CN102060754A - Method for preparing polysubstituted tetrahydropyridine - Google Patents
Method for preparing polysubstituted tetrahydropyridine Download PDFInfo
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Abstract
The invention provides a new method for synthesizing polysubstituted tetrahydropyridine. In the method, a series of polysubstituted tetrahydropyridines are prepared by using low-cost and nontoxic hydrochloric acid as a catalyst and aromatic aldehyde, active methylene substances and aromatic amine as raw materials and by a one-pot process, the polysubstituted tetrahydropyridine yield (which is over 80 percent) is high; and the product quality (the purity is over 99 percent) is high; other organic solvents which are adverse to environment are not used in a reaction, so the pollution of the solvents and the catalyst on the environment is reduced, and the environmentally-friendly chemical synthesis is realized; and the polysubstituted tetrahydropyridine is synthesized by a multicomponent one-pot process, so the preparation method is economic in steps, simple in operation and low in cost, has mild reaction condition, is easy and convenient to operate, and is favorable for industrial production.
Description
Technical field
The invention belongs to organic chemistry filed, relate to a kind of preparation method of polysubstituted tetrahydropyridine, relate in particular to a kind of utilization and utilize aromatic aldehyde, active methylene base class material, aromatic amine to prepare the method for polysubstituted tetrahydropyridine.
Background technology
Polysubstituted tetrahydropyridine is the important organic compound of a class, all has its structural framework in the molecule of many natural products and biologically active, gets more and more people's extensive concerning as the structural unit of many bioactive compoundss.Polysubstituted tetrahydropyridine, its chemical structural formula is as follows:
Wherein, R
1=H, 4-CH
3, 2-NO
2, 3-NO
2, 4-NO
2, 2-Cl, 3-Cl, 4-Cl, 2,4-DiCl, 2-OCH
3, 4-OCH
3, 3,4-DiOCH
3R
2=CH
2CH
3, CH
2CH=CH
2R
3=H, 4-CH
3, 4-Cl, 4-Br.
At present, the report of relevant polysubstituted tetrahydropyridine synthetic method is a lot.Wherein following several method is used comparatively extensive: first method is the cyclisation method, and promptly the C-N key becomes ring or by forming C-C key Cheng Huan, this method is to form one of the most frequently used method of piperidine ring by forming.As by intramolecular nucleophilic substitution reaction (Tetrahedron 2001,57,6955; Chirality 2000,12,342), promote cyclisation (Chem.Lett.1997,221 by organic palladium, silver, mercury, tin compound; Asymmetry 1995,6, and 1077; Heterocycles-cycles2000,53,115), the nucleophilic addition(Adn) (J.Org.Chem.1999,64,1160) of carbanion, the promoted intramolecularly addition of Lewis acid (TetrahedronAsymmetry 1997,8,3387).Second method is the cycloaddition method, and promptly intramolecular Didls-Alder reaction (Tetrahedron 1998,54, and 1317; J.Org.Chem.Soc.2000,122,4583; J.Org.Chem.2001,66.3338), intermolecular Didls-A1der reacts (J.Org.Chem.1996,61,4594; J.Org.Chem.1992,58,2075), intramolecular imines Didls-Alder reacts (Org.Let.2000,2,4007).
In these methods, some method has been used organic solvent, and some method also needs to use conditions such as heavy metal catalyst, low temperature; In addition, some method then side reaction is many, and productive rate is low, can not be applied to reality, does not also meet the requirement of Green Chemistry.
Summary of the invention
Order of the present invention is in order to overcome the problem of existence, and providing a kind of is catalyzer with the concentrated hydrochloric acid, utilizes aromatic aldehyde, active methylene base class material, aromatic amine to be raw material, adopts one kettle way to prepare the method for polysubstituted tetrahydropyridine.
Its specific embodiment is as follows: be to be catalyzer with the concentrated hydrochloric acid, make solvent with ethanol, make aromatic aldehyde, active methylene base class material, aromatic amine with 1: 1: 1～1: 2: 1 mol ratio, 55～60 ℃ of following stirring reactions 19～23 hours; After reaction finishes, use ethyl acetate extraction, separatory boils off behind the solvent with ethanol-DMF recrystallization, must polysubstituted tetrahydropyridine.
