CN108558804B - Synthetic method of 3-fluorophthalic acid - Google Patents
Synthetic method of 3-fluorophthalic acid Download PDFInfo
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- CN108558804B CN108558804B CN201810478145.0A CN201810478145A CN108558804B CN 108558804 B CN108558804 B CN 108558804B CN 201810478145 A CN201810478145 A CN 201810478145A CN 108558804 B CN108558804 B CN 108558804B
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- fluorophthalic
- nitrophthalic
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
- C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/083—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid anhydrides
- C07C51/087—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid anhydrides by hydrolysis
Abstract
The invention discloses a synthesis method of 3-fluorophthalic acid, which comprises the steps of dissolving 3-nitrophthalic acid serving as a raw material, dehydrating the dissolved 3-nitrophthalic acid by using an acetyl chloride solvent, performing denitration and fluorination by using potassium fluoride after dehydration, adding thionyl chloride to remove byproducts generated in the fluorination process, and purifying to obtain a target compound, namely the 3-fluorophthalic acid. The method takes the 3-nitrophthalic acid as a raw material for synthesizing the 3-fluorophthalic acid, and has the advantages of cheap and easily obtained raw material, simple process and high yield; the product is well separated from the sulfolane solvent by a method of adjusting PH, thereby solving the difficulty that the solvent has high boiling point and is difficult to evaporate; acetyl chloride is used as a dehydration solvent, so that the method not only replaces the control of the medicine acetic anhydride, but also reduces the byproduct acetic acid brought by the dehydration process of the acetic anhydride, and has mild reaction conditions and simple and convenient post-treatment.
Description
Technical Field
The invention relates to the field of compound synthesis, in particular to a synthetic method of 3-fluorophthalic acid.
Background
The polyetherimide is synthesized by reacting 3-fluorophthalic acid serving as a raw material with potassium carbonate; the polyimide film can be directly synthesized from 3-fluorophthalic anhydride. The polyetherimide belongs to super engineering plastics manufactured by polyetherimide, has the characteristics of high temperature resistance, stable size and the like, and can be widely applied to high temperature resistant terminals, lighting equipment, flexible circuit boards, liquid conveying equipment, medical equipment, household appliances and the like; the polyetherimide has excellent comprehensive balance performance, is effectively applied to the departments of electronics, motors, aviation and the like, and is used as a metal substitute material for traditional products and cultural living goods.
Disclosure of Invention
In order to solve the problems, the invention provides a synthetic method of 3-fluorophthalic acid.
In order to achieve the purpose, the invention adopts the technical scheme that:
a synthetic method of 3-fluorophthalic acid comprises the following steps:
synthesis of S1, 3-nitrophthalic anhydride
Placing 5g of 3-nitrophthalic acid and 7.5ml of acetyl chloride in a double-mouth bottle, refluxing for 3.5 hours at 51 ℃, introducing hydrogen chloride gas generated in the reaction into a sodium hydroxide solution with the mass fraction of 30%, stopping the reaction when no bubbles are generated in the sodium hydroxide solution, cooling, performing suction filtration through a funnel, washing filter residues through petroleum ether, and drying to obtain 4.3g of a product, namely 3-nitrophthalic anhydride;
synthesis of S2, 3-fluorophthalic anhydride
Placing 1g of 3-nitrophthalic anhydride, 0.7g of potassium fluoride dried by a vacuum drying oven and 2.5ml of sulfolane in a double-mouth bottle, heating to 150 ℃ under stirring to generate a large amount of reddish brown gas, stopping the reaction after reacting for 2h, adding 1ml of thionyl chloride, stirring for 30min at 78 ℃, cooling, and removing the redundant thionyl chloride by reduced pressure distillation; adding 1ml of sulfolane and 0.5g of potassium fluoride into the double-mouth bottle, heating to 150 ℃, reacting for 1.5 hours, stopping the reaction after no reddish brown gas is generated, and obtaining reaction liquid;
synthesis of S3, 3-fluorophthalic acid
Adding part of water into the reaction liquid until powder in the solution disappears, adjusting the pH of the liquid to 8-9, extracting with ethyl acetate for 3 times, extracting sulfolane from the solution, adjusting the pH of the water phase to 4-5, passing through ethyl acetate for 3 times, and distilling under reduced pressure to obtain the product 3-fluorophthalic acid.
Wherein the amount of ethyl acetate used in each extraction in step S3 is 50 ml.
The invention has the following beneficial effects:
the method takes the 3-nitrophthalic acid as a raw material for synthesizing the 3-fluorophthalic acid, and has the advantages of cheap and easily obtained raw material, simple process and high yield; the product is well separated from the sulfolane solvent by a method of adjusting PH, thereby solving the difficulty that the solvent has high boiling point and is difficult to evaporate; acetyl chloride is adopted as a dehydration solvent, so that the method not only replaces the control medicine of acetic anhydride, but also reduces the byproduct acetic acid brought in the dehydration process of acetic anhydride, and has mild reaction conditions and simple and convenient post-treatment; in the process of fluoro denitration, sulfolane is used as a fluoro solvent, compared with solvents such as benzonitrile, N-dimethylformamide and the like, the product is easier to separate by a method of adjusting PH, and the product with high yield is obtained under mild reaction conditions without the action of a phase transfer catalyst.
