CN1760194A - Method for synthesizing 3-(5'-substitution-2-benzoxazole group)-7-diethyl amino group H-1-benzopyrans-2-ketone - Google Patents
Method for synthesizing 3-(5'-substitution-2-benzoxazole group)-7-diethyl amino group H-1-benzopyrans-2-ketone Download PDFInfo
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- CN1760194A CN1760194A CN 200510060415 CN200510060415A CN1760194A CN 1760194 A CN1760194 A CN 1760194A CN 200510060415 CN200510060415 CN 200510060415 CN 200510060415 A CN200510060415 A CN 200510060415A CN 1760194 A CN1760194 A CN 1760194A
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- ethyl cyanoacetate
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Abstract
A process for synthesizing 3-(5'-substituent-2-benzoxazolyl)-7-diethylamino-2H- 1-benzopyran-2-one includes such steps as the reflux reaction between ethyl cyanoacetate, 4-N,N-diethylamino salicylaldehyde and 0-aminophenol derivative in non-protonic polar solvent for 10-24 hr under the action of catalyst, and post-treating.
Description
(1) technical field
The present invention relates to a kind of synthetic method that replaces benzopyrone.
(2) background technology
The research of electroluminescent organic material and device is the key of plane technique of display research.The coumarin series derivative is a kind of organic color material that can send intense fluorescence.3-(5 '-substituting group-2-benzoxazolyl)-7-diethylamino-2H-1-chromen-2-one is a coumarin derivatives, be the good fluorescence chromonic materials of a class, laser dyes and organic non linear optical material, aspect molecular device, have the high and application performances such as coloured light and gorgeous degree uniqueness of fluorescence efficiency.The coumarin series compounds that can adopt high fluorescence efficiency in novel suspension system electroluminescent organic material host and guest luminous body structure is that host emitter is the precursor structure of luminescent material; The hole transport unit carbazole that has the electric transmission Dan Yuan oxadiazole, thiadiazoles etc. of high electron affinity and have a high ionization gesture is a guest emitter.The new organic fluorescent pigment that host emitter and guest emitter binding become to have the suspension system constitutional features.
As the intermediate of typical organic third order non-linear optical material, coumarin derivatives has typical big pi-conjugated structure and stronger photoelectricity coupling feature.Exist very closely between its electronic structure and geometric configuration and get in touch, the instantaneous variation that the geometry relaxation of the molecule that is caused by optical excitation originates from excited state π electric density is the bigger correction of wave function and make whole πDian Zi skeleton have stronger third-order nonlinear optical hyperpolarizability.Might have stronger third-order nonlinear optical polarizability by the organic third order non-linear optical material of coumarin derivatives synthetic.
The general structure of coumarin derivatives is:
In its general structure: substituent X can be hydrogen, C
1～C
4Alkyl, C
1～C
4Alkoxyl group, halogen, nitro, sulfoamido etc.
This material also can be used as the yellow solvent dye of the band green fluorescence of trevira except that such use, performances such as wet preferably fastness, sublimation fastness, washable fastness, light fastness and rapid dyeing are arranged.Except that can be used for coloring plastic, also can be used for the color fluorescence resin of color fluorescence coating, solar collector, sensitization, photochromics, high-technology fields such as video disc recording material are a kind of fluorochrome materials that very big application prospect is arranged.
At present, the chemical synthesis process of 3-(5 '-substituting group-2-benzoxazolyl)-7-diethylamino-2-H-1-chromen-2-one mainly contains:
1, diethyl malonate route:
This route is at first by 4-N, N-diethylamino salicylic aldehyde and diethyl malonate condensation are closed ring and are produced the tonka bean camphor carboxylicesters, then the tonka bean camphor carboxyester hydrolysis generates the tonka bean camphor carboxylic acid, is closed with 4-substituting group-2-amino-phenol condensation by the tonka bean camphor carboxylic acid at last and encircles, Xing Cheng oxazole ring and obtain product.This route closes the ring three-step reaction through condensation, hydrolysis, condensation, and total recovery is about 55%.
2, ethoxy methylene diethyl malonate route
This route is by a 3-N, and N-diethylamino phenol and ethoxy methylene diethyl malonate are at catalyzer TiCl
4ShiShimonoseki ring of existing generate the tonka bean camphor carboxylic acid, close with 4-substituting group-2-amino-phenol condensation by the tonka bean camphor carboxylic acid again and encircle, Xing Cheng oxazole ring and obtain product.Ethoxy methylene diethyl malonate and catalyzer TiCl in this operational path
4Cost an arm and a leg, and TiCl
4The industrialization aftertreatment is difficult, does not generally adopt this technology.
