CN106928175B - A kind of fluorescent pigment and preparation method thereof - Google Patents
A kind of fluorescent pigment and preparation method thereof Download PDFInfo
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- CN106928175B CN106928175B CN201710198243.4A CN201710198243A CN106928175B CN 106928175 B CN106928175 B CN 106928175B CN 201710198243 A CN201710198243 A CN 201710198243A CN 106928175 B CN106928175 B CN 106928175B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
- C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
- C07D311/16—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 7
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/02—Coumarine dyes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
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- Engineering & Computer Science (AREA)
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Abstract
The present invention relates to a kind of fluorescent pigments.The fluorescent pigment is the benzamide butylcoumariii imine compound as shown in formula III:R is selected from methyl, trifluoromethyl, cyano, chloromethyl, bromomethyl or methoxyl methyl in formula III.Amidation process occurs for a kind of preparation method of fluorescent pigment, 4- substitution -7- aminocoumarin and isatoic anhydride, obtains intermediary 4- substitution -7- anthranilamide butylcoumariii；Imidization condensation reaction occurs with 5- bromosalicylaldehyde again, obtains product fluorescent red-orange pigment.Preparation method of the present invention is easy, reaction step is few, raw material is easy to get, it is at low cost, it is environmentally friendly, and space is adjusted with very big structure, synthesized new fluorescent pigment can be used for non-damaged data crack and loophole, for solar collector or as pigment with day-light fluorescence, generate good economic benefit and social benefit.
Description
Technical field
The present invention relates to a kind of fluorescent pigments, and the invention further relates to a kind of preparation methods of fluorescent pigment.
Background technique
The Main way of pigment industry development is the exploitation for strengthening new product and the innovation of manufacturing technology, fluorescent pigment conduct
One of principal item of high performance pigments is widely paid close attention to.Fluorescent pigment be possibly used for textile and plastic products
Color, fluorescent ink, the fluorescent tracing in national defense industry in terms of rocket, the flaw detection of warship and other equipments and biology and medicine.
The kind of fluorescent pigment is still very limited at present, and the exploitation of new fluorescent pigment is of great significance but reports few such as logical
It crosses the Fluorescent Brightening agents based on Coumarin X-10GFF that will be supported on attapulgite and silica gel inclusion prepares novel hybride fluorescent pigment
(Q.Wang,B.Mu,Y.Zhang,J.Zhang,A.Wang,Palygorskite-based hybrid fluorescent
pigment:preparation,spectroscopic characterization and environmental stabili
Ty.Micropor.Mesopor.Mater., 2016,224,107-115), the method be only suitable for by known fluorescent dye by with
The physical mixed of other materials prepares fluorescent pigment, and the tetraethoxysilane hydrolysis under acetic acid catalysis involved in preparation process.
And new structural fluorescent pigment is prepared for raw material using isatoic anhydride cheap and easy to get and waits to develop.Therefore, it is necessary to propose
Effective technical solution, solves the above problems.
Summary of the invention
The present invention in view of the above shortcomings of the prior art, provides a kind of fluorescent pigment and preparation method thereof.This method reaction
Simply, reaction step is few, and raw material is easy to get, at low cost, environmentally friendly.
The technical scheme to solve the above technical problems is that
A kind of fluorescent pigment, the fluorescent pigment are the benzamide butylcoumariii imine compound as shown in formula III:
R is selected from methyl, trifluoromethyl, cyano, chloromethyl, bromomethyl or methoxyl methyl in formula III.
The present invention also provides a kind of preparation methods of fluorescent pigment, include the following steps:
(1) replace -7- aminocoumarin to be dissolved in n,N-Dimethylformamide raw material 4- shown in formula I, then drip
Add isatoic anhydride, 1~4h is stirred at room temperature in reaction solution after titration, addition volume is 6~7 times of the reaction solution, temperature
Degree precipitates product for 40-60 DEG C of water, and solids is obtained after suction filtration；The solids is purified, obtains intermediary such as
4- substitution -7- anthranilamide butylcoumariii shown in Formula II；
(2) -7- anthranilamide butylcoumariii and p-methyl benzenesulfonic acid is replaced to dissolve the 4- that step (1) obtains
In ethanol, then 5- bromosalicylaldehyde is added dropwise, 80~90 DEG C of 5~8h of reaction is warming up to after being added dropwise, reaction mixture is cooling
To room temperature, filtering collects head product, obtains the benzamide butylcoumariii imines as shown in formula III after washed and dry
Class compound.
Preferably, the molar ratio of 4- substitution -7- aminocoumarin and the isatoic anhydride described in step (1) is 1:1.2
~1:1.8.
