CN101368004A - Synthesis of coumarin fluorochromes - Google Patents
Synthesis of coumarin fluorochromes Download PDFInfo
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- CN101368004A CN101368004A CNA200810121332XA CN200810121332A CN101368004A CN 101368004 A CN101368004 A CN 101368004A CN A200810121332X A CNA200810121332X A CN A200810121332XA CN 200810121332 A CN200810121332 A CN 200810121332A CN 101368004 A CN101368004 A CN 101368004A
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Abstract
The invention provides a synthetic method of coumarin fluorescent dye with the structure as seen in formula I, which comprises the following steps: ethyl cyanoacetate, 4-N,N-diethyl amino salicylal and ortho-aminophenol derivative with the structure as seen in formula II have reflux reaction in proton polar solvent for 7h to 9h; after the reaction, the product is separated and purified to obtain the coumarin fluorescent dye; the method does not need to use any catalyst, can synthetize the dye in a boiler, which not only reduces reaction steps, but also has the advantages of simple synthetic process, mild reaction conditions, high yield, low cost, quite high implementation value, social and economic benefit.
Description
(1) technical field
The present invention relates to a kind of synthetic method of coumarins fluorescence dye.
(2) background technology
Coumarin kind compound is the big pi-conjugated structural compounds that contains intramolecular charge transport system of a quasi-representative, is to study a class the most widely in the present fluorescent material.The coumarins fluorochrome has intensive fluorescence, bright-coloured color and luster, excellent application performance energy, and dyestuffs industries developed countries such as Japan, Germany and Switzerland are all paid much attention to.Coumarin kind compound fluorescence quantum efficiency height, film forming properties are good, can be doped in the hole mobile material polyvinyl carbazole (PVK), as electroluminescent organic material.In addition, coumarin kind compound is owing to the blue-greenish colour tuning laser that can export wide region (420-570nm), thereby sudden emergence aspect laser dyes in recent years.Up to the present, in more than 30 kind of commercial grade laser dyes commonly used, existing nearly 20 kinds is coumarin kind compound.The coumarins fluorescence dye has performances such as wet preferably fastness, sublimation fastness, washable fastness, light fastness and rapid dyeing, the color fluorescence resin that can be used for coloring plastic, color fluorescence coating, solar collector, and high-technology field such as sensitive materials, photochromics, video disc recording material, be a kind of fluorochrome material with broad prospect of application.
The general structure of fluorescent coumarin dye is:
In its general structure: substituent X can be hydrogen, C
1～C
4Alkyl, C
1～C
4Alkoxyl group, halogen, nitro, sulfoamido etc.The synthetic method of this compounds can reduce two kinds: the one, make up coumarin ring earlier, as by 4-N, ring (referring to U.S. Pat 3933847) is closed in N-diethylin salicylic aldehyde and diethyl malonate condensation, or 3-N, N-diethylaminophenol and ethoxy methylene diethyl malonate are at catalyzer TiCl
4Have a ShiShimonoseki ring, prepare the tonka bean camphor carboxylicesters, obtain coumarine dye with the o-aminophenol condensation that replaces again; Another kind method is to make up benzoxazole ring earlier, again with 4-N, the symphysis of N-diethylin salicylidene becomes coumarine dye, promptly by ethyl cyanoacetate in the presence of 3 methoxypropyl amine at first with replace 2-amino-phenol Xing and Cheng the oxazole ring, with 4-N, N-diethylin salicylic aldehyde closes ring (referring to German Patent 1329043 and United States Patent (USP) 4146712) again.These methods all need polystep reaction, severe reaction conditions (needing strong acid catalyst), complicated operation, and yield is not high.Chinese patent CN1760194 proposes with ethyl cyanoacetate, 4-N, N-diethylin salicylic aldehyde and replacement Ortho-Aminophenol are raw material, and one kettle way synthesizing coumarin fluorescence dye has been simplified synthesis step greatly, it is catalyzer that novel method still needs with the phenylformic acid, and large usage quantity.
