CN103044315A - Method for preparing 1,4-dihydropyridine by taking acidic ionic liquid as catalyst - Google Patents
Method for preparing 1,4-dihydropyridine by taking acidic ionic liquid as catalyst Download PDFInfo
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Abstract
The invention discloses a method for preparing 1,4-dihydropyridine by taking an acidic ionic liquid as a catalyst, comprising the following steps of: taking an amine compound shown in formula (I), a propiolate compound shown in formula (II) and a benzaldehyde compound shown in formula (III) as raw materials in a solvent-free condition, wherein the ratio of the amounts of substance of the raw materials is 1: (2 to 4): 1; reacting for 0.5 to 2 hours at a reaction temperature of 50-100 DEG C under the catalysis of the acidic ionic liquid; and performing separation treatment on the reaction solution to obtain the 1,4-dihydropyridine shown in formula (IV). According to the method, no solvent is used during the preparation process, thus simplifying operation process and reducing cost; the used catalyst is the acidic ionic liquid and capable of being cyclically used, and the technical process is environment-friendly; and the method is moderate in reaction conditions, simple and convenient to operate, easy to separate products, good in product quality and high in yield.
Description
Technical field
The present invention relates to a kind of method for preparing Isosorbide-5-Nitrae-dihydropyridine, being specifically related to a kind of is raw material by phenyl aldehyde, propiolate and amine compound, utilizes acidic ion liquid to be catalyzer, prepares the method for Isosorbide-5-Nitrae-dihydropyridine under condition of no solvent.
Background technology
Isosorbide-5-Nitrae-dihydropyridine is a kind of important heterogeneous ring compound, and it has good physiologically active, has a wide range of applications at the aspect such as biological, medical.At present, the chemotherapeutics, hypertension, stenocardia etc. that have been used for clinically anti-encephalatrophy agent, the oncotherapy of neuroprotective, anti-platelet aggregation, vasodilation, diabetes, Parkinson disease.In view of, the remarkable pharmacologically active that it is many has caused domestic and international scientific research personnel's concern for the research of Isosorbide-5-Nitrae-dihydropyridine.
Isosorbide-5-Nitrae-dihydropyridine adopts usually that the Hantzsch legal system is standby to be obtained, i.e. aromatic aldehyde, methyl aceto acetate, strong aqua, and refluxing in ethanol obtains.The method exists reflecting time long, the operation inconvenience of the low and strong aqua of productive rate.The people such as Tomy Chennat improve the Hantzsch synthesis method, and they adopt phenyl aldehyde, ethyl propiolate, ammonium acetate or benzylamine is raw material, take acetic acid as solvent, heats in the water-bath, obtains Isosorbide-5-Nitrae-dihydropyridine.The method, although better productive rate obtains Isosorbide-5-Nitrae-dihydropyridine, the pungency of acetic acid and volatility have increased the inconvenience of technological operation, also can cause simultaneously the corrosion to production unit.Therefore, seek a kind of method easy, effectively synthetic Isosorbide-5-Nitrae-dihydropyridine and seem very necessary.
Summary of the invention
The object of the invention is to overcome the defective of prior art, provide that a kind of cost is low, pollution is little, the reaction times is short, yield is high, prepares the method for Isosorbide-5-Nitrae-dihydropyridine take acidic ion liquid as catalyzer.
The technical solution adopted in the present invention is as follows:
Take suc as formula (I) described aminated compounds, the described propiolate compound of formula (II) and the described benzaldehyde compound of formula (III) as raw material, the amount of raw material is than being 1:2 ~ 4:1, under presence of acidic ionic liquid catalyst, temperature of reaction is 50-100 ℃, reacted 0.5～2 hour, the reaction solution separating treatment obtains the Isosorbide-5-Nitrae-dihydropyridine shown in the formula (IV);
In the formula, aminated compounds (I) is NH
4HCO
3, (NH
4)
2CO
3, NH
4OAc, (NH
4)
2SO
4, NH
4A kind of among the Cl; Substituent R
1Be methyl, a kind of in the ethyl; Substituent R
2Be hydrogen, alkyl, halogen, hydroxyl, a kind of in alkoxyl group or the ethoxycarbonyl.
