CN105037260A - 2-pyridone derivative and preparation method thereof - Google Patents
2-pyridone derivative and preparation method thereof Download PDFInfo
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- CN105037260A CN105037260A CN201510406005.9A CN201510406005A CN105037260A CN 105037260 A CN105037260 A CN 105037260A CN 201510406005 A CN201510406005 A CN 201510406005A CN 105037260 A CN105037260 A CN 105037260A
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- phenyl
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- pyridione derivatives
- aryl
- enamine derivates
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen 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
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/80—Acids; Esters in position 3
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen 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
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/803—Processes of preparation
Abstract
The invention relates to the field of organic synthesis, and discloses a 2-pyridone derivative and a preparation method thereof. According to the invention, the 2-pyridone derivative is directly prepared from an enamine derivative and methylene ethoxy diethyl malonate. During production, no solvent system is used or dimethyl sulfoxide is adopted as a solvent, and no catalyst is needed. The novel 2-pyridone derivative provided by the invention is a usable organic intermediate, and can be converted into various compounds. The 2-pyridone derivative is an important structural unit of various natural products, dyes, medicines and pesticides. The preparation method has the advantages of simple operation and high yield. The method accords with the concept of Green Chemistry, and is suitable for industrialized productions.
Description
Technical field
The present invention relates to organic synthesis field, relate to a kind of 2-Pyridione derivatives, particularly relate to the preparation method of 2-Pyridione derivatives.
Background technology
2-pyridone is the important feature unit of many natural products, dyestuff, medicine, agricultural chemicals.This compounds has important purposes, is used to the industrial circles such as dyestuff, medicine, agricultural chemicals.The existing method preparing 2-pyridone, complicated operation, need that under basic conditions (as NaH or sodium alkylate) carries out, productive rate is low, as: the existing synthesis for 2-pyridone is mainly by acetonitrile derivative and α, beta-unsaturated carbonyl compound carries out Michael addition, then hydrolytic cyclization obtains 3,4-dihydropyridone, oxidation obtains 2-pyridone further.Highly basic such as NaH or sodium alkylate is needed to realize this reaction as auxiliary agent in this course.
In addition, the 2-Pyridione derivatives of existing preparation, position does not obtain group to N.
Summary of the invention
The present invention is directed to existing shortcoming, disclose a kind of 2-Pyridione derivatives, also disclose the preparation method of 2-Pyridione derivatives; Easy to prepare in preparation process, condition is simple, productive rate is high, safe and reliable, pollute little, be applicable to suitability for industrialized production.
In order to solve the problems of the technologies described above, the present invention is solved by following technical proposals.
2-Pyridione derivatives, the compound for following structure shown in formula I formula:
Formula I is
Wherein, R
1for carbon atom number is the alkyl of 3-10 or allyl group or aryl;
R
1for carbon atom number be the alkyl of 3-10 time, alkyl is open chain or ring-type;
R
1one in the phenyl that the phenyl that during for aryl, aryl is phenyl, benzyl, low alkyl group replace, lower alkoxy replace, the phenyl of halogen substiuted, naphthyl; R
1during the phenyl that the phenyl replaced for low alkyl group or lower alkoxy replace, its carbon atom number is 1-3; Aryl is that phenyl or more than one get base.
Novel 2-Pyridione derivatives disclosed by the invention is very useful organic intermediate, can change into multiple compounds.Such 2-Pyridione derivatives is the important feature unit of many natural products, dyestuff, medicine, agricultural chemicals; Be used to the industrial circles such as dyestuff, medicine, agricultural chemicals and have important purposes.
The preparation method of above-mentioned 2-Pyridione derivatives, comprises the following steps, and add amount of substance than the enamine derivates and the methene ethoxy-c diethyl adipate that are 1:1, temperature of reaction controls at 110-150 DEG C, preparation 2-Pyridione derivatives.
The present invention is simple to operate, is directly obtained by enamine derivates and methene ethoxy-c diethyl adipate.Catalyst-free catalysis of the present invention, do not need in production process to use the highly basic such as NaH or sodium alkylate, operational safety, environmental protection, meet " Green Chemistry " theory, have wide prospects for commercial application.
As preferably, add enamine derivates and methene ethoxy-c diethyl adipate, temperature of reaction controls to detect stopped reaction to raw material disappearance at 110-150 DEG C, TLC, obtained 2-Pyridione derivatives.By the progress of TLC detection reaction, when stopped reaction after raw material disappears being detected, the carrying out that effective monitoring is reacted.