Described aromatic aldehyde is a phenyl aldehyde, the 4-tolyl aldehyde; 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde; 2-chlorobenzaldehyde, 3-chlorobenzaldehyde, 4-chlorobenzaldehyde, 2,4 dichloro benzene formaldehyde, 2-methoxybenzaldehyde, 4-methoxybenzaldehyde, 3,4-dimethoxy benzaldehyde.
Described active methylene base class material is ethyl ethylacetoacetate or ethyl allylacetylacetate.
Described aromatic amine is aniline, 4-monomethylaniline 4-chloroaniline or 4-bromaniline.
The concentration of described concentrated hydrochloric acid is 10～12mol/L, and the molar weight of concentrated hydrochloric acid is 5～10% of an aromatic aldehyde.
Its building-up process is shown below:
Wherein, R
1=H, 4-CH
3, 2-NO
2, 3-NO
2, 4-NO
2, 2-Cl, 3-Cl, 4-Cl, 2,4-DiCl, 2-OCH
3, 4-OCH
3, 3,4-DiOCH
3R
2=CH
2CH
3, CH
2CH=CH
2R
3=H, 4-CH
3, 4-Cl, 4-Br.
The present invention compared with prior art has the following advantages:
1, make solvent with green ethanol, adopting the hydrochloric acid of non-toxic inexpensive is catalyzer, utilizes aromatic aldehyde, active methylene base class material, aromatic amine to be raw material, adopts one kettle way to obtain a series of single products: polysubstituted tetrahydropyridine, productive rate height: can reach more than 80%; The quality product height: purity is more than 99%.
2, do not use other to the disadvantageous organic solvent of environment in the reaction, reduced the pollution of solvent and catalyzer, realized environment amenable chemosynthesis environment.
3, adopt the polycomponent one kettle way synthetic, step economy, simple to operate, be applicable to multiple aromatic aldehyde and aromatic amine.
4, of the present invention being reflected under 55～60 ℃ carried out, and the reaction conditions gentleness is easy to operation, is beneficial to suitability for industrialized production.
Embodiment
Embodiment 1,1-(4-chloro-phenyl-)-4-(4-chloroanilino)-2,6-phenylbenzene-1,2,5, the preparation of 6-tetrahydropyridine-3-ethyl-carbonate
In the reaction flask that adds ethanol (2mL) (50mL round-bottomed flask), add phenyl aldehyde (0.212g, 2mmol), methyl aceto acetate (0.260g, 2mmol), and the 4-chloroaniline (0.256g, 2mmol), dripping concentration again is the concentrated hydrochloric acid 0.02mL of 12mol/L, and controlled temperature stirred 23 hours down at 60 ℃; Reaction finishes the back and add ethyl acetate (15mL) and water (5mL) in reaction flask, stir and leave standstill after 10 minutes, separatory is told organic phase, after water uses ethyl acetate (10mL) to extract 3 times again, merge all organic phases, carry out recrystallization (3 times) with ethanol-DMF after boiling off solvent, at last pure product 1-(4-chloro-phenyl-)-4-(4-chloroanilino)-2,6-phenylbenzene-1,2,5,6-tetrahydropyridine-3-ethyl-carbonate.Productive rate is: 80%.
This product is a white solid.
The ir data of product of the present invention is as follows:
IR(υ/cm
-1)：3446，3244，2974，2857，1646，1603，1495，1320，1255，1071，941，803，729，697。
The nuclear magnetic resonance data of product of the present invention is as follows:
1H?NMR(400MHz，CDCl
3)：δ＝10.25(s，1H)，7.32-6.99(m，14H)，6.43(t，J＝9.6Hz，3H)，6.18(d，J＝8.0Hz，2H)，5.12(s，1H)，4.50-4.32(m，2H)，2.87-2.68(m，2H)，1.48(t，J＝8.0Hz，3H)；
13C?NMR(100MHz，CDCl
3)：δ＝168.10，155.32，145.48，143.21，142.23，136.38，131.31，128.93，128.70，128.70，128.30，127.38，126.96，126.47，126.47，126.24，121.20，113.98，98.68，59.85，58.25，55.23，33.42，14.73。
1 H at proton nmr spectra chemical shift 10.25 places is a H on the NH on the anilino, 7.32-6.99 be 14 hydrogen on the phenyl ring, 6.43 3 H that locate and 2 H at 6.18 places are four hydrogen on the phenyl ring and 1 hydrogen on methyne, 5.12 1 H that locates is 1 hydrogen on the another one methyne, 4.50-4.32 2 H are 2 hydrogen on the methylene radical on the pyridine ring, 2.87-2.68 2 H on the methylene radical of locating that 2 H are with ester group links to each other, three H at 1.48 places are 3 H of methyl on the ester group end.The 24 class carbon atoms of this product structure all occur in the carbon spectrum.
