CN110156681A - A kind of synthetic method of 2- ester group quinoline - Google Patents
A kind of synthetic method of 2- ester group quinoline Download PDFInfo
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- CN110156681A CN110156681A CN201910464156.8A CN201910464156A CN110156681A CN 110156681 A CN110156681 A CN 110156681A CN 201910464156 A CN201910464156 A CN 201910464156A CN 110156681 A CN110156681 A CN 110156681A
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- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/48—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
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Abstract
The present invention provides a kind of synthetic methods of 2- ester group quinoline, and aniline or substituted aniline, phenylacetylene or substituted phenylacetylene and montmorillonite KSF are mixed, and make solvent, heating reaction with chlorobenzene；Then acetoacetic ester and manganese acetate dihydrate catalyst, heating reaction is added；To after reaction, after filtering, filtrate is separated after extraction, drying, filtering and concentration through silica gel column chromatography, 2- ester group quinoline is finally obtained.Compared with prior art, raw material of the present invention is all conventional cheap and easily-available raw material；One pot of two-step reaction progress, it is high-efficient without separating intermediate product；Catalyst montmorillonite and manganese acetate dihydrate are inexpensive, safe and non-toxic reagents；Reaction condition is mild, and selectivity is high, and side reaction is few, isolates and purifies etc. easy to operate, is not related to the extraordinary operation such as anhydrous and oxygen-free high temperature and pressure.Separation and purification of products is simple, and yield is high.From the angle of reaction mechanism, this is a kind of synthesis novel reaction path of 2- ester group quinoline.
Description
Technical field
The invention belongs to organic synthesis fields, and in particular to a kind of synthetic method of 2- ester group quinoline.
Background technique
2- ester group quinoline is due to its potential anticancer, anti-AIDS, anti-inflammatory, antibacterial and anti-tubercular and as biology
The purposes of compatibility fluorescent marker and attract wide attention.Currently, the synthetic method of 2- ester group quinoline is mainly the following
Reaction: (1) coupling reaction of arylamine, glyoxylate and phenylacetylene；(2) N- aryl glycine derivative or iminoethyl glyoxalic acid
Salt intersects dehydrogenation coupling reaction with alkene, tetrahydrofuran or alkynes；(3) addition-cyclisation-aromatization of beta-amino ester and styrene
Change tandem reaction；(4) photochemical reaction that adjacent amino alkynes and alkynes ester pass through palladium chtalyst；(5) N- aryl amine butenoate and benzene second
Cyclization etc. of the alkene under indium trichloride and nitrite tert-butyl catalysis.
But in these synthetic methods, the following limitations exist in various degree: raw material sources are limited or expensive, catalysis
Agent is expensive or toxicity is big, and severe reaction conditions, separation and purification of products is cumbersome, and yield is more low.
Summary of the invention
The purpose of the present invention is to provide a kind of synthetic methods of 2- ester group quinoline, using two step one pot process 2- ester groups
Quinoline has many advantages, such as that raw material is cheap and easily-available, catalyst is inexpensive safe and non-toxic, easy to operate, high-efficient.
The technical solution adopted by the present invention are as follows:
A kind of synthetic method of 2- ester group quinoline, comprising the following steps:
(a) aniline or substituted aniline, phenylacetylene or substituted phenylacetylene and montmorillonite KSF are mixed, solvent are made with chlorobenzene,
Heating reaction；
(b) acetoacetic ester after the cooling of step (a) reaction system, will be added and two hydration manganese acetate (III) catalyst adds
Thermal response；
(c) to after reaction, after filtering, filtrate is separated after extraction, drying, filtering and concentration through silica gel column chromatography,
Finally obtain 2- ester group quinoline.
Substituted aniline described in step (a) is open-chain crown ether, para-bromoaniline；The substituted phenylacetylene is to methylbenzene
Acetylene；
In step (a), the heating reaction temperature is 120 DEG C of 3~5h of reaction.
The aniline or substituted aniline, phenylacetylene or substituted phenylacetylene, acetoacetic ester, two hydrations manganese acetate (III)
Substance amount ratio 1:1.1~1.3:1:2.