As preferably, after adding enamine derivates and methene ethoxy-c diethyl adipate, add methyl-sulphoxide.Use methyl-sulphoxide for solvent in production process or do not use solvent, do not need to use the highly basic such as NaH or sodium alkylate, operational safety, environmental protection, meet " Green Chemistry " theory, have wide prospects for commercial application.
As preferably, stopped reaction after TLC detects and disappears to raw material, uses column chromatography, obtained 2-Pyridione derivatives.When using column chromatography, the sherwood oil of eluent to be volume ratio be 4:1: ethyl acetate.
As preferably, temperature of reaction controls at 130 DEG C.
As preferably, the molecular formula of enamine derivates is
wherein, R
2for carbon atom number is the alkyl of 3-10 or allyl group or aryl;
R
2for carbon atom number be the alkyl of 3-10 time, alkyl is open chain or ring-type;
R
2one in the phenyl that the phenyl that during for aryl, aryl is phenyl, benzyl, low alkyl group replace, lower alkoxy replace, the phenyl of halogen substiuted, naphthyl; R
2during the phenyl that the phenyl replaced for low alkyl group or lower alkoxy replace, its carbon atom number is 1-3; Aryl is that phenyl or more than one get base.
Part particular compound table of the present invention is as shown in the table:
Compared with prior art, beneficial effect of the present invention is:
(1) novel 2-Pyridione derivatives disclosed by the invention is very useful organic intermediate, can change into multiple compounds.Such 2-Pyridione derivatives is the important feature unit of many natural products, dyestuff, medicine, agricultural chemicals; Be used to the industrial circles such as dyestuff, medicine, agricultural chemicals and have important purposes.
(2) the invention discloses a kind of new 2-Pyridione derivatives, N position is provided with and replaces group.
(3) the present invention's whole production technique stable operation, yield are higher, are applicable to suitability for industrialized production.
(4) catalyst-free catalysis of the present invention, need not use in production process and need the highly basic such as NaH or sodium alkylate, operational safety, environmental protection, economy, efficient, nontoxic, meets " Green Chemistry " theory, has wide prospects for commercial application.
(5) the present invention is simple to operate, is directly obtained by enamine derivates and methene ethoxy-c diethyl adipate, uses methyl-sulphoxide for solvent, or do not use solvent, effectively raise yield in production process.
Embodiment
Embodiment 1
The preparation method of 2-Pyridione derivatives, comprise the following steps: add amount of substance than the enamine derivates (namely Compound numbers is the enamine derivates of 1) and the methene ethoxy-c diethyl adipate that are 1:1, temperature of reaction controls at 110 DEG C, obtain pale solid (namely Compound numbers is the 2-Pyridione derivatives of 31), productive rate is 69%.
Embodiment 2
The preparation method of 2-Pyridione derivatives, comprise the following steps: add amount of substance than the enamine derivates (namely Compound numbers is the enamine derivates of 2) and the methene ethoxy-c diethyl adipate that are 1:1, temperature of reaction controls at 150 DEG C, stopped reaction after TLC detects and disappears to raw material, obtain pale solid (namely Compound numbers is the 2-Pyridione derivatives of 32), productive rate is 63%.
Embodiment 3
The preparation method of 2-Pyridione derivatives, comprise the following steps: add amount of substance than the enamine derivates (namely Compound numbers is the enamine derivates of 2) and the methene ethoxy-c diethyl adipate that are 1:1, after adding enamine derivates and methene ethoxy-c diethyl adipate, add methyl-sulphoxide.Temperature of reaction controls at 130 DEG C, and stopped reaction after TLC detects and disappears to raw material, obtain pale solid (namely Compound numbers is the 2-Pyridione derivatives of 32), productive rate is 65%.
Embodiment 4
The preparation method of 2-Pyridione derivatives, comprise the following steps: add amount of substance than the enamine derivates (namely Compound numbers is the enamine derivates of 3) and the methene ethoxy-c diethyl adipate that are 1:1, after adding enamine derivates and methene ethoxy-c diethyl adipate, add methyl-sulphoxide.Temperature of reaction controls at 130 DEG C, and stopped reaction after TLC detects and disappears to raw material, use column chromatography, obtain pale solid (namely Compound numbers is the 2-Pyridione derivatives of 33), productive rate is 65%.
Embodiment 5
Take Compound numbers as the enamine derivates of 4 be raw material, operation is as embodiment 4, and obtain white solid 34, productive rate is 68%.
Embodiment 6
Take Compound numbers as the enamine derivates of 5 be raw material, operation is as embodiment 4, and obtain pale solid 35, productive rate is 65%.
