CN103848839A - Synthesis method of pyran[2,3-b]pyridine derivatives - Google Patents
Synthesis method of pyran[2,3-b]pyridine derivatives Download PDFInfo
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- CN103848839A CN103848839A CN201210509957.XA CN201210509957A CN103848839A CN 103848839 A CN103848839 A CN 103848839A CN 201210509957 A CN201210509957 A CN 201210509957A CN 103848839 A CN103848839 A CN 103848839A
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- pyridine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/04—Ortho-condensed systems
- C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
- C07D491/052—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being six-membered
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Abstract
The invention relates to the synthesis of pyran[2,3-b]pyridine derivatives, and specifically relates to the synthesis of 2-amino-4-phenyl-5-oxo-5,8-dihydroxyl-4-H-pyran[2,3-b]-3-nitrile, which is prepared by taking aldehyde, 2,4-dihydroxylpyridine, and malononitrile as the raw materials, and then subjecting the three components to an one-step reaction. The synthesis method has the advantages of simple synthesis technology route and mild reaction conditions, and the total yield of the synthesis method can reach 70% or more.
Description
Technical field
The invention belongs to technical field of organic synthesis, relate to 2-amino-4-phenyl-5-oxo-5,8-dihydroxyl-4-H-pyrans is the synthetic method of [2,3-b] pyridine-3-nitrile also.
Background technology
Pyrans also [2,3-b] pyridine is that a class has important physiology and the heterogeneous ring compound of pharmacologically active.There is antimicrobial, anti-inflammatory, antibacterial isoreactivity.Therefore pyrans pyridine derivatives are the focuses that chemist and pharmaceutical science worker pay close attention to always.There is bibliographical information to synthesize and have 1 take 2-methoxypyridine as raw material, the pyrans of 4-naphthaquinone also [2,3-b] pyridine derivatives (H.J.Finlay et al./Bioorg.Med.Chem.Lett.18 (2008) 2714-2718), or with 6-(the chloro-phenyl of 2-)-5-(the chloro-phenyl of 4-)-2-oxygen-1,2-dihydropyridine-3-nitrile is raw material, THF is solvent, and room temperature is synthesized this compounds (C.B.Madsen-Duggan et al./Bioorg.Med.Chem.Lett.20 (2010) 3750-3754).Above-mentioned synthetic method is used special reaction unit, reaction process complexity.And in dehydrated alcohol by aldehyde, 2,4-dihydroxy-pyridine and propane dinitrile and derivative thereof are raw material, take ammonium acetate as catalyzer one-step synthesis 2-amino-4-phenyl-5-oxo-5, the 8-dihydroxyl-4-H-pyrans also method of [2,3-b] pyridine-3-carbonitrile derivatives have not been reported.
Summary of the invention
The object of the present invention is to provide a kind of synthetic 2-amino-4-phenyl-5-oxo-5,8-dihydroxyl-4-H-pyrans is the method for [2,3-b] pyridine-3-nitrile also: aldehyde, 2,4-dihydroxy-pyridine and propane dinitrile and derivative thereof are raw material, NH
4oAc is catalyzer, within 1: 1: 1 in molar ratio, in dehydrated alcohol, generates (as shown in Figure 1) through three component one kettle way one steps.The present invention take dehydrated alcohol as solvent, provides a kind of applied range in building-up process, and productive rate is high, and the simple synthetic method of aftertreatment.
The present invention realizes by following method: the aldehyde that adds 1 mmole in 5 milliliters of dehydrated alcohols, 2 of 1 mmole, propane dinitrile and the derivative thereof of 4-dihydroxy-pyridine and 1 mmole react 10-40 minute under reflux state, obtain also [2,3-b] pyridine derivatives of corresponding pyrans.
Described aldehyde is aromatic aldehyde, alkanoic or heterocyclic aldehydes.
Embodiment
Below in conjunction with accompanying drawing 1 and embodiment, the invention will be further described.
Embodiment 1:
2-amino-4-(2-chloro-phenyl-)-5-oxo-5, 8-dihydroxyl-4-H-pyrans also [2, 3-b] preparation of pyridine-3-nitrile: the 2-chlorobenzaldehyde (0.14g) that adds 1 mmole in 5 milliliters of dehydrated alcohols, 2 of 1 mmole, the propane dinitrile (0.066g) of 4-dihydroxy-pyridine (0.11g) and 1 mmole, under reflux state, react 30min, TLC tracking monitor, after reaction finishes, directly cooling, obtain corresponding product 2-amino-4-phenyl-5-oxo-5, 8-dihydroxyl-4-H-pyrans also [2, 3-b] pyridine-3-nitrile (0.23g, productive rate 82%).This product is white powder, mp:276-278 ℃.
