CN102827096A - Synthesis of naphthoxazinone derivatives through functional ionic liquid solvent-free catalysis - Google Patents
Synthesis of naphthoxazinone derivatives through functional ionic liquid solvent-free catalysis Download PDFInfo
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- CN102827096A CN102827096A CN2012102726220A CN201210272622A CN102827096A CN 102827096 A CN102827096 A CN 102827096A CN 2012102726220 A CN2012102726220 A CN 2012102726220A CN 201210272622 A CN201210272622 A CN 201210272622A CN 102827096 A CN102827096 A CN 102827096A
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- nai
- oxazinone
- ionic liquid
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- 0 *CCCNC=CC=CC=* Chemical compound *CCCNC=CC=CC=* 0.000 description 1
- NUAMXCNOSNVFHG-UHFFFAOYSA-N O=C(NC1c2ccccc2)Oc2c1c1ccccc1cc2 Chemical compound O=C(NC1c2ccccc2)Oc2c1c1ccccc1cc2 NUAMXCNOSNVFHG-UHFFFAOYSA-N 0.000 description 1
- HUMNYLRZRPPJDN-UHFFFAOYSA-N O=Cc1ccccc1 Chemical compound O=Cc1ccccc1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a novel synthesis method for naphthoxazinone derivatives through functional ionic liquid solvent-free catalysis. According to the method, acid functionalized ionic liquid is used as a catalyst, beta-naphthol, aromatic aldehyde and urea are used as raw materials, and then the naphthoxazinone derivatives are synthesized by heating the catalyst and the raw materials under normal pressure. Compared with the prior art, the invention has the following advantages: (1) the functional ionic liquid with excellent thermal stability is employed, the raw materials are widely available and are convenient to prepare, the catalyst has high activity, is stable in water and will not be inactivated, and usage amount of the catalyst is small; (2) the ionic liquid catalyst is recoverable and recycled and is environment friendly; and (3) no organic solvent is used in the reaction, environmental and economic benefits are obtained, and the method is high-efficiency and environment-friendly synthesis method for the naphthoxazinone derivatives.
Description
One technical field
The present invention relates to the synthetic novel method of the solvent-free catalysis Nai of a kind of functional ionic liquids Bing oxazinone verivate, belong to the chemical material preparing technical field.Present method is applicable to that with β-Nai Fen, aromatic aldehyde, urea be raw material, the occasion of synthetic Nai Bing oxazinone verivate.
Two background technologies
Nai Bing oxazinone compounds (naphthoxazinone) is that the skeleton structure of one type of important pharmaceutical intermediate oxazinone (oxazinone) extensively is present in the natural compounds of many biologically actives; And various structure presents different performances, and different space structures manifests different biological activitys.Nai Bing oxazine also is the midbody of synthetic multiple medicine, has been found that it has antitumor, antiviral, antibiotic, anti-inflammatory and the anti-activity of implanting.Therefore, the research of this compounds becomes one of focus of scientific research personnel's research in recent years gradually.
Based on naphthalene and the unique physiologically active of oxazinone verivate, synthesizing of relevant this compounds causes people's attention gradually.The researchist has attempted a lot of methods and has designed various synthetic routes, and Szatmari has reported method (I.Szatmari, A.Hetenyi, L.Lazar, the F.Fulop that obtains naphthalene and oxazinone with cyclisation under the phosgene effect; J.Heterocyclic Chem., 2004,41,367.), Cimarelli etc. have reported with the synthetic Nai Bing oxazinone verivate (C.Cimarelli of two imidazolyl catalyzer; G.Palmieri, E.Volpini, Can.J.Chem., 2004,82; 1314.), Bazgir etc. have reported synthetic (M.Dabiri, A.S.Delbari, the A.Bazgir that uses microwave radiation to promote Nai Bing oxazinone verivate; Synlett., 2008,7,821.); Mahdavinia etc. are with synthetic (H.Abbastabar Ahangar, G.H.Mahdavinia, K.Marjani, the A.Hafezian of silica gel load perchloric acid catalysis Nai Bing oxazinone verivate; J.Iran.Chem.Soc., 2010,7,770.).There is following shortcoming more than 1 or 1 in these methods: use hypertoxic starting material such as phosgene etc.; The expensive preparation process of the cost of catalyzer is complicated; Can not recycling of catalyzer; Equipment corrosion is serious; Operating procedure is complicated; Can only be suitable for laboratory or small-scale operations, not possess heavy industrialization application etc.