Drawings
Fig. 1 is a composite circuit diagram of step S1 in the embodiment of the present invention.
Fig. 2 is a composite circuit diagram of step S2 in the embodiment of the present invention.
Fig. 3 is a composite circuit diagram of step S3 in the embodiment of the present invention.
FIG. 4 is an overall composite circuit diagram of an embodiment of the present invention.
Detailed Description
In order that the objects and advantages of the invention will be more clearly understood, the invention is further described in detail below with reference to examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a method for synthesizing 3-fluorophthalic acid, which comprises the following steps:
synthesis of S1, 3-nitrophthalic anhydride
Adding 5g (0.0237mol) of 3-nitrophthalic acid and 7.5ml of acetyl chloride into a double-mouth bottle, refluxing for 3.5 hours at 51 ℃, introducing hydrogen chloride gas generated in the reaction into 30% sodium hydroxide solution, generating a large amount of needle-shaped objects in the double-mouth bottle after a period of time, stopping the reaction when no bubbles are generated in the sodium hydroxide solution, cooling, performing suction filtration through a funnel, washing filter residues with petroleum ether, and drying to obtain 4.3g (0.021mol) of the product 3-nitrophthalic anhydride, wherein the yield is 94%.
Synthesis of S2, 3-fluorophthalic anhydride
Adding 1g of 3-nitrophthalic anhydride, 0.7g (0.012mol) of potassium fluoride dried by a vacuum drying oven and 2.5ml of sulfolane into a double-mouth bottle, heating to 150 ℃ under stirring to generate a large amount of reddish brown gas, stopping the reaction after reacting for 2h, and detecting through nuclear magnetic data after cooling to find that the conversion rate of the raw materials is 68%. 1ml of thionyl chloride (for removing by-products generated during the reaction) was added thereto, stirred at 78 ℃ for 30min, and after cooling, the excess thionyl chloride was distilled off under reduced pressure. And adding 1ml of sulfolane and 0.5g of potassium fluoride into the double-mouth bottle, heating to 150 ℃, generating a small amount of reddish brown gas again, reacting for 1.5 hours, stopping the reaction after no reddish brown gas is generated, and finally obtaining the conversion rate of 95%.
After nuclear magnetic data analysis, byproducts are generated in the reaction process, and the byproducts are changed into raw materials to carry out the next reaction by adding thionyl chloride again, so that the final conversion rate is improved, and the reaction path is as follows:
synthesis of S3, 3-fluorophthalic acid
Adding part of water into the reaction liquid until powder in the solution disappears, adjusting the pH of the liquid to 8-9, extracting sulfolane in the solution by using ethyl acetate (3 x 50ml), adjusting the pH of the water phase to 4-5, extracting a product in the water phase by using ethyl acetate (3 x 50ml), distilling the organic solvent under reduced pressure to obtain a product 3-fluorophthalic acid, recrystallizing to obtain a pure product 0.66g (0.0036mol), wherein the yield is 70%. The compound is a yellow solid, and the compound is a yellow solid,1H NMR(DMSO,400MHz)δ:7.56(m,2H),7.73(d,J＝8.0Hz,1H),13.52(s,2H)；13C NMR(DMSO,100MHz)δ:(120.21,125.00,126.11,131.01,131.43,157.32,159.77,166.30)。
the foregoing is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (2)
1. A synthetic method of 3-fluorophthalic acid is characterized by comprising the following steps:
synthesis of S1, 3-nitrophthalic anhydride
Placing 5g of 3-nitrophthalic acid and 7.5ml of acetyl chloride in a double-mouth bottle, refluxing for 3.5 hours at 51 ℃, introducing hydrogen chloride gas generated in the reaction into a sodium hydroxide solution with the mass fraction of 30%, stopping the reaction when no bubbles are generated in the sodium hydroxide solution, cooling, performing suction filtration through a funnel, washing filter residues through a small amount of petroleum ether, and drying to obtain 4.3g of a product, namely 3-nitrophthalic anhydride;
synthesis of S2, 3-fluorophthalic anhydride
Placing 1g of 3-nitrophthalic anhydride, 0.7g of potassium fluoride dried by a vacuum drying oven and 2.5ml of sulfolane in a double-mouth bottle, heating to 150 ℃ under stirring to generate a large amount of reddish brown gas, stopping the reaction after reacting for 2h, adding 1ml of thionyl chloride, stirring for 30min at 78 ℃, cooling, and removing the redundant thionyl chloride by reduced pressure distillation; adding 1ml of sulfolane and 0.5g of potassium fluoride into the double-mouth bottle, heating to 150 ℃, reacting for 1.5 hours, stopping the reaction after no reddish brown gas is generated, and obtaining reaction liquid;
synthesis of S3, 3-fluorophthalic acid
Adding part of water into the reaction liquid until powder in the solution disappears, adjusting the pH value of the liquid to 8-9, extracting with ethyl acetate for 3 times, extracting sulfolane from the solution, adjusting the pH value of the water phase to 4-5, passing through ethyl acetate for 3 times, and distilling under reduced pressure to obtain the product 3-fluorophthalic acid.
2. The method of claim 1, wherein the amount of ethyl acetate used in each extraction in step S3 is 50 ml.
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