CN107903203B - Synthetic method of 3, 4-dinitrophthalimide - Google Patents
Synthetic method of 3, 4-dinitrophthalimide Download PDFInfo
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- CN107903203B CN107903203B CN201710979520.5A CN201710979520A CN107903203B CN 107903203 B CN107903203 B CN 107903203B CN 201710979520 A CN201710979520 A CN 201710979520A CN 107903203 B CN107903203 B CN 107903203B
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- sulfuric acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
Abstract
The invention provides a method for synthesizing 3, 4-dinitrophthalimide, which comprises the following steps: adding phthalimide and phosphorus pentoxide into a solvent concentrated sulfuric acid, dropwise adding a nitration reagent in an ice bath at 0 ℃, controlling the temperature below 10 ℃, heating to room temperature after dropwise adding, stirring for reacting for 2-10 hours, adding the obtained reaction liquid into water after stopping the reaction, washing to obtain a precipitate, washing the filter residue obtained after suction filtration of the precipitate with water, and recrystallizing with ethanol to obtain 3, 4-dinitrophthalimide. The method has the advantages of cheap and easily obtained raw materials and reagents, low cost, mild reaction conditions, simple post-treatment operation and contribution to large-scale industrial production of products.
Description
Technical Field
The invention relates to a synthetic method of 3, 4-dinitrophthalimide.
Background
Nitro-substituted phthalimide is an important drug intermediate and dye intermediate, and is mainly synthesized by the nitration reaction of phthalimide. According to the reports at home and abroad, the nitration methods of phthalimide and derivatives thereof mainly comprise two methods: the first method is to use concentrated sulfuric acid and ammonium nitrate as nitration reagents to carry out nitration reaction, and the reaction yield is less than 60%; one is to use concentrated sulfuric acid and concentrated nitric acid as nitration reagent, and the reaction yield is over 80%. Most of the prior reports on the nitration method of phthalimide and the derivatives thereof focus on the aspect of mononitro substitution reaction of phthalimide and the derivatives thereof, and the synthesis method of dinitro substitution products of phthalimide and the derivatives thereof is not related basically.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for synthesizing 3, 4-dinitrophthalimide, which has the advantages of cheap and easily-obtained raw materials and reagents, low cost, mild reaction conditions, simple post-treatment operation and contribution to large-scale industrial production of products.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a method for synthesizing 3, 4-dinitrophthalimide comprises the following steps:
adding phthalimide and phosphorus pentoxide into a solvent concentrated sulfuric acid, dropwise adding a nitration reagent in an ice bath at 0 ℃, controlling the temperature below 10 ℃, heating to room temperature after dropwise adding, stirring for reacting for 2-10 hours, adding the obtained reaction liquid into water after stopping the reaction, washing to obtain a precipitate, washing the filter residue obtained after suction filtration of the precipitate with water, and recrystallizing with ethanol to obtain 3, 4-dinitrophthalimide.
Preferably, the mass fraction of the solvent concentrated sulfuric acid is 98%, and the mass ratio of the phthalimide to the solvent concentrated sulfuric acid is (2.7-13.7): 1.
Preferably, the mass ratio of the phthalimide to the solvent concentrated sulfuric acid is 8.2: 1. When the nitration reagent is dripped into a reaction system, exothermic reaction can occur, the exothermic reaction is serious if the dosage of the solvent is too small, so that the temperature is difficult to control, and the cost is increased if the dosage of the solvent is too large, so that the optimal dosage of the solvent is that the mass ratio of concentrated sulfuric acid to phthalimide is 8.2: 1.
Preferably, the nitrating reagent is prepared by mixing 65 mass percent of concentrated nitric acid and 98 mass percent of concentrated sulfuric acid, and the molar ratio of the concentrated nitric acid, the concentrated sulfuric acid and the phthalimide in the nitrating reagent is (2-3.2):1: 1.
Preferably, the molar ratio of the concentrated nitric acid, the concentrated sulfuric acid and the phthalimide in the nitrating reagent is 2.8:1: 1.
Preferably, the molar ratio of phosphorus pentoxide to phthalimide in the present invention is (0-3): 1.
Preferably, the molar ratio of phosphorus pentoxide to phthalimide in the present invention is 2.5: 1. The phosphorus pentoxide serving as a catalyst can absorb the byproduct water generated in the reaction and promote the reaction to proceed in the positive reaction direction, thereby improving the yield of the nitration reaction. Theoretically, the proper molar amount of phosphorus pentoxide is 2 times of the molar amount of phthalimide, but due to the influence of solvents and moisture in the environment, the optimal amount is larger than the theoretical amount, so the optimal amount is 2.5 times of the molar amount of phthalimide in comprehensive cost consideration.