(3) summary of the invention
The object of the invention provides a kind of synthetic method that need not catalyst, technology is simple, yield is high coumarins fluorescence dye.
The technical solution used in the present invention is:
A kind of structure is suc as formula the synthetic method of the coumarins fluorescence dye shown in (I), described method comprises: with ethyl cyanoacetate, 4-N, N-diethylamino salicylic aldehyde and structure are suc as formula the back flow reaction 7～9 hours in proton polar solvent of the O-aminophenol derivatives shown in (II), and reaction finishes the back separation and purification and obtains described coumarins fluorescence dye;
In formula (I), the formula (II): X is hydrogen, C
1～C
4Alkyl, C
1～C
4Alkoxyl group, halogen, nitro or sulfonamido, be hydrogen, chlorine, methyl, nitro or sulfonamido;
Described proton polar solvent is one of following: the alcohol of C1～C8, the ketone of C1～C8 or dimethyl sulfoxide (DMSO).
Key of the present invention is directly to make ethyl cyanoacetate, 4-N under the condition without catalyzer, and N-diethylamino salicylic aldehyde, O-aminophenol derivatives carry out the one kettle way reaction, the synthetic coumarins fluorescence dye that obtains.Ethyl cyanoacetate, 4-N, N-diethylamino salicylic aldehyde, O-aminophenol derivatives consumption can use conventional amount used, described proton polar solvent is advisable with capacity, excessive also can, can't considerable influence be arranged to reacting itself.
Described ethyl cyanoacetate, 4-N, the ratio of the amount of substance of N-diethylamino salicylic aldehyde and O-aminophenol derivatives is 1:1～2:1～2, is preferably 1:1～1.2:1～1.2, more preferably 1:1:1.
Described proton polar solvent consumption is 1～10L/mol ethyl cyanoacetate, is preferably 5～7L/mol ethyl cyanoacetate, more preferably the 5L/mol ethyl cyanoacetate.
It is one of following that described proton polar solvent is preferably: propyl carbinol, Pentyl alcohol, primary isoamyl alcohol, hexalin, butanone, 2 pentanone.
Described separation and purification can be carried out according to a conventional method, and general only the need filtered, filtration cakes torrefaction get final product product; Also can be cooled to room temperature after reaction finishes, add an amount of strong alkali aqueous solution again and remove impurity in the reactant, filter, filtration cakes torrefaction obtains product.Among the present invention, described separation purification method is as follows: reaction is cooled to room temperature after finishing, and the adding volume is that 1～5%NaOH aqueous solution of 1～3 times of solvent volume stirred 0.5～2 hour, and filtration, filter cake oven dry obtain described coumarins fluorescence dye.
Preferably, described method is as follows: with the ratio of amount of substance is ethyl cyanoacetate, the 4-N of 1:1～1.2:1～1.2, N-diethylamino salicylic aldehyde and structure are suc as formula the back flow reaction 7～9 hours in proton polar solvent of the O-aminophenol derivatives shown in (II), after reaction finishes, be cooled to room temperature, the adding volume is that the 1%NaOH aqueous solution of 2 times of residual solvent volumes stirred 0.5 hour, filters, dries, and obtains described coumarins fluorescence dye; Described proton polar solvent is one of following: propyl carbinol, Pentyl alcohol, primary isoamyl alcohol, hexalin, butanone, 2 pentanone, and described proton polar solvent consumption is 5～7L/mol ethyl cyanoacetate; In formula (I), the formula (II), X is hydrogen, chlorine, methyl, nitro or sulfonamido.
According to synthetic method of the present invention, the yield of general product can reach 60～80%.
Beneficial effect of the present invention is mainly reflected in: need not to use any catalyzer, can carry out in one pot, not only reduced reactions steps, and synthesis technique is simple, reaction conditions is gentle, yield is high, cost is low, have big implementary value and economic results in society.
