CN102134219A - Preparation method of quinoline derivative - Google Patents
Preparation method of quinoline derivative Download PDFInfo
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- CN102134219A CN102134219A CN2010106212477A CN201010621247A CN102134219A CN 102134219 A CN102134219 A CN 102134219A CN 2010106212477 A CN2010106212477 A CN 2010106212477A CN 201010621247 A CN201010621247 A CN 201010621247A CN 102134219 A CN102134219 A CN 102134219A
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- WUKKWHCFNBZLBD-UHFFFAOYSA-N Cc1ccc(c(Cl)cc(Cl)c2OC)c2n1 Chemical compound Cc1ccc(c(Cl)cc(Cl)c2OC)c2n1 WUKKWHCFNBZLBD-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
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- 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 relates to a preparation method of quinoline derivative, which mainly comprises the following steps: with the existence of a rare earth catalyst, substitutional aniline reacts with an Alpha, Beta unsaturated aldehyde, ketone or esters compound so as to obtain a target compound. The preparation method has the advantages of being simple and quick in synthetic procedures, mild in synthetic condition, low in synthetic cost, higher in synthetic yield, and applicable to multiple reaction substrates, etc.
Description
Technical field
The present invention relates to a kind of preparation method of quinoline.
Background technology
Quinolines is the very important compound of a class, and it extensively is distributed in occurring in nature, is the important intermediate of multiple fine chemicals indispensability, is effectively applied to some functional material, as dyestuff, pigment, luminescent material or the like.The quinolines that has been found that also has multiple pharmaceutical activity, for example treats malaria, anti-inflammation and sterilization, kills the cancer cells isoreactivity.
Because quinolines has purposes widely, development in recent years a variety of synthetic methods, mainly contain Doebner-von Miller, Combes, Conrad-Limpach-Knorr, synthetic methods such as Skraup (Tetrahedron.Lett, 2000,41,531-533; Org.lett, 2004,6,3965-3968; Eur.J.Org.Chem, 2008,2693-2696 and J.Org.Chem, 2003,68,3966-3975), wherein the most widely used is Skraup and Doebner-von Miller method.
Yet, the method ubiquity of existing synthesis of quinoline derivatives: need active reaction substrate, react the too single shortcomings such as (causing institute's synthetic product that significant limitation is arranged) of form that rate is low, the reaction times is long, how difficult by product is and react.The preparation method of the quinoline of Given this, research and development novelty seems particularly important.
Summary of the invention
The objective of the invention is to, a kind of preparation side of quinoline of novelty is provided, overcome the defective that exists in the prior art.
The method for preparing quinoline provided by the present invention, its key step is: having under the rare earth catalyst existence condition, by the reaction of compound shown in compound shown in the formula I and formula II a or the II b, making target compound;
Wherein: said rare earth catalyst is selected from: trifluoromethanesulfonic acid rare earth [RE (OTf)
3], rare earth trichloride [RECl
3] or Perfluorocaprylic Acid rare earth [RE (PFO)
3] one or two or more kinds (containing two kinds), RE is a kind of in the rare earth element, promptly is selected from: in scandium element, yttrium or 15 lanthanon a kind of [specifically: lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), scandium (Sc) or yttrium (Y)];
R
1Be hydrogen (H), C
1～C
6Chain (straight or branched) alkyl, C
1～C
6Chain (straight or branched) alkoxyl group, nitro (NO
2) or hydroxyl is (OH);
R
2Be hydrogen (H), F, Cl, Br, I or phenyl (said substituted-phenyl links with biphenyl mode or acene mode with female ring benzene);
R
3Be hydrogen (H) or C
1～C
6Chain (straight or branched) alkyl;
R
4Be hydrogen (H), C
1～C
6Chain (straight or branched) alkyl, C
1～C
6Chain (straight or branched) alkoxyl group or phenyl; N is 1～3 integer.
In optimized technical scheme of the present invention, R
1Be hydrogen (H), C
1～C
3Chain (straight or branched) alkyl, C
1～C
3Chain (straight or branched) alkoxyl group, nitro (NO
2) or hydroxyl is (OH);
Preferred R
1Be hydrogen (H), sec.-propyl, methoxyl group, nitro (NO
2) or hydroxyl is (OH).
In another optimized technical scheme of the present invention, R
2Be hydrogen (H) or Cl.
In a further preferred technical solution of the present invention, R
3Be hydrogen (H) or C
1～C
3Chain (straight or branched) alkyl.
