, 2H, Ar-H), 7.35～7.32 (m, 1H, Ar-H)；HR-ESI/MS(m/z)calcdforC23H14ClN2O4[M+H]+=417.0637, found417.0651.
Compound 1d:IR (KBr, υ/cm-1):3365,3101,2924,2850,1742,1694,1610,1541,1508,1465,1342,1264,1185,1124,1094,1031,999,963,912,863,800,756,691.1HNMR(500MHz,CDCl3) δ 8.89 (s, 1H, CO-NH), 8.86 (s, 1H, C=CH), 8.80～8.78 (d, 1H, Ar-H), 8.41～8.40 (d, 1H, Ar-H), 8.12 ,～8.10 (dd, 1H, Ar-H), 8.03～8.01 (dd, 1H, Ar-H), 7.85～7.84 (d, 1H, Ar-H), 7.80～7.79 (d, 1H, Ar-H), 7.75,～7.71 (m, 1H, Ar-H), 7.49～7.42 (m, 2H, Ar-H), 4.11 (s, 3H, OCH3)；HR-ESI/MS(m/z)calcdforC24H15N3NaO7[M+Na]+=480.0802, found480.0793.
Compound 1e:IR (KBr, υ/cm-1):3355,3061,1745,1688,1614,1585,1517,1453,1383,1276,1221,1124,960,828,757.1HNMR(500MHz,CDCl3) δ 11.35 (s, 1H, CO-NH), 8.90 (s, 1H, C=CH), 8.89～8.88 (d, 1H, Ar-H), 8.52～8.51 (d, 1H, Ar-H), 8.13～8.11 (m, 2H, Ar-H), 7.81～7.79 (d, 1H, Ar-H), 7.75～7.70 (m, 2H, Ar-H), 7.58～7.56 (dd, 1H, Ar-H), 7.48～7.46 (d, 1H, Ar-H), 7.44～7.41 (d, 1H, Ar-H), 2.45 (s, 3H, CH3)；HR-ESI/MS(m/z)calcdforC24H16N3O6[M+H]+=442.1034, found442.1046.
Compound 1f:IR (KBr, υ/cm-1):3360,1758,1700,1608,1553,1501,1420,1337,1282,1170,1121,1090,960,831,764,735,664.1HNMR(500MHz,DMSO-d6) δ 10.90 (s, 1H, CO-NH), 9.16 (s, 1H, C=CH), 8.46～8.45 (d, 1H, Ar-H), 8.11～8.09 (dd, 1H, Ar-H), 8.07～8.02 (m, 3H, Ar-H), 7.84～7.78 (m, 3H, Ar-H), 7.54～7.53 (d, 1H, Ar-H), 7.50～7.45 (m, 2H, Ar-H)；HR-ESI/MS(m/z)calcdforC23H14N3O6[M+H]+=428.0877, found428.0866.
Compound 1g:IR (KBr, υ/cm-1):3375,3095,2924,2851,2754,1748,1688,1608,1566,1495,1433,1290,1244,1180,1155,1096,1042,991,960,881,829,756,689.1HNMR(500MHz,CDCl3) δ 10.25 (s, 1H, CO-NH), 8.88 (s, 1H, C=CH), 8.77～8.76 (d, 1H, Ar-H), 8.37～8.35 (dd, 1H, Ar-H), 8.00～7.98 (dd, 1H, Ar-H), 7.81～7.79 (d, 1H, Ar-H), 7.75～7.72 (t, 3H, Ar-H), 7.50～7.46 (m, 2H, Ar-H), 7.43～7.39 (m, 2H, Ar-H)；HR-ESI/MS(m/z)calcdforC22H14N3O4[M+H]+=384.0979, found384.0972.
