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Simple synthetic method of trans-p-methylthiocinnamyl alcohol used for industrial production

A technology of methylmercaptocinnamyl alcohol and a synthetic method, which is applied in the field of medicinal chemistry, can solve problems such as difficult control of particularly smelly methylmercaptan, high potential safety hazards, and high price, and achieve easy operation of reaction conditions, cheap and easy-to-obtain raw materials, and reaction selection sex high effect

Active Publication Date: 2014-05-14
XINFA PHARMA
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

But the deficiency of method is: in the reaction of sodium methyl mercaptide replacing p-chlorobenzaldehyde and the aftertreatment process, be difficult to control the generation of peculiar smelly methyl mercaptan, the generation of special smelly methyl mercaptan is unfavorable for environmental protection
In the subsequent Grignard reaction, expensive vinyl magnesium halides or difficult-to-operate vinyl bromide should be used, and the reaction should be carried out in ether solvents, anhydrous and oxygen-free conditions, and the operation process has high safety hazards. Facilitate the implementation of industrialization
It is easy to generate polymers initiated by carbocations during the rearrangement process, which is not conducive to the purification of the final product

Method used

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  • Simple synthetic method of trans-p-methylthiocinnamyl alcohol used for industrial production
  • Simple synthetic method of trans-p-methylthiocinnamyl alcohol used for industrial production
  • Simple synthetic method of trans-p-methylthiocinnamyl alcohol used for industrial production

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Experimental program
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Effect test

Embodiment 1

[0041] Embodiment 1: the preparation of p-methylmercaptobenzaldehyde

[0042] Add 124.0 g (1.0 mol) of sulfide anisole and 200 g of N,N-dimethylformamide into a 500 mL four-necked flask equipped with stirring, thermometer, reflux condensing device and dropping funnel, and cool to minus 10°C , Slowly add 161.1 g (1.05 moles) of phosphorus oxychloride dropwise, after dropping, react at 0°C for 2 hours, naturally rise to 20°C for 2 hours, then rise to 60-70°C for 2 hours. The reaction is over.

[0043] Cool down to 20°C, pour the reaction liquid into 1500g of ice-water mixture, adjust the pH value to 6-7 with 40% aqueous sodium hydroxide solution, extract three times with ethyl acetate (250g×3, 750g in total), and combine the organic phases , washed with 200 grams of saturated sodium chloride, layered, and 40 grams of anhydrous sodium sulfate dried the organic phase. After precipitation, 144.5 grams of light yellow liquid p-methylmercaptobenzaldehyde was obtained. The gas phase ...

Embodiment 2

[0044] Embodiment 2: Preparation of p-methylmercaptobenzaldehyde (II)

[0045]Add 124.0 g (1.0 mol) of sulfide anisole and 100 g of N,N-dimethylformamide into a 500 mL four-necked flask equipped with stirring, thermometer, reflux condensing device and dropping funnel, and cool to -10°C , slowly add dropwise a solution containing 109 grams (1.1 moles) of solid phosgene and 300 grams of 1,2-dichloroethane, after the drop is completed, react at 0°C for 2 hours, then naturally rise to room temperature (20°C) for 2 hours, then Rise to 60-70°C for 2 hours. After the reaction is completed, cool down to 20°C, pour the reaction liquid into 1500 g of ice-water mixture, adjust the pH value to 6-7 with 40% aqueous sodium hydroxide solution, extract three times with 1,2-dichloroethane (200g×3, 600 grams in total), combined organic phases, washed with 200 grams of saturated sodium chloride, separated layers, dried the organic phases with anhydrous sodium sulfate (40 grams), obtained 145.9 ...

Embodiment 3

[0047] Embodiment 3: the preparation of trans-mercaptocinnamaldehyde

[0048] Add 300 grams of water and 10.0 grams of potassium acetate to a 1000 mL four-neck flask equipped with a stirring, thermometer and dropping funnel, heat up to 30°C, add 76.0 grams (0.5 moles) of p-mercaptobenzaldehyde and 66 grams of 40% ethyl alcohol dropwise. Aldehyde aqueous solution and the mixed solution of 200 grams of methanol, add about 3 hours. Thereafter, the reaction was carried out at 30°C for 2 hours. Adjust the pH value to 6 with dilute hydrochloric acid, extract three times with ethyl acetate (450 g in total), combine the organic phases, wash with 200 g of saturated sodium chloride, separate layers, dry the organic phase with anhydrous sodium sulfate (30 g), and remove the solvent Obtain 82.8 grams of light yellow liquid, which is trans-mercaptocinnamaldehyde, with a gas phase purity of 98.9% and a yield of 93.1%.

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Abstract

The invention relates to a simple synthetic method of trans-p-methylthiocinnamyl alcohol used for industrial production. The method comprises the following steps: performing a formylation reaction on thioanisole and a formylation reagent to prepare p-methylthiobenzaldehyde; condensing the p-methylthiobenzaldehyde and acetaldehyde in the presence of a catalyst to prepare trans-p-methylthiocinnamyl aldehyde; reducing the trans-p-methylthiocinnamyl aldehyde to obtain the trans-p-methylthiocinnamyl alcohol. The method has the advantages of readily-available raw materials, easiness in operation of reaction conditions, high reaction selectivity, low product cost, safety, environmental friendliness and suitability for industrial production.

Description

technical field [0001] The invention relates to a synthetic method for industrial production of trans-p-methylmercaptocinnamyl alcohol, which belongs to the technical field of medicinal chemistry. Background technique [0002] Trans-p-methylmercaptocinnamyl alcohol is the key raw material for the synthesis of trans-p-thiamphenicol, which is a key intermediate for the synthesis of antibiotics such as thiamphenicol and fluthiamphenicol. The structural formula of trans-methylmercaptocinnamyl alcohol is shown in formula (I): [0003] [0004] U.S. Patent No. 5,352,832 and Oida et al. (see Chem.Pharm.Bull.2000, 48,6940) respectively announced the synthesis method of trans-p-thiamphenicyl cinnamyl alcohol, all of which use p-thiamphenicyl phthalaldehyde as the initial raw material. However, the cost of raw materials used in its synthesis is high, the reaction conditions are harsh, and some raw materials are also flammable and explosive, which is not conducive to the disadvanta...

Claims

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Application Information

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IPC IPC(8): C07C323/19C07C319/20C07C317/22C07C315/02
Inventor 戚聿新陈军鞠立柱李新发
Owner XINFA PHARMA
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