CN104151225A - 3,5-dimethyl-1H-pyrrole-2,4-biformaldehyde and preparation method thereof - Google Patents
3,5-dimethyl-1H-pyrrole-2,4-biformaldehyde and preparation method thereof Download PDFInfo
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- CN104151225A CN104151225A CN201310179529.XA CN201310179529A CN104151225A CN 104151225 A CN104151225 A CN 104151225A CN 201310179529 A CN201310179529 A CN 201310179529A CN 104151225 A CN104151225 A CN 104151225A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D207/33—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D207/333—Radicals substituted by oxygen or sulfur atoms
Abstract
The invention relates to a compound 3,5-dimethyl-1H-pyrrole-2,4-biformaldehyde and a preparation method thereof. According to the method, 3,5-dimethyl-1H-pyrrole-2,4-biformaldehyde with a complicated structure is synthesized from the raw materials such as ethyl acetoacetate and acetic acid for the first time, the yield of the prepared final product can be up to 38%, the 3,5-dimethyl-1H-pyrrole-2,4-biformaldehyde is good in crystallization effect and high in purity, and high-purity guide samples and samples are provided for subsequent chemical and biological equipments. The invention also provides a detailed synthesis and purification method of the 3,5-dimethyl-1H-pyrrole-2,4-biformaldehyde. The production method is scientific and reasonable, so as to provide detailed theoretical and practical guidance for subsequent expanded production.
Description
Technical field
The invention belongs to compound preparation field, especially a kind of 3,5-dimethyl-1H-pyrroles-2,4-dicarbaldehyde and preparation method thereof.
Background technology
At present, because Bioexperiment makes new breakthroughs, make us in treatment and find in the process of the cause of disease, means are more, result is more accurate, property pharmaceutical requirements is also increased gradually for the various diseases for the treatment of so, therefore, the various compounds with new function are in a large amount of being developed, 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 in these numerous new compounds, find useful, there is the molecule for the treatment of use, 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, the present invention is synthetic and this compound of purifying first, make its purity reach certain requirement, can further test or application it.
The object of the invention is to be achieved through the following technical solutions:
Compound 3,5-dimethyl-1H-pyrroles-2,4-dicarbaldehyde, its structural formula is as follows:
The preparation method of this compound is as follows:
(1) compound 2 is synthetic
In the time of 10 DEG C, will in the acetum of methyl aceto acetate, drip sodium nitrite in aqueous solution, continue reaction 1 hour, reaction solution is heated to room temperature and under violent stirring, adds zinc powder.Reaction solution is refluxed 1 hour, after TLC detection reaction finishes, reaction solution is poured into water, stirring was filtered after half an hour.Filter cake washes with water three times, is at room temperature dried and obtains faint yellow solid powder in 12 hours, is compound 2.
The mol ratio of described methyl aceto acetate, Sodium Nitrite, zinc powder is 1.3:0.7:1.31; The acetum concentration of described methyl aceto acetate is: every 1.3mol methyl aceto acetate adopts 500ml acetate dissolution.
(2) compound 3 is synthetic
Compound 2 is suspended in potassium hydroxide aqueous solution, and backflow is spent the night.After TLC detection reaction finishes, reaction solution is cooled under the stirring of room temperature ice bath and adds concentrated hydrochloric acid, regulate pH to stir 1 hour to acid., be extracted with ethyl acetate three times to neutral with saturated potassium carbonate regulator solution, merge organic phase dried over sodium sulfate, filter, be spin-dried for and obtain dark-brown oily liquids.80 DEG C of underpressure distillation obtain white transparent liquid compound 3.
Described compound 2 is 0.3:2 with the mol ratio of potassium hydroxide.
(3) compound 3,5-dimethyl-1H-pyrroles-2,4-dicarbaldehyde synthetic
Compound 3 is dissolved in DMF, and slowly the slow phosphorus oxychloride that drips, at room temperature stirs and spends the night.Reaction solution is slowly poured in 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 with PE:EA recrystallization.
Described compound 3 is 4:9 with the mol ratio of phosphorus oxychloride; The concentration that described compound 3 is dissolved in DMF is: every 40mmol compound 3 adopts 25mlDMF to dissolve.
The structural formula of described compound 2 is
the structural formula of described compound 3 is
Advantage of the present invention and positively effect are:
1, the present invention uses the raw material such as methyl aceto acetate, acetic acid to synthesize first to have 3 of complex construction, 5-dimethyl-1H-pyrroles-2,4-dicarbaldehyde, prepare the productive rate of end product 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 synthetic and purification process that 4-dicarbaldehyde is detailed, 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 4-dicarbaldehyde building-up process, and the nuclear magnetic spectrum of synthetic after product, for the analysis and identification of intermediate product in building-up process provides detailed support.
