CN100546979C - A kind of 4-[4-(diethyl amido) phenyl] methene-5-oxyethyl group-2, the preparation method of 4-dihydro-2-phenyl-3H-pyrazoles-3-ketone - Google Patents
A kind of 4-[4-(diethyl amido) phenyl] methene-5-oxyethyl group-2, the preparation method of 4-dihydro-2-phenyl-3H-pyrazoles-3-ketone Download PDFInfo
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- CN100546979C CN100546979C CNB200610012859XA CN200610012859A CN100546979C CN 100546979 C CN100546979 C CN 100546979C CN B200610012859X A CNB200610012859X A CN B200610012859XA CN 200610012859 A CN200610012859 A CN 200610012859A CN 100546979 C CN100546979 C CN 100546979C
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Abstract
A kind of 4-[4-(diethyl amido) phenyl] methene-5-oxyethyl group-2, the preparation method of 4-dihydro-2-phenyl-3H-pyrazoles-3-ketone, this method comprise the steps: that (1) adds phenylhydrazine, 3 in reaction vessel, the 3-diethoxy ethyl acrylate, alcohol, back flow reaction 1～2 hour; (2) add pure sodium solution, back flow reaction 1～2 hour; (3) with diluted acid pH=4～5 that neutralize, obtain intermediate A; (4) intermediate A and 4-N, N-diethyl amino benzaldehyde reacted in organic solvent 2～5 hours, temperature of reaction is 50～90 ℃, obtains 4-[4-(diethyl amido) phenyl] and methene-5-oxyethyl group-2,4-dihydro-2-phenyl-3H-pyrazoles-3-ketone compound.Synthesis technique advanced person of the present invention, aftertreatment is simple, the product purity height that obtains.
Description
Technical field
The present invention relates to a kind of preparation method of pyrazolone compound, particularly a kind ofly be used for 4-[4-(diethyl amido) phenyl that the heat sublimation printing consumables is used] methene-5-oxyethyl group-2, the preparation method of 4-dihydro-2-phenyl-3H-pyrazoles-3-ketone.
Background technology
As everyone knows, in various types of heat sublimation dyestuffs, a kind of pyrazolone derivative is arranged, its structural formula is as follows:
On the Japanese Patent that this compound appears at 2004 the earliest, its patent No. is JP2004230878, this patent is one piece and uses patent, disclose this compound and be used for the heat sublimation printing consumables as a kind of heat sublimation dyestuff, it does not disclose the synthetic of this compound, and relevant synthetic method is not seen any disclosed document and patent.
Summary of the invention
The purpose of this invention is to provide a kind of 4-[4-(diethyl amido) phenyl] methene-5-oxyethyl group-2, the preparation method of 4-dihydro-2-phenyl-3H-pyrazoles-3-ketone compound.
Technical scheme of the present invention is:
A kind of 4-[4-(diethyl amido) phenyl] methene-5-oxyethyl group-2, the preparation method of 4-dihydro-2-phenyl-3H-pyrazoles-3-ketone, it may further comprise the steps:
(1) in reaction vessel, adds phenylhydrazine, 3,3-diethoxy ethyl acrylate and alcohol, back flow reaction 1～2 hour;
(2) add pure sodium solution, back flow reaction 1～2 hour;
(3) with acid pH=4～5 that neutralize, obtain intermediate A;
(4) intermediate A and 4-N, N-diethyl amino benzaldehyde reacted in organic solvent 2～5 hours, and temperature of reaction is 50～90 ℃, obtained 4-[4-(diethyl amido) phenyl] methene-5-oxyethyl group-2,4-dihydro-2-phenyl-3H-pyrazoles-3-ketone compound, its reaction formula is:
Described alcohol is methyl alcohol or ethanol, and pure sodium solution is the alcoholic solution of sodium methylate or the alcoholic solution of sodium ethylate.
Above-mentioned 4-[4-(diethyl amido) phenyl] methene-5-oxyethyl group-2, the preparation method of 4-dihydro-2-phenyl-3H-pyrazoles-3-ketone, described organic solvent is methyl alcohol, ethanol or N, dinethylformamide.
