Overview[1][2]
Ethyl anthranilate is a colorless liquid, soluble in alcohol and propylene glycol, and slightly soluble in water. The alcohol solution fluoresces purple. Ethyl anthranilate occurs naturally in grapes and has an aroma of orange blossom and grape. Its aroma is gentler than that of methyl anthranilate. Ethyl anthranilate can be used in daily chemical fragrance formulas, and can be used to prepare jasmine, orange blossom and other fragrances.
Preparation[1]
At present, the edible flavoring ethyl anthranilate can be mainly produced by the following two methods: ① Using anthranilic acid as raw material, esterification with ethanol under the action of concentrated sulfuric acid or hydrochloric acid; ② Using Ethyl anthranilate was synthesized by amidation, oxidation, hydrolysis and esterification of o-toluidine as raw material. The raw material of the first method, anthranilic acid, is easy to produce poison and can cause harm to the human body and the environment. It is a national controlled chemical, which is difficult to purchase and the cost is high. Although the raw material prices of the second method are relatively cheap, the synthesis route is longer, the reaction steps are many, and the overall yield is low.
Wang Hongkai and others introduced a new synthesis method, which uses cheap phthalic anhydride as raw material to synthesize ethyl anthranilate through a two-step reaction of amidation and esterification.
(1) Amination reaction
Add 50g of ammonia water with a mass fraction of 25% into a three-necked flask equipped with an ice bath thermostat, start stirring, cool to 10°C, and add 99g of phthalic anhydride. Put 89g of sodium hydroxide solution with a mass fraction of 30% into the dropping funnel. When the temperature rises to 40°C, start slowly dripping the sodium hydroxide solution. After adding the caustic soda, control the temperature and stir for 0.5h at 70°C. Measure the pH value: 9 and does not decrease, keep it warm at 70℃ for 1 hour. After the reaction is completed, turn on the draft device and stir for 1 hour to remove ammonia to obtain the intermediate amidation liquid.
(2)Esterification reaction
Add the amidation solution obtained in the first step and 123g of ethanol into a three-necked flask equipped with a cold bath device, cool to below -10°C, put 374g of 14% sodium hypochlorite solution into the dropping funnel, and drip slowly Add sodium hypochlorite solution and maintain the temperature below -8°C. After the dropwise addition, keep it at -8°C for 40 minutes, place it at room temperature and stir, naturally raise the temperature to 20°C, add 5g of sodium sulfite solution with a mass fraction of 30%, stir for another 10 minutes, add 100g of hot water with a temperature of about 80°C, and take a water bath. Heat to 60°C, keep warm for 30 minutes, and separate into layers. The oil layer is ethyl anthranilate. The total yield was 72.4%, and compared with the standard liquid chromatography, the mass fraction was 99.6%.
Apply[4]
CN201510621130.1 reports the preparation and application of a benzoyl hydrazide derivative. The preparation method includes adding ethyl anthranilate and hydrazine hydrate in absolute ethanol, heating to reflux for 4-6 hours, cooling to room temperature, filtering the precipitated solid, washing with absolute ethanol, and drying to obtain an intermediate compound; the intermediate is in the absence of In water ethanol, react with o-hydroxynaphthalene carboxaldehyde at 70-80°C for 4-6 hours. After cooling, the precipitated solid is suction filtered, then washed and dried to obtain the light yellow solid pure product P; the benzoyl hydrazide derivative P can be used as Fluorescent probes realize the recognition and detection of Mg2+. The benzoyl hydrazide derivative P obtained by the present invention through effective synthesis means has good selectivity for Mg2+. On the basis of optimizing experimental conditions, the detection of Mg2+ can be realized.
Main reference materials
[1] Concise Dictionary of Fine Chemicals
[2]Synthetic Flavors Technical Manual
[3]Wang Hongkai, Zhang Zhen, Duan Zhen, Yu Weixiao, Wang Dan. Improvement of the production process of ethyl anthranilate [J]. Chemical Engineering, 2019, 47(07):73-75+78.
[4] CN201510621130.1 Preparation and application of benzoyl hydrazide derivatives