3, ethyl cyanacetate route
This route at first becomes the oxazole ring with 4-chloro-2-amino-phenol shape by ethyl cyanacetate in the presence of 3 methoxypropyl amine, again with 4-N, coumarin ring obtains product thereby N-diethylamino salicylic aldehyde closes ring formation.This route is through four-step reaction, and total recovery is about 60%.
Generally, more than several routes exist all that step is more relatively, complicated operation, characteristics that yield is not high.
(3) summary of the invention
The object of the invention is to provide the method for the synthetic 3-that a kind of technology is simple, yield is high (5 '-replacement-2-benzoxazolyl)-7-diethylamino-2H-1-chromen-2-one.
Described synthetic method comprises the steps: ethyl cyanoacetate, 4-N, N-diethylamino salicylic aldehyde and suc as formula the O-aminophenol derivatives of (II) under catalyst action in aprotic polar solvent back flow reaction 10～24 hours, aftertreatment gets product; Described catalyzer is organic acid or organic bases;
Its Chinese style (I) and (II) in X be hydrogen, C
1～C
4Alkyl, C
1～C
4Alkoxyl group, halogen, nitro or sulfoamido, be preferably one of following: hydrogen, chlorine, methyl, nitro, sulfoamido.
Described catalyzer can be an acid catalyst, comprises organic aliphatic acid, organic aromatic acid, organic sulfonic acid, as acetate, propionic acid, butyric acid, phenylformic acid, toluylic acid, phenylpropionic acid, Phenylsulfonic acid, tosic acid etc.; Can be organic alkali catalyst also, comprise aliphatic amide, arylamine, substituted aromatic amines, as n-Butyl Amine 99, sec-butylamine, aniline, 3-anisidine etc., wherein preferred catalyzer be an acid catalyst, and most preferred catalyzer is a tosic acid.
The solvent that the present invention adopts is an aprotic polar solvent, can be alcohols, ketone and DMSO etc., as ethanol, n-propyl alcohol, Virahol, sec-butyl alcohol, Pentyl alcohol, primary isoamyl alcohol, hexalin, n-Octanol, acetone, butanone, 2 pentanone, propione, DMSO, preferred solvent is Pentyl alcohol, primary isoamyl alcohol, hexalin, butanone, 2 pentanone, and most preferred solvent is a primary isoamyl alcohol.
Described ethyl cyanoacetate, 4-N, the molar ratio of N-diethylamino salicylic aldehyde, O-aminophenol derivatives be preferably 1: 1～and 2: 1～2, be preferably 1: 1～1.2: 1～1.2 again, most preferably be 1: 1: 1; The mol ratio of catalyzer and ethyl cyanoacetate is preferably 0.2～0.5: 1, be preferably 0.3～0.4: 1 again, and most preferably be 0.35: 1; With the 1mol ethyl cyanoacetate is benchmark, aprotic polar solvent consumption be preferably 1000～5000mL, be preferably 2000～4000mL again, most preferably be 3000mL.
Adopt synthetic method of the present invention reaction to finish, general only need of aftertreatment filtered, drying get final product product.Also can after reaction finishes, reaction solution be steamed most of solvent, be cooled to room temperature, add an amount of strong alkali aqueous solution again and remove impurity in the reactant, carry out filtration drying again and obtain product.Concrete and right, reaction solution can be steamed 3/4ths solvents, be cooled to room temperature, add for an amount of 2% NaOH aqueous solution stirring half an hour, filtering drying promptly gets product.According to synthetic method of the present invention, the yield of general product can reach 70～80%.
The present invention has compared with prior art reduced reactions steps, and its synthesis technique is simple, reaction conditions is gentle, yield is high, cost is low, has big implementary value and economic results in society.
(4) description of drawings
Fig. 1 is the IR spectrogram of the 3-that makes of embodiment 1 (5 '-chloro-2-benzoxazolyl)-7-diethylamino-2H-1-chromen-2-one.