Above-mentioned 4-[4-(diethyl amido) phenyl] methene-5-oxyethyl group-2, the preparation method of 4-dihydro-2-phenyl-3H-pyrazoles-3-ketone, described acid is dilute hydrochloric acid, dilute sulphuric acid or glacial acetic acid.
Above-mentioned 4-[4-(diethyl amido) phenyl] methene-5-oxyethyl group-2, the preparation method of 4-dihydro-2-phenyl-3H-pyrazoles-3-ketone, it carries out as follows:
A. in reaction vessel, add phenylhydrazine, 3,3-diethoxy ethyl acrylate and dehydrated alcohol, back flow reaction 1～2 hour;
B. the ethanolic soln that adds sodium ethylate, back flow reaction 1～2 hour;
C. with glacial acetic acid pH=4～5 that neutralize, obtain intermediate A;
D. intermediate A and 4-N, N-diethyl amino benzaldehyde back flow reaction 2～5 hours in dehydrated alcohol, temperature of reaction is 50～90 ℃, obtains 4-[4-(diethyl amido) phenyl] methene-5-oxyethyl group-2,4-dihydro-2-phenyl-3H-pyrazoles-3-ketone compound.
The invention has the beneficial effects as follows, the synthesis technique advanced person of this method, aftertreatment is simple, the product purity height that obtains.
Embodiment
The invention will be further described below in conjunction with specific examples.
Embodiment 1
In the 500mL there-necked flask, add phenylhydrazine 23.2 grams, 38 grams 3, the 3-diethoxy ethyl acrylate, dehydrated alcohol 80mL, back flow reaction 1 hour, add the 100mL ethanolic soln that contains 17 gram sodium ethylates, continued back flow reaction 2 hours, add the dilution of 70mL water, reaction solution is poured in the 1000mL beaker, add 270mL water dilution again, with the glacial acetic acid pH=4 that neutralizes, 28 gram intermediate A are separated out in cooling, yield 70%, fusing point: 113-115 ℃.12.9 gram intermediate A and 12.9 gram 4-N, N-diethyl amino benzaldehyde back flow reaction 2 hours in the 130mL dehydrated alcohol, red crystallization is separated out in cooling, filters, and obtains 19.5 and restrains Y-D1.Yield 85%.
Ultimate analysis:
Theoretical value: C%:72.73, H%:6.89, N%:11.57;
Measured value: C%:72.93, H%:6.92, N%:11.48.
1H-NMR: δ, 1.27 (6H, CH on the ethyl
3, t), 1.59 (3H, the CH on the oxyethyl group
3, t), 3.49 (4H, the CH on the ethyl
2, m), 4.53 (2H, the CH on the oxyethyl group
2, m), 6.17 (2H, single-substituted ring hydrogen, d), 7.12 (1H, single-substituted ring hydrogen, t), 7.41 (2H, single-substituted ring hydrogen, t), 7.71 (1H ,-CH, t), 8.04-8.10 (4H, disubstituted benzene ring hydrogen, d).
Embodiment 2
In the 250mL there-necked flask, add phenylhydrazine 12 grams, 19 grams 3,-diethoxy ethyl acrylate, 60mL methyl alcohol, back flow reaction 1 hour, add the 50mL methanol solution of 5.8 gram sodium methylates, continued back flow reaction 2 hours, add the dilution of 50mL water, reaction solution is poured in the 500mL beaker, add 120mL water dilution again, with the dilute hydrochloric acid pH=5 that neutralizes, 12.9 gram intermediate A are separated out in cooling, yield: 63%, fusing point: 113-115 ℃.5.3 gram intermediate A and 5.1 gram 4-N, N-diethyl amino benzaldehyde back flow reaction 2 hours in methyl alcohol, red crystallization is separated out in cooling, filters, and obtains 7.6 and restrains Y-D1.Yield 80%.
