CN102887851A - Compound 3,5-dimethyl-1H-pyrrole-2,4-diformaldehyde and preparation method thereof - Google Patents
Compound 3,5-dimethyl-1H-pyrrole-2,4-diformaldehyde and preparation method thereof Download PDFInfo
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- CN102887851A CN102887851A CN2012104318423A CN201210431842A CN102887851A CN 102887851 A CN102887851 A CN 102887851A CN 2012104318423 A CN2012104318423 A CN 2012104318423A CN 201210431842 A CN201210431842 A CN 201210431842A CN 102887851 A CN102887851 A CN 102887851A
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Abstract
The invention relates to a compound 3,5-dimethyl-1H-pyrrole-2,4-diformaldehyde and a preparation method thereof. According to the invention, the 3,5-dimethyl-1H-pyrrole-2,4-diformaldehyde with a complicated structure is synthesized by use of the raw materials such as ethyl acetoacetate and acetic acid for the first time, and the yield of the final product is as high as 38%; and moreover, the crystallization effect is good, the purity is high, and a high-purity master standard or sample is provided for the subsequent chemical and biological experiments. The invention also provides a detailed synthesis and purification method of the 3,5-dimethyl-1H-pyrrole-2,4-diformaldehyde; and the production method is scientific and reasonable, and elaborate theoretical and practical guide is provided for the subsequent expanded production.
Description
Technical field
The invention belongs to the compound preparation field, especially compound 3,5-dimethyl-1H-pyrroles-2,4-dicarbaldehyde and preparation method thereof.
Background technology
At present, because Bioexperiment makes new breakthroughs, make us in the process for the treatment of and the searching cause of disease, means are mistake more, the result is more accurate, so for treating various diseases the property pharmaceutical requirements is also increased gradually, therefore, various compounds with new function are in a large amount of being developed, and the whole world all has the new compound of the various difficult and complicated cases of opposing in searching, so in the process of these new compound exploitations, can produce the compound of numerous new textures and new configuration, and then searching is useful in these numerous new compounds, and the molecule for the treatment of use is arranged, and therefore developing new compound is one and important process.
Summary of the invention
The object of the present invention is to provide a kind of brand-new compound 3,5-dimethyl-1H-pyrroles-2,4-dicarbaldehyde and preparation method thereof, the present invention is synthetic and this compound of purifying first, make its purity arrive certain requirement, can further test or application it.
The present invention realizes that the technical scheme of purpose is as follows:
Compound 3,5-dimethyl-1H-pyrroles-2, the 4-dicarbaldehyde, structural formula is as follows:
Compound 3,5-dimethyl-1H-pyrroles-2, the preparation method of 4-dicarbaldehyde, step is as follows:
(1) compound 2,4-dimethyl pyrrole-3, and the 5-diethyl dicarboxylate's is synthetic
When 5-15 spends, with dripping the aqueous solution of Sodium Nitrite in the acetum of methyl aceto acetate, continue reaction 1 hour, reaction solution is heated to room temperature under violent stirring, adds zinc powder, reaction solution was refluxed one hour, the TLC detection reaction finishes, and reaction solution is poured into water, and stirring was filtered after half an hour, filter cake washes with water three times, at room temperature dry 10-14 hour obtains the faint yellow solid powder is 2,4-dimethyl pyrrole-3, the 5-diethyl dicarboxylate;
Described methyl aceto acetate: Sodium Nitrite: the mol ratio of zinc powder is: 1.3: 0.7: 1.31;
(2) compound 2,4-dimethyl pyrrole synthetic
With 2,4-dimethyl pyrrole-3, the 5-diethyl dicarboxylate is suspended in the aqueous solution of potassium hydroxide, backflow is spent the night, and TLC detects, and after reaction finishes reaction solution is cooled to the room temperature ice bath and stirs the lower concentrated hydrochloric acid that adds, regulating pH stirred one hour to acid, to neutral, use ethyl acetate extraction three times with the saturated potassium carbonate regulator solution, merge the organic phase dried over sodium sulfate, filter, be spin-dried for and obtain the dark-brown oily liquids, 80 ℃ of underpressure distillation obtain white transparent liquid 2,4-dimethyl pyrrole;
Described 2,4-dimethyl pyrrole-3, the 5-diethyl dicarboxylate: the mol ratio of potassium hydroxide is: 0.3:2;
(3) compound 3,5-dimethyl-1H-pyrroles-2,4-dicarbaldehyde synthetic
2,4-dimethyl pyrrole is dissolved among the DMF, slowly drips slowly phosphorus oxychloride, then at room temperature stir and spend the night, reaction solution is slowly poured in the frozen water, regulates pH=8 with saturated potassium carbonate, and ethyl acetate extraction three times merges organic dry filtration that is concerned with and is spin-dried for and obtains thick product.