The mass ratio of aniline described in step (a) or substituted aniline and montmorillonite KSF is 0.4~1:0.54.
Aniline described in step (a) or the substituted aniline concentration in chlorobenzene are 0.2~0.3mol/L.
Acetoacetic ester described in step (b) are as follows: methyl acetoacetate, ethyl acetoacetate or isopropyl acetoacetate.
In step (b), step (a) reaction system is cooled to 90 DEG C, acetoacetic ester is added and two hydration manganese acetates are urged
Agent reacts 5h at this temperature.
It is the ethyl acetate of volume ratio 1:1 and the mixed liquor of water that the extractant used is extracted described in step (c)；
It is dry described in step (c) to refer to using anhydrous magnesium sulfate drying.
Shown in the synthesis mechanism such as Figure 17 (by taking embodiment 3 as an example) of 2- ester group quinoline provided by the invention, reaction process
It is described as follows: firstly, being reacted under montmorillonite (KSF) effect by aniline or substituted aniline and phenylacetylene or substituted phenylacetylene
Generate adjacent amino-stilbene A；At the same time, ethyl acetoacetate is at Mn (OAc)3Oxidation is lower to generate free radical intermediate B, B
Form free radical intermediate C after carrying out free radical addition to A, C is transformed into free radical intermediate D after intramolecular hydrogen migration, D with
Afterwards in other monovalent Mn (OAc)3Mn (III)-enolate E is obtained under promotion, it is (same to form intermediate F after freedom is cyclization
When manganic be converted to bivalent manganese), oxidation then occur for F eliminate dehydration to obtain intermediate G, then aoxidized depickling formed it is final
Target product 3.
Compared with the prior art, the advantages of the present invention are as follows: the raw material of use is all conventional cheap and easily-available raw material；Two
One pot of progress of step reaction, it is high-efficient without separating intermediate product；Used catalyst montmorillonite and two hydration manganese acetates are
Inexpensive, safe and non-toxic reagent；Reaction condition is mild, and selectivity is high, and side reaction is few, isolates and purifies etc. easy to operate, is not related to
The extraordinary operation such as anhydrous and oxygen-free high temperature and pressure.Separation and purification of products is simple, and yield is high.From the angle of reaction mechanism, this is also to arrive
The novel reaction path of synthesis 2- ester group quinoline at present.
Detailed description of the invention
Fig. 1 is the nuclear magnetic resonance spectroscopy of 1 product of embodiment1H-NMR figure；
Fig. 2 is the nuclear magnetic resonance spectroscopy of 1 product of embodiment13C-NMR figure；
Fig. 3 is the nuclear magnetic resonance spectroscopy of 2 product of embodiment1H-NMR figure；
Fig. 4 is the nuclear magnetic resonance spectroscopy of 2 product of embodiment13C-NMR figure；
Fig. 5 is the nuclear magnetic resonance spectroscopy of 3 product of embodiment1H-NMR figure；
Fig. 6 is the nuclear magnetic resonance spectroscopy of 3 product of embodiment13C-NMR figure；
Fig. 7 is the carbon-13 nmr spectra of 4 product of embodiment1H-NMR figure；
Fig. 8 is the carbon-13 nmr spectra of 4 product of embodiment13C-NMR figure；
Fig. 9 is the carbon-13 nmr spectra of 5 product of embodiment1H-NMR figure；
Figure 10 is the carbon-13 nmr spectra of 5 product of embodiment13C-NMR figure；
Figure 11 is the carbon-13 nmr spectra of 6 product of embodiment1H-NMR figure；
Figure 12 is the carbon-13 nmr spectra of 6 product of embodiment13C-NMR figure；
Figure 13 is the carbon-13 nmr spectra of 7 product of embodiment1H-NMR figure；
Figure 14 is the carbon-13 nmr spectra of 7 product of embodiment13C-NMR figure；
Figure 15 is the carbon-13 nmr spectra of 8 product of embodiment1H-NMR figure；
Figure 16 is the carbon-13 nmr spectra of 8 product of embodiment13C-NMR figure；
Figure 17 is the synthesis mechanism figure of 3 product of embodiment.