Ultimate analysis:
Theoretical value: C%:72.73, H%:6.89, N%:11.57;
Measured value: C%:72.83, H%:6.95, N%:11.43.
1H-NMR: δ, 1.27 (6H, CH on the ethyl
3, t), 1.59 (3H, the CH on the oxyethyl group
3, t), 3.49 (4H, the CH on the ethyl
2, m), 4.53 (2H, the CH on the oxyethyl group
2, m), 6.17 (2H, single-substituted ring hydrogen, d), 7.12 (1H, single-substituted ring hydrogen, t), 7.41 (2H, single-substituted ring hydrogen, t), 7.71 (1H ,-CH, t), 8.04-8.10 (4H, disubstituted benzene ring hydrogen, d).
Embodiment 3
In the 250mL there-necked flask, add phenylhydrazine 12 grams, 19 grams 3, the 3-diethoxy ethyl acrylate, 65mL dehydrated alcohol, back flow reaction 1 hour, add the 70mL ethanolic soln of 8.6 gram sodium ethylates, continued back flow reaction 1.5 hours, add the dilution of 50mL water, reaction solution is poured in the 500mL beaker, add 120mL water dilution again, with the glacial acetic acid pH=4 that neutralizes, 13.3 gram intermediate A are separated out in cooling, yield: 63%, fusing point: 113-115 ℃.12.9 gram intermediate A and 12.9 gram 4-N, N-diethyl amino benzaldehyde is at 50mLN, and reaction is 5 hours in the dinethylformamide, and temperature of reaction is 50 ℃, and cooling adds 95% ethanol 100mL, separates out red crystallization, filters, and obtains 17.6 gram Y-D1.Yield 77%.
Ultimate analysis:
Theoretical value: C%:72.73, H%:6.89, N%:11.57;
Measured value: C%:72.63, H%:6.72, N%:11.38.
1H-NMR: δ, 1.27 (6H, CH on the ethyl
3, t), 1.59 (3H, the CH on the oxyethyl group
3, t), 3.49 (4H, the CH on the ethyl
2, m), 4.53 (2H, the CH on the oxyethyl group
2, m), 6.17 (2H, single-substituted ring hydrogen, d), 7.12 (1H, single-substituted ring hydrogen, t), 7.41 (2H, single-substituted ring hydrogen, t), 7.71 (1H ,-CH, t), 8.04-8.10 (4H, disubstituted benzene ring hydrogen, d).
Embodiment 4
In the 250mL there-necked flask, add phenylhydrazine 12 grams, 19 grams 3, the 3-diethoxy ethyl acrylate, 65mL dehydrated alcohol, back flow reaction 2 hours, add the 70mL ethanolic soln of 8.6 gram sodium ethylates, continued back flow reaction 2 hours, add the dilution of 50mL water, reaction solution is poured in the 500mL beaker, add 120mL water dilution again, with the glacial acetic acid pH=5 that neutralizes, 13.8 gram intermediate A are separated out in cooling, yield: 69%, fusing point: 113-115 ℃.12.9 gram intermediate A and 12.9 gram 4-N, N-diethyl amino benzaldehyde is at 70mLN, and reaction is 2 hours in the dinethylformamide, and temperature of reaction is 90 ℃, and cooling adds 95% ethanol 120mL, separates out red crystallization, filters, and obtains 18.5 gram Y-D1.Yield 81%.
Ultimate analysis:
Theoretical value: C%:72.73, H%:6.89, N%:11.57;
Measured value: C%:72.93, H%:6.82, N%:11.52.
1H-NMR: δ, 1.27 (6H, CH on the ethyl
3, t), 1.59 (3H, the CH on the oxyethyl group
3, t), 3.49 (4H, the CH on the ethyl
2, m), 4.53 (2H, the CH on the oxyethyl group
2, m), 6.17 (2H, single-substituted ring hydrogen, d), 7.12 (1H, single-substituted ring hydrogen, t), 7.41 (2H, single-substituted ring hydrogen, t), 7.71 (1H ,-CH, t), 8.04-8.10 (4H, disubstituted benzene ring hydrogen, d).