The reaction equation of Isosorbide-5-Nitrae of the present invention-dihydropyridine synthetic method is as follows:
The aminated compounds of formula of the present invention (I) is NH
4HCO
3, (NH
4)
2CO
3, NH
4OAc, (NH
4)
2SO
4, NH
4A kind of among the Cl is preferably NH
4HCO
3, (NH
4)
2CO
3, NH
4A kind of among the OAc; (II) in the described propiolate compound, substituent R
1Be methyl, a kind of in the ethyl is preferably methyl; (III) in the described benzaldehyde compound, substituent R
2Be hydrogen, alkyl, halogen, hydroxyl, a kind of in alkoxyl group or the ethoxycarbonyl, be preferably hydrogen, methyl, chlorine, bromine, hydroxyl, methoxyl group, ethoxycarbonyl a kind of.
The ratio of the amount of substance of the aminated compounds of formula of the present invention (I), the described propiolate compound of formula (II), the described benzaldehyde compound of formula (III) is 1:2 ~ 4:1, is preferably 1:2 ~ 3:1.
Temperature of reaction of the present invention is 50 ~ 100 ℃, is preferably 60 ~ 80 ℃; 0.5～2 hour reaction times, preferred 0.5～1 hour.
Acidic ion liquid of the present invention is the 1-acetic acid shown in the formula (V)-3-Methylimidazole salt compound; In the formula, X-be the chlorine negative ion, bromine negative ion, iodine negative ion, tetrafluoroborate, the hexafluoro borate, to methanesulfonate, dodecyl sodium sulfonate root, nitrate radical, a kind of in the acetate, preferred chlorine negative ion, bromine negative ion, tetrafluoroborate, a kind of in the hexafluoro borate; The catalytic amount of acidic ion liquid is 5 ~ 40% of benzaldehyde compound quality, preferred 10 ~ 30%.
Separating treatment step of the present invention is: after reaction finished, the reaction solution cooling was poured in the frozen water of 1 ~ 5 times of volume, suction filtration, washing, drying can get 1 shown in the formula (IV), the 4-dihydropyridine, acidic ion liquid is reused after underpressure distillation dehydration, drying.The vacuum tightness of acidic ion liquid underpressure distillation dehydration is 0.1MPa, and temperature is 70 ℃.
Concrete operation step of the present invention:
Take suc as formula (I) described aminated compounds, the described propiolate compound of formula (II) and the described benzaldehyde compound of formula (III) as raw material, the amount of raw material is than being 1:2 ~ 4:1, under presence of acidic ionic liquid catalyst, the catalytic amount of acidic ion liquid is 5 ~ 40% of benzaldehyde compound (III) quality, temperature of reaction is 50-100 ℃, reacted 0.5～2 hour, after reaction finishes, the reaction solution cooling, pour in the frozen water of 1 ~ 5 times of volume suction filtration, washing into, drying can get the Isosorbide-5-Nitrae-dihydropyridine shown in the formula (IV).Acidic ion liquid is 0.1MPa in vacuum tightness, and temperature is under 70 ℃ of conditions, reuses after underpressure distillation dehydration, drying.
The yield that adopts preparation method of the present invention to make Isosorbide-5-Nitrae-dihydropyridine can reach more than 85%, and product purity is high.
Adopt the inventive method to have following beneficial effect:
(1) do not use any solvent, method environmental protection in the preparation process;
(2) take acidic ion liquid as catalyzer, can be recycled, reduce production cost and minimizing to the pollution of environment;
(3) reaction conditions is gentle, and is easy and simple to handle, and product is easy to separate, and product matter is good, yield is high.
