Method for preparing 2-furyl-methylketon from ethenone

Abstract

The invention provides a method for preparing 2-furyl-methylketon from ethenone. In the presence of an acylation catalyst, furan and ethenone react in an organic solvent for 2-5 hours at 5-20 DEG C to prepare crude 2-furyl-methylketon, then the organic solvent is recycled through distillation and the 2-furyl-methylketon is prepared through rectification; the acylation catalyst is one or more of phosphoric acid, sulfuric acid and p-toluenesulfonic acid; the mass ratio of the acylation catalyst to furan is (0.005-0.009) to 1; the organic solvent is one or more of methylene dichloride, ethylene dichloride and chloroform. Compared with the prior art, the method has the advantages and benefits as follows: 1. the method is suitable for continuous production owing to lower raw material cost; 2. the method is suitable for industrial production due to lower reaction temperature; 3. no hydrogen chloride or acetic acid is produced in the production process, the corrosion is light and the discharge of three wastes is low; 4. the solvent can be used directly and indiscriminately after being recycled so as to realize green synthesis, the product yield is up to 95.0% and the purity is up to 99%.

Description

Technical field

[0001] The invention relates to a production method of chemical intermediate 2-acetylfuran. Background technique

[0002] 2-Acetylfuran is an important intermediate of medicines, pesticides and perfumes, and is the main raw material for the synthesis of furan ammonium salt.

[0003] The synthesis process of 2-acetylfuran mainly includes the acetic acid method: Helvetica Chimica Acta, 88(8), 2232-2287, 2005, Tetrahedron, 60(48), 10843-10850, 2004, Synthesis, (13), 2165-2168, Mentioned in 2004, etc.; Acetyl chloride method: Mentioned in Synthetic Communications, 38(2), 255-264, 2008; Acetic anhydride method: Mentioned in Chinese Journal of Antibiotics 30(5), 304-313, 2005, CN101357910A, etc. .

[0004] The conversion rate and yield of acetic acid process products are low, up to 40% based on furan, with serious corrosion, high production cost and low product quality.

[0005] The acetyl chloride route uses acetyl chloride as the acylating agent, and reacts at a lower te...

Examples

Embodiment 1

[0023] Add 136g furan, 1.0g phosphoric acid and 260g chloroform into a four-necked flask equipped with electric stirring, ketene gas tube, thermometer and vent tube, turn on the stirring, and pour 85g ketene within 3 hours at 15℃ . After recovering the solvent under normal pressure, rectifying under reduced pressure, collecting 78-81°C fractions at -0.099Mpa to obtain 210.2g of 2-acetylfuran with a purity of 99% (the yield is 95.5% based on furan).

[0024] After the solvent recovery is directly applied for 6 times, the effect of recovered solvent applied on the product yield and purity is shown in the following table:

[0025] Number of applications Yield(%) purity(%) 195.099.3 295.399.1 395.299.2 495.099.4 595.299.2 695.199.1

Embodiment 2

[0027] In a four-necked flask equipped with electric stirring, ketene gas tube, thermometer and exhaust tube, add 68g furan, 0.5g phosphoric acid, 150g dichloromethane, turn on the stirring, and pour ethylene within 3 hours at 20℃ Ketone 42.0g. After recovering the solvent at normal pressure, rectifying under reduced pressure, collecting 78-81°C fractions at -0.099Mpa to obtain 104.8 g of 2-acetylfuran with a purity of 99.1% (the yield is 95.2% based on furan). .

Embodiment 3

[0029] In a four-necked flask equipped with electric stirring, ketene gas tube, thermometer and exhaust tube, add 136g furan, 1.0g phosphoric acid, 280g methylene chloride, turn on the stirring, and pour ethylene within 3 hours at 20℃ Ketone 86g. After recovering the solvent under normal pressure, rectifying under reduced pressure, collecting 78-81°C fractions at -0.099Mpa to obtain 209 g of 2-acetylfuran with a purity of 99.3% (the yield is 95.0% based on furan).

Technical field

[0001] The invention relates to a production method of chemical intermediate 2-acetylfuran. Background technique

[0002] 2-Acetylfuran is an important intermediate of medicines, pesticides and perfumes, and is the main raw material for the synthesis of furan ammonium salt.

[0003] The synthesis process of 2-acetylfuran mainly includes the acetic acid method: Helvetica Chimica Acta, 88(8), 2232-2287, 2005, Tetrahedron, 60(48), 10843-10850, 2004, Synthesis, (13), 2165-2168, Mentioned in 2004, etc.; Acetyl chloride method: Mentioned in Synthetic Communications, 38(2), 255-264, 2008; Acetic anhydride method: Mentioned in Chinese Journal of Antibiotics 30(5), 304-313, 2005, CN101357910A, etc. .

[0004] The conversion rate and yield of acetic acid process products are low, up to 40% based on furan, with serious corrosion, high production cost and low product quality.

[0005] The acetyl chloride route uses acetyl chloride as the acylating agent, and reacts at a lower te...

Examples

Embodiment 1

[0023] Add 136g furan, 1.0g phosphoric acid and 260g chloroform into a four-necked flask equipped with electric stirring, ketene gas tube, thermometer and vent tube, turn on the stirring, and pour 85g ketene within 3 hours at 15℃ . After recovering the solvent under normal pressure, rectifying under reduced pressure, collecting 78-81°C fractions at -0.099Mpa to obtain 210.2g of 2-acetylfuran with a purity of 99% (the yield is 95.5% based on furan).

[0024] After the solvent recovery is directly applied for 6 times, the effect of recovered solvent applied on the product yield and purity is shown in the following table:

[0025] Number of applications Yield(%) purity(%) 195.099.3 295.399.1 395.299.2 495.099.4 595.299.2 695.199.1

Embodiment 2

[0027] In a four-necked flask equipped with electric stirring, ketene gas tube, thermometer and exhaust tube, add 68g furan, 0.5g phosphoric acid, 150g dichloromethane, turn on the stirring, and pour ethylene within 3 hours at 20℃ Ketone 42.0g. After recovering the solvent at normal pressure, rectifying under reduced pressure, collecting 78-81°C fractions at -0.099Mpa to obtain 104.8 g of 2-acetylfuran with a purity of 99.1% (the yield is 95.2% based on furan). .

Embodiment 3

[0029] In a four-necked flask equipped with electric stirring, ketene gas tube, thermometer and exhaust tube, add 136g furan, 1.0g phosphoric acid, 280g methylene chloride, turn on the stirring, and pour ethylene within 3 hours at 20℃ Ketone 86g. After recovering the solvent under normal pressure, rectifying under reduced pressure, collecting 78-81°C fractions at -0.099Mpa to obtain 209 g of 2-acetylfuran with a purity of 99.3% (the yield is 95.0% based on furan).

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