Specific embodiment
Embodiment 1
A kind of synthetic method of 2- ester group quinoline, comprising the following steps:
(a) take 0.535 gram of para-totuidine, 0.696 gram to tolacetylene and 0.54 gram of KSF (montmorillonite), be placed in reaction flask
In, 20ml chlorobenzene is added, heating stirring is reacted 3 hours at 120 DEG C；
(b) step (a) system temperature is down to 90 DEG C, 0.580 gram of methyl acetoacetate and 2.68 is added into reaction flask
Grams two hydrations Mn (OAc)3, the reaction was continued at 90 DEG C 5 hours, is cooled to room temperature；
(c) reaction mixture obtained by step (b) is filtered, filtrate is extracted with the ethyl acetate and water mixed liquid of volume ratio 1:1
It takes, merges and collect ethyl acetate phase and filtered after anhydrous magnesium sulfate is dry, filtrate (elutes after being evaporated through silica gel column chromatography separation
Agent: V petroleum ether/V ethyl acetate=3:1) 1.12 grams of 6- methyl -4- p-methylphenyl -2- quinolinecarboxylic acid methyl esters sterlings are obtained, state is
White solid, yield 77%.
Embodiment 2-8
Using aniline or different substituted anilines, phenylacetylene or different substitutedphenylethynyls, acetoacetate first/second/isopropyl ester system
Standby 2- ester group quinoline, described in table 1 specific as follows, solvent and catalyst amount, experimental implementation are the same as embodiment 1.
1 embodiment 1-8 raw material of table and product
The product characteristics of embodiment 1-8, fusing point and nuclear magnetic resoance spectrum map analysis result are as follows:
1 product of embodiment: 6- methyl -4- p-methylphenyl -2- quinolinecarboxylic acid methyl esters:
White solid, mp 77-79 DEG C；
1H NMR(500MHz,DMSO-d6) δ (ppm) 8.15 (d, J=8.5Hz, 1H, ArH), 7.93 (s, 1H, ArH),
7.75 (d, J=8.5Hz, 1H, ArH), 7.72 (s, 1H, ArH), 7.49 (d, J=8.0Hz, 2H, ArH), 7.43 (d, J=
8.0Hz,2H,ArH),3.96(s,3H,OCH3),2.49(s,3H,CH3),2.45(s,3H,CH3)；
13C NMR(125MHz,DMSO-d6)δ(ppm)165.9,148.7,146.8,146.7,139.6,138.9,
134.5,133.2,130.7,129.9(2C),129.8(2C),127.5,124.5,121.2,53.1,22.1,21.4。
2 product of embodiment: 6- methyl 4-phenyl -2- quinolinecarboxylic acid methyl esters:
White solid, mp 83-85 DEG C；
1H NMR(500MHz,DMSO-d6) δ (ppm) 8.16 (d, J=9.0Hz, 1H, ArH), 7.95 (s, 1H, ArH),
7.76 (d, J=8.5Hz, 1H, ArH), 7.70 (s, 1H, ArH), 7.65-7.57 (m, 5H, ArH), 3.97 (s, 3H, OCH3),
2.49(s,3H,CH3)；
13C NMR(125MHz,DMSO-d6)δ(ppm)165.8,148.7,146.8,146.6,139.7,137.4,
133.3,130.7,129.8(2C),129.4(2C),129.3,127.4,124.4,121.3,53.1,22.1。
3 product of embodiment: 6- methyl 4-phenyl -2- quinoline ethyl formate:
White solid, mp 106-108 DEG C；
1H NMR(400MHz,CDCl3) δ (ppm) 8.30 (d, J=8.4Hz, 1H, ArH), 8.12 (s, 1H, ArH), 7.73
(s, 1H, ArH), 7.65 (dd, J=8.6,1.8Hz, 1H, ArH), 7.62-7.52 (m, 5H, ArH), 4.59 (q, J=7.2Hz,
2H,CH2),2.52(s,3H,CH3), 1.51 (t, J=7.2Hz, 3H, CH3)；
13C NMR(100MHz,CDCl3)δ(ppm)165.6,149.0,146.9,146.8,139.0,137.8,132.3,
130.9,129.6(2C),128.7(2C),128.6,127.8,124.4,121.4,62.2,22.1,14.4。