In a further preferred technical solution of the present invention, R
4Be hydrogen (H), C
1～C
3Chain (straight or branched) alkyl, C
1～C
3Chain (straight or branched) alkoxyl group or phenyl;
Preferred R
4Be hydrogen (H), C
1～C
3Chain (straight or branched) alkyl or phenyl.
In sum, compound is shown in the formula I that the present invention recommends to use: aniline, o-Nitraniline, o-isopropyl aniline, ortho-aminophenol or 2-methoxyl group-3,5-dichlorphenamide bulk powder;
The present invention recommends that compound is shown in the formula II a that uses or the II b: crotonic aldehyde, propenyl phenyl ketone or propenyl n-propyl ketone.
Concrete real-time mode
Preparation method's provided by the present invention synthetic route is as follows:
Described preparation method's key step is: RE (OTf) is being arranged
3, RECl
3Or/and RE (PFO)
3Under (rare earth catalyst) existence condition, under reflux state, react in anhydrous organic solvent by compound shown in compound shown in the formula I and formula IIa or the IIb, adopt thin-layer chromatography to follow the tracks of reaction, disappear to raw material point, add the shrend reaction of going out, tell organic phase (reservation water), after the gained organic phase is carried out drying, filters and removed the aftertreatment of steps such as organic solvent, obtain target product (compound shown in the formula III);
The water of above-mentioned gained is dewatered and after crystal water and drying etc. handle, the used catalyzer of promptly recyclable reaction, and the catalyzer that is reclaimed can be recycled.
Wherein: the definition of RE is described identical with preamble; The mol ratio of compound is preferably 1.0 shown in compound shown in the formula I and formula II a or the II b: (1.0～2.0) [more preferably 1.0: (1.1～1.5)]; The mol ratio of compound shown in the formula I and rare earth catalyst is preferably 1.00: (0.01～0.20) [more preferably 1.00: (0.01～0.05)].
In addition, the present invention advises using dry toluene, anhydrous phenylate, anhydrous chlorobenzene or anhydrous bromobenzene to be reaction solvent.
Method provided by the present invention has synthesis step simple and direct (" one kettle way "), synthesis condition gentleness, synthetic (catalyst system therefor can repeatedly recycle) with low cost and the higher advantages such as (being at least 80%) of synthesis yield.
In addition, because method provided by the present invention is applicable to multiple reaction substrate, so through screening or optimization to reactant, can synthesize the abundant quinoline derivatives combinatorial libraries of structure, be expected in preparation natural product and functional materials or bioactive compound, well be used.
The invention will be further elaborated below by embodiment, and the cited case does not limit protection content of the present invention.
Embodiment 1
With o-Nitraniline (0.1mol, 13.8g), crotonic aldehyde (0.12mol, 8.4g), trifluoromethanesulfonic acid yttrium (catalyzer) (5mmol, 0.62g) and anhydrous chlorobenzene (solvent) 130ml place the reactor that has condenser, stir and be heated to reflux state, adopt thin-layer chromatography (silica gel thin sheet, sherwood oil: ethyl acetate=5: 1 (v/v) is a developping agent) the detection reaction process, disappear (about 1 hour) to raw material point, add the shrend reaction of going out, with ethyl acetate washing three times, separatory merges organic layer, activated carbon decolorizing, filter dried over sodium sulfate.Screw out solvent, vacuum-drying, thus obtaining product 15.9g (its structure is suc as formula shown in the IIIa), mp138-139 ℃, product G C purity is 97%, yield is 85%.
1H-NMR(400Hz，CDCl
3)：δ2.83(s，3H)，δ7.38(m，2H)，δ7.80(d，1H)，δ8.03(d，1H)，δ8.00(d，1H)；
13C-NMR(100MHz，CDCl
3)δ24.3，123.3，123.4，123.9，127.2，131.5，136.1，136.4，146.4，162.2；GC/MS：M
+＝188.06；E.A.[FoundC，63.82；H，4.28；N，14.89；C
10H
8N
2O
2?requires?C，63.80；H，4.30；N，14.89].
Used trifluoromethanesulfonic acid yttrium (catalyzer) dewaters by heating, vacuumizes 3 hours 100 ℃ of heating then, and catalyzer can be reused.
Under the same reaction conditions:
The trifluoromethanesulfonic acid yttrium is reused for the first time, obtains the 15.5g product, and yield is 84%.