Embodiment 2:
2-amino-4-(3-chloro-phenyl-)-5-oxo-5, 8-dihydroxyl-4-H-pyrans also [2, 3-b] preparation of pyridine-3-nitrile: the 3-chlorobenzaldehyde (0.14g) that adds 1 mmole in 5 milliliters of dehydrated alcohols, 2 of 1 mmole, the propane dinitrile (0.066g) of 4-dihydroxy-pyridine (0.11g) and 1 mmole, under reflux state, react 20min, TLC tracking monitor, after reaction finishes, directly cooling, obtain corresponding product 2-amino-4-phenyl-5-oxo-5, 8-dihydroxyl-4-H-pyrans also [2, 3-b] pyridine-3-nitrile (0.22g, productive rate 80%).This product is white powder, mp:254-256 ℃.
Embodiment 3:
2-amino-4-(4-chloro-phenyl-)-5-oxo-5, 8-dihydroxyl-4-H-pyrans also [2, 3-b] preparation of pyridine-3-nitrile: the 4-chlorobenzaldehyde (0.14g) that adds 1 mmole in 5 milliliters of dehydrated alcohols, 2 of 1 mmole, the propane dinitrile (0.066g) of 4-dihydroxy-pyridine (0.11g) and 1 mmole, under reflux state, react 30min, TLC tracking monitor, after reaction finishes, directly cooling, obtain corresponding product 2-amino-4-phenyl-5-oxo-5, 8-dihydroxyl-4-H-pyrans also [2, 3-b] pyridine-3-nitrile (0.24g, productive rate 83%).This product is white powder, mp:263-265 ℃.
The reaction raw materials of embodiment 1-20, reaction conditions and productive rate are in table 1.
Reaction raw materials, reaction conditions and the productive rate of table 1 embodiment 1-20
As shown in Table 1, method raw material of the present invention is easy to get, safety simple to operate, and reaction conditions gentleness, yield are high, and aftertreatment is simple, and ethanol can be reused, and economy is high and environmental pollution is little, thereby has great implementary value and potential economic results in society.
Claims (4)
1. the present invention relates to 2-amino-4-phenyl-5-oxo-5,8-dihydroxyl-4-H-pyrans is synthesizing of [2,3-b] pyridine-3-nitrile also, is with aldehyde, 2, and 4-dihydroxy-pyridine and propane dinitrile and derivative thereof are raw material, generate through three component one kettle way single step reactions.
2. according to pyrans claim (1) Suo Shu also [2,3-b] synthetic method of pyridine derivatives, it is characterized in that synthetic reaction conditions is aldehyde, 2,4-dihydroxy-pyridine and propane dinitrile react in dehydrated alcohol, suitable condition is normal pressure, boiling reflux and reaction 10～40 minutes, the mol ratio of raw material is aldehyde: 2,4-dihydroxy-pyridine: propane dinitrile=1: 1: 1.
3. according to the also synthetic method of [2,3-b] pyridine derivatives of pyrans claim (1) Suo Shu, it is characterized in that described aldehyde is aromatic aldehyde or heterocyclic aldehydes.
4. according to the also synthetic method of [2,3-b] pyridine derivate of pyrans claim (1) Suo Shu, it is characterized in that described active methylene compound is propane dinitrile or cyanoacetate.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105884681A (en) * | 2014-10-24 | 2016-08-24 | 江苏师范大学 | Synthesis method of pyridine derivatives in polyethylene glycol |
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- 2012-12-04 CN CN201210509957.XA patent/CN103848839A/en active Pending
Non-Patent Citations (3)
| Title |
|---|
| 杜百祥等: "离子液体中7-氨基-6-氰基-5-芳基吡啶并[2，3-d]嘧啶-2，4（1H，3H）-二酮衍生物的一步合成", 《徐州师范大学学报（自然科学版）》 * |
| 王香善等: "KF/Al2O3催化下吡啶并[2，3-b]嘧啶衍生物的三组分一步合成", 《有机化学》 * |
| 王香善等: "KF/Al2O3催化下吡喃并[2，3-b]嘧啶衍生物的一步合成", 《有机化学》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105884681A (en) * | 2014-10-24 | 2016-08-24 | 江苏师范大学 | Synthesis method of pyridine derivatives in polyethylene glycol |
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Application publication date: 20140611 |