Embodiment 7
Take Compound numbers as the enamine derivates of 6 be raw material, operation is as embodiment 4, and obtain pale solid 36, productive rate is 69%.
Embodiment 8
Take Compound numbers as the enamine derivates of 7 be raw material, operation is as embodiment 4, and obtain white solid 37, productive rate is 63%.
Embodiment 9
Take Compound numbers as the enamine derivates of 8 be raw material, operation is as embodiment 2, and obtain white solid 38, productive rate is 65%.
Embodiment 10
Take Compound numbers as the enamine derivates of 9 be raw material, operation is as embodiment 2, and obtain pale solid 39, productive rate is 67%.
Embodiment 11
Take Compound numbers as the enamine derivates of 10 be raw material, operation is as embodiment 2, and obtain white solid 40, productive rate is 69%.
Embodiment 12
Take Compound numbers as the enamine derivates of 11 be raw material, operation is as embodiment 2, and obtain white solid 41, productive rate is 62%.
Embodiment 13
Take Compound numbers as the enamine derivates of 12 be raw material, operation is as embodiment 2, and obtain white solid 42, productive rate is 64%.
Embodiment 14
Take Compound numbers as the enamine derivates of 13 be raw material, operation is as embodiment 2, and obtain white solid 43, productive rate is 65%.
Embodiment 15
Take Compound numbers as the enamine derivates of 14 be raw material, operation is as embodiment 2, and column chromatography for separation (eluent is, sherwood oil: ethyl acetate=4:1), obtain pale solid 44, productive rate is 43%.
Embodiment 16
Take Compound numbers as the enamine derivates of 15 be raw material, operation is as embodiment 2, and obtain pale solid 45, productive rate is 65%.
Embodiment 17
Take Compound numbers as the enamine derivates of 16 be raw material, operation is as embodiment 2, and obtain white solid 46, productive rate is 68%.
Embodiment 18
Take Compound numbers as the enamine derivates of 17 be raw material, operation is as embodiment 2, and obtain white solid 47, productive rate is 67%.
Embodiment 19
Take Compound numbers as the enamine derivates of 18 be raw material, operation is as embodiment 1, and obtain white solid 48, productive rate is 62%.
Embodiment 20
Take Compound numbers as the enamine derivates of 19 be raw material, operation is as embodiment 1, and obtain white solid 49, productive rate is 66%.
Embodiment 21
Take Compound numbers as the enamine derivates of 20 be raw material, operation is as embodiment 1, and obtain white solid 50, productive rate is 69%.
Embodiment 22
Take Compound numbers as the enamine derivates of 21 be raw material, operation is as embodiment 1, and obtain white solid 51, productive rate is 65%.
Embodiment 23
Take Compound numbers as the enamine derivates of 22 be raw material, operation is as embodiment 1, and obtain pale solid 52, productive rate is 66%.
Embodiment 24
The preparation method of 2-Pyridione derivatives, comprise the following steps: add amount of substance than the enamine derivates (namely Compound numbers is the enamine derivates of 23) and the methene ethoxy-c diethyl adipate that are 1:1, after adding enamine derivates and methene ethoxy-c diethyl adipate, add methyl-sulphoxide.Temperature of reaction controls at 130 DEG C, after reaction 6h, TLC detects stopped reaction to raw material disappearance, column chromatography for separation (eluent petroleum ether: ethyl acetate=4:1), obtain pale solid (namely Compound numbers is the 2-Pyridione derivatives of 53), productive rate is 58%.
Embodiment 25
The preparation method of 2-Pyridione derivatives, comprise the following steps: add amount of substance than the enamine derivates (namely Compound numbers is the enamine derivates of 24) and the methene ethoxy-c diethyl adipate that are 1:1, temperature of reaction controls at 130 DEG C, stopped reaction after TLC detects and disappears to raw material, obtain pale solid (namely Compound numbers is the 2-Pyridione derivatives of 54), (eluent is column chromatography for separation, sherwood oil: ethyl acetate=4:1), productive rate is 64%.
Embodiment 26
Take Compound numbers as the enamine derivates of 25 be raw material, operation is as embodiment 26, and obtain pale solid 55, productive rate is 63%.
In a word, the foregoing is only preferred embodiment of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to the covering scope of patent of the present invention.
