CN103804283A - Preparation method for 1, 2-dihydropyridine derivative - Google Patents
Preparation method for 1, 2-dihydropyridine derivative Download PDFInfo
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- CN103804283A CN103804283A CN201210439628.2A CN201210439628A CN103804283A CN 103804283 A CN103804283 A CN 103804283A CN 201210439628 A CN201210439628 A CN 201210439628A CN 103804283 A CN103804283 A CN 103804283A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/92—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with a hetero atom directly attached to the ring nitrogen atom
- C07D211/96—Sulfur atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/02—Preparation by ring-closure or hydrogenation
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Abstract
The invention relates to a preparation method for a 1, 2-dihydropyridine derivative, particularly a new method for preparation of the 1, 2-dihydropyridine derivative from a 3-aza-1, 5-eneyne derivative under the promotion (catalysis) of protonic acid through cyclization reaction. The method takes the 3-aza-1, 5-eneyne derivative as the raw material to generate the 1, 2-dihydropyridine derivative under two conditions. According to the condition A, alcohol is adopted as a solvent (also serving as a catalyst), other catalysts or additives are unnecessary, and reaction is carried out at a temperature ranging from room temperature to 140DEG C; or according to the condition B, alcohol, phenol or protonic acid is added into another organic solvent to serve as a catalyst. The yield of 1, 2-dihydropyridine derivative can reach up to 97%.
Description
Technical field
The present invention relates to the preparation 1 that a kind of protonic acid promotes, the method for 2-dihydrogen pyridine derivative, specifically promotes (catalysis) 3-azepine-1 by alcohols, phenols or protonic acid, and 5-eneyne derivative generates the novel method of 1,2-dihydrogen pyridine derivative.
Background technology
Dihydropyridine is one of most important heterocycle, is not only the key structure unit of many natural products, organic materials and medicine, is also structure module very useful in organic synthesis.Because Isosorbide-5-Nitrae-dihydropyridine is as primary structure unit (document 1:(a) Kappe of a lot of medicines, C.O.Eur.J.Med.Chem.2000,35,1043; (b) Rampe, D.; Kane, J.M.Drug Dev.Res.1994,33,344; (c) Triggle, D.J.Cell.Mol.Neurobiol.2003,23,293; (d) Goldmann, S.; Stoltefuss, J.Angew.Chem., Int.Ed.1991,30,1559), thereby this compounds is studied (civilian 2:(a) Lavilla, R.J.Chem.Soc., PerkinsTrans.1.2002,1141 widely; (b) Gaudio, A.C.; Korolskovas, A.; Takahata, Y.J.Pharm.Sci.1994,83,1110).Relative, the research of 1,2-dihydrogen pyridine derivative relatively less (document 3:(a) Stout, D.M.; Meyers, A.I.Chem.Rev.1982,82,233; (b) Comins, D.L.; Hong, H.; Salvador, J.M.J.Org.Chem.1991,56,7197; (c) Ichikawa, E.; Suzuki, M.; Yabu, K.; Albert, M.; Kanai, M.; Shibasaki, M.J.Am.Chem.Soc.2004,126,11808.; (d) Brunner, B.; Stoigaitis, N.; Lautens, M.Org.Lett.2006,8,3473).The most frequently used method of synthesizing dihydro pyridine is the nucleophilic addition(Adn) of nucleophilic reagent to N-ethanoyl or N-Fixanol; the main drawback of these methods is severe reaction conditions; because nucleophilic species can add to the 2-of pyridinium salt; 4-or 6-position and often obtain multiple mixture (document 4:Bull, J.A.; Mousseau, J.J.; Pelletier, G.; Charette, A.B.Chem.Rev.2012,112,2642).Thereby the novel method of development synthetic 1,2-dihydropyridine of efficient green under mild conditions has great significance.Along with being on the increase of the substituting group pattern of this compounds, their physiologically active is studied, thereby more may to this compounds as drug provision.We have developed one and have not used metal catalyst, only promote synthetic 1, the 2-dihydrogen pyridine derivative novel method of (catalysis) with alcohols, phenols or protonic acid.Reaction conditions is simple, and yield is high, has very strong practicality.
Summary of the invention
The object of the present invention is to provide a kind of novel method of synthetic 1,2-dihydrogen pyridine derivative.
The present invention realizes by following measure:
(1) reference literature, synthesizes N-sulphonyl-allylamine through two steps: the first step, aromatic aldehyde and sulphonamide react and generate imines (document 5:Love, B.E. in ethyl orthosilicate; Raje, P.S.; Williams II, T.C.Synlett 1994,493.) (following formula 1, reaction equation 1); In the time that aldehyde is alkanoic, aldehyde, sulphonamide and SPTS are dissolved in formic acid and water and are reacted, obtain aliphatics imines (document 6:Chemla, F.; Hebbe, V.; Normant, J.F.Synthesis 2000,75.) (following formula, reaction equation 2).Second step, is added drop-wise to the tetrahydrofuran solution of alkynyl lithium at low temperatures reaction in the tetrahydrofuran solution of imines and obtains allyl amine solid (document 7:Katritzky, A.R.; Li, J.Q.; Gordeev, M.F.Synthesis 1994,93.) (following formula reaction equation 3).
