CN102060851B - Method for preparing polyhydroquinolines - Google Patents
Method for preparing polyhydroquinolines Download PDFInfo
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- CN102060851B CN102060851B CN2010105677763A CN201010567776A CN102060851B CN 102060851 B CN102060851 B CN 102060851B CN 2010105677763 A CN2010105677763 A CN 2010105677763A CN 201010567776 A CN201010567776 A CN 201010567776A CN 102060851 B CN102060851 B CN 102060851B
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Abstract
The invention provides a method for synthesizing polyhydroquinolines in the absence of a catalyst, which is to synthesize polyhydroquinolines by one-pot reaction of an aromatic aldehyde, 1,3-cyclohexanedione, ethyl acetoacetate and ammonium acetate in a PEG-400-H2O system. The method avoids using any catalyst, thereby reducing environmental pollution caused by catalysts, simplifying post treatment process and realizing environmentally-friendly synthesis; the method makes process simple and operation convenient; and the method realizes mild reaction conditions, short reaction time and high yield (over 80 percent), and contributes to industrial production.
Description
Technical field
The invention belongs to the organic chemistry synthesis technical field, relate to a kind of preparation method of many hydrogen quinoline, relate in particular to a kind of method that under the on-catalytic condition, prepares many hydrogen quinoline.
Background technology
Many hydrogen quinolines removes has sterilization widely, outside the anti-inflammatory biological activity, also is used in antimalaric; Clinically also as the medicine of treating cardiovascular disorder; As treating cardiovascular disorder as calcium channel blocker, therefore antihypertensive drug etc. get more and more people's extensive concerning.1, many hydrogen quinoline compound, its chemical structural formula is following:
Wherein, R=2-Thienyl, 5-Methyl-2-furyl, 4-OH-3-C
2H
5OC
6H
3, 2-CH
3OC
6H
4
At present, the compound method of relevant many hydrogen quinolines, that has reported is a lot.Wherein remarkable, also maximum with catalyzed reaction, such as: Lewis acid catalyzed process, L-proline(Pro) catalysis method, inorganic metal salt catalysis method, organo-metallic catalysis method etc.Other method also has microwave irradiation, ultrasonic radiation and optical radiation method etc.All these methods all exist uses expensive catalyzer, a large amount of organic solvents, and long reaction time, aftertreatment is complicated, and productive rate is low etc., and problem, especially catalyzed reaction cause bigger pollution to environment, do not meet the requirement of Green Chemistry, are unfavorable for industrial production.
Summary of the invention
The object of the invention provides a kind of method that under the on-catalytic condition, prepares many hydrogen quinoline to the problem that exists in the prior art.
The present invention prepares the method for many hydrogen quinoline, is at PEG-400-H
2In the O system, with aromatic aldehyde, hydroresorcinol, methyl aceto acetate and ammonium acetate reacted 3 ~ 8 minutes down in 70 ~ 90 ℃ with the mixed in molar ratio of 1:1:1:1.5 ~ 1:1:1:2.2; Reaction finishes postcooling, uses water washing, uses the absolute ethyl alcohol recrystallization, many hydrogen quinolines.
Said PEG-400-H
2In the O system, PEG-400 and H
2O mixes with the mass ratio of 1:1 ~ 1:1.5.
Said aromatic aldehyde is the 2-thiophene aldehyde, or 5-methyl-2 Furan Aldehydes, or 4-hydroxyl-3 ethoxy-benzaldehyde, or the 2-methoxybenzaldehyde.
Its building-up process is following:
Wherein, R=2-Thienyl, 5-Methyl-2-furyl, 4-OH-3-C
2H
5OC
6H
3, 2-CH
3OC
6H
4
The present invention compared with prior art has the following advantages:
1, the present invention is at green environment PEG-400-H
2Among the O, utilize aromatic aldehyde, hydroresorcinol, methyl aceto acetate and ammonium acetate reaction have obtained a series of many hydrogen quinoline.This method is not used any catalyzer, has reduced the pollution of catalyzer to environment, has simplified last handling process yet, has realized environment amenable chemosynthesis;
2, the present invention adopts the reaction of four component one kettle ways, and technology is simple, and is easy to operate;
3, reaction conditions is gentle, and in the reaction times short (just can accomplish in 3 minutes), productive rate high (can reach more than 80%) helps suitability for industrialized production.