(4) embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
Embodiment 1:3-(5 '-chloro-2-benzoxazolyl)-7-diethylamino-2H-1-chromen-2-one synthetic
In being housed, the 50mL four-hole boiling flask of reflux adds 0.23g (2mmol) ethyl cyanoacetate, 0.40g (2mmol) 4-N, N-diethylamino salicylic aldehyde, 0.30g (2mmol) 4-chlorine Ortho-Aminophenol, the 10mL propyl carbinol, reflux was reacted 7 hours, be cooled to room temperature, the NaOH aqueous solution 20mL of adding 1% stirs half an hour, and filtration, filter cake oven dry get yellow powder 0.52g, yield 68%, fusing point are 205～207 ℃.
1H?NMR(CDCl
3，500MHz)δ：8.60(s，1H，4-H)，7.74(s，1H，4’-H)，7.50-7.48(d，1H，7’-H)，7.42-7.40(d，1H，6’-H)，7.29-7.27(m，1H，5-H)，6.65-6.63(d，1H，6-H)，6.52-6.51(d，1H，8-H)，3.48-3.44(q，4H，NC
H 2CH
3)，1.26-1.23(t，6H，NCH
2C
H 3)
Embodiment 2:3-(5 '-chloro-2-benzoxazolyl)-7-diethylamino-2H-1-chromen-2-one synthetic
In being housed, the 50mL four-hole boiling flask of reflux adds 0.23g (2mmol) ethyl cyanoacetate, 0.40g (2mmol) 4-N, N-diethylamino salicylic aldehyde, 0.30g (2mmol) 4-chlorine Ortho-Aminophenol, the 10mL Pentyl alcohol, reflux was reacted 7 hours, was cooled to room temperature, the NaOH aqueous solution 15mL of adding 2% stirs half an hour, filtration, filter cake oven dry get yellow powder, yield 54%.
Embodiment 3:3-(5 '-methyl-2-benzoxazolyl)-7-diethylamino-2H-1-chromen-2-one synthetic
In being housed, the 50mL four-hole boiling flask of reflux adds 0.23g (2mmol) ethyl cyanoacetate, 0.40g (2mmol) 4-N, N-diethylamino salicylic aldehyde, 0.25g (2mmol) 4-methyl Ortho-Aminophenol, the 10mL propyl carbinol, reflux was reacted 9 hours, be cooled to room temperature, the NaOH aqueous solution 20mL of adding 1% stirred 1 hour, and filtration, filter cake oven dry get yellow powder 0.44g, yield 61%, fusing point are 205～208 ℃.
1H?NMR(CDCl
3，500MHz)δ：8.61(s，1H，4-H)，7.58(s，1H，7’-H)，7.46-7.41(m，2H，5-H，6’-H)，7.15-7.13(d，1H，4’-H)，6.65-6.64(d，1H，6-H)，6.54(s，1H，8-H)，3.48-3.44(q，4H，NC
H 2CH
3)，2.48(s，3H，Ar-C
H 3)，1.26-1.23(t，6H，NCH
2C
H 3)
Embodiment 4:3-(5 '-methyl-2-benzoxazolyl)-7-diethylamino-2H-1-chromen-2-one synthetic
In being housed, the 50mL four-hole boiling flask of reflux adds 0.23g (2mmol) ethyl cyanoacetate, 0.40g (2mmol) 4-N, N-diethylamino salicylic aldehyde, 0.25g (2mmol) 4-methyl Ortho-Aminophenol, the 10mL hexalin, reflux was reacted 9 hours, was cooled to room temperature, the NaOH aqueous solution 30mL of adding 1% stirred 2 hours, filtration, filter cake oven dry get yellow powder, yield 46%.
Synthesizing of embodiment 5:3-2-benzoxazolyl-7-diethylamino-2H-1-chromen-2-one
In being housed, the 50mL four-hole boiling flask of reflux adds 0.23g (2mmol) ethyl cyanoacetate, 0.40g (2mmol) 4-N, N-diethylamino salicylic aldehyde, 0.23g (2mmol) Ortho-Aminophenol, the 10mL propyl carbinol, reflux was reacted 9 hours, be cooled to room temperature, the NaOH aqueous solution 10mL of adding 5% stirs half an hour, and filtration, filter cake oven dry get yellow powder 0.53g, yield 77%, fusing point are 185～187 ℃.