Reaction equation 1
Reaction equation 2
Reaction equation 3
Reaction equation 4
Formula 1.3-azepine-1, the synthesis step of 5-eneyne derivative
(2) prepare class 3-azepine-1,5-eneyne.
Concrete operation step following (above formula 1, reaction equation 4):
In reactor, react, reactor vacuumizes after rear logical argon replaces three times, adds the new CH steaming of 40ml
2cl
2, then add N-sulphonyl-allylamine (III) of 5mmol and the alkynes (IV) of 5.5mmol, finally add the Cs of 5-20mol%
2cO
3, 0 ° of C-stirring at room temperature 4-24 hour; After reaction finishes, revolve that to evaporate partial solvent be the 1/4-1/5 that does not evaporate front liquor capacity to liquor capacity, loading is carried out silica gel column chromatography, and eluent is the mixed solvent of sherwood oil: ethyl acetate=10:1-5:1, obtain 3-azepine-1 of formula (I), 5-eneyne.
(3), by 3-azepine-1,5-eneyne derivative is prepared 1,2-dihydrogen pyridine derivative
Formula 2.1,2-dihydrogen pyridine derivative synthetic
Reaction equation is shown in formula 2, in reactor, reacts, and reactor vacuumizes rear logical argon replaces three times.
Method A: add 3-azepine-1 of 0.2mmol, 5-eneyne (I), then adds 1-4mL alcohols, reaction under ° C of room temperature-140 is until raw material disappearance.After reaction finishes, revolve and evaporate after solvent, solid carries out silica gel column chromatography, obtains 1,2-dihydrogen pyridine derivative (II).
Method B: add 3-azepine-1 of 0.2mmol, 5-eneyne (I), then adds 0.5-5ml organic solvent, finally adds alcohol, phenol or the protonic acid of 5-95mol% to make catalyzer.Reaction under ° C of room temperature-140 is until raw material disappearance.After reaction finishes, revolve and evaporate after solvent, solid carries out silica gel column chromatography, obtains 1,2-dihydrogen pyridine derivative (II).
The present invention has following advantage:
1. reactant 3-azepine-1,5-eneyne is obtained through simple reaction step by raw material aldehyde, sulphonamide and Terminal Acetylenes cheap and easy to get and interior alkynes.
Generate 1, the operation of 2-dihydropyridine is simple; Do not use metal catalyst, environmental friendliness; Atom in reactant all appears in product, atom economy.
Embodiment
In order to understand better the present invention, describe by following instance.
Embodiment 1
Step 1 (raw materials Ia):
In reactor, react, reactor vacuumizes after rear logical argon replaces three times, adds N-alkylsulfonyl-allylamine IIIa of 5mmol, adds the new CH steaming of 40mL
2cl
2, then add the alkynes IVa of 5.5mmol, finally add the Cs of 10mol%
2cO
3, stirring reaction 12 hours under 0 ° of C.After reaction finishes, revolve that to evaporate partial solvent to liquor capacity be not evaporate 1/5th of front liquor capacity, loading is carried out silica gel column chromatography, and eluent is the mixed solvent of sherwood oil: ethyl acetate=10:1, obtains 3-azepine-1,5-eneyne Ia.
The characterization data of Ia is as follows:
1H?NMR(400MHz,CDCl
3)δ7.92(d,J=8.3Hz,2H),7.64(d,J=7.7Hz,2H),7.40–7.27(m,8H),7.16(dd,J=8.1,1.4Hz,2H),6.54(s,1H),6.10(s,1H),3.76(s,3H),3.60(s,3H),2.31(s,3H);
13C?NMR(100MHz,CDCl
3)δ164.9,164.2,144.9,139.7,135.3,133.9,131.7,129.8,129.1,128.8,128.7,128.5,128.4,128.0,121.7,117.4,89.7,82.8,55.0,53.0,52.0,21.7;
HRMS?Calculated?for?C
28H
25NO
6NaS[M+Na]
+526.1300,found?526.1300。
Step 2 (preparation 1,2-dihydropyridine IIa):
In reactor, react, reactor vacuumizes rear logical argon replaces, adds 0.2mmol (100.7 mg) 3-azepine-1, and 5-eneyne Ia, then adds 2mL methyl alcohol, at lower 60 ℃ of argon shield, reacts 2 days.Take out after solvent with Rotary Evaporators, solid is dissolved in methylene dichloride loading and carries out silica gel column chromatography, with the eluent flushing pillar of sherwood oil: ethyl acetate=10:1, obtains 1 of 95.3mg, 2-dihydropyridine IIa, and separation yield is 95%.
