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Method for synthesizing p-hydroxypropiophenone

A technology of p-hydroxybenzene and a synthesis method, which is applied in the field of synthesis of pharmaceutical intermediates, can solve the problems of a large number of catalysts, low propionic acid reaction activity, no reports on yields, etc., and achieves easy follow-up treatment of the reaction, and cheap and easy-to-obtain catalysts. , post-processing simple effects

Inactive Publication Date: 2015-02-25
ZHEJIANG SCI-TECH UNIV
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Problems solved by technology

[0003] About the synthesis of p-hydroxypropiophenone, there are relevant reports both at home and abroad, and the synthesis mainly contains the following three methods: 1. Lota, R K et al. reported that phenol and Propionyl chloride is raw material, generates p-hydroxypropiophenone through Friedel-Crafts reaction, although this method can obtain target product in one step, yield is relatively low, only has 50%, and AlCl 3 The dosage is twice that of propionyl chloride
② Devis, R et al. used phenol and propionic acid as raw materials in the literature Bull.Soc.Chim.Fr., (9), 3185-3190 (1967). The reactivity of p-hydroxypropiophenone and propionic acid was generated by Nencki reaction Relatively low, the yield has not been reported
③Miller, E et al reported in the literature Organic Syntheses, 1943, 2:543-545 that phenyl propionate was used as raw material and AlCl 3 Fries rearrangement is used as a catalyst to generate p-hydroxypropiophenone, but the literature yield is only 34% to 39%, and the highly toxic nitrobenzene is used as a solvent
4. Murashige, the people such as R are in literature Tetrahedron, 67,641-649 (2011).Report is to take phenol and propionyl chloride as raw material, under trifluoromethanesulfonic acid catalysis, generate p-hydroxypropiophenone through Friedel-Crafts reaction, although this method can The target product can be obtained in one step, and the yield is relatively high, but trifluoromethanesulfonic acid is used as a catalyst in chemical production, and the cost is too high
⑤Wang Liping and others used BF in "Zhejiang Chemical Industry" Vol.41No.1 (2010) 3 ·H 2 O is used as a Fries rearrangement catalyst to obtain better selectivity and yield, and the reaction conditions are mild, but the catalyst needs to be put in a large amount

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  • Method for synthesizing p-hydroxypropiophenone
  • Method for synthesizing p-hydroxypropiophenone
  • Method for synthesizing p-hydroxypropiophenone

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Embodiment 1

[0021] Embodiment 1: the synthesis of p-hydroxyacetophenone

[0022] 1) Preparation of Propionylphenol

[0023] Phenol (10.0g, 0.106mol) was added to 30ml of dichloromethane, sodium bicarbonate (0.8904g, 10.6mmol) was added, propionyl chloride (12.0g, 0.129mol) was added dropwise under heating and reflux, and the reaction was refluxed for 4h under stirring . TLC monitors that the reaction is completed, the reaction solution is poured into 100ml ice water, and the 3 The pH of the solution was adjusted to 7, the organic phase was separated, and the aqueous phase was extracted twice with 50 ml of dichloromethane, the organic phases were combined, dried, evaporated at normal pressure, and the organic solvent was recovered to obtain 13.2 g of the product with a yield of 82.8%. .

[0024] 2) preparation of p-hydroxypropiophenone

[0025] Propionylphenol (8.0g, 0.052mol) was added to methanesulfonic acid (14.0ml, 0.212mol), the temperature was controlled at 30°C, and the reaction...

Embodiment 2

[0026] Embodiment 2: the synthesis of p-hydroxyacetophenone

[0027] 1) Preparation of Propionylphenol

[0028] Phenol (10.0g, 0.106mol) was added to 30ml of dichloroethane, sodium bicarbonate (0.89g, 10.6mmol) was added, propionyl chloride (13.8g, 0.148mol) was added dropwise under heating and reflux, and the reaction was reflux under stirring 5h. TLC monitors that the reaction is completed, and the reaction solution is poured into 100ml ice water, and the 2 CO 3 The pH of the solution adjustment system was 8, the organic phase was separated, and the aqueous phase was extracted three times with 50 ml of dichloroethane, the organic phases were combined, dried, evaporated at normal pressure, and the organic solvent was recovered to obtain 13.9 g of the product with a yield of 87.5%. .