1H?NMR(CDCl
3，500MHz)δ：8.60(s，1H，4-H)，7.81-7.79(m，1H，4’-H)，7.59-7.57(m，1H，7’-H)，7.42-7.40(d，1H，5-H)，7.34-7.32(m，2H，5’-H，6’-H)，6.65-6.63(d，1H，6-H)，6.53-6.52(d，1H，8-H)，3.47-3.43(q，4H，NC
H 2CH
3)，1.25-1.23(t，6H，NC
H 2C
H 3)
Synthesizing of embodiment 6:3-2-benzoxazolyl-7-diethylamino-2H-1-chromen-2-one
In being housed, the 50mL four-hole boiling flask of reflux adds 0.23g (2mmol) ethyl cyanoacetate, 0.40g (2mmol) 4-N, N-diethylamino salicylic aldehyde, 0.23g (2mmol) Ortho-Aminophenol, the 10mL butanone, reflux was reacted 9 hours, was cooled to room temperature, the NaOH aqueous solution 20mL of adding 1% stirs half an hour, filtration, filter cake oven dry get yellow powder, yield 47%.
Synthesizing of embodiment 7:3-2-benzoxazolyl-7-diethylamino-2H-1-chromen-2-one
In being housed, the 50mL four-hole boiling flask of reflux adds 0.23g (2mmol) ethyl cyanoacetate, 0.40g (2mmol) 4-N, N-diethylamino salicylic aldehyde, 0.23g (2mmol) Ortho-Aminophenol, the 10mL n-Octanol, reflux was reacted 9 hours, was cooled to room temperature, the NaOH aqueous solution 20mL of adding 1% stirs half an hour, filtration, filter cake oven dry get yellow powder, yield 38%.
Synthesizing of embodiment 8:3-2-benzoxazolyl-7-diethylamino-2H-1-chromen-2-one
In being housed, the 50mL four-hole boiling flask of reflux adds 0.23g (2mmol) ethyl cyanoacetate, 0.40g (2mmol) 4-N, N-diethylamino salicylic aldehyde, 0.23g (2mmol) Ortho-Aminophenol, the 10mL Virahol, reflux was reacted 9 hours, was cooled to room temperature, the NaOH aqueous solution 20mL of adding 1% stirs half an hour, filtration, filter cake oven dry get yellow powder, yield 52%.
Embodiment 9:3-(5 '-nitro-2-benzoxazolyl)-7-diethylamino-2H-1-chromen-2-one synthetic
In being housed, the 50mL four-hole boiling flask of reflux adds 0.23g (2mmol) ethyl cyanoacetate, 0.40g (2mmol) 4-N, N-diethylamino salicylic aldehyde, 0.32g (2mmol) 4-nitro Ortho-Aminophenol, the 10mL propyl carbinol is heated to backflow, reacts 9 hours, be cooled to room temperature, the NaOH aqueous solution 20mL of adding 1% stirs half an hour, and filtration, filter cake oven dry get yellow powder 4.70g, yield 69%, fusing point are 263～265 ℃.
1H?NMR(CDCl
3，500MHz)δ：8.62-8.61(m，2H，4’-H，6’-H)，8.28-8.26(d，1H，4-H)，7.67-7.65(d，1H，5-H)，7.43-7.42(d，1H，7’-H)，6.67-6.65(d，1H，6-H)，6.51(s，1H，8-H)，3.50-3.46(q，4H，NC
H 2CH
3)，1.28-1.25(t，6H，NCH
2C
H 3)
Embodiment 10:3-(5 '-nitro-2-benzoxazolyl)-7-diethylamino-2H-1-chromen-2-one synthetic
In being housed, the 50mL four-hole boiling flask of reflux adds 0.23g (2mmol) ethyl cyanoacetate, 0.40g (2mmol) 4-N, N-diethylamino salicylic aldehyde, 0.32g (2mmol) 4-nitro Ortho-Aminophenol, the 10mL2-pentanone, be heated to backflow, reacted 9 hours, be cooled to room temperature, the NaOH aqueous solution 20mL of adding 1% stirs half an hour, filtration, filter cake oven dry get yellow powder, yield 39%.