The results of elemental analyses of this product is as follows:
Anal.Calcd.for?C
32H
28Cl
2N
2O
2：C，70.72；H，5.19；N，5.15；Found：C，71.12；H，5.22；N，5.18％。
The structural formula of this product is as follows:
Embodiment 2,1-phenyl-4-anilino-2,6-two (3, the 4-Dimethoxyphenyl)-1,2,5, the preparation of 6-tetrahydropyridine-3-carbonic acid allyl ester
In the reaction flask that adds ethanol (2mL) (50mL round-bottomed flask), add 3,4-dimethoxy benzaldehyde (0.332g, 2mmol), and acetoacetic acid allyl ester (0.284g, 2mmol), aniline (0.186g, 2mmol), dripping concentration again is the concentrated hydrochloric acid 0.02mL of 12mol/L, and controlled temperature stirred 19 hours down at 60 ℃; Reaction finishes the back and add ethyl acetate (15mL) and water (5mL) in reaction flask, stirs and leaves standstill separatory after 10 minutes, tell organic phase, water merges all organic phases after using ethyl acetate (10mL) extraction 3 times again, carries out recrystallization (3 times) with ethanol-DMF after boiling off solvent, at last pure product 1-phenyl-4-anilino-2,6-two (3, the 4-Dimethoxyphenyl)-1,2,5,6-tetrahydropyridine-3-carbonic acid allyl ester.Productive rate is: 87%.
This product is a white solid.
The ir data of product of the present invention is as follows:
IR(υ/cm
-1)：3429，3251，2933，2835，1659，1592，1502，1132，1028，765。
The nuclear magnetic resonance data of product of the present invention is as follows:
1H?NMR(400MHz，CDCl
3)：δ＝10.31(s，1H)，7.16-7.06(m，4H)，6.99(s，1H)，6.78-6.39(m，12H)，6.16-6.07(m，1H)，5.49-5.30(m，2H)，5.07(s，1H)，4.92-4.73(m，2H)，3.87(s，3H)，3.84(s，3H)，3.80(s，3H)，3.72(s，3H)，2.98-2.77(m，2H)；
13C?NMR(100MHz，CDCl
3)：δ＝167.65，157.04，149.03，148.88，147.94，147.44，146.94，137.77，136.24，134.96，133.06，128.81，128.78，125.94，125.83，118.56，118.44，117.96，116.21，113.01，111.13，110.40，110.04，109.15，97.40，64.37，57.75，55.91，55.79，55.72，55.68，54.93，33.74。
1 H at proton nmr spectra chemical shift 10.31 places is a H on the NH on the anilino, 7.16-7.06 be 4 hydrogen on the phenyl ring, 6.99 1 H that locates is 1 hydrogen on the methyne, 6.78-6.39 locate to be other 12 hydrogen on the phenyl ring, 6.16-6.07 1 H that locates is 1 hydrogen on the another one methyne, 5.49-5.30 2 H are 2 H of methylene radical on the pyridine ring, 5.07 1 H that locates is 1 H on two keys, 4.92-4.73 be 2 H of two key ends, 3.87,3.84,3.80,3.72 locate altogether 12 H and be on the phenyl ring 12 H on four methoxyl groups, 2 H on the methylene radical that 2 H are with ester group links to each other at 2.98-2.77 place.The 33 class carbon atoms of this product structure all occur in the carbon spectrum.