Preferably, the molar ratio of 4- substitution -7- aminocoumarin and the isatoic anhydride described in step (1) is 1:1.6.
Preferably, mole of 4- substitution -7- anthranilamide butylcoumariii and 5- bromosalicylaldehyde described in step (2)
Than for 1:1.
Preferably, the gross mass of 4- substitution -7- aminocoumarin and isatoic anhydride described in step (1) accounts for the N, N- bis-
The volume of methylformamide is 1g:6mL~1g:10mL.
Preferably, total matter of 4- substitution -7- anthranilamide butylcoumariii and 5- bromosalicylaldehyde described in step (2)
The quality that amount accounts for the p-methyl benzenesulfonic acid is 100:1~100:3.
Preferably, the condition that the solids is purified is silicagel column rapid column chromatography, eluant, eluent CH2Cl2。
Indicator and solar energy collecting of the fluorescent pigment of the present invention as non-damaged data crack and loophole
The application of device fluorescent pigment.
Application of the fluorescent pigment of the present invention as pigment with day-light fluorescence.
The utility model has the advantages that preparation method of the present invention is easy, reaction step is few, and raw material is easy to get, at low cost, environmentally friendly, and
And space is adjusted with very big structure, synthesized new fluorescent pigment can be used for the leak detection of non-destructive gap and solar energy is received
Storage or as pigment with day-light fluorescence, generates good economic benefit and social benefit.
Detailed description of the invention
Some specific embodiments of the present invention is described in detail by way of example and not limitation with reference to the accompanying drawings hereinafter.
Identical appended drawing reference denotes same or similar part or part in attached drawing.It should be appreciated by those skilled in the art that these
What attached drawing was not necessarily drawn to scale.In attached drawing:
Fig. 1 is the infrared spectrogram of fluorescent pigment of the present invention；
Fig. 2 is the carbon-13 nmr spectra figure of fluorescent pigment of the present invention.
Specific embodiment
The present invention provides a kind of preparation method of fluorescent pigment, and the present invention is (following from raw material 4- substitution -7- aminocoumarin
Abbreviation compound 1) it sets out, by the way that amidation process occurs with isatoic anhydride, obtain intermediary 4- substitution -7- anthraniloyl
Amido cumarin (hereinafter referred to as compound 2)；Imidization condensation reaction occurs with 5- bromosalicylaldehyde again, it is orange red glimmering to obtain product
Delustering pigment (hereinafter referred to as FP1).
The synthetic route of fluorescent pigment of the present invention is as follows:
The preparation method of fluorescent pigment of the present invention, specifically comprises the following steps:
(1) compound 1 is dissolved in n,N-Dimethylformamide (DMF), then isatoic anhydride is added dropwise, it will after titration
1~4h is stirred at room temperature in reaction solution, and addition volume is 6~7 times of the reaction solution, the water that temperature is 40-60 DEG C keeps product heavy
It forms sediment, obtains solids after suction filtration；The solids is purified, intermediate compound 2 is obtained；Wherein, reactant 1 and solvent
The ratio of n,N-Dimethylformamide is 1g:6mL~1g:10mL, preferably 1g:7mL, and the reactant 1 is compound 1 and indigo
The general name of red acid acid anhydride；
(2) in ethanol by intermediate compound 2 and p-methyl benzenesulfonic acid dissolution, then 5- bromosalicylaldehyde is added dropwise, is added dropwise
After be warming up to 80~90 DEG C of 5~8h of reaction, after reaction mixture is cooled to room temperature, filtering, collect head product, it is washed and dry
FP1 is obtained after dry；Wherein, the mass ratio between reactant 2 and catalyst p-methyl benzenesulfonic acid is 100:1~100:3, preferably
100:2, the reactant 2 are the general name of compound 2 and 5- bromosalicylaldehyde；The molar ratio of the compound 2 and 5- bromosalicylaldehyde
For 1:1.
Compound used therefor 1 of the present invention can be the various coumarin kind compounds containing amino-substituent, concretely 4-
Methyl -7- aminocoumarin, 4- trifluoromethyl -7- aminocoumarin, 4- cyano -7- aminocoumarin, 4- chloromethyl -7- amino
One of cumarin, 4- bromomethyl -7- aminocoumarin and 4- methoxyl methyl -7- aminocoumarin.
The compatibility of compound 1 and isatoic anhydride in the step (1), is important for purposes of the invention.On specifically,
Stating compound 1 and stating the molar ratio of isatoic anhydride is 1:1.2~1:1.8, preferably 1:1.6.When compound 1 and isatoic anhydride two
When person's molar ratio is 1:1.2, the yield of product Compound 2 is up to 90%；When both compound 1 and isatoic anhydride molar ratio are
When 1:1.5, the yield of product Compound 2 is up to 95%；When both compound 1 and isatoic anhydride molar ratio are 1:1.6, produce
The yield of compounds 2 reaches as high as 96%.