Embodiment 11:3-(5 '-sulfonamido-2-benzoxazolyl)-7-diethylamino-2H-1-chromen-2-one synthetic
In being housed, the 50mL four-hole boiling flask of reflux adds 0.23g (2mmol) ethyl cyanoacetate, 0.40g (2mmol) 4-N, N-diethylamino salicylic aldehyde, 0.39g (2mmol) 4-sulfonamido Ortho-Aminophenol, the 10mL propyl carbinol, reflux was reacted 9 hours, be cooled to room temperature, the NaOH aqueous solution 20mL of adding 1% stirs half an hour, and filtration, filter cake oven dry get yellow powder 5.30g, yield 73%, fusing point is〉300 ℃.
1H?NMR(CDCl
3，500MHz)δ：8.83(s，1H，4-H)，8.15(s，1H，4’-H)，7.94-7.92(d，1H，6’-H)，7.89-7.87(d，1H，7’-H)，7.71-7.70(d，1H，5-H)，7.48(s，2H，SO
2N
H 2)，6.82-6.79(d，1H，6-H)，6.60(s，1H，8-H)，3.51-3.47(q，4H，NC
H 2CH
3)，1.17-1.14(t，6H，NCH
2C
H 3)
Embodiment 12:3-(5 '-sulfonamido-2-benzoxazolyl)-7-diethylamino-2H-1-chromen-2-one synthetic
In being housed, the 50mL four-hole boiling flask of reflux adds 0.23g (2mmol) ethyl cyanoacetate, 0.40g (2mmol) 4-N, N-diethylamino salicylic aldehyde, 0.39g (2mmol) 4-sulfonamido Ortho-Aminophenol, 10mL DMSO, reflux, reacted 9 hours, and be cooled to room temperature, add for 1% NaOH aqueous solution 20mL stirring half an hour, filtration, filter cake oven dry get yellow powder yield 53%.
Claims (9)
1. a structure is suc as formula the synthetic method of the coumarins fluorescence dye shown in (I), described method comprises: with ethyl cyanoacetate, 4-N, N-diethylamino salicylic aldehyde and structure are suc as formula the back flow reaction 7～9 hours in proton polar solvent of the O-aminophenol derivatives shown in (II), and reaction finishes the back separation and purification and obtains described coumarins fluorescence dye;
In formula (I), the formula (II): X is hydrogen, C
1～C
4Alkyl, C
1～C
4Alkoxyl group, halogen, nitro or sulfonamido;
Described proton polar solvent is one of following: the alcohol of C1～C8, the ketone of C1～C8 or dimethyl sulfoxide (DMSO).
2. the method for claim 1 is characterized in that described ethyl cyanoacetate, 4-N, and the ratio of the amount of substance of N-diethylamino salicylic aldehyde and O-aminophenol derivatives is 1:1～2:1～2.
3. method as claimed in claim 2 is characterized in that described ethyl cyanoacetate, 4-N, and the ratio of the amount of substance of N-diethylamino salicylic aldehyde and O-aminophenol derivatives is 1:1～1.2:1～1.2.
4. the method for claim 1 is characterized in that described proton polar solvent consumption is 1～10L/mol ethyl cyanoacetate.
5. method as claimed in claim 4 is characterized in that described proton polar solvent is one of following: propyl carbinol, Pentyl alcohol, primary isoamyl alcohol, hexalin, butanone, 2 pentanone.
6. method as claimed in claim 5 is characterized in that described proton polar solvent consumption is 5～7L/mol ethyl cyanoacetate.
7. the method for claim 1, it is characterized in that: in described formula (I), the formula (II), X is hydrogen, chlorine, methyl, nitro or sulfonamido.