Description of drawings:
Fig. 1 is general structure (I) figure of aminated compounds;
Fig. 2 is general structure (II) figure of propiolate compound;
Fig. 3 is general structure (III) figure of benzaldehyde compound;
Fig. 4 is general structure (IV) figure of Isosorbide-5-Nitrae-dihydropyridine;
Fig. 5 is the reaction equation figure of Isosorbide-5-Nitrae-dihydropyridine synthetic method;
Fig. 6 is general structure (V) figure of acidic ion liquid.
Embodiment
The below is described further technical solution of the present invention with specific embodiment, but protection scope of the present invention is not limited to this:
With ammonium acetate (7.7g, 100mmol), Methyl propiolate (16.8g, 200mmol) and phenyl aldehyde (10.6g, 100mmol) fully mix, 1-acetic acid-3-Methylimidazole villaumite (1.1g) is made catalyzer, in 50 ℃ of reactions 1.0 hours, cooling, pour in the frozen water 30ml frozen water, suction filtration, washing, drying, get product 25.5g, yield 93.5%.
Embodiment 2
With bicarbonate of ammonia (7.9g, 100mmol), Methyl propiolate (25.2g, 300mmol) and p-tolyl aldehyde (12.0g, 100mmol) fully mix, 1-acetic acid-3-Methylimidazole bromine salt (2.4g) is made catalyzer, in 80 ℃ of reactions 0.5 hour, cooling, pour in the frozen water 100ml frozen water, suction filtration, washing, drying, get product 25.6g, yield 89.2%.
Embodiment 3
With bicarbonate of ammonia (7.9g, 100mmol), Methyl propiolate (16.8g, 200mmol) and NSC 43794 (13.6g, 100mmol) fully mix, 1-acetic acid-3-Methylimidazole bromine salt (0.7g) is made catalyzer, in 70 ℃ of reactions 1.0 hours, cooling, pour in the frozen water 150ml frozen water, suction filtration, washing, drying, get product 27.5g, yield 91.0%.
Embodiment 4
With volatile salt (9.6g, 100mmol), Methyl propiolate (16.8g, 200mmol) and aubepine (13.6g, 100mmol) fully mix, 1-acetic acid-3-methyl imidazolium tetrafluoroborate (1.4g) is made catalyzer, in 70 ℃ of reactions 1.0 hours, cooling, pour in the frozen water 110ml frozen water, suction filtration, washing, drying, get product 27.0g, yield 89.3%.
Embodiment 5
With ammonium acetate (7.7g, 100mmol), Methyl propiolate (33.6g, 400mmol) and 4-chloro-benzaldehyde (14.1g, 100mmol) fully mix, 1-acetic acid-3-Methylimidazole hexafluoro borate (2.8g) is made catalyzer, in 90 ℃ of reactions 1.0 hours, cooling, pour in the frozen water 250ml frozen water, suction filtration, washing, drying, get product 26.6g, yield 86.4%.
Embodiment 6
With ammonium chloride (5.4g, 100mmol), ethyl propiolate (19.6g, 200mmol) and p-bromobenzaldehyde (18.5g, 100mmol) fully mix, 1-acetic acid-3-Methylimidazole hexafluoro borate (5.6g) is made catalyzer, in 90 ℃ of reactions 1.0 hours, cooling, pour in the frozen water 200ml frozen water, suction filtration, washing, drying, get product 32.4g, yield 85.2%.
Embodiment 7
With bicarbonate of ammonia (7.9g, 100mmol), ethyl propiolate (29.4g, 300mmol) and p-Hydroxybenzaldehyde (12.2g, 100mmol) fully mix, 1-acetic acid-3-Methylimidazole dodecane sulfonate (3.7g) is made catalyzer, in 100 ℃ of reactions 0.5 hour, cooling, pour in the frozen water 150ml frozen water, suction filtration, washing, drying, get product 27.9g, yield 88.0%.