The results of elemental analyses of this product is as follows:
Anal.Calcd.for?C
37H
38N
2O
6：C，73.25；H，6.31；N，4.62.Found：C，73.65；H，6.34；N，4.65％。
The structural formula of this product is as follows:
Embodiment 3,1-(4-chloro-phenyl-)-4-(4-chloroanilino)-2,6-two (2-p-methoxy-phenyl)-1,2,5, the preparation of 6-tetrahydropyridine-3-allyl carbonate
In the reaction flask that adds ethanol (2mL) (50mL round-bottomed flask), add 2-methoxybenzaldehyde (0.272g, 2mmol), acetoacetic acid allyl ester (0.284g, 2mmol), and the 4-chloroaniline (0.256g, 2mmol), dripping concentration again is the concentrated hydrochloric acid 0.02mL of 12mol/L, and controlled temperature stirred 19 hours down at 60 ℃; Reaction finishes the back and add ethyl acetate (15mL) and water (5mL) in reaction flask, stir and leave standstill after 10 minutes, separatory is told organic phase, after water uses ethyl acetate (10mL) to extract 3 times again, merge all organic phases, carry out recrystallization (3 times) with ethanol-DMF after boiling off solvent, at last pure product 1-(4-chloro-phenyl-)-4-(4-chloroanilino)-2,6-two (2-p-methoxy-phenyl)-1,2,5,6-tetrahydropyridine-3-allyl carbonate.Productive rate is: 80%.
This product is a white solid.
The ir data of product of the present invention is as follows:
IR(υ/cm
-1)：3448，3250，2935，2836，1662，1594，1491，1462，1374，1241，1096，1029，752。
The nuclear magnetic resonance data of product of the present invention is as follows:
1H?NMR(400MHz，CDCl
3)：δ＝9.72(s，1H)，7.30-6.82(m，12H)，6.46(s，1H)，6.38-6.19(m，4H)，6.17-6.10(m，1H)，5.51-5.42(m，2H)，5.34-5.31(m，1H)，4.93-4.78(m，2H)，3.84(s，3H)，3.70(s，3H)，2.98-2.84(m，2H)；
13C?NMR(100MHz，CDCl
3)：δ＝168.18，157.36，156.14，156.00，154.49，145.33，137.08，133.24，130.70，129.70，129.41，128.87，128.61，128.37，127.98，127.83，127.11，120.77，120.69，119.62，117.09，113.70，111.11，109.91，98.33，64.31，55.19，54.94，53.26，53.22，29.16。
1 H at proton nmr spectra chemical shift 9.72 places is a H on the NH on the anilino, 7.30-6.82 be 12 hydrogen on the phenyl ring, 6.46 1 H that locates is 1 hydrogen on the methyne, 6.38-6.19 4 H that locate are 4 other on phenyl ring H, 6.17-6.10 locate to be 1 H on the another one methyne, 5.51-5.42 2 H that locate are 2 H of methylene radical on the pyridine ring, 5.34-5.31 locating is a H on two keys, 4.93-4.78 locate to be 2 H on two keys, 3.84,3.70 locating is 6 H on two methoxyl groups on the phenyl ring, 2 hydrogen on the methylene radical that 2.98-2.84 is with ester group links to each other.The 31 class carbon atoms of this product structure all occur in the carbon spectrum.
The results of elemental analyses of this product is as follows:
Anal.Calcd.for?C
35H
32Cl
2N
2O
4：C，68.29；H，5.24；N，4.55.Found：C，68.69；H，5.28；N，4.59％。
The structural formula of this product is as follows:
Embodiment 4,1-(4-bromophenyl)-4-(4-bromobenzene amido)-2,6-two (4-p-methoxy-phenyl)-1,2,5, the preparation of 6-tetrahydropyridine-3-ethyl-carbonate
In the reaction flask that adds ethanol (2mL) (50mL round-bottomed flask), add 4-methoxybenzaldehyde (0.0.272g, 2mmol), methyl aceto acetate (0.260g, 2mmol), and the 4-bromaniline (0.344g, 2mmol), dripping concentration again is the concentrated hydrochloric acid 0.02mL of 12mol/L, and controlled temperature stirred 23 hours down at 60 ℃; Reaction finishes the back and add ethyl acetate (15mL) and water (5mL) in reaction flask, stir and leave standstill after 10 minutes, separatory is told organic phase, after water uses ethyl acetate (10mL) to extract 3 times again, merge all organic phases, carry out recrystallization (3 times) with ethanol-DMF after boiling off solvent, at last pure product 1-(4-bromophenyl)-4-(4-bromobenzene amido)-2,6-two (4-p-methoxy-phenyl)-1,2,5,6-tetrahydropyridine-3-ethyl-carbonate.Productive rate is: 88%.