Ionic liquid is meant in room temperature range, (to be generally under 100 ℃) and presents the liquid substance system that is made up of ion fully.Generally be made up of organic cation and inorganic anion, organic anion, its performance is mainly determined by positively charged ion of forming and negatively charged ion jointly, can adopt molecular designing, and it is adjusted.Ion liquid Lewis acid-basicity can be regulated with
acidity as required; Therefore, ionic liquid is also become " solvent that can design ".In recent years, the application of ionic liquid in organic synthesis is very active, but comes catalysis to use β-Nai Fen, aromatic aldehyde, urea not to appear in the newspapers as synthetic naphthalene of raw material and oxazinone verivate as catalyzer.
Three summary of the invention
The object of the present invention is to provide a kind of solvent-free reaction technology, catalyzer and product is easily separated, product purity is high, the method for the catalytic synthetic Nai Bing oxazinone verivate of functionalized ion liquid.
The technical solution that realizes the object of the invention is: the synthetic novel method of the solvent-free catalysis Nai of a kind of functional ionic liquids Bing oxazinone verivate; Be catalyzer promptly with
acid function property ionic liquid; β-Nai Fen, aromatic aldehyde, urea are raw material, and heating realizes the synthetic of Nai Bing oxazinone verivate under normal pressure.
Aromatic aldehyde has the structure suc as formula (II),
In the formula, R is H, 4-OH, 4-OCH
3, 3-OCH
3, 4-OH-3-OCH
3, 4-F, 4-Cl, 2-Cl, 3-NO
2Deng group.
The mol ratio of the used material of the present invention is a β-Nai Fen: aromatic aldehyde: urea=1: 1: 1～2, catalyst levels are 5～15% of aromatic aldehyde mole number, and described material, ionic liquid proportionally feed intake to mix and stir.
The temperature of the present invention's reaction is 150～160 ℃.
The time of the present invention's reaction is 0.5～2.5 hour.
The present invention's reaction finishes postcooling to 50-55 ℃, adds 95% ethanol that is equivalent to 1～2 times of material TV, continues to stir 5～10 minutes, and cold filtration, 95% washing with alcohol, drying obtain the solid pure product; Contain ionic-liquid catalyst in the filtrating, steam that to desolventize rear catalyst reusable, in β-Nai Fen: aromatic aldehyde: the ratio of urea=1: 1: 1～2 feeds intake and carries out the next batch building-up reactions.
The chemical principle of institute of the present invention foundation is shown in equation (I):
Wherein: the substituent R of aromatic aldehyde such as structural formula (II) definition.
The used catalyzer of the present invention also can be by the method preparation of document public reported from the commercial goods, and all the other starting material are all from the commercial goods.
According to synthesizing of the solvent-free catalysis Nai of functional ionic liquids provided by the invention Bing oxazinone verivate; Its key problem in technology is that employing
acid function property ionic liquid is a catalyzer; This ionic liquid has good thermostability, and fcc raw material β-Nai Fen, aromatic aldehyde, urea are that raw material reacts and obtains Nai Bing oxazinone compounds.The present invention compared with prior art; Its advantage is:
acid function property ionic liquid of good heat stability is adopted in (1); Raw material sources are extensive, and preparation is convenient; Catalyst activity is high, consumption is few,, non-inactivation stable to water; (2) ionic-liquid catalyst is recyclable and recycle environmental friendliness; (3) any organic solvent is not used in reaction, has environment, economical effects, is a kind of method of efficient, eco-friendly synthetic Nai Bing oxazinone verivate, helps large-scale industrial production.
Four embodiments
Below through embodiment the present invention is detailed, these embodiment are only for clear open the present invention, not as limitation of the present invention.
Embodiment 1
In the 25mL round-bottomed flask, add 10mmol (1.442g) β-Nai Fen, 10mmol (1.061g) phenyl aldehyde, 10mmol (0.601g) urea successively, the ionic liquid of 0.5mmol; Mix stirring 2.5 hours for following 160 ℃ in normal pressure, reaction finishes postcooling to 50-55 ℃, adds 95% ethanol that is equivalent to 1 times of material TV; Continue to stir 10 minutes; Cold filtration, 95% washing with alcohol, drying obtain 1,2-dihydro-1-phenyl naphtho-[1,2-e] [1; 3] oxazine-3-ketone pure products, productive rate is 85%.