Preferably, the volume ratio of the water to the solvent concentrated sulfuric acid in the water washing process is (1-2): 1.
Preferably, the dropping speed of the nitrating agent is 2 seconds per drop.
Preferably, the stirring reaction time of the present invention is 6 hours.
Compared with the prior art, the invention has the following beneficial effects:
1) the invention takes phthalimide as an initial raw material, takes mixed solution of concentrated sulfuric acid and concentrated nitric acid as a nitration reagent, synthesizes 3, 4-dinitrophthalimide in ice bath under the catalysis of phosphorus pentoxide, and has the reaction principle that:
the invention selects proper raw material molar ratio, catalyst dosage, solvent dosage and reaction time, the yield of the obtained dinitration product of the phthalimide can reach more than 65.5 percent, the yield of the prior mononitration product of the phthalimide generally can reach 80 percent, but the nitro is an inert group, the benzene ring is passivated, and the yield is reduced by introducing a nitro group to the benzene ring, so the yield which can be achieved by the invention is more ideal.
2) The raw materials and reagents used in the invention are cheap and easily available, so the cost is lower, the reaction condition is mild, the post-treatment operation is simple, and the large-scale industrial production of the product is facilitated.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the principles of the invention:
FIG. 1 is a drawing of 3, 4-dinitrophthalimide as described in example 11H-NMR spectrum.
FIG. 2 is an FTIR spectrum of 3, 4-bis-nitrophthalimide as described in example 1.
Detailed Description
The present invention will be described in detail with reference to specific embodiments, which are illustrative of the invention and are not to be construed as limiting the invention. Among these, concentrated H in examples 1 to 62SO4The mass fraction is 98 percent, and the HNO is concentrated3The mass fraction of (A) is 65%.
Example 1
In a 500mL three-necked flask, 29.4g of phthalimide and concentrated H were placed2SO4100mL and 52.8g of phosphorus pentoxide, cooled to 0 ℃ in an ice-water bath, and slowly dropwise adding a nitrating agent (concentrated HNO) at a rate of 2 seconds per drop328mL and concentrated H2SO411mL of mixed solution), controlling the temperature below 10 ℃, heating to room temperature after dropwise addition, stirring for reaction for 4 hours, adding the obtained reaction solution into water after the reaction is stopped, slowly pouring the obtained reaction solution into 100-200mL of water for water washing, separating out yellow solid, carrying out suction filtration on the yellow solid to obtain filter residue, soaking and washing the filter residue with water, and then recrystallizing with ethanol to obtain light yellow crystals of 12.8g of 3, 4-bis (nitrophthalimide), wherein the yield is 43.4%, and the melting point is 242-243 ℃. Structural analysis of the product1The H-NMR spectrum is shown in figure 1, and the FTIR spectrum of the product is shown in figure 2.
Example 2
In a 500mL three-necked flask, 29.4g of phthalimide and concentrated H were placed2SO4100mL and 52.8g of phosphorus pentoxide, cooled to 0 ℃ in an ice-water bath, and slowly dropwise adding a nitrating agent (concentrated HNO) at a rate of 2 seconds per drop334mL and concentrated H2SO411mL of mixed solution), controlling the temperature below 10 ℃, heating to room temperature after dropwise addition, stirring for reaction for 8 hours, adding the obtained reaction solution into water after the reaction is stopped, slowly pouring the obtained reaction solution into 100-200mL of water for water washing, separating out yellow solid, carrying out suction filtration on the yellow solid to obtain filter residue, soaking and washing the filter residue with water, and then recrystallizing with ethanol to obtain light yellow crystals of 15.7g of 3, 4-dinitrophthalimide, wherein the yield is 53.2%, and the melting point is 242-243 ℃.
Example 3
In a 500mL three-necked flask, 29.4g of phthalimide and concentrated H were placed2SO4150mL and 66.0g of phosphorus pentoxide, cooled to 0 ℃ in an ice-water bath, and slowly dropwise adding a nitrating agent (concentrated HNO) at a rate of 2 seconds per drop334mL and concentrated H2SO411mL of mixed solution) at a temperature of 10 ℃ or lower, heating to room temperature after completion of the dropwise addition, stirring for 10 hours, and stopping the reaction to obtain a reaction solutionAdding water, slowly pouring the mixture into 200mL of 100-plus-material water for washing to separate out yellow solid, carrying out suction filtration on the yellow solid to obtain filter residue, washing the filter residue with water, and then recrystallizing the filter residue with ethanol to obtain light yellow crystals of 17.3g of 3, 4-dinitrophthalimide, wherein the yield is 58.4 percent, and the melting point is 242-plus-material 243 ℃.