This product is a white solid.
The ir data of product of the present invention is as follows:
IR(υ/cm
-1)：3445，3245，2976，2835，1648，1605，1504，1319，1250，1178，1068，1034，809。
The nuclear magnetic resonance data of product of the present invention is as follows:
1H?NMR(400MHz，CDCl
3)：δ＝10.24(s，1H)，7.26-7.03(m，8H)，6.40-6.38(m，2H)，6.28(s，1H)，6.21-6.18(m，6H)，5.02(s，1H)，4.47-4.30(m，2H)，3.80(s，3H)，3.78(s，3H)，2.86-2.67(m，2H)，1.46(t，J＝6.8Hz，3H)；
13C?NMR(100MHz，CDCl
3)：δ＝168.12，158.90，158.22，155.28，145.95，137.04，135.06，133.94，131.97，131.53，127.53，127.34，127.13，118.96，114.62，114.12，113.69，108.31，99.02，60.82，59.87，57.54，55.26，54.65，33.56，14.76。
1 H at proton nmr spectra chemical shift 10.24 places is a H on the NH on the anilino, 7.26-7.03 be 8 hydrogen on the phenyl ring, 6.40-6.38 2 and 6 H at 6.21-6.18 place be 8 other on phenyl ring H, 6.28 locating is 1 hydrogen on the methyne, 5.02 1 H that locates is 1 hydrogen on the another one methyne, 4.47-4.30 2 H are 2 H of methylene radical on the pyridine ring, 3.80,3.78 6 H that locate are 6 hydrogen on two methoxyl groups on the phenyl ring, 2.86-2.67 2 H on the methylene radical of locating that 2 H are with ester group links to each other, three H at 1.46 places are 3 H of methyl on the ester group end.The 26 class carbon atoms of this product structure all occur in the carbon spectrum.
The results of elemental analyses of this product is as follows:
Anal.Calcd.for?C
34H
32Br
2N
2O
4：C，58.97；H，4.66；N，4.05.Found：C，59.38；H，4.70；N，4.10％。
The structural formula of this product is as follows:
Embodiment 5,1-(4-aminomethyl phenyl)-4-(4-toluidine)-2,6-two (4-aminomethyl phenyl)-1,2,5, the preparation of 6-tetrahydropyridine-3-carbonic acid allyl ester
In the reaction flask that adds ethanol (2mL) (50mL round-bottomed flask), add 4-tolyl aldehyde (0.280g, 2mmol), acetoacetic acid allyl ester (0.284g, 2mmol), and the 4-monomethylaniline (0.214g, 2mmol), dripping concentration again is the concentrated hydrochloric acid 0.02mL of 12mol/L, and controlled temperature stirred 22 hours down at 60 ℃; Reaction finishes the back and add ethyl acetate (15mL) and water (5mL) in reaction flask, stir and leave standstill after 10 minutes, separatory is told organic phase, after water uses ethyl acetate (10mL) to extract 3 times again, merge all organic phases, carry out recrystallization (3 times) with ethanol-DMF after boiling off solvent, at last pure product 1-(4-aminomethyl phenyl)-4-(4-toluidine)-2,6-two (4-aminomethyl phenyl)-1,2,5, the preparation of 6-tetrahydropyridine-3-carbonic acid allyl ester.Productive rate is: 81%.
This product is a white solid.