Claims (4)
1, a kind of 4-[4-(diethyl amido) phenyl] methene-5-oxyethyl group-2, the preparation method of 4-dihydro-2-phenyl-3H-pyrazoles-3-ketone is characterized in that it carries out according to the following steps:
(1) in reaction vessel, adds phenylhydrazine, 3,3-diethoxy ethyl acrylate and alcohol, back flow reaction 1～2 hour;
(2) add pure sodium solution, back flow reaction 1～2 hour;
(3) with acid pH=4～5 that neutralize, obtain intermediate A;
(4) intermediate A and 4-N, N-diethyl amino benzaldehyde reacted in organic solvent 2～5 hours, temperature of reaction is 50～90 ℃, obtains 4-[4-(diethyl amido) phenyl] and methene-5-oxyethyl group-2,4-dihydro-2-phenyl-3H-pyrazoles-3-ketone compound;
Described alcohol is methyl alcohol or ethanol, and pure sodium solution is the alcoholic solution of sodium methylate or the alcoholic solution of sodium ethylate.
2, according to the described 4-[4-of claim 1 (diethyl amido) phenyl methene]-5-oxyethyl group-2, the preparation method of 4-dihydro-2-phenyl-3H-pyrazoles-3-ketone is characterized in that described organic solvent is methyl alcohol, ethanol or N, dinethylformamide.
3, according to the described 4-[4-of claim 2 (diethyl amido) phenyl] methene-5-oxyethyl group-2, the preparation method of 4-dihydro-2-phenyl-3H-pyrazoles-3-ketone is characterized in that described acid is dilute hydrochloric acid, dilute sulphuric acid or glacial acetic acid.
4, according to claim 1,2 or 3 described 4-[4-(diethyl amido) phenyl] methene-5-oxyethyl group-2, the preparation method of 4-dihydro-2-phenyl-3H-pyrazoles-3-ketone is characterized in that it carries out as follows:
(1) in reaction vessel, adds phenylhydrazine, 3,3-diethoxy ethyl acrylate and dehydrated alcohol, back flow reaction 1 hour;
(2) ethanolic soln of adding sodium ethylate, back flow reaction 2 hours;
(3) with glacial acetic acid pH=4～5 that neutralize, obtain intermediate A;
(4) intermediate A and 4-N, N-diethyl amino benzaldehyde back flow reaction 2 hours in dehydrated alcohol obtains 4-[4-(diethyl amido) phenyl] methene-5-oxyethyl group-2,4-dihydro-2-phenyl-3H-pyrazoles-3-ketone compound.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4866029A (en) * | 1988-03-16 | 1989-09-12 | Eastman Kodak Company | Arylidene pyrazolone dye-donor element for thermal dye transfer |
| US5081101A (en) | 1990-10-31 | 1992-01-14 | Eastman Kodak Company | Yellow dye mixture for thermal color proofing |
-
2006
- 2006-06-23 CN CNB200610012859XA patent/CN100546979C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4866029A (en) * | 1988-03-16 | 1989-09-12 | Eastman Kodak Company | Arylidene pyrazolone dye-donor element for thermal dye transfer |
| US5081101A (en) | 1990-10-31 | 1992-01-14 | Eastman Kodak Company | Yellow dye mixture for thermal color proofing |
Non-Patent Citations (3)
| Title |
|---|
| 昭61-268760A 1986.11.28 |
| 特开JP2004-230878A 2004.08.19 |
| 特开昭JP49-114420A 1974.10.31 |
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Application publication date: 20061122 Assignee: SHENZHEN RESEARCH INSTITUTE OF THE PHOTOGRAPHIC MATERIALS & CHEMICAL INDUSTRY Assignor: China Lucky Group Corporation Contract record no.: 2013130000027 Denomination of invention: 4-[4-(diethylaminoethyl )phenyl]methylene-5-ethoxy-2,4-dihydro-2-phenyl-3H-pyrazolyl -3-one preparation method Granted publication date: 20091007 License type: Exclusive License Record date: 20130424 |
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