[0029] 2) preparation of p-hydroxypropiophenone

[0030] Propionylphenol (8.0g, 0.052mol) was added to methanesulfonic acid (14.0ml, 0.212mol), the temperature was controlled at 50°C, and t...

Embodiment 3

[0031] Embodiment 3: the synthesis of p-hydroxyacetophenone

[0032] 1) Preparation of Propionylphenol

[0033]Phenol (10.0g, 0.106mol) was added to 30ml of chloroform, sodium bicarbonate (0.8904g, 10.6mmol) was added, propionyl chloride (15.7g, 0.170mol) was added dropwise under heating and reflux, and the reaction was refluxed for 6h under stirring . TLC monitors that the reaction is completed, the reaction solution is poured into 100ml ice water, and the 3 The pH of the solution was adjusted to 7, the organic phase was separated, and the aqueous phase was extracted three times with 50 ml of chloroform. The organic phases were combined, dried, evaporated under normal pressure, and the organic solvent was recovered to obtain 14.2 g of the product with a yield of 88.8%.

[0034] 2) preparation of p-hydroxypropiophenone

[0035] Propionylphenol (8.0g, 0.052mol) was added to methanesulfonic acid (14.0ml, 0.212mol), the temperature was controlled at 50°C, and the reaction was ...

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Abstract

The invention discloses a method for synthesizing p-hydroxypropiophenone. The method specifically comprises the following steps: adding phenol and an organic solvent into a reactor, then adding a weak alkali, and adding a propionyl chloride reagent under heating reflux, wherein the reflux reaction time is 4h-6h; pouring into ice water after the reaction, regulating the pH to 6-8 with an alkaline solution, further extracting a reaction solution with the organic solvent for a plurality of times, and drying to evaporate out the solvent to obtain a product, namely propionyl phenol; putting a certain mount of propionyl phenol and methanesulfonic acid in a dry reaction container, wherein the heating temperature is 30-90 DEG C and the reaction time is 0.5-2h; and pouring a reaction solution into a certain amount of ice water, regulating the pH to 6-7 with a weak alkali reagent, further extracting with the organic solvent for a plurality of times, and drying to evaporate out the solvent to obtain a final product. The method disclosed by the invention has the advantages of simplicity in operation, mild reaction conditions and simple post-treatment, and a catalyst is low in price and easy to obtain.

Description

technical field [0001] The present invention relates to a kind of synthetic method of medicine intermediate, specifically a kind of synthetic method of p-hydroxypropiophenone. Background technique [0002] 4-Hydroxypropiophenone (English name 4-Hydroxypropiophenone), as an important intermediate in chemical production, has a wide range of uses in chemical production such as medicine and pesticides, and is a necessary intermediate for drugs such as Litodrine and Naomaining. [0003] About the synthesis of p-hydroxypropiophenone, there are relevant reports both at home and abroad, and the synthesis mainly contains the following three methods: 1. Lota, R K et al. reported that phenol and Propionyl chloride is raw material, generates p-hydroxypropiophenone through Friedel-Crafts reaction, although this method can obtain target product in one step, yield is relatively low, only has 50%, and AlCl 3 The dosage is twice that of propionyl chloride. ② Devis, R et al. used phenol and...

Claims

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Application Information

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IPC IPC(8): C07C49/825C07C45/46
CPCB01J31/0225B01J2231/52C07C45/54C07C67/14C07C69/24C07C49/825
Inventor 朱锦桃仇龙周俊鹏吴江
Owner ZHEJIANG SCI-TECH UNIV
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