4 product of embodiment: 4- phenyl -2- quinoline ethyl formate:
White solid, mp 117-119 DEG C；
1H NMR(400MHz,DMSO-d6) δ (ppm) 8.27 (d, J=8.4Hz, 1H, ArH), 7.98 (s, 1H, ArH),
7.96-7.88 (m, 2H, ArH), 7.74 (t, J=8.2Hz, 1H, ArH), 7.64-7.58 (m, 5H, ArH), 4.45 (q, J=
7.2Hz,2H,CH2), 1.39 (t, J=7.1Hz, 3H, CH3)；
13C NMR(100MHz,DMSO-d6)δ(ppm)167.7,164.7,149.0,147.5,136.8,130.5,
130.4,129.4(2C),129.1,128.9,128.8(2C),126.8,125.4,120.6,61.6,14.1。
5 product of embodiment: 6- methyl -4- p-methylphenyl -2- quinoline ethyl formate:
White solid, mp 96-98 DEG C；
1H NMR(400MHz,DMSO-d6) δ (ppm) 8.14 (d, J=8.4Hz, 1H, ArH), 7.91 (s, 1H, ArH),
7.73 (d, J=8.8Hz, 1H, ArH), 7.70 (s, 1H, ArH), 7.47 (d, J=8.0Hz, 2H, ArH), 7.41 (d, J=
8.0Hz, 2H, ArH), 4.43 (q, J=7.2Hz, 2H, CH2),2.48(s,3H,CH3),2.43(s,3H,CH3), 1.38 (t, J=
7.0Hz,3H,CH3)；
13C NMR(100MHz,DMSO-d6)δ(ppm)164.8,148.2,146.6,146.1,139.0,138.3,
134.1,132.6,130.2,129.4(2C),129.2(2C),126.9,124.0,120.7,61.4,21.5,20.8,14.2。
6 product of embodiment: the bromo- 4- phenyl -2- quinoline ethyl formate of 6-:
Faint yellow solid, mp 134-136 DEG C；
1H NMR(500MHz,DMSO-d6) δ (ppm) 8.22 (d, J=9.0Hz, 1H, ArH), 8.05 (dd, J=9.0,
2.0Hz, 1H, ArH), 8.02 (s, 1H, ArH), 8.01 (d, J=2.0Hz, 1H, ArH), 7.67-7.59 (m, 5H, ArH), 4.45
(q, J=7.0Hz, 2H, CH2), 1.39 (t, J=7.0Hz, 3H, CH3)；
13C NMR(125MHz,DMSO-d6)δ(ppm)165.0,148.8,148.5,146.6,136.6,134.2,
133.2,129.9(2C),129.7,129.5(2C),128.6,127.8,123.2,122.0,62.2,14.6。
7 product of embodiment: 4- phenyl -2- quinolinecarboxylic acid isopropyl ester:
White solid, mp 103-105 DEG C；
1H NMR(500MHz,DMSO-d6) δ (ppm) 8.28 (d, J=8.0Hz, 1H, ArH), 7.98 (s, 1H, ArH),
7.95-7.89 (m, 2H, ArH), 7.75 (t, J=7.8Hz, 1H, ArH), 7.65-7.59 (m, 5H, ArH), 5.31-5.23 (m,
1H, CH), 1.40 (d, J=6.0Hz, 6H, CH3)；
13C NMR(125MHz,DMSO-d6)δ(ppm)164.7,149.5,148.3,148.0,137.3,131.01,
130.95,129.9(2C),129.6,129.4,129.3(2C),127.3,125.9,121.1,69.8,22.1(2C)。
8 product of embodiment: the bromo- 4- phenyl -2- quinolinecarboxylic acid isopropyl ester of 6-:
Faint yellow solid, mp 122-124 DEG C；
1H NMR(500MHz,DMSO-d6) δ (ppm) 8.23 (d, J=9.0Hz, 1H, ArH), 8.04 (dd, J=9.0,
2.0Hz, 1H, ArH), 8.01 (s, 1H, ArH), 8.00 (d, J=2.5Hz, 1H, ArH), 7.66-7.60 (m, 5H, ArH),
5.31-5.23 (m, 1H, CH), 1.40 (d, J=6.0Hz, 6H, CH3)；
13C NMR(125MHz,DMSO-d6)δ(ppm)164.4,148.8,148.8,146.6,136.7,134.2,
133.2,129.8(2C),129.7,129.5(2C),128.6,127.8,123.1,122.0,70.0,22.1(2C)。
Claims (9)
1. a kind of synthetic method of 2- ester group quinoline, which is characterized in that the synthetic method the following steps are included:
(a) aniline or substituted aniline, phenylacetylene or substituted phenylacetylene and montmorillonite KSF are mixed, solvent is made with chlorobenzene, heated
Reaction；
(b) by after the cooling of step (a) reaction system, acetoacetic ester and two hydration manganese acetate catalysts, reaction is added；
(c) to which after reaction, after filtering, filtrate is separated after extraction, drying, filtering and concentration through silica gel column chromatography, finally
Obtain 2- ester group quinoline.