Embodiment 8
With ammonium sulfate (13.2g, 100mmol), Methyl propiolate (25.2g, 300mmol) with to methoxycarbonyl phenyl aldehyde (16.4g, 100mmol) fully mix, 1-acetic acid-3-Methylimidazole nitrate (4.9g) is made catalyzer, in 70 ℃ of reactions 1.0 hours, cooling, pour in the frozen water 200ml frozen water, suction filtration, washing, drying, get product 30.0g, yield 90.6%.
Embodiment 9
With ammonium acetate (7.7g, 100mmol), ethyl propiolate (19.6g, 200mmol) and o-methoxybenzaldehyde (13.6g, 100mmol) fully mix, 1-acetic acid-3-Methylimidazole villaumite (1.6g) is made catalyzer, in 60 ℃ of reactions 1.0 hours, cooling, pour in the frozen water 100ml frozen water, suction filtration, washing, drying, get product 26.3g, yield 86.8%.
Embodiment 10
With bicarbonate of ammonia (7.9g, 100mmol), ethyl propiolate (29.4g, 300mmol) and p-tolyl aldehyde (12.0g, 100mmol) fully mix, 1-acetic acid-3-Methylimidazole is made catalyzer to mesylate (3.6g), in 80 ℃ of reactions 0.5 hour, cooling, pour in the frozen water 100ml frozen water, suction filtration, washing, drying, get product 27.9g, yield 92.3%.
With bicarbonate of ammonia (7.9g, 100mmol), Methyl propiolate (16.8g, 200mmol) and o-chlorobenzaldehyde (14.1g, 100mmol) fully mix, 1-acetic acid-3-methyl imidazolium tetrafluoroborate (2.8g) is made catalyzer, in 60 ℃ of reactions 1.0 hours, cooling, pour in the frozen water 100ml frozen water, suction filtration, washing, drying, get product 26.9g, yield 87.5%.
Embodiment 12
With ammonium acetate (7.7g, 100mmol), Methyl propiolate (33.6g, 400mmol) and an ethoxycarbonyl phenyl aldehyde (17.8g, 100mmol) fully mix, 1-acetic acid-3-Methylimidazole hexafluorophosphate (0.9g) is made catalyzer, in 70 ℃ of reactions 1.0 hours, cooling, pour in the frozen water 200ml frozen water, suction filtration, washing, drying, get product 30.5g, yield 88.3%.
Claims (9)
1. one kind prepares 1 take acidic ion liquid as catalyzer, the method of 4-dihydropyridine, it is characterized in that: take suc as formula (I) described aminated compounds, the described propiolate compound of formula (II) and the described benzaldehyde compound of formula (III) as raw material, the amount of raw material is than being 1:2 ~ 4:1, under presence of acidic ionic liquid catalyst, temperature of reaction is 50-100 ℃, reacts 0.5～2 hour, the reaction solution separating treatment obtains the Isosorbide-5-Nitrae-dihydropyridine shown in the formula (IV);
In the formula, aminated compounds (I) is NH
4HCO
3, (NH
4)
2CO
3, NH
4OAc, (NH
4)
2SO
4, NH
4A kind of among the Cl; Substituent R
1Be methyl, a kind of in the ethyl; Substituent R
2Be hydrogen, alkyl, halogen, hydroxyl, a kind of in alkoxyl group or the ethoxycarbonyl.
2. according to claim 1 method is characterized in that aminated compounds (I) is NH
4HCO
3, (NH
4)
2CO
3, NH
4A kind of among the OAc; Substituent R
1Be methyl; Substituent R
2Be hydrogen, methyl, chlorine, bromine, hydroxyl, methoxyl group, a kind of in the ethoxycarbonyl.
3. according to claim 1 and 2 method is characterized in that the molar ratio of aminated compounds (I), described propiolate compound (II) and benzaldehyde compound (III) is 1:2 ~ 3:1.
4. according to claim 1 and 2 method is characterized in that temperature of reaction is 60～80 ℃, 0.5～1 hour reaction times.
