CN105418476A - Synthesis method for 2-formyl-3,4-dimethyl-5-acetyl pyrrole - Google Patents
Synthesis method for 2-formyl-3,4-dimethyl-5-acetyl pyrrole Download PDFInfo
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- CN105418476A CN105418476A CN201510922072.6A CN201510922072A CN105418476A CN 105418476 A CN105418476 A CN 105418476A CN 201510922072 A CN201510922072 A CN 201510922072A CN 105418476 A CN105418476 A CN 105418476A
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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 discloses a synthesis method for 2-formyl-3,4-dimethyl-5-acetyl pyrrole, and belongs to the field of chemical synthesis. The synthesis method comprises the steps that acetic anhydride is taken as a raw material, glacial acetic acid is added into the acetic anhydride, and sodium nitrite is dropwise added by controlling the temperature for a reaction; after the reaction is finished, acetylacetone and zinc powder are added, a reaction is performed after the pH value is regulated, and cooling crystallizing and suction filtering are performed after the reaction is finished; filter residues are cleaned and recrystallized with petroleum ether to obtain 2,5-diacetyl-3,4-dimethyl pyrrole, the 2,5-diacetyl-3,4-dimethyl pyrrole is taken to be dissolved in glacial acetic acid, and sulfuryl chloride is dropwise added into the mixture for a reaction; cooling crystallizing, suction filtering and drying are performed, and then the 2-formyl-3,4-dimethyl-5-acetyl pyrrole is obtained.
Description
Technical field
The invention discloses a kind of synthetic method of 2-formyl radical-3,4-dimethyl-5-acetyl pyrrole, belong to the field of chemical synthesis.
Background technology
Azole compounds is extensively present in the natural product such as alkaloid, protein, and some of them have stronger physiologically active.Diacetylpyrrole is the basic intermediate of this compounds of synthesis, is also the important monomer that poly quinoline is prepared in reaction.Due to pyrrole ring containing reactive hydrogen, the polymkeric substance of Diacetylpyrrole and diamines has unique proton conduction property, is the non-fluorine protonically conductive polymer film of new class type, in polymer electrolyte fuel cells modification, has potential using value.Aromatic series acetyl compounds reacts directly obtained by Friedel-Crafts usually, but on pyrrole ring, the one-step acylation of non-nitrogen position is very difficult.The one-step acylation of reporting pyrroles carries out under 300 ~ 320 DEG C of high temperature, obtains being difficult to the sticky mixture be separated, the productive rate of its unitary substituent 22 acetyl pyrrole only 33%.The people such as BarberoM use the self-control reagent (A or B) of following structure through being oxidized high mercury, fluoroboric acid catalytic hydrolysis obtains 2,4-diacyl pyrroles or 2,5-diacyl pyrroles substituent.The acylation reaction productive rate of this method to benzoyl structure higher (all more than 80%), and to the reaction yield of ethanoyl structure lower (being less than 40%).
The invention provides the synthetic method of a kind of 2-formyl radical-3,4-dimethyl-5-acetyl pyrrole that a kind of reaction conditions is gentle, yield is high.
For achieving the above object, the synthetic route of 2-formyl radical-3,4-dimethyl-5-acetyl pyrrole of the present invention is:
The building-up process of 2-formyl radical-3, the 4-dimethyl-5-acetyl pyrrole that the present invention relates to comprises the following steps:
(1) in the 500mL there-necked flask that magnetic stirring apparatus, thermometer and reflux condensing tube are housed, add diacetyl oxide and the anhydrous Glacial acetic acid of 50 ~ 80mL of 30 ~ 40g, flask is placed in the ice bath of-5 DEG C and stirs, stir 30 ~ 40min, be that the sodium nitrite in aqueous solution dropping of 0.3mol/L is in bottle afterwards by 50mL mass concentration, control to drip off in 25 ~ 30min, in dropping process, temperature in bottle is kept to be no more than 8 DEG C, afterwards by reaction mixture stirring reaction 2 ~ 3h at 8 ~ 10 DEG C;
(2) after above-mentioned reaction terminates, the diacetyl oxide of 18 ~ 20g and the zinc powder of 20 ~ 30g is added respectively in bottle, bath temperature is warming up to 80 ~ 90 DEG C, keep refluxing at this temperature, backflow is rear is 3 ~ 4 by the nitric acid regulator solution pH value of massfraction 60%, continues stirring reaction 2 ~ 3h;
(3) after above-mentioned reaction terminates, reaction mixture in bottle is poured in the Erlenmeyer flask of 500mL, and in Erlenmeyer flask, add the frozen water of 200 ~ 300mL immediately, filter after stirring 3 ~ 5min, filtrate retains, the filter residue dichloromethane solution obtained is cleaned 3 ~ 5 times, wash away unreacted impurity, filtrate is distilled at 70 ~ 80 DEG C, except desolventizing, remaining solid sherwood oil is carried out recrystallization and obtains solid, and mix with filter residue, mixture is put into the dry 40 ~ 50min of baking oven of 65 ~ 75 DEG C, obtain 2, 5-diacetyl-3, 4-dimethyl pyrrole,
(4) above-mentioned for the 15 ~ 20g product be obtained by reacting is dissolved in the anhydrous Glacial acetic acid of 200 ~ 250mL, backward reaction system in drip the sulfuryl chloride of 30 ~ 45mL massfraction 0.2mol/L, control to drip off in 30 ~ 40min, temperature of reaction is warming up to 80 DEG C, carry out backflow 1 ~ 2h at this temperature, room temperature is cooled to after backflow, the mixture be obtained by reacting is poured in the Erlenmeyer flask of 500mL, and in Erlenmeyer flask, add the frozen water of 250 ~ 300mL immediately, suction filtration is carried out after separating out without solid, by throw out distilled water wash 1 ~ 3 time, be placed on dry 60 ~ 80min in the baking oven of 80 ~ 85 DEG C afterwards, obtain pale orange solid, be 2-formyl radical-3, 4-dimethyl-5-acetyl pyrrole.