2. synthetic method according to claim 1, which is characterized in that substituted aniline described in step (a) is to methylbenzene
Amine or para-bromoaniline.
3. synthetic method according to claim 1 or 2, which is characterized in that substituted phenylacetylene described in step (a) are as follows:
To methyl phenylacetylene.
4. synthetic method according to claim 1, which is characterized in that in step (a), the heating reaction temperature is 120
DEG C reaction 3~5h.
5. synthetic method according to claim 1, which is characterized in that the aniline or substituted aniline, phenylacetylene or substitution
Phenylacetylene, acetoacetic ester, two hydration manganese acetate (III) substance amount ratio 1:1.1~1.3:1:2.
6. synthetic method according to claim 1, which is characterized in that aniline described in step (a) or substituted aniline and illiteracy
The mass ratio of de- soil KSF is 0.4~1:0.54.
7. synthetic method according to claim 1, which is characterized in that aniline described in step (a) or substituted aniline are in chlorine
Concentration is 0.2~0.3mol/L in benzene.
8. synthetic method according to claim 1, which is characterized in that acetoacetic ester described in step (b) are as follows: acetyl second
Sour methyl esters, ethyl acetoacetate or isopropyl acetoacetate.
9. synthetic method according to claim 1, which is characterized in that in step (b), step (a) reaction system is cooled down
To 90 DEG C, acetoacetic ester and two hydration manganese acetate catalysts is added, reacts 5h at this temperature.
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| JP2002173484A (en) * | 2000-12-07 | 2002-06-21 | Japan Science & Technology Corp | New method for producing substituted quinoline from substituted aniline |
| CN106336378A (en) * | 2016-08-08 | 2017-01-18 | 江西师范大学 | Preparation method of quinoline-2-formic ether series |
| CN106366035A (en) * | 2016-08-30 | 2017-02-01 | 南阳师范学院 | Method for synthesizing quinoline derivative |
| CN107739333A (en) * | 2017-11-14 | 2018-02-27 | 大连理工大学 | A kind of preparation method of green quinoline compound |
| CN109053566A (en) * | 2018-09-13 | 2018-12-21 | 江苏师范大学 | A kind of synthetic method of 2- methylquinoline |
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2019
- 2019-05-30 CN CN201910464156.8A patent/CN110156681B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002173484A (en) * | 2000-12-07 | 2002-06-21 | Japan Science & Technology Corp | New method for producing substituted quinoline from substituted aniline |
| CN106336378A (en) * | 2016-08-08 | 2017-01-18 | 江西师范大学 | Preparation method of quinoline-2-formic ether series |
| CN106366035A (en) * | 2016-08-30 | 2017-02-01 | 南阳师范学院 | Method for synthesizing quinoline derivative |
| CN107739333A (en) * | 2017-11-14 | 2018-02-27 | 大连理工大学 | A kind of preparation method of green quinoline compound |
| CN109053566A (en) * | 2018-09-13 | 2018-12-21 | 江苏师范大学 | A kind of synthetic method of 2- methylquinoline |
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