Being purified using rapid column chromatography (with CH in the step (1)2Cl2For eluant, eluent), recrystallization can also be used
Mode, but purification effect is bad, and product purity reduces.
Washing concrete technology in the step (2) is successively to use water and ethanol washing；Dry concrete technology is in vacuum
Dry 2h at 50 DEG C in drying box.
Ratio between reactant (4- substitution -7- aminocoumarin and isatoic anhydride) and etoh solvent be 1g:30mL~
1g:50mL.By the amount of reactant compared with solvent volume, it is determined that suitable quantity of solvent, preferably 1g:40mL.Quantity of solvent is few
It is difficult to ensure that reactant is completely dissolved, influences the progress of reaction；Quantity of solvent is excessive, causes waste and inconvenience.
Preparation method of the present invention is easy, and reaction step is few, and raw material is easy to get, at low cost, environmentally friendly, and has very big
Structure adjust space, synthesized new fluorescent pigment can be used for the leak detection of non-destructive gap and solar collector or conduct
Pigment with day-light fluorescence generates good economic benefit and social benefit.
Embodiment 1
(1) synthesis of compound 2: compound 1 (0.9g, 5mmol) is dissolved in 15mL solvent DMF, thereto slowly
It is added dropwise isatoic anhydride (1.3g, 8mmol), titration finishes in 0.5h.2h is stirred at room temperature in reaction solution, is then added thereto
100mL hot water (50 DEG C).Solid product is obtained after suction filtration, is purified using rapid column chromatography (with CH2Cl2For eluant, eluent), it obtains
To white solid powder 1.4g, yield 96%.
Mp:179-180℃。
IR (KBr) v=3438.51,3355.51,3245.48,3181.59,3113.09,2941.69,1767.7 7,
1694.24,1613.90,1013.40cm-1。
1H NMR(400MHz,DMSO-d6) δ=11.72 (s, 1H), 7.95-7.72 (m, 1H), 7.42-7.39 (m, 1H),
7.29-7.14 (m, 1H), 6.55-6.58 (m, 1H), 6.40 (d, 1H, J=2.4Hz), 6.10 (s, 2H), 5.90 (s, 1H),
2.30(s,3H)。
13C NMR(100MHz,DMSO-d6) δ=161.17 (C=O), 155.92 (C=O), 154.17 (Ph-C),
153.53 (Ph-C), 147.54 (Ph-C), 141.87 (Ph-C), 137.39 (=CH), 129.40 (Ph-C), 126.64 (Ph-
), C 123.98 (Ph-C), 115.80 (Ph-C), 111.64 (Ph-C), 110.72 (Ph-C), 109.33 (Ph-C), 107.95 (=
), CH 99.02 (=CH), 18.45 (CH3)。MS(EI):m/z 295(M++1)。
(2) synthesis of fluorescent pigment FP1: compound 2 (0.29g, 1mmol) is added in 100mL three-necked bottle and to toluene
Sulfonic acid (0.01g) is then added 20mL ethyl alcohol as solvent, is warming up to 60 DEG C of stirrings until solid is completely dissolved, into solution
5- bromosalicylaldehyde (0.20g, 1mmol) slowly is added dropwise, 85 DEG C are warming up to after being added dropwise, and the reaction was continued, and TCL tracking reaction is about
Terminate after 6h.There is orange red precipitation after reaction mixture is cooled to room temperature, solid is collected after filtering, is obtained after washed and dry
To fluorescent pigment FP1 Orange red solid 0.34g, yield 71%.
Mp:244℃。
IR (KBr) v=3449.82,3050.05,2917.14,1716.13,1606.00,1477.03,1068.5 8cm-1。
1H NMR(400MHz,DMSO-d6) δ=12.51 (s, 1H), 8.99 (s, 1H), 7.84-7.91 (m, 3H), 7.58-
7.68(m,2H),7.39-7.44(m,3H),6.97-7.00(m,2H),6.40(s,1H),2.51(s,3H)。
13C NMR(100MHz,DMSO-d6) δ=189.99 (C=N), 163.72 (C=O), 160.25 (C=O),
159.71 (Ph-C), 154.29 (Ph-C), 153.45 (=CH), 151.89 (Ph-C), 138.94 (Ph-C), 136.58 (Ph-
C),134.24(Ph-C),130.82(Ph-C),126.94(Ph-C),126.63(Ph-C),121.79(Ph-C),120.54
(Ph-C),119.65(Ph-C),118.77(Ph-C),114.25(Ph-C),111.62(Ph-C),110.62(Ph-C),
109.21 (Ph-C), 107.92 (Ph-C), 98.88 (=CH), 18.61 (CH3)。
4- methyl -7- aminocoumarin of the present invention can directly be bought, and can also refer to method (Zhou reported in the literature
J.,Fang J.,One-pot synthesis of quinazolinones via iridium-catalyzed hydrogen
Transfers, J.Org.Chem., 2011,76:7730-7736) synthesis 4- methyl -7- aminocoumarin, it is solid to obtain khaki
Body, yield 82%.