Compound 1h:IR (KBr, υ/cm-1):3384,3062,2930,2835,1728,1667,1609,1539,1483,1448,1269,1218,1152,1121,1049,1006,962,926,880,844,755,687,640.1HNMR(500MHz,CDCl3) δ 8.85 (s, 1H, C=CH), 8.34 (s, 1H, CO-NH), 8.02～8.00 (d, 1H, Ar-H), 7.91 (s, 1H, Ar-H), 7.76～7.70 (m, 3H, Ar-H), 7.47～7.41 (m, 3H, Ar-H), 7.32～7.30 (d, 1H, Ar-H), 7.15～7.13 (d, 1H, Ar-H), 6.76～6.74 (d, 1H, Ar-H), 3.87 (s, 3H, OCH3)；HR-ESI/MS(m/z)calcdforC24H17N2O5[M+H]+=413.1132, found413.1118.
1.4 target compounds spectrum property in dichloromethane
(concentration of 1a, 1c, 1d, 1e is 1 × 10 as shown in Fig. 1 and table 2 to test 8 compounds uv-visible absorption spectra in dichloromethane solution and fluorescence spectrum, its maximum absorption wavelength (λ max) and maximum emission wavelength (λ em)-5Mol/L, 1b, 1g, 1h concentration be 2 × 10-5The concentration of mol/L, 1f is 2.2 × 10-5mol/L)。
The table 2 spectroscopic data in dichloromethane
From Fig. 1 and Biao 2 it can be seen that the ultraviolet spectra of target compound all presents two obvious maximum absorption bands, that occur in 250nm place is π → π*The absworption peak that electron transition produces；The absworption peak occurring in about 350nm then comes from Intramolecular electron transfer (ICT) absorption.Excitation wavelength is 350nm, and maximum emission wavelength λ em is about 90nm in about 440nm, Stokes displacement；Stokes displacement with the Coumarins fluorescent material reported is close, it depends primarily on N-phenyl-2-(2-carbonyl-2H-1-.alpha.-5:6-benzopyran-3-base) this parent framework of benzothiazole-5-Methanamide, when the ortho position of substituted aromatic amines amino is with strong electron-withdrawing group group (1e, time 1f), maximum absorption wavelength and the emission maximum of corresponding compound have a little red shift and have bigger molar absorption coefficient, because the strong electron-withdrawing group group of end is conducive to the Intramolecular electron transfer of compound.The molar absorption coefficient of the coumarin kind compound being abutment with thiophene in prior art is 4.5 × 104M-1·cm-1；The target compound molar absorption coefficient at maximum absorption wavelength λ max place has reached 105M-1·cm-1The order of magnitude, it was shown that light is had good absorbability by it at maximum absorption wavelength λ max place, it is possible to become optical material.
Test compound 1a uv-visible absorption spectra in different solvents and fluorescence spectrum, its maximum absorption wavelength (λ max) and maximum emission wavelength (λ em) are as shown in Fig. 2 and table 3, and its fluorescence photo in different solvents is as shown in Figure 3.
Table 3 compound 1a spectroscopic data in opposed polarity solvent
As can be known from Fig. 2, the ultra-violet absorption spectrum of compound 1a and fluorescence emission spectrum change not quite in different solvents, and increasing with solvent polarity has a little red shift.Being likely due under ground state, in compound molecule, electric charge transfer is more weak, and its ultra-violet absorption spectrum is the not significant change with solvent polarity change just.
As can be seen from Figure 3, compound 1a fluorescence in middle low polar solvent (toluene, dichloromethane) is more apparent, and after solvent polarity increases, fluorescence substantially disappears.Being probably in DMF and methanol, the hydrogen bond action of solvent and compound can affect stablizing of ground state and excited state, causes that fluorescence disappears.
In sum, 8 new Diarbarone compounds of present invention synthesis, yield 41%～65%, its structure warp1HNMR, MS and IR characterize confirmation, determine uv-visible absorption spectra and the fluorescence spectrum of target compound, it has been found that its π-π * transition characteristics peak is between 250nm～255nm；Its maximum absorption wavelength is between 345nm～360nm；Maximum emission wavelength λ em is about 90nm in about 440nm, Stokes displacement；Its molar absorption coefficient has reached 105M-1·cm-1The order of magnitude, when there is electron withdraw group at the ortho position of substituted aromatic amines amino, the maximum absorption wavelength of compound and emission maximum have a little red shift and have bigger molar absorption coefficient.Its ultra-violet absorption spectrum and fluorescence emission spectrum change not quite in different solvents.