Example 4
In a 500mL three-necked flask, 29.4g of phthalimide and concentrated H were placed2SO4150mL and 66.0g of phosphorus pentoxide, cooled to 0 ℃ in an ice-water bath, and slowly dropwise adding a nitrating agent (concentrated HNO) at a rate of 2 seconds per drop339mL and concentrated H2SO411mL of mixed solution), controlling the temperature below 10 ℃, heating to room temperature after dropwise addition, stirring for reaction for 6h, adding the obtained reaction solution into water after the reaction is stopped, slowly pouring the obtained reaction solution into 100-200mL of water for water washing, separating out yellow solid, carrying out suction filtration on the yellow solid to obtain filter residue, soaking and washing the filter residue with water, and then recrystallizing with ethanol to obtain light yellow crystals of 19.4g of 3, 4-bis (nitrophthalimide), wherein the yield is 65.5%, and the melting point is 242-243 ℃.
Example 5
In a 500mL three-necked flask, 29.4g of phthalimide and concentrated H were placed2SO4200mL and 79.2g of phosphorus pentoxide, cooling to 0 ℃ in an ice water bath, and slowly dropwise adding a nitrating agent (concentrated HNO) at the speed of 2 seconds per drop339mL and concentrated H2SO411mL of mixed solution), controlling the temperature below 10 ℃, heating to room temperature after dropwise addition, stirring for reaction for 10 hours, adding the obtained reaction solution into water after the reaction is stopped, slowly pouring the obtained reaction solution into 100-200mL of water for water washing, separating out yellow solid, carrying out suction filtration on the yellow solid to obtain filter residue, soaking and washing the filter residue with water, and then recrystallizing with ethanol to obtain light yellow crystals of 18.3g of 3, 4-dinitrophthalimide, wherein the yield is 62.0%, and the melting point is 242-243 ℃.
Example 6
In a 500mL three-necked flask, 29.4g of phthalimide and concentrated H were placed2SO4200mL and 79.2g of phosphorus pentoxide, cooling to 0 ℃ in an ice water bath, and slowly dropwise adding a nitrating agent (concentrated HNO) at the speed of 2 seconds per drop345mL and concentrated H2SO411mL of mixed solution), controlling the temperature below 10 ℃, heating to room temperature after dropwise addition, stirring for reaction for 8 hours, adding the obtained reaction solution into water after the reaction is stopped, slowly pouring the obtained reaction solution into 100-200mL of water for water washing, separating out yellow solid, carrying out suction filtration on the yellow solid to obtain filter residue, soaking and washing the filter residue with water, and then recrystallizing with ethanol to obtain 16.7g of light yellow crystal 3, 4-dinitrophthalimide, wherein the yield is 56.3%, and the melting point is 242-243 ℃.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (2)
1. A method for synthesizing 3, 4-dinitrophthalimide is characterized by comprising the following steps: the method comprises the following steps:
adding phthalimide and phosphorus pentoxide into a solvent concentrated sulfuric acid, dropwise adding a nitration reagent in an ice bath at 0 ℃, controlling the temperature below 10 ℃, heating to room temperature after dropwise adding, stirring for reacting for 2-10 hours, adding the obtained reaction liquid into water after stopping the reaction, washing to obtain a precipitate, wherein the volume ratio of the water to the solvent concentrated sulfuric acid is (1-2):1 during washing, washing filter residue obtained after suction filtration of the precipitate with water, and recrystallizing with ethanol to obtain 3, 4-dinitrophthalimide; the mass fraction of the solvent concentrated sulfuric acid is 98%, and the mass ratio of the phthalimide to the solvent concentrated sulfuric acid is 8.2: 1; the nitration reagent is formed by mixing 65 mass percent of concentrated nitric acid and 98 mass percent of concentrated sulfuric acid, the molar ratio of the concentrated nitric acid to the concentrated sulfuric acid to the phthalimide in the nitration reagent is 2.8:1:1, and the dripping speed of the nitration reagent is 2 seconds per drop; the molar ratio of the phosphorus pentoxide to the phthalimide is 2.5: 1.
2. The method for synthesizing 3, 4-bis (nitrophthalimide) according to claim 1, wherein: the reaction time with stirring was 6 hours.
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| CN104086476A (en) * | 2014-05-26 | 2014-10-08 | 湖北新舟化工有限公司 | Preparation method for N-methyl-4-nitrophthalimide |
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| CN104086476A (en) * | 2014-05-26 | 2014-10-08 | 湖北新舟化工有限公司 | Preparation method for N-methyl-4-nitrophthalimide |
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| 4-氨基邻苯二甲酰亚胺合成的新工艺;吕亮等;《南京工业大学学报自然科学版》;20081231;第30卷(第6期);第51-53页 * |
| 侧链含邻苯二甲酰亚胺的聚酰亚胺液晶垂直取向剂的制备与表征;夏森林等;《高分子学报》;20131231(第11期);第1376-1383页 * |
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