Fig. 2 is the 3-that makes of embodiment 1 (5 '-chloro-2-benzoxazolyl)-7-diethylamino-2H-1-chromen-2-one
1The H-NMR spectrum
Fig. 3 is the IR spectrogram of the 3-that makes of embodiment 2 (5 '-methyl-2-benzoxazolyl)-7-diethylamino-2H-1-chromen-2-one.
Fig. 4 is the 3-that makes of embodiment 2 (5 '-methyl-2-benzoxazolyl)-7-diethylamino-2H-1-chromen-2-one
1The H-NMR spectrum.
Fig. 5 is the IR spectrogram of 3-2-benzoxazolyl-7-diethylamino-2H-1-chromen-2-one of making of embodiment 3.
Fig. 6 is 3-2-benzoxazolyl-7-diethylamino-2H-1-chromen-2-one that embodiment 3 makes
1The H-NMR spectrum
Fig. 7 is the IR spectrogram of the 3-that makes of embodiment 4 (5 '-nitro-2-benzoxazolyl)-7-diethylamino-2H-1-chromen-2-one.
Fig. 8 is the 3-that makes of embodiment 4 (5 '-nitro-2-benzoxazolyl)-7-diethylamino-2H-1-chromen-2-one
1The H-NMR spectrum.
Fig. 9 is the IR spectrogram of the 3-that makes of embodiment 5 (5 '-sulfonamido-2-benzoxazolyl)-7-diethylamino-2H-1-chromen-2-one.
(5) embodiment
The invention will be further described below in conjunction with embodiment, but protection scope of the present invention is not limited to this.
In being housed, the 100mL four-hole boiling flask of reflux adds 2g (0.017mol) ethyl cyanoacetate, 3.4g (0.017mol) 4-N, N-diethylamino salicylic aldehyde, 2.5g (0.017mol) 4-chlorine Ortho-Aminophenol, 0.8g (0.0058mol) toluylic acid, 50mL Pentyl alcohol, be heated to backflow, reacted 10 hours, steam about 3/4 solvent, be cooled to room temperature, the NaOH aqueous solution of adding 2% stirs half an hour, and filtering drying gets yellow powder 5.0g, yield: 77.4%, fusing point is 195～196 ℃.
Embodiment 2 3-(5 '-methyl-2-benzoxazolyl)-7-diethylamino-2H-1-chromen-2-one synthetic
In being housed, the 100mL four-hole boiling flask of reflux adds 2g (0.017mol) ethyl cyanoacetate, 3.4g (0.017mol) 4-N, N-diethylamino salicylic aldehyde, 2.2g (0.017mol) 4-methyl Ortho-Aminophenol, 1.0g (0.0058mol) tosic acid, 50mL n-Octanol, be heated to backflow, reacted 15 hours, steam about 3/4 solvent, be cooled to room temperature, the NaOH aqueous solution of adding 2% stirs half an hour, and filtering drying gets yellow powder 4.8g, yield: 78%, fusing point is 209～210 ℃.
Synthesizing of embodiment 3 3-2-benzoxazolyl-7-diethylamino-2H-1-chromen-2-one
In being housed, the 100mL four-hole boiling flask of reflux adds 2g (0.017mol) ethyl cyanoacetate, 3.4g (0.017mol) 4-N, N-diethylamino salicylic aldehyde, 1.9g (0.017mol) Ortho-Aminophenol, 0.9g (0.0058mol) phenylpropionic acid, 50mL butanone, be heated to backflow, reacted 15 hours, steam about 3/4 solvent, be cooled to room temperature, the NaOH aqueous solution of adding 2% stirs half an hour, and filtering drying gets yellow powder 4.5g, yield: 74.8%, fusing point is 185～186 ℃.
Embodiment 4 3-(5 '-nitro-2-benzoxazolyl)-7-diethylamino-2H-1-chromen-2-one synthetic
In being housed, the 100mL four-hole boiling flask of reflux adds 2g (0.017mol) ethyl cyanoacetate, 4.1g (0.020mol) 4-N, N-diethylamino salicylic aldehyde, 2.9g (0.020mol) 4-nitro Ortho-Aminophenol, 0.35g (0.0058mol) acetate, 50mL 2 pentanone, be heated to backflow, reacted 15 hours, steam about 3/4 solvent, be cooled to room temperature, the NaOH aqueous solution of adding 2% stirs half an hour, and filtering drying gets yellow powder 4.7g, yield: 70.4%, fusing point is 264～265 ℃.