Embodiment
First in the 500mL there-necked flask that magnetic stirring apparatus, thermometer and reflux condensing tube are housed, add benzyl acetoacetate and the anhydrous Glacial acetic acid of 50 ~ 80mL of 30 ~ 40g, flask is placed in the ice bath of-5 DEG C and stirs, stir 30 ~ 40min, be that the sodium nitrite in aqueous solution dropping of 0.3mol/L is in bottle afterwards by 50mL mass concentration, control to drip off in 25 ~ 30min, in dropping process, temperature in bottle is kept to be no more than 8 DEG C, afterwards by reaction mixture stirring reaction 2 ~ 3h at 8 ~ 10 DEG C, after question response terminates, in bottle, add the diacetyl oxide of 18 ~ 20g and the zinc powder of 20 ~ 30g respectively, bath temperature is warming up to 80 ~ 90 DEG C, keep refluxing at this temperature, backflow is rear is 3 ~ 4 by the nitric acid regulator solution pH value of massfraction 60%, continues stirring reaction 2 ~ 3h, after question response terminates, reaction mixture in bottle is poured in the Erlenmeyer flask of 500mL, and in Erlenmeyer flask, add the frozen water of 200 ~ 300mL immediately, filter after stirring 3 ~ 5min, filtrate retains, the filter residue dichloromethane solution obtained is cleaned 3 ~ 5 times, wash away unreacted impurity, filtrate is distilled, except desolventizing at 70 ~ 80 DEG C, remaining solid sherwood oil is carried out recrystallization and obtains solid, and mix with filter residue, mixture is put into the dry 40 ~ 50min of baking oven of 65 ~ 75 DEG C, obtain 2,5-diacetyl-3,4-dimethyl pyrrole, above-mentioned for the 15 ~ 20g product be obtained by reacting is dissolved in the anhydrous Glacial acetic acid of 200 ~ 250, backward reaction system in drip the sulfuryl chloride of 30 ~ 45mL massfraction 0.2mol/L, control to drip off in 30 ~ 40min, temperature of reaction is warming up to 80 DEG C, carry out backflow 1 ~ 2h at this temperature, room temperature is cooled to after backflow, the mixture be obtained by reacting is poured in the Erlenmeyer flask of 500mL, and in Erlenmeyer flask, add the frozen water of 250 ~ 300mL immediately, suction filtration is carried out after separating out without solid, by throw out distilled water wash 1 ~ 3 time, be placed on dry 60 ~ 80min in the baking oven of 80 ~ 85 DEG C afterwards, obtain pale orange solid, be 2-formyl radical-3, 4-dimethyl-5-acetyl pyrrole.