8. the method for claim 1, it is characterized in that described separation purification method is as follows: reaction is cooled to room temperature after finishing, and the adding volume is that 1～5%NaOH aqueous solution of 1～3 times of solvent volume stirred 0.5～2 hour, filtration, filter cake oven dry obtain described coumarins fluorescence dye.
9. the method for claim 1, it is characterized in that described method is as follows: with the ratio of amount of substance is ethyl cyanoacetate, the 4-N of 1:1～1.2:1～1.2, N-diethylamino salicylic aldehyde and structure are suc as formula the back flow reaction 7～9 hours in proton polar solvent of the O-aminophenol derivatives shown in (II), after reaction finishes, be cooled to room temperature, the adding volume is that the 1%NaOH aqueous solution of 2 times of solvent volume stirred 0.5 hour, filtration, filter cake oven dry obtain structure suc as formula the coumarins fluorescence dye shown in (I); Described proton polar solvent is one of following: propyl carbinol, Pentyl alcohol, primary isoamyl alcohol, hexalin, butanone, 2 pentanone, and described proton polar solvent consumption is 5～7L/mol ethyl cyanoacetate; In formula (I), the formula (II), X is hydrogen, chlorine, methyl, nitro or sulfonamido.
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|---|---|---|---|
| CN200810121332XA CN101368004B (en) | 2008-09-25 | 2008-09-25 | Synthesis of coumarin fluorochromes |
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| CN101368004B CN101368004B (en) | 2011-08-31 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103194087A (en) * | 2013-03-29 | 2013-07-10 | 万隆化工有限公司 | Solvent-based yellow dye for environment-friendly fluorescent pigment |
| CN103365088A (en) * | 2012-04-04 | 2013-10-23 | 住友化学株式会社 | Colored curable resin composition |
| CN105777729A (en) * | 2016-05-31 | 2016-07-20 | 浙江工业大学 | Coumarin amides compound as well as preparation method and application of coumarin amides compound |
| CN114806213A (en) * | 2022-05-23 | 2022-07-29 | 万隆化工有限公司 | A solvent yellow 160:1 green synthesis process |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5529110B2 (en) * | 1972-12-25 | 1980-08-01 | ||
| US4146712A (en) * | 1976-03-11 | 1979-03-27 | Ciba-Geigy Corporation | Process for the manufacture of coumarin dyes |
| CN1279121C (en) * | 2004-06-17 | 2006-10-11 | 上海交通大学 | Fluorescent coumarin dye |
| CN1304392C (en) * | 2005-08-16 | 2007-03-14 | 浙江工业大学 | Method for synthesizing 3-(5'-substitution-2-benzoxazole group)-7-diethyl amino group H-1-benzopyrans-2-ketone |
-
2008
- 2008-09-25 CN CN200810121332XA patent/CN101368004B/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103365088A (en) * | 2012-04-04 | 2013-10-23 | 住友化学株式会社 | Colored curable resin composition |
| CN103365088B (en) * | 2012-04-04 | 2019-01-11 | 住友化学株式会社 | Colored curable resin composition |
| CN103194087A (en) * | 2013-03-29 | 2013-07-10 | 万隆化工有限公司 | Solvent-based yellow dye for environment-friendly fluorescent pigment |
| CN103194087B (en) * | 2013-03-29 | 2015-12-23 | 万隆化工有限公司 | Environmental protection high-visibility pigment solvent-borne type yellow dye |
| CN105777729A (en) * | 2016-05-31 | 2016-07-20 | 浙江工业大学 | Coumarin amides compound as well as preparation method and application of coumarin amides compound |
| CN114806213A (en) * | 2022-05-23 | 2022-07-29 | 万隆化工有限公司 | A solvent yellow 160:1 green synthesis process |
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Application publication date: 20090218 Assignee: WANLONG CHEMICAL Co.,Ltd. Assignor: Zhejiang University of Technology Contract record no.: 2012330000434 Denomination of invention: Synthesis of coumarin fluorochromes Granted publication date: 20110831 License type: Exclusive License Record date: 20120718 |
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