The present invention can be summarized with others without prejudice to the concrete form of spirit or essential characteristics of the invention.Therefore, nothing
By from the point of view of which point, the embodiment above of the invention can only all be considered the description of the invention and cannot limit this hair
Bright, claims indicate the scope of the present invention, and above-mentioned explanation does not point out the scope of the present invention, therefore, with this
Any change in the comparable meaning and scope of claims of invention is all considered as including in claim of the invention
In the range of book.
Claims (7)
1. a kind of preparation method of fluorescent pigment, which comprises the steps of:
(1) replace -7- aminocoumarin to be dissolved in n,N-Dimethylformamide raw material 4- shown in formula I, then indigo is added dropwise
After titration 1~4h is stirred at room temperature in reaction solution by red acid acid anhydride, and addition volume is 6~7 times of the reaction solution, temperature is
40-60 DEG C of water precipitates product, and solids is obtained after suction filtration；The solids is purified, intermediary such as Formula II is obtained
Shown in 4- substitution -7- anthranilamide butylcoumariii；
(2) -7- anthranilamide butylcoumariii and p-methyl benzenesulfonic acid is replaced to be dissolved in second the 4- that step (1) obtains
In alcohol, then 5- bromosalicylaldehyde is added dropwise, 80~90 DEG C of 5~8h of reaction are warming up to after being added dropwise, reaction mixture is cooled to room
Wen Hou, filtering collect head product, obtain the benzamide butylcoumariii imines as shown in formula III after washed and dry
Close object
R is selected from methyl, trifluoromethyl, cyano, chloromethyl, bromomethyl or methoxyl methyl in the formula III.
2. preparation method as described in claim 1, which is characterized in that 4- substitution -7- aminocoumarin described in step (1) and
The molar ratio of the isatoic anhydride is 1:1.2~1:1.8.
3. preparation method as claimed in claim 2, which is characterized in that 4- substitution -7- aminocoumarin described in step (1) and
The molar ratio of the isatoic anhydride is 1:1.6.
4. preparation method as claimed in claim 3, which is characterized in that 4- substitution -7- anthraniloyl described in step (2)
The molar ratio of amido cumarin and 5- bromosalicylaldehyde is 1:1.
5. preparation method as claimed in claim 4, which is characterized in that 4- substitution -7- aminocoumarin described in step (1) and
The volume that the gross mass of isatoic anhydride accounts for the N,N-dimethylformamide is 1g:6mL~1g:10mL.
6. preparation method as claimed in claim 5, which is characterized in that 4- substitution -7- anthraniloyl described in step (2)
The quality that the gross mass of amido cumarin and 5- bromosalicylaldehyde accounts for the p-methyl benzenesulfonic acid is 100:1~100:3.
7. preparation method as claimed in claim 6, which is characterized in that the condition that the solids is purified is that silicagel column is fast
Fast column chromatography, eluant, eluent CH2Cl2。
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105017195A (en) * | 2015-07-09 | 2015-11-04 | 中国药科大学 | 4-hydroxycoumarin-3-Schiff base derivate and use thereof for curing Alzheimer's disease |
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|---|---|---|---|---|
| CN105017195A (en) * | 2015-07-09 | 2015-11-04 | 中国药科大学 | 4-hydroxycoumarin-3-Schiff base derivate and use thereof for curing Alzheimer's disease |
Non-Patent Citations (3)
| Title |
|---|
| Coumarins and other fused bicyclic heterocycles with selective tumorassociated carbonic anhydrase isoforms inhibitory activity;Murat Bozdag et al.;《Bioorganic & Medicinal Chemistry》;20161129;第25卷;677-683 |
| Palygorskite-based hybrid fluorescent pigment: Preparation,spectroscopic characterization and environmental stability;Qin Wang et al.;《Microporous and Mesoporous Materials》;20151130;第224卷;107-115 |
| 含香豆素骨架水杨醛Schiff base荧光材料的制备及光谱性能研究;冯雷等;《化学试剂》;20121231;第34卷(第3期);257-260 |
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