Embodiment 2
In the 25mL round-bottomed flask, add 10mmol (1.442g) β-Nai Fen, 10mmol (1.061g) phenyl aldehyde, 20mmol (1.201g) urea successively, the ionic liquid of 1.5mmol; Mix stirring 0.5 hour for following 155 ℃ in normal pressure, reaction finishes postcooling to 50-55 ℃, adds 95% ethanol that is equivalent to 2 times of material TVs; Continue to stir 5 minutes, cold filtration, 95% washing with alcohol, drying obtain 1,2-dihydro-1-phenyl naphtho-[1; 2-e] [1,3] oxazine-3-ketone pure products, productive rate is 86%.
Embodiment 3
In the 25mL round-bottomed flask, add 10mmol (1.442g) β-Nai Fen, 10mmol (1.061g) phenyl aldehyde, 15mmol (0.901g) urea successively, the ionic liquid of 1.3mmol; Mix stirring 1.5 hours for following 150 ℃ in normal pressure, reaction finishes postcooling to 50-55 ℃, adds 95% ethanol that is equivalent to 1 times of material TV; Continue to stir 8 minutes, cold filtration, 95% washing with alcohol, drying obtain 1,2-dihydro-1-phenyl naphtho-[1; 2-e] [1,3] oxazine-3-ketone pure products, productive rate is 85%.
Embodiment 4
In the 25mL round-bottomed flask, add 10mmol (1.442g) β-Nai Fen, 10mmol (1.221g) 4-hydroxy benzaldehyde, 15mmol (0.901g) urea successively, the ionic liquid of 0.8mmol; Mix stirring 2.0 hours for following 155 ℃ in normal pressure, reaction finishes postcooling to 50-55 ℃, adds 95% ethanol that is equivalent to 1 times of material TV; Continue to stir 8 minutes; Cold filtration, 95% washing with alcohol, drying obtain 1,2-dihydro-1-(4-hydroxy phenyl) naphtho-[1,2-e] [1; 3] oxazine-3-ketone pure products, productive rate is 85%.
Embodiment 5
In the 25mL round-bottomed flask, add 10mmol (1.442g) β-Nai Fen, 10mmol (1.361g) 3-methoxybenzaldehyde, 12mmol (0.721g) urea successively, the ionic liquid of 1.0mmol; Mix stirring 1.2 hours for following 150 ℃ in normal pressure, reaction finishes postcooling to 50-55 ℃, adds 95% ethanol that is equivalent to 2 times of material TVs; Continue to stir 5 minutes; Cold filtration, 95% washing with alcohol, drying obtain 1,2-dihydro-1-(3-p-methoxy-phenyl) naphtho-[1,2-e] [1; 3] oxazine-3-ketone pure products, productive rate is 87%.
Embodiment 6
In the 25mL round-bottomed flask, add 10mmol (1.442g) β-Nai Fen, 10mmol (1.522g) 3-methoxyl group-4-hydroxy benzaldehyde, 13mmol (0.7807g) urea successively, the ionic liquid of 1.5mmol; Mix stirring 0.8 hour for following 150 ℃ in normal pressure, reaction finishes postcooling to 50-55 ℃, adds 95% ethanol that is equivalent to 2 times of material TVs; Continue to stir 5 minutes; Cold filtration, 95% washing with alcohol, drying obtain 1,2-dihydro-1-(3-methoxyl group-4-hydroxy phenyl) naphtho-[1,2-e] [1; 3] oxazine-3-ketone pure products, productive rate is 83%.
Embodiment 7
In the 25mL round-bottomed flask, add 10mmol (1.442g) β-Nai Fen, 10mmol (1.241g) 4-fluorobenzaldehyde, 14mmol (0.8407g) urea successively, the ionic liquid of 1.2mmol; Mix stirring 1.5 hours for following 150 ℃ in normal pressure, reaction finishes postcooling to 50-55 ℃, adds 95% ethanol that is equivalent to 2 times of material TVs; Continue to stir 5 minutes; Cold filtration, 95% washing with alcohol, drying obtain 1,2-dihydro-1-(4-fluorophenyl) naphtho-[1,2-e] [1; 3] oxazine-3-ketone pure products, productive rate is 82%.
Embodiment 8
In the 25mL round-bottomed flask, add 10mmol (1.442g) β-Nai Fen, 10mmol (1.40g) 2-chlorobenzaldehyde, 12mmol (0.721g) urea successively, the ionic liquid of 1.0mmol; Mix stirring 1.0 hours for following 150 ℃ in normal pressure, reaction finishes postcooling to 50-55 ℃, adds 95% ethanol that is equivalent to 2 times of material TVs; Continue to stir 5 minutes; Cold filtration, 95% washing with alcohol, drying obtain 1,2-dihydro-1-(2-chloro-phenyl-) naphtho-[1,2-e] [1; 3] oxazine-3-ketone pure products, productive rate is 86%.