Claims (7)
1.2-Pyridione derivatives, is the compound of following structure shown in formula I formula, it is characterized in that:
Formula I is
Wherein, R
1for carbon atom number is the alkyl of 3-10 or allyl group or aryl;
R
1for carbon atom number be the alkyl of 3-10 time, alkyl is open chain or ring-type;
R
1one in the phenyl that the phenyl that during for aryl, aryl is phenyl, benzyl, low alkyl group replace, lower alkoxy replace, the phenyl of halogen substiuted, naphthyl; R
1during the phenyl that the phenyl replaced for low alkyl group or lower alkoxy replace, its carbon atom number is 1-3; Aryl is that phenyl or more than one get base.
2. the preparation method of 2-Pyridione derivatives according to claim 1, it is characterized in that: comprise the following steps, add amount of substance than the enamine derivates and the methene ethoxy-c diethyl adipate that are 1:1, temperature of reaction controls at 110-150 DEG C, preparation 2-Pyridione derivatives.
3. the preparation method of 2-Pyridione derivatives according to claim 2, it is characterized in that: add enamine derivates and methene ethoxy-c diethyl adipate, temperature of reaction controls to detect stopped reaction to raw material disappearance at 110-150 DEG C, TLC, obtained 2-Pyridione derivatives.
4. the preparation method of 2-Pyridione derivatives according to claim 3, is characterized in that: add methyl-sulphoxide after adding enamine derivates and methene ethoxy-c diethyl adipate.
5. the preparation method of the 2-Pyridione derivatives according to claim 3 or 4, is characterized in that: stopped reaction after TLC detects and disappears to raw material, uses column chromatography, obtained 2-Pyridione derivatives.
6. the preparation method of 2-Pyridione derivatives according to claim 5, is characterized in that: temperature of reaction controls at 130 DEG C.
7. the preparation method of 2-Pyridione derivatives according to claim 5, is characterized in that: the molecular formula of enamine derivates is
wherein, R
2for alkyl or aryl that carbon atom number is 3-10;
R
2for carbon atom number be the alkyl of 3-10 time, alkyl is open chain or ring-type;
R
2one in the phenyl that the phenyl that during for aryl, aryl is phenyl, benzyl, low alkyl group replace, lower alkoxy replace, the phenyl of halogen substiuted, naphthyl; R
2during the phenyl that the phenyl replaced for low alkyl group or lower alkoxy replace, its carbon atom number is 1-3; Aryl is that phenyl or more than one get base.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510406005.9A CN105037260A (en) | 2015-07-09 | 2015-07-09 | 2-pyridone derivative and preparation method thereof |
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| CN201510406005.9A CN105037260A (en) | 2015-07-09 | 2015-07-09 | 2-pyridone derivative and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008011131A2 (en) * | 2006-07-21 | 2008-01-24 | Takeda Pharmaceutical Company Limited | Amide compounds |
| WO2008085119A1 (en) * | 2007-01-12 | 2008-07-17 | Astrazeneca Ab | New pyridine analogues viii 518 |
| CN102993088A (en) * | 2012-12-31 | 2013-03-27 | 东华大学 | 4-hydroxy-2-pyridone preparation method |
-
2015
- 2015-07-09 CN CN201510406005.9A patent/CN105037260A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008011131A2 (en) * | 2006-07-21 | 2008-01-24 | Takeda Pharmaceutical Company Limited | Amide compounds |
| WO2008085119A1 (en) * | 2007-01-12 | 2008-07-17 | Astrazeneca Ab | New pyridine analogues viii 518 |
| CN102993088A (en) * | 2012-12-31 | 2013-03-27 | 东华大学 | 4-hydroxy-2-pyridone preparation method |
Non-Patent Citations (6)
| Title |
|---|
| CE´CILE G. SAVARIN等: "An Expedient Synthesis of Highly Functionalized Naphthyridones and Quinolines from a Common N-Aryl Pyridinone Template", 《ORGANIC LETTERS》 * |
| D. LEAVER等: "Heterocyclic compounds with bridgehead nitrogen atoms part II. Condensation of diethyl β-Oxoglutarate with electrophilic ethoxymethylene compounds; Synthesis of a 6-hydroxyquinolizin-4-one", 《JOURNAL OF THE CHEMICAL SOCIETY》 * |
| MARIA TERESA COCCO等: "New synthesis of 2(1H)-pyridone derivatives", 《J. HETEROCYCLIC CHEM.》 * |
| MARIA TERESA COCCO等: "Synthesis of 6-mino and 6-ethoxy-2(1H)-pyridone derivatives", 《J. HETEROCYCLIC CHEM.》 * |
| S.T.FLYNN等: "A rhodium-catalysed synthesis of pyridones", 《JOURNAL OF MOLECULAR CATALYSIS》 * |
| 赵圣印等: "4-羟基-2-吡啶酮类化合物的合成研究进展", 《有机化学》 * |
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