Embodiment
Be further described through the preparation of specific embodiment below many hydrogen of the present invention quinoline.
Embodiment 1,2-methyl-4-(2-thienyl)-5-oxo-1,4,5,6,7, the preparation of 8-six hydrogen quinoline-3-carboxylic acid ethyl esters
Filling 0.30g PEG-400-H
2O (PEG-400 0.15g, H
2O 0.15g) in the reaction flask of mixed solution (50 mL round-bottomed flask), add thiophene aldehyde 1mmol successively, hydroresorcinol 1mmol, methyl aceto acetate 1mmol, ammonium acetate 1.5mmol was 90 ℃ of following stirring reactions 3 minutes; Reaction finishes the postcooling reaction flask to room temperature, adding distil water 6mL, washing reaction mixture at twice; Use the absolute ethyl alcohol heating for dissolving, recrystallization 4-5 time gets pure article 2-methyl-4-(2-thienyl)-5-oxo-1,4,5,6,7, the preparation of 8-six hydrogen quinoline-3-carboxylic acid ethyl esters.
This product is a yellow solid, and fusing point is: 251-253 ℃, productive rate is: 94 %.
The ir data of product of the present invention is following:
IR?(υ/cm
-1):3289,?3213,?3073,?2945,?1693,?1609,?1480,?1284,?1219,?1179,?698
Above-mentioned data show, contain thiphene ring, carbonyl and saturated hydrocarbon structure in the structure of this product.
The nuclear magnetic resonance data of product of the present invention is following:
1H?NMR?(400?MHz,?CDCl
3):?
δ?=?9.29?(s,?1H),?7.17?(d,?J?=?5.2?Hz,?1H),?6.81?(q,?J?=?4.8Hz,?3.6Hz,?1H),?6.64?(d,?J?=?3.2?Hz,?1H),?5.19?(s,?1H),?4.11-4.05?(m,?2H),?2.51?(m,?2H),?2.27-2.22?(m,?5H),?1.97-1.91?(m,?1H),?1.85-1.80?(m,?1H),?1.19?(t,?J?=?7.2?Hz,?3H);
?13C?NMR?(100?MHz,?CDCl
3):?
δ?=?194.5,?166.6,?151.7,?151.6,?145.4,?126.4,?123.3,?122.5,?110.4,?103.1,?59.2,?36.7,?30.4,?26.1,?20.8,?18.2,?14.2.
A H of proton nmr spectra chemical shift 9.29 is a nitrogen hydrogen; 7.17-6.64 3 H be three hydrogen on the thiphene ring, 5.19 is tertiary carbon hydrogen, 2 H at 4.11-4.05 place are the methylene radical hydrogen on the side chain; 2.51 2 H that locate are 6 hydrogen on the carbon; 2.27-2.22 5 H that locate are two hydrogen and three hydrogen on 2 methyl on 8 carbon, 2 H at 1.97-1.91 and 1.85-1.80 two places are 7 hydrogen on the carbon, and 1.19 is pendant methyl hydrogen.11 types of carbon atoms of this product structure all occur in the carbon spectrum.
The results of elemental analyses of this product is following:
Anal.?Calcd?for?C
17H
19NO
3S:?C?64.33,?H?6.03,?N?4.41?Found:?C?64.30,?H?6.05,?N?4.39
The structural formula of this product is following:
。
Embodiment 2,2-methyl-4-(5-methyl-2-furyl)-5-oxo-1,4,5,6,7, the preparation of 8-six hydrogen quinoline-3-carboxylic acid ethyl esters
Filling 0.30g PEG-400-H
2O (PEG-400 0.15g, H
2O 0.15g) in the reaction flask of mixed solution (50 mL round-bottomed flask), add 5-methyl-2 Furan Aldehydes 1mmol successively, hydroresorcinol 1mmol, methyl aceto acetate 1mmol, ammonium acetate 1.8mmol was 80 ℃ of following stirring reactions 5 minutes; Reaction finishes the postcooling reaction flask to room temperature, adding distil water 6mL, washing reaction mixture at twice; Use the absolute ethyl alcohol heating for dissolving, recrystallization 4-5 time gets pure article 2-methyl-4-(5-methyl-2-furyl)-5-oxo-1,4,5,6,7, the preparation of 8-six hydrogen quinoline-3-carboxylic acid ethyl esters.