Example 1
First in the 500mL there-necked flask that magnetic stirring apparatus, thermometer and reflux condensing tube are housed, add benzyl acetoacetate and the anhydrous Glacial acetic acid of 50mL of 30g, flask is placed in the ice bath of-5 DEG C and stirs, stir 30min, be that the sodium nitrite in aqueous solution dropping of 0.3mol/L is in bottle afterwards by 50mL mass concentration, control to drip off in 25min, in dropping process, temperature in bottle is kept to be no more than 8 DEG C, afterwards by reaction mixture stirring reaction 2h at 8 DEG C, after question response terminates, add the diacetyl oxide of 18g and the zinc powder of 20g respectively, bath temperature is warming up to 80 DEG C in bottle, keep refluxing at this temperature, backflow is rear is 3 by the nitric acid regulator solution pH value of massfraction 60%, continues stirring reaction 2h, after question response terminates, reaction mixture in bottle is poured in the Erlenmeyer flask of 500mL, and in Erlenmeyer flask, add the frozen water of 200mL immediately, filter after stirring 3min, filtrate retains, the filter residue dichloromethane solution obtained is cleaned 3 times, wash away unreacted impurity, filtrate is distilled, except desolventizing at 70 DEG C, remaining solid sherwood oil is carried out recrystallization and obtains solid, and mix with filter residue, mixture is put into the dry 40min of baking oven of 65 DEG C, obtain 2,5-diacetyl-3,4-dimethyl pyrrole, above-mentioned for the 15g product be obtained by reacting is dissolved in the anhydrous Glacial acetic acid of 200, backward reaction system in drip the sulfuryl chloride of 30mL massfraction 0.2mol/L, control to drip off in 30min, temperature of reaction is warming up to 80 DEG C, carry out backflow 1h at this temperature, room temperature is cooled to after backflow, the mixture be obtained by reacting is poured in the Erlenmeyer flask of 500mL, and in Erlenmeyer flask, add the frozen water of 250mL immediately, suction filtration is carried out after separating out without solid, by throw out distilled water wash 1 time, be placed on dry 60min in the baking oven of 80 DEG C afterwards, obtain pale orange solid, be 2-formyl radical-3, 4-dimethyl-5-acetyl pyrrole.
Example 2
First in the 500mL there-necked flask that magnetic stirring apparatus, thermometer and reflux condensing tube are housed, add benzyl acetoacetate and the anhydrous Glacial acetic acid of 65mL of 35g, flask is placed in the ice bath of-5 DEG C and stirs, stir 35min, be that the sodium nitrite in aqueous solution dropping of 0.3mol/L is in bottle afterwards by 50mL mass concentration, control to drip off in 27min, in dropping process, temperature in bottle is kept to be no more than 8 DEG C, afterwards by reaction mixture stirring reaction 2.5h at 9 DEG C, after question response terminates, add the diacetyl oxide of 19g and the zinc powder of 25g respectively, bath temperature is warming up to 85 DEG C in bottle, keep refluxing at this temperature, backflow is rear is 3.5 by the nitric acid regulator solution pH value of massfraction 60%, continues stirring reaction 2.5h, after question response terminates, reaction mixture in bottle is poured in the Erlenmeyer flask of 500mL, and in Erlenmeyer flask, add the frozen water of 250mL immediately, filter after stirring 4min, filtrate retains, the filter residue dichloromethane solution obtained is cleaned 4 times, wash away unreacted impurity, filtrate is distilled, except desolventizing at 75 DEG C, remaining solid sherwood oil is carried out recrystallization and obtains solid, and mix with filter residue, mixture is put into the dry 45min of baking oven of 70 DEG C, obtain 2,5-diacetyl-3,4-dimethyl pyrrole, above-mentioned for the 17g product be obtained by reacting is dissolved in the anhydrous Glacial acetic acid of 225mL, backward reaction system in drip the sulfuryl chloride of 40mL massfraction 0.2mol/L, control to drip off in 35min, temperature of reaction is warming up to 80 DEG C, carry out backflow 1.5h at this temperature, room temperature is cooled to after backflow, the mixture be obtained by reacting is poured in the Erlenmeyer flask of 500mL, and in Erlenmeyer flask, add the frozen water of 275mL immediately, suction filtration is carried out after separating out without solid, by throw out distilled water wash 2 times, be placed on dry 70min in the baking oven of 83 DEG C afterwards, obtain pale orange solid, be 2-formyl radical-3, 4-dimethyl-5-acetyl pyrrole.
Example 3
First in the 500mL there-necked flask that magnetic stirring apparatus, thermometer and reflux condensing tube are housed, add benzyl acetoacetate and the anhydrous Glacial acetic acid of 80mL of 40g, flask is placed in the ice bath of-5 DEG C and stirs, stir 40min, be that the sodium nitrite in aqueous solution dropping of 0.3mol/L is in bottle afterwards by 50mL mass concentration, control to drip off in 30min, in dropping process, temperature in bottle is kept to be no more than 8 DEG C, afterwards by reaction mixture stirring reaction 3h at 10 DEG C, after question response terminates, add the diacetyl oxide of 20g and the zinc powder of 30g respectively, bath temperature is warming up to 90 DEG C in bottle, keep refluxing at this temperature, backflow is rear is 4 by the nitric acid regulator solution pH value of massfraction 60%, continues stirring reaction 3h, after question response terminates, reaction mixture in bottle is poured in the Erlenmeyer flask of 500mL, and in Erlenmeyer flask, add the frozen water of 300mL immediately, filter after stirring 5min, filtrate retains, the filter residue dichloromethane solution obtained is cleaned 5 times, wash away unreacted impurity, filtrate is distilled, except desolventizing at 80 DEG C, remaining solid sherwood oil is carried out recrystallization and obtains solid, and mix with filter residue, mixture is put into the dry 50min of baking oven of 75 DEG C, obtain 2,5-diacetyl-3,4-dimethyl pyrrole, above-mentioned for the 20g product be obtained by reacting is dissolved in the anhydrous Glacial acetic acid of 250, backward reaction system in drip the sulfuryl chloride of 45mL massfraction 0.2mol/L, control to drip off in 40min, temperature of reaction is warming up to 80 DEG C, carry out backflow 2h at this temperature, room temperature is cooled to after backflow, the mixture be obtained by reacting is poured in the Erlenmeyer flask of 500mL, and in Erlenmeyer flask, add the frozen water of 300mL immediately, suction filtration is carried out after separating out without solid, by throw out distilled water wash 3 times, be placed on dry 80min in the baking oven of 85 DEG C afterwards, obtain pale orange solid, be 2-formyl radical-3, 4-dimethyl-5-acetyl pyrrole.