5. according to claim 1 and 2 method is characterized in that described acidic ion liquid is the 1-acetic acid shown in the formula (V)-3-Methylimidazole salt compound; In the formula, X-be the chlorine negative ion, the bromine negative ion, the iodine negative ion, tetrafluoroborate, the hexafluoro borate, to methanesulfonate, dodecyl sodium sulfonate root, nitrate radical, a kind of in the acetate; The catalytic amount of acidic ion liquid is 5 ~ 40% of benzaldehyde compound quality.
6. according to claim 5 method is characterized in that described acidic ion liquid is the 1-acetic acid shown in the formula (V)-3-Methylimidazole salt compound, wherein, and X-be the chlorine negative ion, bromine negative ion, tetrafluoroborate, a kind of in the hexafluoro borate; The catalytic amount of acidic ion liquid is 10 ~ 30% of benzaldehyde compound quality.
7. according to claim 1 and 2 method, it is characterized in that, described separating treatment step is: after reaction finishes, suction filtration is poured in the frozen water of 1 ~ 5 times of volume in the reaction solution cooling into, washing, drying can get the Isosorbide-5-Nitrae-dihydropyridine shown in the formula (IV), and acidic ion liquid is reused after underpressure distillation dehydration, drying.
8. according to claim 7 method, the vacuum tightness of acidic ion liquid underpressure distillation dehydration is 0.1MPa, temperature is 70 ℃.
9. according to claim 1 and 2 method, prepare 1 take acidic ion liquid as catalyzer, the method of 4-dihydropyridine, it is characterized in that, with suc as formula (I) described aminated compounds, the described propiolate compound of formula (II) and the described benzaldehyde compound of formula (III) are raw material, the amount of raw material is than being 1:2 ~ 3:1, and under presence of acidic ionic liquid catalyst, the catalytic amount of acidic ion liquid is 10 ~ 30% of benzaldehyde compound (III) quality, temperature of reaction is 60～80 ℃, reacted 0.5～1 hour, after reaction finishes, the reaction solution cooling, pour in the frozen water of 1 ~ 5 times of volume, suction filtration, washing, drying can get 1 shown in the formula (IV), the 4-dihydropyridine, acidic ion liquid is 0.1MPa in vacuum tightness, and temperature is under 70 ℃ of conditions, dewaters through underpressure distillation, reuse after the drying.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104030973A (en) * | 2014-06-13 | 2014-09-10 | 上海应用技术学院 | Preparation method of 1, 4-dihydropyridine compound |
| CN106399686A (en) * | 2016-09-05 | 2017-02-15 | 厦门稀土材料研究所 | Acidic ionic liquid and method for separating and purifying rare earth or rare and precious metals by solvent extraction coupling electrolytic process |
| CN112939855A (en) * | 2021-02-08 | 2021-06-11 | 马鞍山市泰博化工科技有限公司 | Method for preparing 1, 4-dihydropyridine derivative containing azulene ring structure |
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| CN101704779A (en) * | 2009-11-03 | 2010-05-12 | 中国科学院亚热带农业生态研究所 | Preparation method for feed additive dihydropyridine |
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2013
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104030973A (en) * | 2014-06-13 | 2014-09-10 | 上海应用技术学院 | Preparation method of 1, 4-dihydropyridine compound |
| CN106399686A (en) * | 2016-09-05 | 2017-02-15 | 厦门稀土材料研究所 | Acidic ionic liquid and method for separating and purifying rare earth or rare and precious metals by solvent extraction coupling electrolytic process |
| CN112939855A (en) * | 2021-02-08 | 2021-06-11 | 马鞍山市泰博化工科技有限公司 | Method for preparing 1, 4-dihydropyridine derivative containing azulene ring structure |
| CN112939855B (en) * | 2021-02-08 | 2024-03-26 | 马鞍山市泰博化工科技有限公司 | Process for preparing 1, 4-dihydropyridine derivatives containing azulene ring structure |
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Application publication date: 20130417 |