The trifluoromethanesulfonic acid yttrium is reused for the second time, obtains the 15.4g product, and yield is 84%.
The trifluoromethanesulfonic acid yttrium is reused for the third time, obtains the 15.0g product, and yield is 81.5%.
Embodiment 2
Aniline (0.1mol, 9.3g), propenyl phenyl ketone (0.12mol, 17.52g), trifluoromethanesulfonic acid scandium (catalyzer) (5mmol, 0.60g) and dry toluene (solvent) 130ml place the reactor that has condenser, stir and be heated to reflux state, adopt thin-layer chromatography (silica gel thin sheet, sherwood oil: ethyl acetate=5: 1 (v/v) is a developping agent) the detection reaction process, to raw material point disappearance (about 1 hour), add entry, with ethyl acetate washing three times, separatory merges organic layer, activated carbon decolorizing, filter dried over sodium sulfate.Screw out solvent, vacuum-drying, thus obtaining corresponding product 19.1g (its structure is suc as formula shown in the IIIb), mp118-119 ℃, productive rate is 87.2%.
1H-NMR(400MHz，CDCl
3)：δ2.28(s，3H)，δ7.23(s，1H)，δ7.41-7.53(m，6H)，δ7.68(t，1H)，δ7.86(d，1H)，δ8.09(d，1H).
13C-NMR(100MHz，CDCl
3)δ27.98，124.86，127.70，128.27，128.37，130.94，131.15，131.62，131.94，132.11，140.76，151.01，151.15，161.11；GC/MS：M
+＝219.1；E.A.[FoundC，87.64；H，6.39；N，5.98；C
16H
13N?requires?C，87.60；H，6.70；N，6.01].
Embodiment 3
Aniline (0.1mol, 9.3g), propenyl n-propyl ketone (0.12mol, 13.2g), catalyzer LaCl
3(5mmol 0.327g) places the reactor that has condenser with anhydrous phenylate (solvent) 130ml, stirs and be heated to reflux state, adopt thin-layer chromatography (silica gel thin sheet, sherwood oil: ethyl acetate=5: 1 (v/v) is a developping agent) the detection reaction process, disappear (about 1 hour) to raw material point, slowly add the shrend reaction of going out, with ethyl acetate washing three times, separatory merges organic layer, activated carbon decolorizing, filter dried over sodium sulfate.Screw out solvent, vacuum-drying, thus obtaining corresponding product 15.7g (its structure is suc as formula shown in the IIIc), productive rate is 85.8%.
1H-NMR(400MHz，CDCl
3)：δ1.04(t，3H)，δ1.75-1.84(m，2H)，δ2.71(s，3H)，δ3.00(t，2H)，δ7.13(s，1H)，δ7.48(t，1H)，δ7.65(t，1H)，δ7.98(d，1H)，δ8.02(d，1H).
13C-NMR(100MHz，CDCl
3)δ14.60，23.63，25.73，34.53，122.07，123.81，125.70，126.26，129.34，129.70，148.43，148.75，159.00；GC/MS：M
+＝185.1；E.A.[FoundC，84.28；H，8.16；N，7.56；C
13H
15N?requires?C，84.32；H，8.17；N，7.59].
Embodiment 4
O-isopropyl aniline (0.1mol, 13.5g), crotonic aldehyde (0.12mol, 8.4g), YCl
3(5mmol 0.29g) places the reactor that has condenser with anhydrous chlorobenzene (solvent) 130ml, stirs and be heated to reflux state, adopt thin-layer chromatography (silica gel thin sheet, sherwood oil: ethyl acetate=5: 1 (v/v) is a developping agent) the detection reaction process, disappear (about 1 hour) to raw material point, slowly add the shrend reaction of going out, with ethyl acetate washing three times, separatory merges organic layer, activated carbon decolorizing, filter dried over sodium sulfate.Screw out solvent, vacuum-drying, thus obtaining corresponding product 17.3g (its structure is suc as formula shown in the IIId), productive rate is 93.5%.
1H-NMR(400MHz，CDCl
3)：δ1.39(d，6H)，δ2.75(s，3H)，δ4.40(s，1H，6.9Hz)，δ7.26(d，1H)，δ7.44(t，1H)，δ7.56-7.62(m，2H)，δ8.01(d，1H).