Embodiment 5 3-(5 '-sulfonamido-2-benzoxazolyl)-7-diethylamino-2H-1-chromen-2-one synthetic
In being housed, the 100mL four-hole boiling flask of reflux adds 2g (0.017mol) ethyl cyanoacetate, 4.1g (0.020mol) 4-N, N-diethylamino salicylic aldehyde, 3.9g (0.020mol) 4-sulfonamido Ortho-Aminophenol, 0.8g (0.0058mol) toluylic acid, 50mL Virahol, be heated to backflow, reacted 18 hours, steam about 3/4 solvent, be cooled to room temperature, the NaOH aqueous solution of adding 2% stirs half an hour, and filtering drying gets yellow powder 5.3g, yield: 72.6%, fusing point is 298～299 ℃.
Embodiment 6 3-(5 '-methyl-2-benzoxazolyl)-7-diethylamino-2H-1-chromen-2-one synthetic
In being housed, the 100mL four-hole boiling flask of reflux adds 2g (0.017mol) ethyl cyanoacetate, 4.1g (0.020mol) 4-N, N-diethylamino salicylic aldehyde, 2.6g (0.020mol) 4-methyl Ortho-Aminophenol, 0.7g (0.0058mol) 3-anisidine, 50mL DMSO, be heated to backflow, reacted 18 hours, steam about 3/4 solvent, be cooled to room temperature, the NaOH aqueous solution of adding 2% stirs half an hour, and filtering drying gets yellow powder 4.6g, yield: 74.8%, fusing point is 209～210 ℃.
Embodiment 7 3-(5 '-chloro-2-benzoxazolyl)-7-diethylamino-2H-1-chromen-2-one synthetic
In being housed, the 100mL four-hole boiling flask of reflux adds 2g (0.017mol) ethyl cyanoacetate, 4.1g (0.020mol) 4-N, N-diethylamino salicylic aldehyde, 2.9g (0.020mol) 4-chlorine Ortho-Aminophenol, 0.8g (0.0058mol) toluylic acid, 70mL DMSO, be heated to backflow, reacted 18 hours, steam about 3/4 solvent, be cooled to room temperature, the NaOH aqueous solution of adding 2% stirs half an hour, and filtering drying gets yellow powder 5.0g, yield: 77.4%, fusing point is 195～196 ℃.
Embodiment 8 3-(5 '-methyl-2-benzoxazolyl)-7-diethylamino-2H-1-chromen-2-one synthetic
In being housed, the 100mL four-hole boiling flask of reflux adds 2g (0.017mol) ethyl cyanoacetate, 5.1g (0.026mol) 4-N, N-diethylamino salicylic aldehyde, 3.3g (0.026mol) 4-methyl Ortho-Aminophenol, 1.0g (0.0058mol) tosic acid, 100mL n-Octanol, be heated to backflow, reacted 20 hours, steam about 3/4 solvent, be cooled to room temperature, the NaOH aqueous solution of adding 2% stirs half an hour, and filtering drying gets yellow powder 4.8g, yield: 78%, fusing point is 209～210 ℃.
Embodiment 9 3-(5 '-chloro-2-benzoxazolyl)-7-diethylamino-2H-1-chromen-2-one synthetic
In being housed, the 100mL four-hole boiling flask of reflux adds 2g (0.017mol) ethyl cyanoacetate, 5.1g (0.026mol) 4-N, N-diethylamino salicylic aldehyde, 3.8g (0.017mol) 4-chlorine Ortho-Aminophenol, 1.0g (0.0058mol) tosic acid, 50mL primary isoamyl alcohol, be heated to backflow, reacted 10 hours, steam about 3/4 solvent, be cooled to room temperature, the NaOH aqueous solution of adding 2% stirs half an hour, and filtering drying gets yellow powder 5.2g, yield: 80.0%, fusing point is 195～196 ℃.
Claims (10)
1, the synthetic method of a kind of 3-(5 '-replacement-2-benzoxazolyl)-7-diethylamino-2H-1-chromen-2-one suc as formula (I), comprise the steps: ethyl cyanoacetate, 4-N, N-diethylamino salicylic aldehyde and suc as formula the O-aminophenol derivatives of (II) under catalyst action in aprotic polar solvent back flow reaction 10～24 hours, aftertreatment gets product; Described catalyzer is organic acid or organic bases;
Its Chinese style (I) and (II) in X be hydrogen, C
1～C
4Alkyl, C
1～C
4Alkoxyl group, halogen, nitro or sulfoamido.
