CN113773221B - P-benzoquinone compound and preparation method thereof - Google Patents
P-benzoquinone compound and preparation method thereof Download PDFInfo
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- CN113773221B CN113773221B CN202111170476.6A CN202111170476A CN113773221B CN 113773221 B CN113773221 B CN 113773221B CN 202111170476 A CN202111170476 A CN 202111170476A CN 113773221 B CN113773221 B CN 113773221B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/22—Separation; Purification; Stabilisation; Use of additives
- C07C231/24—Separation; Purification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
Abstract
The application discloses a p-benzoquinone compound and a preparation method thereof, and belongs to the technical field of p-benzoquinone compounds. A preparation method of a p-benzoquinone compound comprises the following steps: adding one or two of p-methylacetanilide and p-ethylacetanilide, iodobenzene acetate and N, N-dimethylformamide into a reactor, and stirring and reacting at 20-40 ℃ to obtain the p-benzoquinone compound. The application also comprises the p-benzoquinone compound prepared by the preparation method. The preparation method is simple, and the yield of the prepared p-benzoquinone compound is high.
Description
Technical Field
The application relates to the technical field of p-benzoquinone compounds, in particular to a p-benzoquinone compound and a preparation method thereof.
Background
P-benzoquinone compounds are useful as dye intermediates, or in assays for determining amino acids. P-benzoquinone compounds are also useful for qualitative identification of phellandrene, pyridine, azole, tyrosine and hydroquinone, identifying many natural product pigment alpha-naphthoquinone containing structures, such as vitamins k1 and k2.
The chemical structure of vitamins k1 and k2 and their derivatives is related to coagulation, based on which the prior art has proposed a number of compounds related to p-benzoquinone and their preparation, for example, p-benzoquinone can be prepared from sodium chlorate and hydroquinone sulfate oxidation; the p-benzoquinone can be industrially prepared by oxidizing aniline or phenol; however, the existing method for preparing the p-benzoquinone compound has the problems of complex process and low yield.
Disclosure of Invention
The application aims to overcome the technical defects, provide a p-benzoquinone compound and a preparation method thereof, and solve the technical problems of complex process and low yield of the preparation method of the p-benzoquinone compound in the prior art.
In order to achieve the technical aim, the technical scheme of the application provides a preparation method of a p-benzoquinone compound, which comprises the following steps: adding one or two of p-methylacetanilide and p-ethylacetanilide, iodobenzene acetate and N, N-dimethylformamide into a reactor, and stirring and reacting at 20-40 ℃ to obtain the p-benzoquinone compound.
Further, the stirring reaction time is 12-16 hours.
Further, the stirring reaction is carried out under the stirring action of a magnetic stirrer, and the stirring speed is 600-1000 revolutions/s.
Further, the molar ratio of one or two of the p-methylacetanilide and the p-ethylacetanilide to the iodobenzene acetate is 1 (1-2).
Further, the material ratio of one or two of the methylacetanilide and the ethylacetanilide to the N, N-dimethylformamide is 1mmol (10-20) mL.
Further, the stirring reaction is carried out in an oil bath.
Further, the method further comprises the step of purifying the p-benzoquinone compound prepared by stirring reaction.
Further, the purification comprises mixing the p-benzoquinone compound prepared by stirring reaction with ethyl acetate, and then adding water for back extraction to obtain an organic phase.
Further, the method also comprises the step of decompressing and distilling the organic phase to obtain a crude product.
Further, the method also comprises the step of separating the crude product by column chromatography to obtain the purified p-benzoquinone compound.
In addition, the application also provides a p-benzoquinone compound prepared by the preparation method.
Compared with the prior art, the application has the beneficial effects that: the p-methylacetanilide or the p-ethylacetanilide has electron donating methyl or ethyl, the esterification reaction of the para-position of the anilide can be avoided, the methyl or ethyl can activate benzene rings, the p-benzoquinone compound is prepared by stirring reaction at 20-40 ℃ under the oxidation action of periodic acid, the yield of the p-benzoquinone compound can reach 61 percent, and the preparation method is simple and the yield of the prepared p-benzoquinone compound is high.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of 2-acetamido-5-methyl-p-benzoquinone prepared in example 1 of the present application.
FIG. 2 is a nuclear magnetic resonance carbon spectrum of 2-acetamido-5-methyl-p-benzoquinone prepared in example 1 of the present application.
Detailed Description
The specific embodiment provides a preparation method of a p-benzoquinone compound, which comprises the following steps: adding one or two of methylacetanilide and ethylacetanilide and iodobenzene acetate (namely PhI (OAc)) into the reactor 2 ) And N, N-dimethylformamide (abbreviated as DMF) is stirred and reacted in an oil bath at 20-40 ℃ for 12-16 hours to obtain the p-benzoquinone compound, wherein the stirring reaction is carried out under the stirring action of a magnetic stirrer, the stirring speed is 600-1000 revolutions/s, the mol ratio of one or two of the p-methylacetanilide and the p-ethylacetanilide to the iodobenzene acetate is 1 (2-3), and the material ratio of one or two of the p-methylacetanilide and the p-ethylacetanilide to the N, N-dimethylformamide is 1mmol (10-20) mL;
purifying the p-benzoquinone compound prepared by stirring reaction, wherein the purification comprises the steps of mixing the p-benzoquinone compound prepared by stirring reaction with ethyl acetate, adding water for back extraction to obtain an organic phase, distilling the organic phase under reduced pressure to obtain a crude product, and separating the crude product by column chromatography to obtain the purified p-benzoquinone compound.