Described 2, the 4-dimethyl pyrrole: the mol ratio of phosphorus oxychloride is 40:90.
And the concentration of the acetum of described methyl aceto acetate is: per 1.3 moles of methyl aceto acetates adopt the 500ml acetate dissolution.
Advantage of the present invention and beneficial effect are:
1, the present invention uses the raw materials such as methyl aceto acetate, acetic acid to synthesize first to have 3 of complex construction, 5-dimethyl-1H-pyrroles-2, the 4-dicarbaldehyde, the productive rate of preparation end product is up to 38%, and crystallization effect is good, purity is high, for follow-up chemistry and Bioexperiment provide highly purified standard specimen or sample.
2, the present invention also provides 3,5-dimethyl-1H-pyrroles-2, the detailed synthetic and purification process of 4-dicarbaldehyde, and production method science, reasonable instructs for follow-up expanding production provides detailed theory and practice.
3, the invention provides 3,5-dimethyl-1H-pyrroles-2, synthesis condition, the raw material of each step in the 4-dicarbaldehyde building-up process, and the nuclear-magnetism figure of synthetic after product are for the analysis and identification of intermediate product in the building-up process provides detailed support.
Description of drawings
Fig. 1 is the compounds of this invention 3(2, the 4-dimethyl pyrrole) nuclear magnetic spectrogram,
1H NMR:(300MHz, CDCl3);
Fig. 2 is the compounds of this invention 4(3,5-dimethyl-1H-pyrroles-2,4-dicarbaldehyde) nuclear magnetic spectrogram,
1H NMR:(300MHz, CDCl3).
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention is further specified, following embodiment is illustrative, is not determinate, can not limit protection scope of the present invention with following embodiment.
3 of the present invention's preparation, 5-dimethyl-1H-pyrroles-2, the structural formula of 4-dicarbaldehyde (3,5-dimethyl-1H-pyrrole-2,4-dicarbaldehyde) is:
The synthetic route of this compound
Raw material
The raw materials such as methyl aceto acetate are market and buy, without particular requirement.
The synthetic method step of this chemical combination is as follows:
The present invention 3,5-dimethyl-1H-pyrroles-2, and the synthetic method of 4-dicarbaldehyde, step is as follows:
(1) compound 2 (2,4-dimethyl pyrrole-3,5-diethyl dicarboxylate) is synthetic
When 10 spend, drip the aqueous solution of Sodium Nitrite (0.7mol) in acetic acid (500mL) solution with methyl aceto acetate (1.3mol), continue reaction 1 hour, reaction solution is heated to room temperature under violent stirring, adds zinc powder (1.31mol).Reaction solution was refluxed one hour, and the TLC detection reaction finishes.Reaction solution is poured into water, and stirring was filtered after half an hour.Filter cake washes with water three times, and at room temperature drying obtained faint yellow solid powder 80g in 12 hours.
(2) compound 3(2,4-dimethyl pyrrole) synthetic
With 2,4-dimethyl pyrrole-3,5-diethyl dicarboxylate (0.3mol) is suspended in the aqueous solution of potassium hydroxide (2mol), and backflow is spent the night.TLC detects, and after reaction finishes reaction solution is cooled to the room temperature ice bath and stirs the lower concentrated hydrochloric acid that adds, and regulates pH and stirs one hour to acid.To neutral, use ethyl acetate extraction three times with the saturated potassium carbonate regulator solution, merge the organic phase dried over sodium sulfate, filter, be spin-dried for and obtain the dark-brown oily liquids.80 ℃ of underpressure distillation obtain white transparent liquid 2,4-dimethyl pyrrole (11.5g, 36.2%).
