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Synthesis method of aromatic benzyl ketone

A technology of aromatic benzyl ketone and synthesis method, applied in the field of synthesis of aromatic benzyl ketone, can solve problems such as hidden danger, waste safety, pollution, etc., and achieve the effects of promoting reaction temperature, reducing dosage, and promoting self-oxidation

Active Publication Date: 2020-09-01
ZHEJIANG MEDICAL COLLEGE
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

CN101759542B and CN101759540B have used iron, manganese or cobalt and ligands, and ethylbenzene or propylbenzene are oxidized to obtain corresponding ketones. The metal catalysts used in the reaction are mainly manganese or cobalt, which are easy to cause pollution and require the use of large molecular weight bionic compounds. The body cannot be recycled and applied mechanically, the reaction system is complex, and the atom economy is low
The autoxidation reaction of p-nitrotoluene disclosed in CN108238946A does not use a heavy metal catalyst, but the reaction needs to be carried out under relatively high pressure, and more than 5 equivalents of alkali are used, which causes waste and has certain safety hazards
CN106423170A then used cobalt / graphene compound and NHPI cocatalyzed ethylbenzene self-oxidation is acetophenone, although the cobalt consumption used in reaction is less, oxygen pressure is gentler, but the preparation process of catalyst cobalt / graphene compound is more loaded down with trivial details
[0007] In summary, the autoxidation reaction of aromatic benzyl compounds usually uses metals such as cobalt, cadmium, manganese, etc. as catalysts. combined, limiting its application in the pharmaceutical and food industries

Method used

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  • Synthesis method of aromatic benzyl ketone
  • Synthesis method of aromatic benzyl ketone
  • Synthesis method of aromatic benzyl ketone

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0037]

[0038]A round bottom flask equipped with a mechanical stirring bar and a reflux condenser was charged with 42.5 g of ethylbenzene, 4.8 g of ferric nitrate nonahydrate, 3.2 g of NHPI, 200 mL of acetic acid. After the addition, the temperature of the oil bath was raised to 100° C., and the reaction was carried out under open-open stirring for 12 hours. Gas chromatography detection showed that the conversion rate of ethylbenzene was 98%, and the reaction was stopped. After the acetic acid in the reaction system was distilled off under reduced pressure, 45.2 g of the product acetophenone (colorless liquid) was obtained by distillation under reduced pressure, with a yield of 94%.

[0039] Product NMR identification data:

[0040] 1 H NMR (500MHz, Chloroform-d) δ7.93-7.91 (m, 2H), 7.52 (tt, J=7.5, 1.5Hz, 1H), 7.43–7.40 (m, 2H), 2.55 (s, 3H).

[0041] 13 C NMR (125MHz, Chloroform-d) δ198.06, 137.09, 133.09, 128.55, 128.28, 26.54.

Embodiment 2

[0043]

[0044] A round bottom flask equipped with a magnetic stirring bar and a reflux condenser was charged with 5.3 g of butylbenzene, 0.4 g of ferric nitrate nonahydrate, 0.3 g of NHPI, and 30 mL of acetonitrile. After the addition, put on the three-way valve and connect the oxygen ball, and perform three ventilations under the action of the air pump to replace the air in the reaction system with oxygen, raise the temperature of the oil bath to 100°C, and react for 15 hours under stirring and reflux Afterwards, gas chromatographic detection showed that the conversion rate of butylbenzene was 91%, and the reaction was stopped. After the solvent in the reaction system was distilled off under reduced pressure, it was separated by column chromatography (petroleum ether / ethyl acetate=100:1-30:1) to obtain 5.28 g of the product butyrophenone (colorless liquid), with a yield of 89% .

[0045] Product NMR identification data:

[0046] 1 H NMR (500MHz, Chloroform-d) δ7.95-7.9...

Embodiment 3

[0049]

[0050] A round bottom flask equipped with a mechanical stirring bar and a reflux condenser was charged with 6.6 g of diphenylmethane, 0.4 g of ferric nitrate nonahydrate, 0.3 g of NHPI, 20 mL of benzonitrile. After the addition, put on the three-way valve to connect the oxygen ball, and perform three air changes under the action of the air pump to replace the air in the reaction system with oxygen, and raise the temperature of the oil bath to 90 °C. After 12 hours of reaction, the gas phase Chromatographic detection showed that the conversion rate of diphenylmethane was 100%, and the reaction was stopped. After the benzonitrile in the reaction system was distilled off under reduced pressure, it was separated by column chromatography (petroleum ether / ethyl acetate=100:1-50:1) to obtain 7.13 g of the product benzophenone (white solid, melting point 47-50:1). 48°C), yield 99%.

[0051] Product NMR identification data:

[0052] 1 H NMR (500MHz, Chloroform-d) δ7.88–7...

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Abstract

The invention discloses a synthesis method of aromatic benzyl ketone, which comprises the following step: by using oxygen and / or air as an oxidant, oxidizing an aromatic benzyl compound shown in a formula (I) under the action of a catalytic system to obtain aromatic benzyl ketone shown in a formula (II). The catalytic system is formed by combining ferric ions, nitrate radicals and N-hydroxyimide derivatives and does not contain heavy metal ions harmful to human bodies, wherein the molar ratio of the ferric ions to the nitrate radicals is 1: (0.5-5), and the molar ratio of the ferric ions to the N-hydroxyimide derivatives is (0.01-0.1): (0.03-0.2). The method disclosed by the invention is wide in substrate applicability and high in atom utilization rate, avoids the use of harmful heavy metals such as copper and cobalt, and has the characteristics of high efficiency, economy and environmental protection. The formulas are as follows: Ar-CH2-R (I) and Ar-CO-R (II).

Description

[0001] (1) Technical field: [0002] The invention relates to a method for generating an aromatic benzyl ketone through oxidation of the benzylic methylene group of an aromatic benzyl compound. [0003] (two) background technology: [0004] The benzylic position of methylene compounds is oxidized to form ketones, which is an important organic reaction and has important applications in pharmaceuticals, cosmetics, dye synthesis and other related industries. Among the many oxidants that can be used in this oxidation reaction, oxygen is undoubtedly the cheapest and most readily available oxidant. [0005] The oxidation reaction of methylene or methyl compound in oxygen or air is called autoxidation reaction. CN101759542B and CN101759540B have used iron, manganese or cobalt and ligands, and ethylbenzene or propylbenzene are oxidized to obtain corresponding ketones. The metal catalysts used in the reaction are mainly manganese or cobalt, which are easy to cause pollution and require...

Claims

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Application Information

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IPC IPC(8): C07C45/36C07C49/78C07C49/76C07C49/786C07C49/67C07C253/30C07C255/56C07C49/675C07C201/12C07C205/45C07D311/86C07D311/76C07C49/807C07C67/29C07C69/157C07C49/813
CPCC07C45/36C07C253/30C07C201/12C07D311/86C07D311/76C07C67/29C07C2602/10C07C2603/18C07C2602/08C07C2531/28C07C49/78C07C49/76C07C49/786C07C49/67C07C255/56C07C49/675C07C205/45C07C49/807C07C69/157C07C49/813
Inventor 王剑王荣辉全海迪杜文婷徐建宏王玮周倩
Owner ZHEJIANG MEDICAL COLLEGE
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