The specific embodiment also comprises a p-benzoquinone compound which is prepared by the preparation method.
The reaction general formula is as follows:
wherein R is 1 Represents methyl or ethyl, R 2 Represents methyl.
The present application will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present application more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application.
Example 1
The embodiment provides a p-benzoquinone compound, which is prepared by the following steps:
adding 0.2mmol of p-methylacetanilide, 0.4mmol of iodobenzene acetate and 2mL of N, N-dimethylformamide into a reactor, and stirring at 40 ℃ in an oil bath for 16 hours to obtain the p-benzoquinone compound, wherein the stirring reaction is carried out under the stirring action of a magnetic stirrer, and the stirring speed is 800 revolutions per second; the spherical container at the bottom end of the reactor is immersed in the silicone oil in the oil bath pot, and the immersion depth is that the height of the silicone oil is higher than that of the reaction liquid in the spherical container of the micro-reaction tube;
after the reaction is finished, pouring the reaction solution into a separating funnel, adding 10mL of ethyl acetate, back-extracting for 3 times with 15mL of distilled water, collecting an organic phase, performing reduced pressure distillation to obtain a crude product, and separating by column chromatography to obtain red solid 2-acetamido-5-methyl p-benzoquinone with the yield of 60%.
The chemical formula of the 2-acetamido-5-methyl-p-benzoquinone is as follows:
with reference to fig. 1-2, the structure is determined from nuclear magnetic resonance hydrogen and carbon spectra: 1 H NMR(400MHz,CDCl 3 ):δ2.07(d,J＝1.59Hz,3H),2.23(s,3H),6.60(q,J＝1.59Hz,1H),7.53(s,1H),8.05(s,1H),； 13 C NMR(100MHz,CDCl 3 ):δ16.2,24.9,114.8,129.9,138.1,148.2,169.3,182.8,188.2。
example 2
The embodiment provides a p-benzoquinone compound, which is prepared by the following steps:
adding 0.2mmol of p-methylacetanilide, 0.5mmol of iodobenzene acetate and 4mL of N, N-dimethylformamide into a reactor, and stirring at 20 ℃ in an oil bath for reacting for 12 hours to obtain the p-benzoquinone compound, wherein the stirring reaction is carried out under the stirring action of a magnetic stirrer, and the stirring speed is 1000 revolutions per s; the spherical container at the bottom end of the reactor is immersed in the silicone oil in the oil bath pot, and the immersion depth is that the height of the silicone oil is higher than that of the reaction liquid in the spherical container of the micro-reaction tube;
after the reaction, pouring the reaction solution into a separating funnel, adding 10mL of ethyl acetate, back-extracting for 3 times with 15mL of distilled water, collecting an organic phase, performing reduced pressure distillation to obtain a crude product, and separating by column chromatography to obtain red solid 2-acetamido-5-methyl p-benzoquinone with the yield of 58%.
Example 3
The embodiment provides a p-benzoquinone compound, which is prepared by the following steps:
adding 0.2mmol of p-methylacetanilide, 0.6mmol of iodobenzene acetate and 3mL of N, N-dimethylformamide into a reactor, and stirring at 35 ℃ in an oil bath for 14 hours to obtain the p-benzoquinone compound, wherein the stirring reaction is carried out under the stirring action of a magnetic stirrer, and the stirring speed is 800 revolutions per second; the spherical container at the bottom end of the reactor is immersed in the silicone oil in the oil bath pot, and the immersion depth is that the height of the silicone oil is higher than that of the reaction liquid in the spherical container of the micro-reaction tube;
after the reaction, pouring the reaction solution into a separating funnel, adding 10mL of ethyl acetate, back-extracting for 3 times with 15mL of distilled water, collecting an organic phase, performing reduced pressure distillation to obtain a crude product, and separating by column chromatography to obtain red solid 2-acetamido-5-methyl p-benzoquinone with the yield of 61%.
Example 4
The embodiment provides a p-benzoquinone compound, which is prepared by the following steps:
adding 0.2mmol of p-ethylacetanilide, 0.5mmol of iodobenzene acetate and 4mL of N, N-dimethylformamide into a reactor, and stirring at 30 ℃ in an oil bath for reacting for 12 hours to obtain the p-benzoquinone compound, wherein the stirring reaction is carried out under the stirring action of a magnetic stirrer, and the stirring speed is 1000 revolutions per s; the spherical container at the bottom end of the reactor is immersed in the silicone oil in the oil bath pot, and the immersion depth is that the height of the silicone oil is higher than that of the reaction liquid in the spherical container of the micro-reaction tube;
after the reaction, pouring the reaction solution into a separating funnel, adding 10mL of ethyl acetate, back-extracting for 3 times with 15mL of distilled water, collecting an organic phase, performing reduced pressure distillation to obtain a crude product, and separating by column chromatography to obtain the 2-acetamido-5-ethyl p-benzoquinone with the yield of 57%.