The preparation IIa of amplification quantity: add 3.0mmol (1.5108g) Ia in 100mL reaction flask, then add 50mL methyl alcohol, (uncovered reaction) reaction 2 days under the atmosphere of air.Reaction finishes rear room temperature placement spends the night, and separates out solid 1.0374g.Solution with revolve steam be spin-dried for after, ethyl acetate for solid (3mL) and sherwood oil (15mL) recrystallization, obtain solid 0.3247g.Product total mass 1.3621g, separation yield 90%.
The sign number of IIa is as follows:
1H?NMR(400MHz,CDCl
3)δ7.80(d，J=8.1Hz,2H),7.47(d，J=7.4Hz,2H),7.34(m,5H),7.24(m,3H),6.80(d,J=7.1Hz,2H),5.86(d,J=6.2Hz,1H),5.67(d,J=6.2Hz,1H),3.80(s,3H),3.49(s,3H),2.42(s,3H)；
13C?NMR(100MHz,CDCl
3)δ165.6，164.3,144.8,137.0,136.6,135.8,135.1,130.9,129.9,128.8,128.6,128.2,128.1,128.0,127.9,127.8,127.2,127.1,56.6,53.1,52.5,21.7；
HR?S?Calculated?for?C
28H
25NO
6NaS[M+Na]
+526.1300,found?526.1308。
Embodiment 2
In reactor, react, reactor vacuumizes rear logical argon replaces, adds 0.2mmol (100.7mg) 3-azepine-1,5-eneyne Ia, 1mL THF, then adds the Hydroquinone (Resorcinol of 0.02mmol, 10mol%), react 2 days at 60 ℃.Take out after solvent with Rotary Evaporators, solid is dissolved in methylene dichloride loading and carries out silica gel column chromatography, with the eluent flushing pillar of sherwood oil: ethyl acetate=10:1, obtains 1 of 95.7mg, 2-dihydropyridine IIa, and separation yield is 95%.
Embodiment 3
In reactor, react, reactor vacuumizes rear logical argon replaces, adds 0.2mmol (104.3mg) 3-azepine-1, and 5-eneyne Ib, then adds 2mL methyl alcohol, at lower 60 ℃ of argon shield, reacts 2 days.Take out after solvent with Rotary Evaporators, solid is dissolved in methylene dichloride loading and carries out silica gel column chromatography, with the eluent flushing pillar of sherwood oil: ethyl acetate=10:1, obtains 1 of 91.9mg, 2-dihydropyridine IIb, and separation yield is 88%.
The characterization data of Ib is as follows:
1H?NMR(400MHz,CDCl
3)δ7.91(d,J=7.8Hz,2H),7.63(m,2H),7.32(m,5H),7.15(d,J=7.4Hz,2H),7.06(t,J=8.2Hz,2H),6.50(s,1H),6.12(s,1H),3.77(s,3H),3.63(s,3H),2.32(s,3H);
13C?NMR(100MHz,CDCl
3)δ164.8,164.2,162.9(d,J=244.7Hz),145.0,139.5,135.2,131.7,130.0,129.9,129.8,129.2,128.5,128.4,121.5,118.1,115.7(d,J=21.9Hz),89.8,82.7,54.4,53.1,52.2,21.7;
HRMS?Calculated?for?C
28H
24NO
6FNaS[M+Na]
+544.1206,found?544.1205.
The characterization data of IIb is as follows:
1H?NMR(500MHz,CDCl
3)δ7.79(d,J=8.3Hz,2H),7.44(m,2H),7.32(d,J=8.0Hz,2H),7.24(m,3H),7.05(m,2H),6.80(m,2H),5.82(d,J=6.2Hz,1H),5.64(d,J=6.2Hz,1H),3.81(s,3H),3.50(s,3H),2.43(s,3H);
13C?NMR(125MHz,CDCl
3)δ165.5,164.2,163.0(d,J=247.3Hz),144.9,136.5,135.9,135.4,132.8,130.7,130.0,129.1,129.0,128.3,128.1,128.0,127.8,126.6,115.8(d,J=21.6Hz),55.9,53.1,52.5,21.7;
HRMS?Calculated?for?C
28H
24NO
6FNaS[M+Na]
+544.1206,found?544.1210。
Claims (7)
1. prepare the method for 1,2-dihydrogen pyridine derivative for one kind, it is characterized in that:
With 3-azepine-1 shown in following formula, 5-eneyne (I) is that raw material generates 1,2-dihydrogen pyridine derivative (II) by ring-closure reaction, and reaction formula is as follows:
Wherein R
1, R
2, R
3for the phenyl of C1-C8 alkyl, pyridyl, phenyl or replacement, the substituting group on phenyl is C1-C8 alkyl, C1-C8 alkoxyl group, F, Cl, Br, I, NO
2in one or two kinds or three kinds; R
1, R
5for C1-C4 ester group, phenyl, C1-C8 alkyl, alkylsulfonyl, trifluoromethyl, F, Cl, Br or I.