Brief description of the drawings
Fig. 1 is the nuclear-magnetism figure of the compounds of this invention 2,
1h NMR (300MHz, D2O);
Fig. 2 is the nuclear-magnetism figure of the compounds of this invention 3,
1h NMR (300MHz, D2O);
Fig. 3 is the compounds of this invention 3,5-dimethyl-1H-pyrroles-2, and the nuclear-magnetism figure of 4-dicarbaldehyde,
1hNMR (300MHz, D2O).
Embodiment
Below in conjunction with embodiment, the present invention is further described, and following embodiment is illustrative, is not determinate, can not limit protection scope of the present invention with following embodiment.
Reaction scheme of the present invention is as follows:
Raw material
The raw materials such as methyl aceto acetate are market and buy, without particular requirement.
The synthetic method of this compound is as follows:
(1) compound 2 is synthetic
In the time that 10 spend, will in the acetic acid of methyl aceto acetate (1.3mol) (500mL) solution, drip the aqueous solution of Sodium Nitrite (0.7mol), continue reaction hour, reaction solution is heated to room temperature and under violent stirring, adds zinc powder (1.31mol).Reaction solution is refluxed one hour, and 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, at room temperature the dry faint yellow solid powder 80g that obtains for 12 hours.
(2) compound 3 is synthetic
By 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 under the stirring of room temperature ice bath and adds concentrated hydrochloric acid, regulates pH to stir one hour to acid., be extracted with ethyl acetate three times to neutral with saturated potassium carbonate regulator solution, merge organic phase dried over sodium sulfate, filter, be spin-dried for and obtain dark-brown oily liquids.80 DEG C of underpressure distillation obtain white transparent liquid 2,4-dimethyl pyrrole (11.5g, 36.2%).
(3) 3,5-dimethyl-1H-pyrroles-2,4-dicarbaldehyde synthetic
2,4-dimethyl pyrrole (40mmol) is dissolved in DMF (25mL), and slowly the slow phosphorus oxychloride (90mmol) that drips, then at room temperature stirs and spends the night.Reaction solution is slowly poured in 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, productive rate 38% with PE:EA recrystallization.
Claims (4)
1. a compound 3,5-dimethyl-1H-pyrroles-2,4-dicarbaldehyde, is characterized in that: structural formula is as follows:
2. the preparation method of compound according to claim 1, is characterized in that: step is as follows:
(1) compound 2 is synthetic
In the time of 10 DEG C, will in the acetum of methyl aceto acetate, drip sodium nitrite in aqueous solution, continue reaction 1 hour, reaction solution is heated to room temperature and under violent stirring, adds zinc powder.Reaction solution is refluxed 1 hour, after TLC detection reaction finishes, reaction solution is poured into water, stirring was filtered after half an hour.Filter cake washes with water three times, is at room temperature dried and obtains faint yellow solid powder in 12 hours, is compound 2.
The mol ratio of described methyl aceto acetate, Sodium Nitrite, zinc powder is 1.3:0.7:1.31; The acetum concentration of described methyl aceto acetate is: every 1.3mol methyl aceto acetate adopts 500ml acetate dissolution.
(2) compound 3 is synthetic
Compound 2 is suspended in potassium hydroxide aqueous solution, and backflow is spent the night.After TLC detection reaction finishes, reaction solution is cooled under the stirring of room temperature ice bath and adds concentrated hydrochloric acid, regulate pH to stir 1 hour to acid., be extracted with ethyl acetate three times to neutral with saturated potassium carbonate regulator solution, merge organic phase dried over sodium sulfate, filter, be spin-dried for and obtain dark-brown oily liquids.80 DEG C of underpressure distillation obtain white transparent liquid compound 3.
Described compound 2 is 0.3:2 with the mol ratio of potassium hydroxide.
(3) compound 3,5-dimethyl-1H-pyrroles-2,4-dicarbaldehyde synthetic
Compound 3 is dissolved in DMF, and slowly the slow phosphorus oxychloride that drips, at room temperature stirs and spends the night.Reaction solution is slowly poured in 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 with PE:EA recrystallization.
Described compound 3 is 4:9 with the mol ratio of phosphorus oxychloride; The concentration that described compound 3 is dissolved in DMF is: every 40mmol compound 3 adopts 25mlDMF to dissolve.
3. preparation method according to claim 2, is characterized in that: the structure of described compound 2 is as follows:
4. preparation method according to claim 2, is characterized in that: the structure of described compound 3 is as follows:
。
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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- 2013-05-15 CN CN201310179529.XA patent/CN104151225A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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Application publication date: 20141119 |