13C-NMR(100MHz，CDCl
3)δ23.80，25.90，27.20，121.63，125.17，125.38，125.64，126.65，136.47，145.96，147.10，157.69；GC/MS：M
+＝185.1；E.A.[FoundC，84.28；H，8.16；N，7.56；C
13H
15N?requires?C，84.30；H，8.15；N，7.55].
Embodiment 5
Ortho-aminophenol (0.1mol, 10.9g), crotonic aldehyde (0.12mol, 8.4g), catalyst S c (PFO)
3(5mmol 0.73g) places the reactor that has condenser with anhydrous bromobenzene (solvent) 130ml, stirs and be heated to reflux state, adopt thin-layer chromatography (silica gel thin sheet, sherwood oil: ethyl acetate=4: 1 (v/v) is a developping agent) the detection reaction process, disappear (about 1 hour) to raw material point, slowly add the shrend reaction of going out, with ethyl acetate washing three times, separatory merges organic layer, activated carbon decolorizing, filter dried over sodium sulfate.Screw out solvent, vacuum-drying, thus obtaining corresponding product 13.7g (its structure is suc as formula shown in the IIIe), 74 ℃ of mp, productive rate are 86.2%.
1H-NMR(400MHz，CDCl
3)：δ2.73(s，3H)，δ7.19(d，1H)，δ7.29(d，1H)，δ7.29(d，1H)，δ7.40(t，1H)，δ8.02(d，1H).
13C-NMR(100Mz，CDCl
3)δ24.75，109.87，117.49，122.60，126.53，126.57，136.11，137.51，151.61，156.77；GC/MS：M
+＝159.7；E.A.[FoundC，75.45；H，5.70；N，8.80；C
10H
9NOrequires?C，75.50；H，5.75；N，8.90].
Embodiment 6
2-methoxyl group-3, and the 5-dichlorphenamide bulk powder (0.1mol, 19.2g), crotonic aldehyde (0.12mol, 8.4g), Y (PFO)
3(catalyzer) (5mmol 0.70g) places the reactor that has condenser with anhydrous chlorobenzene solvent 130ml, stirs and be heated to reflux state, adopt thin-layer chromatography (silica gel thin sheet, sherwood oil: ethyl acetate=7: 1 (v/v) is a developping agent) the detection reaction process, disappear (about 1 hour) to raw material point, slowly add the shrend reaction of going out, with ethyl acetate washing three times, separatory merges organic layer, activated carbon decolorizing, filter dried over sodium sulfate.Screw out solvent, vacuum-drying, thus obtaining corresponding product 22.0g (its structure is suc as formula shown in the IIIf), 110 ℃ of mp, productive rate are 90.9%.
1H-NMR(400MHz，CDCl
3)：δ2.80(s，3H)，δ4.17(s，3H)，δ7.38(d，1H)，δ7.56(s，1H)，δ8.38(d，1H)；
13C-NMR(100Mz，CDCl
3)δ25.55，62.27，122.89，124.59，126.09，126.55，126.80，133.30，143.29，151.05，160.14；GC/MS：M
+＝241.1；E.A.[FoundC，54.53；H，3.58；N，5.49；C
11H
9Cl
2NO?requiresC，54.57；H，3.75；N，5.79％]。
Claims (10)
1. method for preparing quinoline, its key step is: having under the rare earth catalyst existence condition, by the reaction of compound shown in compound shown in the formula I and formula II a or the II b, making target compound;
Wherein: said rare earth catalyst is selected from: RE (OTf)
3, RECl
3Or RE (PFO)
3One or two or more kinds, RE is a kind of in the rare earth element; R
1Be H, C
1～C
6Chain-like alkyl, C
1～C
6The chain alkoxyl group ,-NO
2Or-OH; R
2Be H, F, Cl, Br, I or phenyl; R
3Be H or C
1～C
6Chain-like alkyl; R
4Be H, C
1～C
6Chain-like alkyl, C
1～C
6Chain alkoxyl group or phenyl; N is 1～3 integer.
2. the method for claim 1 is characterized in that, wherein R
1Be H, C
1～C
3Chain-like alkyl, C
1～C
3The chain alkoxyl group ,-NO
2Or-OH.
3. method as claimed in claim 2 is characterized in that, wherein R
1Be H, CH
3CHCH
3, CH
3O-,-NO
2Or-OH.
4. the method for claim 1 is characterized in that, wherein R
2Be H or Cl.