This product is a yellow solid, and fusing point is: 239-241 ℃, productive rate is: 88 %.
The ir data of product of the present invention is following:
IR?(υ/cm
-1):?3291,?3213,?3072,?2950,?1694,?1609,?1520,?1474,?1379,?1284,?1219,?1182
Above-mentioned data declaration contains furan nucleus in the structure of this product, carbonyl, saturated hydrocarbon structure.
The nuclear magnetic resonance data of product of the present invention is following:
1H?NMR?(400?MHz,?CDCl
3):?
δ?=?9.16?(s,?1H),?5.80?(q,?J?=?2.8Hz,?0.8Hz,?1H),?5.64?(d,?J?=?3.2?Hz,?1H),?4.98?(s,?1H),?4.15-4.01?(m,?2H),?2.49-2.45?(m,?2H),?2.29-2.18?(m,?5H),?2.12?(s,?3H),1.94-1.90?(m,?1H),?1.84-1.81?(m,?1H),?1.19?(t,?J?=?6.8?Hz,?3H);
?13C?NMR?(100?MHz,?CDCl
3):?
δ?=?194.4,?166.7,?156.8,?152.2,?149.1,?145.2,?107.6,?106.0,?104.6,?101.0,?58.9,?36.6,?29.3,?26.1,?20.7,?18.1,?14.2,?13.3;
Proton nmr spectra chemical shift 9.16 is a nitrogen hydrogen, and 5.80,5.64 are the furans ring hydrogen, and 4.98 is 4 hydrogen on the carbon; 4.15-4.01 2 H be positioned on the side chain methylene radical; 2.49-2.45 2 H be positioned on 6 carbon, 5 H at 2.29-2.18 place are 2 hydrogen and the methyl hydrogen on 2 carbon on 7 carbon, 2.12 is the methyl hydrogen on the substituted furan ring; 1.94-1.90 with 2 H at 1.84-1.81 place be 6 hydrogen on the carbon, 1.19 is pendant methyl hydrogen.18 types of carbon atoms of this product structure all occur in the carbon spectrum.
The results of elemental analyses of this product is following:
Anal.?Calcd?for?C
18H
21NO
4:?C?68.55,?H?6.71,?N?4.44?Found:?C?68.58,?H?6.68,?N?4.41.
The structural formula of this product is following:
Embodiment 3,2-methyl-4-(3-oxyethyl group-4-hydroxy phenyl)-5-oxo-1,4,5,6,7, the preparation of 8-six hydrogen quinoline-3-carboxylic acid ethyl esters
Filling 0.30g PEG-400-H
2O (PEG-400 0.15g, H
2O 0.15g) in the reaction flask of mixed solution (50 mL round-bottomed flask), add 4-hydroxyl-3 ethoxy-benzaldehyde 1mmol successively, hydroresorcinol 1mmol, methyl aceto acetate 1mmol, ammonium acetate 2mmol was 70 ℃ of following stirring reactions 8 minutes; Reaction finishes the postcooling reaction flask to room temperature, adding distil water 6mL, washing reaction mixture at twice; Use the absolute ethyl alcohol heating for dissolving, recrystallization 4-5 time gets pure article 2-methyl-4-(3-oxyethyl group-4-hydroxy phenyl)-5-oxo-1,4,5,6,7, the preparation of 8-six hydrogen quinoline-3-carboxylic acid ethyl esters.
This product is a faint yellow solid, and fusing point is: 213-214 ℃.Productive rate is: 98%.
The ir data of product of the present invention is following:
IR?(υ/cm
-1):?3431,?3270,?3181,?3066,?2972,?2930,?1698,?1605,?1496,?1385,?1279,?1229,?1179,?1075
Above-mentioned data declaration contains hydroxyl in the structure of this product, phenyl ring, carbonyl and saturated hydrocarbon structure.