Claims (1)
1. the synthetic method of 2-formyl radical-3, a 4-dimethyl-5-acetyl pyrrole, is characterized in that the synthesis of 2-formyl radical-3,4-dimethyl-5-acetyl pyrrole:
(1) in the 500mL there-necked flask that magnetic stirring apparatus, thermometer and reflux condensing tube are housed, add diacetyl oxide and the anhydrous Glacial acetic acid of 50 ~ 80mL of 30 ~ 40g, flask is placed in the ice bath of-5 DEG C and stirs, stir 30 ~ 40min, be that the sodium nitrite in aqueous solution dropping of 0.3mol/L is in bottle afterwards by 50mL mass concentration, control to drip off in 25 ~ 30min, in dropping process, temperature in bottle is kept to be no more than 8 DEG C, afterwards by reaction mixture stirring reaction 2 ~ 3h at 8 ~ 10 DEG C;
(2) after above-mentioned reaction terminates, the methyl ethyl diketone of 18 ~ 20g and the zinc powder of 20 ~ 30g is added respectively in bottle, bath temperature is warming up to 80 ~ 90 DEG C, keep refluxing at this temperature, backflow is rear is 3 ~ 4 by the nitric acid regulator solution pH value of massfraction 60%, continues stirring reaction 2 ~ 3h;
(3) after above-mentioned reaction terminates, reaction mixture in bottle is poured in the Erlenmeyer flask of 500mL, and in Erlenmeyer flask, add the frozen water of 200 ~ 300mL immediately, filter after stirring 3 ~ 5min, filtrate retains, the filter residue dichloromethane solution obtained is cleaned 3 ~ 5 times, wash away unreacted impurity, filtrate is distilled at 70 ~ 80 DEG C, except desolventizing, remaining solid sherwood oil is carried out recrystallization and obtains solid, and mix with filter residue, mixture is put into the dry 40 ~ 50min of baking oven of 65 ~ 75 DEG C, obtain 2, 5-diacetyl-3, 4-dimethyl pyrrole,
(4) above-mentioned for the 15 ~ 20g product be obtained by reacting is dissolved in the anhydrous Glacial acetic acid of 200 ~ 250mL, backward reaction system in drip the sulfuryl chloride of 30 ~ 45mL massfraction 0.2mol/L, control to drip off in 30 ~ 40min, temperature of reaction is warming up to 80 DEG C, carry out backflow 1 ~ 2h at this temperature, room temperature is cooled to after backflow, the mixture be obtained by reacting is poured in the Erlenmeyer flask of 500mL, and in Erlenmeyer flask, add the frozen water of 250 ~ 300mL immediately, suction filtration is carried out after separating out without solid, by throw out distilled water wash 1 ~ 3 time, be placed on dry 60 ~ 80min in the baking oven of 80 ~ 85 DEG C afterwards, obtain pale orange solid, be 2-formyl radical-3, 4-dimethyl-5-acetyl pyrrole.
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| JP2013073124A (en) * | 2011-09-28 | 2013-04-22 | Jsr Corp | Composition for liquid immersion upper layer film formation |
| CN104151225A (en) * | 2013-05-15 | 2014-11-19 | 天津希恩思生化科技有限公司 | 3,5-dimethyl-1H-pyrrole-2,4-biformaldehyde and preparation method thereof |
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2015
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| JP2013073124A (en) * | 2011-09-28 | 2013-04-22 | Jsr Corp | Composition for liquid immersion upper layer film formation |
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| CN104151225A (en) * | 2013-05-15 | 2014-11-19 | 天津希恩思生化科技有限公司 | 3,5-dimethyl-1H-pyrrole-2,4-biformaldehyde and preparation method thereof |
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