2, synthetic method as claimed in claim 1 is characterized in that described X is one of following: hydrogen, chlorine, methyl, nitro, sulfoamido.
3, synthetic method as claimed in claim 1 is characterized in that described catalyzer is one of following: acetate, propionic acid, butyric acid, phenylformic acid, toluylic acid, phenylpropionic acid, Phenylsulfonic acid, tosic acid, n-Butyl Amine 99, sec-butylamine, aniline, 3-anisidine.
4, synthetic method as claimed in claim 3 is characterized in that described catalyzer is one of following: toluylic acid, tosic acid, phenylpropionic acid, acetate, 3-anisidine.
5, synthetic method as claimed in claim 1 is characterized in that described aprotic polar solvent is one of following: ethanol, n-propyl alcohol, Virahol, sec-butyl alcohol, Pentyl alcohol, primary isoamyl alcohol, hexalin, n-Octanol, acetone, butanone, 2 pentanone, propione, DMSO.
6, synthetic method as claimed in claim 5 is characterized in that described aprotic polar solvent is one of following: Pentyl alcohol, primary isoamyl alcohol, hexalin, butanone, 2 pentanone.
7, synthetic method as claimed in claim 6 is characterized in that described catalyzer is a tosic acid, and described aprotic polar solvent is a primary isoamyl alcohol.
8, as the described synthetic method of one of claim 1～7, it is characterized in that described ethyl cyanoacetate, 4-N, the molar ratio of N-diethylamino salicylic aldehyde, O-aminophenol derivatives is 1: 1～2: 1～2; The mol ratio of catalyzer and ethyl cyanoacetate is 0.2～0.5: 1; With the 1mol ethyl cyanoacetate is benchmark, and the consumption of aprotic polar solvent is 1000～5000mL.
9, synthetic method as claimed in claim 8 is characterized in that described ethyl cyanoacetate, 4-N, and the molar ratio of N-diethylamino salicylic aldehyde, O-aminophenol derivatives is 1: 1～1.2: 1～1.2; The mol ratio of catalyzer and ethyl cyanoacetate is 0.3～0.4: 1; With the 1mol ethyl cyanoacetate is benchmark, and the consumption of aprotic polar solvent is 2000～4000mL.
10, synthetic method as claimed in claim 9 is characterized in that described ethyl cyanoacetate, 4-N, and the molar ratio of N-diethylamino salicylic aldehyde, O-aminophenol derivatives is 1: 1: 1; The mol ratio of catalyzer and ethyl cyanoacetate is 0.35: 1; With the 1mol ethyl cyanoacetate is benchmark, and the consumption of aprotic polar solvent is 3000mL.
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| CN 200510060415 CN1304392C (en) | 2005-08-16 | 2005-08-16 | Method for synthesizing 3-(5'-substitution-2-benzoxazole group)-7-diethyl amino group H-1-benzopyrans-2-ketone |
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| CN 200510060415 CN1304392C (en) | 2005-08-16 | 2005-08-16 | Method for synthesizing 3-(5'-substitution-2-benzoxazole group)-7-diethyl amino group H-1-benzopyrans-2-ketone |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101368004B (en) * | 2008-09-25 | 2011-08-31 | 浙江工业大学 | Synthesis of coumarin fluorochromes |
| 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 |
| CN108752327A (en) * | 2018-04-17 | 2018-11-06 | 浙江工业大学 | 3- (2- benzoxazoles) Diarbarone compound and its preparation method and application |
| CN114806213A (en) * | 2022-05-23 | 2022-07-29 | 万隆化工有限公司 | A solvent yellow 160:1 green synthesis process |
-
2005
- 2005-08-16 CN CN 200510060415 patent/CN1304392C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101368004B (en) * | 2008-09-25 | 2011-08-31 | 浙江工业大学 | Synthesis of coumarin fluorochromes |
| 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 |
| CN108752327A (en) * | 2018-04-17 | 2018-11-06 | 浙江工业大学 | 3- (2- benzoxazoles) Diarbarone compound and its preparation method and application |
| CN108752327B (en) * | 2018-04-17 | 2020-11-13 | 浙江工业大学 | 3- (2-benzoxazole) coumarin amide compound and preparation method and application thereof |
| 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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