The nuclear magnetic resonance data of product of the present invention is following:
1H?NMR?(400?MHz,?CDCl
3):?
δ?=?9.02?(s,?1H),?8.48?(s,?1H),?6.69-6.49?(m,?3H),?4.78?(s,?1H),?4.00?(q,?J?=?7.2Hz,?2H),?3.95-3.89?(m,?2H),?3.48-3.41?(m,?2H),?2.26-2.17?(m,?5H),?1.92-1.75?(m,?2H),?1.29?(t,?J?=?6.8?Hz,?3H),?1.14?(t,?J?=?7.2?Hz,?3H);?
13C?NMR?(100?MHz,?CDCl
3):?
δ?=?194.7,?167.1,?151.0,?145.7,?144.9,?144.2,?139.0,?119.5,?115.1,?113.5,?111.3,?104.0,?63.8,?58.9,?36.8,?34.7,?26.1,?20.9,?18.5,?14.7,?14.2
Proton nmr spectra chemical shift 9.02 places are nitrogen hydrogen; 8.48 be hydroxyl hydrogen, 6.69-6.49 is three hydrogen on the phenyl ring, 1 H at 4.78 places is a tertiary carbon hydrogen; 4.00 2 H that locate are the methylene radical hydrogen on the benzene ring side chain; 3.95-3.89 2 H that locate 2 are the methylene radical on the carbon side chain, 2 H at 3.48-3.41 place are 6 hydrogen on the carbon, and 5 H at 2.26-2.17 place are the hydrogen on 2 substituent methyl hydrogen and 8 carbon; Be the methyl hydrogen of benzene ring side chain 1.92-1.75 2 H that locate are 7 hydrogen 1.29 on the carbon, 1.14 is 3 methyl hydrogen on the carbon.21 types of carbon atoms of this product structure all occur in the carbon spectrum.
The results of elemental analyses of this product is following:
Anal.?Calcd?for?C
21H
25NO
5:?C?67.91,?H?6.78,?N?3.77?Found:?C?67.77,?H?6.75,?N?3.79.
The structural formula of this product is following:
Embodiment 4,2-methyl-4-(2-p-methoxy-phenyl)-5-oxo-1,4,5,6,7, the preparation of 8-six hydrogen quinoline-3-carboxylic acid ethyl esters
Filling 0.30g PEG-400-H
2O (PEG-400 0.15g, H
2O 0.15g) in the reaction flask of mixed solution (50 mL round-bottomed flask), add 2-methoxybenzaldehyde 1mmol successively, hydroresorcinol 1mmol, methyl aceto acetate 1mmol, ammonium acetate 2.2mmol was 90 ℃ of following stirring reactions 3 minutes; Reaction finishes the postcooling reaction flask to room temperature, adding distil water 6mL, washing reaction mixture at twice; Use the absolute ethyl alcohol heating for dissolving, continuous recrystallization 4-5 time gets pure article 2-methyl-4-(2-p-methoxy-phenyl)-5-oxo-1,4,5,6,7, the preparation of 8-six hydrogen quinoline-3-carboxylic acid ethyl esters.
This product is a yellow solid, fusing point: 186-188 ℃. productive rate is: 88 %.
The ir data of product of the present invention is following:
IR?(υ/cm
-1):?3291,?3207,?3073,?2988,?1686,?1615,?1484,?1377,?1291,?1223,?1181,?1073,?745;
Above-mentioned data declaration contains phenyl ring in the structure of this product, carbonyl and saturated hydrocarbon structure.
The nuclear magnetic resonance data of product of the present invention is following:
1H?NMR?(400?MHz,?DMSO-d
6):?δ?=?8.99?(s,?1H),?7.06-6.74?(m,?4H),?5.08?(s,?1H),?3.98-3.89?(m,?2H),?3.70?(s,?3H),?2.48-2.44?(m,?2H),?2.16-2.08?(m,?5H),?1.91-1.86?(m,?1H),?1.77-1.72?(m,?1H),?1.13?(t,?J?=?7.2?Hz,?3H);?