1.5 target compounds are as fluorescent pigment application in coating
Respectively potassium dihydrogen phosphate, dipotassium hydrogen phosphate, dodecylbenzene sodium sulfonate, fatty alcohol-polyoxyethylene ether and Ammonium persulfate. are configured to 10% aqueous solution standby；
Pre-emulsification tank adds 60g dodecylbenzene sodium sulfonate solution, 60g fatty alcohol-polyoxyethylene ether solution, 20g potassium dihydrogen phosphate, 20g dipotassium hydrogen phosphate solution and 200g deionized water, make pre-emulsification tank constant temperature 10 DEG C, add the vinylidene chloride 300g of cold preservation, butyl acrylate 50g, 2-Propenoic acid, 2-methyl-, isooctyl ester 60g, butyl methacrylate 40g and azo-bis-iso-dimethyl 3g while stirring, stirring 30min, adds 15g ammonium persulfate solution and prepares pre-emulsion；
Add 40g dodecylbenzene sodium sulfonate solution, 40g fatty alcohol-polyoxyethylene ether solution, 15g ammonium persulfate solution, 12g potassium dihydrogen phosphate, 12g dipotassium hydrogen phosphate solution and 300g deionized water and stirring in a kettle. uniform；The logical nitrogen deoxygenation of reactor to control pressure be 0.4MPa, mixing speed is 30～90r/min, the pre-emulsion of 10% in reactor is once added when reaction temperature is 60 DEG C, remaining pre-emulsion at the uniform velocity adds reactor in 4h, by reactor release after insulation 1h, it is warmed up to 70 DEG C～90 DEG C insulation 60min, obtains latex；
By sodium tripolyphosphate 6g, ammonium polyacrylate 2g, defoamer 2g, nano zine oxide 80g, the coating fluorescent pigment 220g of embodiment 1 preparation, zinc phosphate 100g, after adipyl trap 50g, thickening agent 5g, levelling agent 8g and deionized water 500g mixing, sand milling is to fineness less than 40 microns, slurry good for sand milling and latex are pressed the mass mixing of 1:1, stirs and obtain fluorescent paint.
Owing to the Hydrogen Energy on the amide groups in the compounds of this invention can form intermolecular hydrogen bond with the ketonic oxygen on coumarin ring, form structure stable as follows:
Meanwhile, the hydrogen on intramolecule, amide groups also can form hydrogen bond with benzothiazole ring nitrogen in molecule, forms structure stable as follows:
Therefore, after this compound is applied to fluorescent paint, the fluorescence of coating has excellent weather resistance.Because general fluorescent paint is at the sunlight of nature, especially the ultraviolet light in sunlight, can cause the structural deterioration of fluorescent chemicals in fluorescent paint, and the compound of the present invention is because stable circulus can be formed in intermolecular or molecule, is therefore not readily susceptible to the destruction of ultraviolet light.
Embodiment 2
A kind of synthetic method of Diarbarone compounds:
Basic step is with embodiment 1, and difference is in step (2), and chloride reagent adopts thionyl chloride, and solvent is toluene, and reaction temperature is 120 DEG C, and the response time is 12h, and yield is 85.6%；
In step (3), amino-compound is aniline, after reacting 10h, reacts 20h under room temperature at-5 DEG C, and yield is 61.7%.
Embodiment 3
A kind of synthetic method of Diarbarone compounds:
Basic step is with embodiment 1, and difference is in step (2), and chloride reagent adopts triphosgene, and solvent is toluene, and reaction temperature is 80 DEG C, and the response time is 7h, and yield is 81.3%；
In step (3), amino-compound is aniline, after reacting 5h, reacts 10h under room temperature at 10 DEG C, and yield is 48.9%.