Embodiment 9
In the 25mL round-bottomed flask, add 10mmol (1.442g) β-Nai Fen, 10mmol (1.511g) 3-nitrobenzaldehyde, 15mmol (0.901g) urea successively, the ionic liquid of 1.0mmol; Mix stirring 1.0 hours for following 150 ℃ in normal pressure, reaction finishes postcooling to 50-55 ℃, adds 95% ethanol that is equivalent to 2 times of material TVs; Continue to stir 5 minutes; Cold filtration, 95% washing with alcohol, drying obtain 1,2-dihydro-1-(3-nitrophenyl) naphtho-[1,2-e] [1; 3] oxazine-3-ketone pure products, productive rate is 87%.
Embodiment 10
After embodiment 1 reaction finishes, contain ionic-liquid catalyst in the filtrating, it is reusable that steaming desolventizes rear catalyst; Feed ratio and reaction conditions by embodiment 1 react, and obtain 1,2-dihydro-1-phenyl naphtho-[1; 2-e] [1,3] oxazine-3-ketone pure products, productive rate is 85%.
Claims (5)
1. the solvent-free catalysis Nai of functional ionic liquids Bing oxazinone verivate is synthetic; It is characterized in that: with
acid function property ionic liquid is catalyzer; β-Nai Fen, aromatic aldehyde, urea are raw material, and heating realizes the synthetic of Nai Bing oxazinone verivate under normal pressure; Functional ionic liquids as catalyzer has the structure suc as formula (I),
Aromatic aldehyde has the structure suc as formula (II),
In the formula, R is H, 4-OH, 4-OCH
3, 3-OCH
3, 4-OH-3-OCH
3, 4-F, 4-Cl, 2-Cl, 3-NO
2Deng group.
2. synthesizing of the solvent-free catalysis Nai of functional ionic liquids according to claim 1 Bing oxazinone verivate; It is characterized in that: the mol ratio of used material is a β-Nai Fen: aromatic aldehyde: urea=1: 1: 1～2; Catalyst levels is 5～15% of an aromatic aldehyde mole number, and described material, ionic liquid proportionally feed intake to mix and stir.
3. synthesizing of the solvent-free catalysis Nai of functional ionic liquids according to claim 1 Bing oxazinone verivate, it is characterized in that: the temperature of reaction is 150～160 ℃.
4. synthesizing of the solvent-free catalysis Nai of functional ionic liquids according to claim 1 Bing oxazinone verivate, it is characterized in that: the time of reaction is 0.5～2.5 hour.
5. synthesizing of the solvent-free catalysis Nai of functional ionic liquids according to claim 1 Bing oxazinone verivate; It is characterized in that: reaction finishes postcooling to 50-55 ℃; Add 95% ethanol that is equivalent to 1～2 times of material TV; Continue to stir 5～10 minutes, cold filtration, 95% washing with alcohol, drying obtain the solid pure product; Contain ionic-liquid catalyst in the filtrating, steam that to desolventize rear catalyst reusable, in β-Nai Fen: aromatic aldehyde: the ratio of urea=1: 1: 1～2 feeds intake and carries out the next batch building-up reactions.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104892540A (en) * | 2015-05-20 | 2015-09-09 | 安徽工业大学 | Simple preparation method of naphthoxazine ketone derivative |
| CN106543096A (en) * | 2016-10-25 | 2017-03-29 | 安徽工业大学 | A kind of method that catalysis prepares naphthalene oxazine ketone derivatives |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1692984A (en) * | 2005-03-18 | 2005-11-09 | 清华大学 | Method for synthesizing D,L-alpha-tocopherol catalyzed by ion-liquid |
| CN1865235A (en) * | 2006-06-16 | 2006-11-22 | 浙江大学 | Method for amide carbonylation reaction in ion liquid |
| US20110184207A1 (en) * | 2010-01-28 | 2011-07-28 | Cpc Corporation | Method of Fabricating Glycol Monoalkyl Ether Acetate Using Acidic Ionic Liquid Catalyst |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104892540A (en) * | 2015-05-20 | 2015-09-09 | 安徽工业大学 | Simple preparation method of naphthoxazine ketone derivative |
| CN106543096A (en) * | 2016-10-25 | 2017-03-29 | 安徽工业大学 | A kind of method that catalysis prepares naphthalene oxazine ketone derivatives |
| CN106543096B (en) * | 2016-10-25 | 2019-01-04 | 安徽工业大学 | A kind of method that catalysis prepares naphtho- oxazines ketone derivatives |
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