13C?NMR?(DMSO-d
6,?100?MHz):?δ?=194.1,?167.4,?157.1,?151.9,?143.4,?135.3,?130.0,?126.9,?119.7,?111.4,?109.7,?103.4,?58.8,?55.4,?36.8,?32.2,?26.3,?20.9,?17.8,?14.1;
Proton nmr spectra chemical shift 8.99 places are nitrogen hydrogen, and 4 H at 7.06-6.74 place are four hydrogen on the phenyl ring, and 1 H at 5.08 places is a hydrogen on the tertiary carbon; 3.98-3.89 2 H that locate are side chain methylene radical hydrogen; 3.70 be methoxyl group hydrogen, 2 hydrogen of 2.48-2.44 are 6 hydrogen on the carbon, 5 H of 2.16-2.08 are respectively 2 substituent methyl hydrogen and 8 methylene radical hydrogen; 1.91-1.86 be 7 methylene radical hydrogen on the carbon with the hydrogen at 1.77-1.72 place, 1.13 is pendant methyl hydrogen.20 types of carbon atoms of this product structure all occur in the carbon spectrum.
The results of elemental analyses of this product is following:
Anal.?Calcd?for?C
20H
23NO
4:?C?70.36,?H?6.79,?N?4.10?Found:?C?70.33,?H?6.77,?N?3.39.
The structural formula of this product is following:
Reagent and instrument that product of the present invention is identified: IR is an Alpha Centauri FI-IR type instrument; Nuclear magnetic resonance spectrum is solvent with the Mercury-Plus of Bruker company 400 MHz type nmr determinations with the deuterated dimethyl sulfoxide, and TMS is interior mark; Mass spectrum is measured with QP-1000A GC-MS, the EI source; Used aromatic aldehyde or heterocyclic aldehydes and hydroresorcinol are Alfa Aesar reagent in the experiment, and methyl aceto acetate and ammonium acetate and other solvent are homemade A.R. level reagent.
Claims (2)
1. the preparation method of hydrogen quinoline more than a kind is at PEG-400-H
2In the O system, with aromatic aldehyde, hydroresorcinol, methyl aceto acetate and ammonium acetate reacted 3 ~ 8 minutes down in 70 ~ 90 ℃ with the mixed in molar ratio of 1:1:1:1.5 ~ 1:1:1:2.2; Reaction finishes postcooling, uses water washing, uses the absolute ethyl alcohol recrystallization, many hydrogen quinoline;
Said aromatic aldehyde is the 2-thiophene aldehyde, 5-methyl-2-Furan Aldehydes, 4-hydroxyl-3-ethoxy-benzaldehyde, or 2-methoxybenzaldehyde;
Wherein, R=2-Thienyl, 5-Methyl-2-furyl, 4-OH-3-C
2H
5OC
6H
3, 2-CH
3OC
6H
4
2. the preparation method of many hydrogen quinoline according to claim 1 is characterized in that: said PEG-400-H
2In the O system, PEG-400 and H
2O mixes with the mass ratio of 1:1 ~ 1:1.5.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101723880A (en) * | 2009-11-20 | 2010-06-09 | 西北师范大学 | 1-phenyl-4-(anilino)-2,6-diaryl-1,2,5,6-tetrahydropyridine-3-etyl carbonate compound and synthesis method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101723880A (en) * | 2009-11-20 | 2010-06-09 | 西北师范大学 | 1-phenyl-4-(anilino)-2,6-diaryl-1,2,5,6-tetrahydropyridine-3-etyl carbonate compound and synthesis method thereof |
Non-Patent Citations (2)
| Title |
|---|
| S. Kumar，et al..An efficient, catalyst- and solvent-free, four-component, and one-pot synthesis of polyhydroquinolines on grinding.《Tetrahedron》.2007,第64卷536-542. * |
| 荣良策等.无溶剂、无催化剂条件下合成1,4,5,6,7,8-六氢喹啉-5-酮衍生物.《有机化学》.2008,第28卷(第5期),837-840. * |
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