Example 5
The embodiment provides a p-benzoquinone compound, which is prepared by the following steps:
adding 0.2mmol of p-ethylacetanilide, 0.4mmol of iodobenzene acetate and 3mL of N, N-dimethylformamide into a reactor, and stirring at 25 ℃ in an oil bath for 13 hours to obtain the p-benzoquinone compound, wherein the stirring reaction is carried out under the stirring action of a magnetic stirrer, and the stirring speed is 700 revolutions per second; the spherical container at the bottom end of the reactor is immersed in the silicone oil in the oil bath pot, and the immersion depth is that the height of the silicone oil is higher than that of the reaction liquid in the spherical container of the micro-reaction tube;
after the reaction, pouring the reaction solution into a separating funnel, adding 10mL of ethyl acetate, back-extracting for 3 times with 15mL of distilled water, collecting an organic phase, performing reduced pressure distillation to obtain a crude product, and separating by column chromatography to obtain the 2-acetamido-5-ethyl p-benzoquinone with the yield of 56%.
Example 6
The embodiment provides a p-benzoquinone compound, which is prepared by the following steps:
adding 0.2mmol of p-ethylacetanilide, 0.6mmol of iodobenzene acetate and 4mL of N, N-dimethylformamide into a reactor, and stirring at 40 ℃ in an oil bath for 15 hours to obtain the p-benzoquinone compound, wherein the stirring reaction is performed under the stirring action of a magnetic stirrer, and the stirring speed is 900 revolutions per s; the spherical container at the bottom end of the reactor is immersed in the silicone oil in the oil bath pot, and the immersion depth is that the height of the silicone oil is higher than that of the reaction liquid in the spherical container of the micro-reaction tube;
after the reaction, pouring the reaction solution into a separating funnel, adding 10mL of ethyl acetate, back-extracting for 3 times with 15mL of distilled water, collecting an organic phase, performing reduced pressure distillation to obtain a crude product, and separating by column chromatography to obtain the 2-acetamido-5-ethyl p-benzoquinone with the yield of 55%.
Comparative example 1
The difference between the comparative example and the example 1 is that the comparative example uses potassium persulfate to replace iodobenzene acetate for reaction, other raw materials and reaction conditions are the same, and as a result, 2-acetamido-5-methyl-p-benzoquinone is not prepared, which shows that the target product of the application can be obtained only by combining specific oxidant iodobenzene acetate with other process conditions.
Comparative example 2
The difference between this comparative example and example 1 is that the temperature of the stirring reaction is 80℃and the other raw materials and reaction conditions are the same, so that the yield of 2-acetamido-5-methyl-p-benzoquinone is 21%, indicating that the too high temperature is unfavorable for the formation of the target product.
Comparative example 3
This comparative example is different from example 1 in that p-methylacetanilide was replaced with anilide having no substituent on the benzene ring, and other raw materials and reaction conditions were the same, with the result that p-benzoquinone could not be obtained because of esterification of the para-position of anilide.
The preparation method provided by the application has mild and simple conditions, the temperature is at normal temperature, and dangerous operation is avoided; the selectivity is good, no by-product is generated basically, and the preparation is very easy; the atomic utilization rate is high, and the method accords with the modern synthetic chemistry environment-friendly and efficient concept; the prepared p-benzoquinone compound can be used in various life fields such as pesticides, medicines and the like.
The above-described embodiments of the present application do not limit the scope of the present application. Any other corresponding changes and modifications made in accordance with the technical idea of the present application shall be included in the scope of the claims of the present application.
Claims (4)
1. The preparation method of the p-benzoquinone compound is characterized by comprising the following steps of: adding one or two of p-methylacetanilide and p-ethylacetanilide, iodobenzene acetate and N, N-dimethylformamide into a reactor, and stirring and reacting at 20-40 ℃ to obtain the p-benzoquinone compound, and purifying the p-benzoquinone compound prepared by stirring and reacting; the purification comprises the steps of mixing the p-benzoquinone compound prepared by stirring reaction with ethyl acetate, adding water for back extraction to obtain an organic phase, decompressing and distilling the organic phase to obtain a crude product, and separating the crude product by column chromatography to obtain the purified p-benzoquinone compound, wherein the molar ratio of one or two of the p-methylacetanilide and the p-ethylacetanilide to the iodobenzene acetate is 1 (2-3), and the material ratio of one or two of the p-methylanilide and the p-ethylacetanilide to the N, N-dimethylformamide is 1mmol (10-20) mL.
2. The method for producing p-benzoquinone compound according to claim 1, wherein the stirring reaction time is 12 to 16 hours.
3. The method for preparing p-benzoquinone compounds according to claim 1, wherein the stirring reaction is performed under the stirring action of a magnetic stirrer, and the stirring speed is 600-1000 rpm.
4. The method for producing p-benzoquinone compounds according to claim 1, wherein the stirring reaction is performed in an oil bath.
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