(3) compound 4(3,5-dimethyl-1H-pyrroles-2,4-dicarbaldehyde) synthetic
2,4-dimethyl pyrrole (40mmol) is dissolved among the DMF (25mL), slowly drips slowly phosphorus oxychloride (90mmol), then at room temperature stir and spend the night.Reaction solution is slowly poured in the frozen water, regulates pH=8 with saturated potassium carbonate, and ethyl acetate extraction three times merges organic relevant dry filtration and is spin-dried for and obtains thick product.Obtain product 2.7g with the PE:EA recrystallization, productive rate 38%.
Claims (3)
1. compound 3,5-dimethyl-1H-pyrroles-2, and the 4-dicarbaldehyde is characterized in that: structural formula is as follows:
2. compound 3,5-dimethyl-1H-pyrroles-2, and the preparation method of 4-dicarbaldehyde is characterized in that: step is as follows:
(1) compound 2,4-dimethyl pyrrole-3, and the 5-diethyl dicarboxylate's is synthetic
When 5-15 spends, with dripping the aqueous solution of Sodium Nitrite in the acetum of methyl aceto acetate, continue reaction 1 hour, reaction solution is heated to room temperature under violent stirring, adds zinc powder, reaction solution was refluxed one hour, the TLC detection reaction finishes, and reaction solution is poured into water, and stirring was filtered after half an hour, filter cake washes with water three times, at room temperature dry 10-14 hour obtains the faint yellow solid powder is 2,4-dimethyl pyrrole-3, the 5-diethyl dicarboxylate;
Described methyl aceto acetate: Sodium Nitrite: the mol ratio of zinc powder is: 1.3: 0.7: 1.31;
(2) compound 2,4-dimethyl pyrrole synthetic
With 2,4-dimethyl pyrrole-3, the 5-diethyl dicarboxylate is suspended in the aqueous solution of potassium hydroxide, backflow is spent the night, and TLC detects, and after reaction finishes reaction solution is cooled to the room temperature ice bath and stirs the lower concentrated hydrochloric acid that adds, regulating pH stirred one hour to acid, to neutral, use ethyl acetate extraction three times with the saturated potassium carbonate regulator solution, merge the organic phase dried over sodium sulfate, filter, be spin-dried for and obtain the dark-brown oily liquids, 80 ℃ of underpressure distillation obtain white transparent liquid 2,4-dimethyl pyrrole;
Described 2,4-dimethyl pyrrole-3, the 5-diethyl dicarboxylate: the mol ratio of potassium hydroxide is: 0.3:2;
(3) compound 3,5-dimethyl-1H-pyrroles-2,4-dicarbaldehyde synthetic
2,4-dimethyl pyrrole is dissolved among the DMF, slowly drips slowly phosphorus oxychloride, then at room temperature stir and spend the night, reaction solution is slowly poured in the frozen water, regulates pH=8 with saturated potassium carbonate, and ethyl acetate extraction three times merges organic dry filtration that is concerned with and is spin-dried for and obtains thick product.
Described 2, the 4-dimethyl pyrrole: the mol ratio of phosphorus oxychloride is 40:90.
3. compound 3 according to claim 2,5-dimethyl-1H-pyrroles-2, the preparation method of 4-dicarbaldehyde is characterized in that: the concentration of the acetum of described methyl aceto acetate is: per 1.3 moles of methyl aceto acetates adopt the 500ml acetate dissolution.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105418476A (en) * | 2015-12-12 | 2016-03-23 | 常州大学 | Synthesis method for 2-formyl-3,4-dimethyl-5-acetyl pyrrole |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1311775A (en) * | 1998-05-29 | 2001-09-05 | 苏根公司 | Pyrrole substituted 2-indolinone protein kinase inhibitors |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1311775A (en) * | 1998-05-29 | 2001-09-05 | 苏根公司 | Pyrrole substituted 2-indolinone protein kinase inhibitors |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105418476A (en) * | 2015-12-12 | 2016-03-23 | 常州大学 | Synthesis method for 2-formyl-3,4-dimethyl-5-acetyl pyrrole |
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