2. it is characterized in that in accordance with the method for claim 1:
In condition A, do the double catalyzer that does of solvent, the triol of the monohydroxy-alcohol that alcoholic solvent is C1-C10, the dibasic alcohol of C2-C10 or C3-C10 with alcohol.
3. it is characterized in that in accordance with the method for claim 1:
In condition B, make catalyzer with alcohols, phenols or protonic acid, make solvent with other organic solvent;
Organic solvent is one or two or more kinds in tetrahydrofuran (THF), DMF, benzene, tetracol phenixin, Isosorbide-5-Nitrae-dioxane, methylene dichloride, ethyl acetate or acetonitrile;
Consumption of organic solvent is every mmole reactant I solvent 1-20 milliliter.
4. it is characterized in that in accordance with the method for claim 3:
In condition B, monohydroxy-alcohol, the dibasic alcohol of C2-C10 or the triol of C3-C10 that the alcohols catalyzer that can use is C1-C10; Protonic acid is the one in the organic acid of C1-C10 or hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid; Phenol is phenol.
5. according to the method described in claim 1 or 2, it is characterized in that:
In condition A, the consumption of alcoholic solvent is every mmole reactant I solvent 5-20 milliliter.
6. according to the method described in claim 1 or 3, it is characterized in that:
In condition B, the consumption of alcohol, phenol or bronsted acid catalyst is the 5-95mol% of reactant I.
7. in accordance with the method for claim 1, it is characterized in that: no matter still use condition B with condition A, temperature of reaction is room temperature-140 ° C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105693593A (en) * | 2014-11-25 | 2016-06-22 | 中国科学院大连化学物理研究所 | Preparation method for 2-aza-dicyclo[3.2.0]-2-hexene derivative |
| CN110981802A (en) * | 2019-12-10 | 2020-04-10 | 广东药科大学 | Method for preparing nitrogen-containing heterocyclic compound |
Citations (2)
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|---|---|---|---|---|
| CN1130505A (en) * | 1994-12-16 | 1996-09-11 | 拜尔公司 | Use of 5-acyl-1,4-dihydropyridines |
| WO2004058148A2 (en) * | 2002-12-20 | 2004-07-15 | Merck & Co., Inc. | Mitotic kinesin inhibitors |
-
2012
- 2012-11-06 CN CN201210439628.2A patent/CN103804283B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1130505A (en) * | 1994-12-16 | 1996-09-11 | 拜尔公司 | Use of 5-acyl-1,4-dihydropyridines |
| WO2004058148A2 (en) * | 2002-12-20 | 2004-07-15 | Merck & Co., Inc. | Mitotic kinesin inhibitors |
Non-Patent Citations (4)
| Title |
|---|
| AKIO SAITO，等: "Synthesis of Pyrroles by Gold(I)-Catalyzed Amino−Claisen Rearrangement of N-Propargyl Enaminone Derivatives", 《ORGANIC LETTERS》 * |
| AKIO SAITO，等: "Synthesis of Pyrroles by Gold(I)-Catalyzed Amino−Claisen Rearrangement of N-Propargyl Enaminone Derivatives", 《ORGANIC LETTERS》, vol. 12, no. 2, 21 December 2009 (2009-12-21), pages 372 - 374 * |
| HAHN KIM，等: "Rhodium-Catalyzed Cycloisomerization of N-Propargyl Enamine Derivatives", 《J. AM. CHEM. SOC.》, vol. 128, 26 April 2006 (2006-04-26), pages 6336 - 6337 * |
| HIDETOMO IMASE，等: "Convergent and Rapid Assembly of Substituted 2-Pyridones through Formation of N-Alkenyl Alkynylamides Followed by Gold-Catalyzed Cycloisomerization", 《ORG. LETT.》, vol. 10, no. 16, 18 July 2008 (2008-07-18), pages 3563 - 3566 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105693593A (en) * | 2014-11-25 | 2016-06-22 | 中国科学院大连化学物理研究所 | Preparation method for 2-aza-dicyclo[3.2.0]-2-hexene derivative |
| CN105693593B (en) * | 2014-11-25 | 2018-06-12 | 中国科学院大连化学物理研究所 | A kind of method for preparing 2- aza-bicyclos [3.2.0] -2- hexene derivatives |
| CN110981802A (en) * | 2019-12-10 | 2020-04-10 | 广东药科大学 | Method for preparing nitrogen-containing heterocyclic compound |
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