The ir data of product of the present invention is as follows:
IR?(υ/cm
-1)：3448，3239，3024，2868，1642，1592，1323，1256，1177，800，492。
The nuclear magnetic resonance data of product of the present invention is as follows:
1H?NMR(400MHz，CDCl
3)：δ＝10.19(s，1H)，7.26-6.88(m，12H)，6.44-6.17(m，5H)，6.15-6.06(m，2H)，5.48-5.29(m，1H)，4.88(s，1H)，4.85-4.79(m，2H)，2.85-2.72(m，2H)，2.33(s，3H)，2.26(s，3H)，2.23(s，3H)，2.15(s，3H)；
13C?NMR(100MHz，CDCl
3)：δ＝167.79，156.97，144.90，141.28，139.85，136.47，135.64，135.51，135.19，133.18，129.39，129.35，129.20，128.87，126.58，126.33，125.94，124.84，117.44，112.80，97.39，64.21，57.83，54.91，33.61，21.09，20.99，20.86，20.11。
1 H at proton nmr spectra chemical shift 10.19 places is a H on the NH on the anilino, 7.26-6.88 be 12 hydrogen on the phenyl ring, 6.44-6.17 5 H that locate are four hydrogen on the phenyl ring and 1 hydrogen on methyne, 6.15-6.06 2 H that locate are 2 H of methylene radical on the pyridine ring, 5.48-5.29 a H who locates is 1 hydrogen on the another one methyne, 4.88 1 H that locates is a H on two keys, 4.85-4.79 locate 2 H into two key ends, 2.85-2.72 locate be with methylene radical that ester group links to each other on 2 hydrogen, 2.33,2.26,2.23 and 12 H at 2.15 places are 12 H on four methyl on the phenyl ring.The 29 class carbon atoms of this product structure all occur in the carbon spectrum.
The results of elemental analyses of this product is as follows:
Anal.Calcd.for?C
37H
38N
2O
2：C，81.88；H，7.06；N，5.16.Found：C，82.27；H，7.11；N，5.18％。
The structural formula of this product is as follows:
Claims (5)
1. the preparation method of a polysubstituted tetrahydropyridine was to be catalyzer with the concentrated hydrochloric acid, makes solvent with ethanol, makes aromatic aldehyde, active methylene base class material, aromatic amine with 1: 1: 1～1: 2: 1 mol ratio, 55～60 ℃ of following stirring reactions 19～23 hours; After reaction finishes, use ethyl acetate extraction, separatory boils off behind the solvent with ethanol-DMF recrystallization, must polysubstituted tetrahydropyridine.
2. the preparation method of polysubstituted tetrahydropyridine according to claim 1, it is characterized in that: described aromatic aldehyde is a phenyl aldehyde, the 4-tolyl aldehyde; 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde; 2-dichlorobenzaldehyde, 3-dichlorobenzaldehyde, 4 dichlorobenzaldehydes, 2,4 dichloro benzene formaldehyde, 2-dimethoxy benzaldehyde, 4-dimethoxy benzaldehyde, 3,4-dimethoxy benzaldehyde.
3. the preparation method of polysubstituted tetrahydropyridine according to claim 1, it is characterized in that: described active methylene base class material is ethyl ethylacetoacetate or ethyl allylacetylacetate.
4. the preparation method of polysubstituted tetrahydropyridine according to claim 1, it is characterized in that: described aromatic amine is aniline, 4-monomethylaniline 4-chloroaniline or 4-bromaniline.
5. the preparation method of polysubstituted tetrahydropyridine according to claim 1, it is characterized in that: the concentration of described concentrated hydrochloric acid is 10～12mol/L, the molar weight of concentrated hydrochloric acid is 5～10% of an aromatic aldehyde.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102690227A (en) * | 2012-05-30 | 2012-09-26 | 浙江大学 | Optical active tetrahydropyridine derivative and preparation method thereof |
| CN104926713A (en) * | 2015-05-24 | 2015-09-23 | 西北大学 | Synthetic method of polysubstitution 1,2,5,6-tetrahydropyridine compound |
| CN115073359A (en) * | 2022-05-26 | 2022-09-20 | 上海大学 | Preparation method of polysubstituted-1, 4,5, 6-tetrahydro-3-pyridinecarboxylic acid ethyl ester |
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| 《The Journal of Organic Chemistry》 20081008 Abu T. Khan et al Effects of Substituents in the beta-Position of 1,3-Dicarbonyl Compounds in Bromodimethylsulfonium Bromide-Catalyzed Multicomponent Reactions: A Facile Access to Functionalized Piperidines 8398-8402 第73卷, 第21期 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102690227A (en) * | 2012-05-30 | 2012-09-26 | 浙江大学 | Optical active tetrahydropyridine derivative and preparation method thereof |
| CN104926713A (en) * | 2015-05-24 | 2015-09-23 | 西北大学 | Synthetic method of polysubstitution 1,2,5,6-tetrahydropyridine compound |
| CN115073359A (en) * | 2022-05-26 | 2022-09-20 | 上海大学 | Preparation method of polysubstituted-1, 4,5, 6-tetrahydro-3-pyridinecarboxylic acid ethyl ester |
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