Embodiment described above is the one preferably scheme of the present invention, not the present invention is done any pro forma restriction, also has other variant and remodeling under the premise without departing from the technical scheme described in claim.
Claims (7)
1. a Diarbarone compounds, it is characterised in that: its structural formula is as follows:
Described R group is phenyl, substituted-phenyl or pyridine radicals.
2. Diarbarone compounds according to claim 1, it is characterised in that described substituent group is selected from any one in substituents:
3. the preparation method of the Diarbarone compounds described in a claim 1, it is characterised in that: described preparation method carries out as follows:
(1) with salicylide, cyan-acetic ester, 3,4-AHBA for raw material, one pot process 2-(2-carbonyl-2H-1-.alpha.-5:6-benzopyran-3-base) benzothiazole-5-carboxylic acid；
(2) 2-(2-carbonyl-2H-1-.alpha.-5:6-benzopyran-3-base) benzothiazole-5-carboxylic acid that above-mentioned steps is synthetically derived and chloride reagent carry out acyl chloride reaction and are synthetically derived 2-(2-carbonyl-2H-1-.alpha.-5:6-benzopyran-3-base) benzothiazole-5-formyl chloride；
(3) 2-(2-carbonyl-2H-1-.alpha.-5:6-benzopyran-3-base) benzothiazole-5-formyl chloride that above-mentioned steps obtains reacts with amino-compound and carries out acylation reaction, is synthetically derived Diarbarone compounds.
4. the preparation method of Diarbarone compounds according to claim 3, it is characterised in that: described chloride reagent is oxalyl chloride, thionyl chloride or triphosgene, and described amino-compound is aniline, replacement, aniline or aminopyridine.
5. the preparation method of Diarbarone compounds according to claim 4, it is characterised in that: described amino-compound is any one in following amino-compound:
6. the preparation method of Diarbarone compounds according to claim 3, it is characterised in that: described preparation method is specific as follows:
(1) in 100mL there-necked flask, salicylide 17mmol, cyan-acetic ester 17mmol, 3,4-AHBA 17mmol, benzoic acid 5.8mmol and n-amyl alcohol 50mL it are sequentially added into, it is heated to reflux 5-12h, it is cooled to room temperature, reactant liquor is poured in 100mL water, precipitate out a large amount of precipitation, sucking filtration, washes with water dried, obtains orange solids 2-(2-carbonyl-2H-1-.alpha.-5:6-benzopyran-3-base) benzothiazole-5-carboxylic acid；
(2) in 50mL there-necked flask, 2-(2-carbonyl-2H-1-.alpha.-5:6-benzopyran-3-base) benzothiazole-5-carboxylic acid 1mmol and solvent 30mL is added, chloride reagent 1.2mmol is dripped under room temperature, add DMF1 and drip as catalyst, solvent and residue chloride reagent are evaporated off after reacting 2-10h at 20-120 DEG C, obtaining khaki solid 2-(2-carbonyl-2H-1-.alpha.-5:6-benzopyran-3-base) benzothiazole-5-formyl chloride, described solvent is dichloromethane or toluene；
(3) in 100mL there-necked flask, it is sequentially added into amino-compound 1mmol, Na2CO31.1mmol and anhydrous CH2Cl220mL, is cooled to 0～5 DEG C, drips 2-(2-carbonyl-2H-1-.alpha.-5:6-benzopyran-3-base) benzothiazole-5-formyl chloride 1mmol and anhydrous CH2Cl2The mixed liquor of 30mL, after reacting 3-106h in-5～10 DEG C, reacts 5-20h, filters under room temperature, filtrate adds saturated NaHCO3Solution 25mL, stratification, the anhydrous CH of water layer2Cl2Extracting, merge organic facies, solvent is evaporated off, column chromatography purifies, and the volume ratio=4:1 of developing solvent petroleum ether and ethyl acetate obtains Diarbarone compounds.
7. the application of the Diarbarone compounds described in a claim 1-6 any one, it is characterised in that: as fluorescent pigment application in coating.
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