5. the method for claim 1 is characterized in that, wherein R
3Be H or C
1～C
3Chain-like alkyl.
6. the method for claim 1 is characterized in that, wherein R
4Be H, C
1～C
3Chain-like alkyl, C
1～C
3Chain alkoxyl group or phenyl.
7. method as claimed in claim 6 is characterized in that, wherein R
4Be H, C
1～C
3Chain-like alkyl or phenyl.
8. as claim 3 or 4 described methods, it is characterized in that compound is shown in the wherein used formula I: aniline, o-Nitraniline, o-isopropyl aniline, ortho-aminophenol or 2-methoxyl group-3,5-dichlorphenamide bulk powder.
9. as claim 5 or 7 described methods, it is characterized in that compound is shown in wherein used formula IIa or the IIb: crotonic aldehyde, propenyl phenyl ketone or propenyl n-propyl ketone.
10. as any described method in the claim 1～9, it is characterized in that wherein used rare earth catalyst is recyclable to be recycled.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103113293A (en) * | 2013-01-21 | 2013-05-22 | 清华大学 | Polysubstituted quinoline derivative and preparation method thereof |
| CN103483253A (en) * | 2013-10-17 | 2014-01-01 | 江苏双乐化工颜料有限公司 | Synthesis method of 8-hydroxyquinaldine |
| CN104072406A (en) * | 2014-06-30 | 2014-10-01 | 青岛农业大学 | Method for synthesizing pyridine and quinoline derivative |
| CN104529888A (en) * | 2015-01-20 | 2015-04-22 | 江苏兰健药业有限公司 | Preparation method of quinoline compound |
| CN108727261A (en) * | 2018-06-21 | 2018-11-02 | 济南大学 | A kind of preparation method of that pyridine of nitro substitution quinoline |
| CN114213394A (en) * | 2021-12-03 | 2022-03-22 | 上海瀚诺威生物科技有限公司 | Synthesis method of N-sugar analysis reagent fluorogenic substrate |
| CN114292231A (en) * | 2021-12-17 | 2022-04-08 | 江苏广域化学有限公司 | 2-methyl-8-substituent-quinoline and preparation method thereof |
Citations (1)
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| CN101367762A (en) * | 2008-09-10 | 2009-02-18 | 中国科学院嘉兴应用化学工程中心 | Preparation method of midbody 7-chloroquinaldine |
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| CN101367762A (en) * | 2008-09-10 | 2009-02-18 | 中国科学院嘉兴应用化学工程中心 | Preparation method of midbody 7-chloroquinaldine |
Non-Patent Citations (1)
| Title |
|---|
| 《湖南大学学报( 自然科学版)》 20100131 吴天泉等 8-取代喹哪啶的合成与晶体结构 63-66 1-10 第37卷, 第1期 2 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103113293A (en) * | 2013-01-21 | 2013-05-22 | 清华大学 | Polysubstituted quinoline derivative and preparation method thereof |
| CN103483253A (en) * | 2013-10-17 | 2014-01-01 | 江苏双乐化工颜料有限公司 | Synthesis method of 8-hydroxyquinaldine |
| CN104072406A (en) * | 2014-06-30 | 2014-10-01 | 青岛农业大学 | Method for synthesizing pyridine and quinoline derivative |
| CN104072406B (en) * | 2014-06-30 | 2016-05-25 | 青岛农业大学 | A kind of method of pyridine synthesis and quinoline |
| CN104529888A (en) * | 2015-01-20 | 2015-04-22 | 江苏兰健药业有限公司 | Preparation method of quinoline compound |
| CN108727261A (en) * | 2018-06-21 | 2018-11-02 | 济南大学 | A kind of preparation method of that pyridine of nitro substitution quinoline |
| CN108727261B (en) * | 2018-06-21 | 2021-09-24 | 济南大学 | Preparation method of nitro-substituted quinaldine |
| CN114213394A (en) * | 2021-12-03 | 2022-03-22 | 上海瀚诺威生物科技有限公司 | Synthesis method of N-sugar analysis reagent fluorogenic substrate |
| CN114292231A (en) * | 2021-12-17 | 2022-04-08 | 江苏广域化学有限公司 | 2-methyl-8-substituent-quinoline and preparation method thereof |
| CN114292231B (en) * | 2021-12-17 | 2023-09-22 | 江苏广域化学有限公司 | 2-methyl-8-substituent-quinoline and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN102134219B (en) | 2012-07-04 |
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