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Preparation method of α-oximinoacetophenone derivative

A technology of oximinoacetophenone and its derivatives, which is applied in the field of preparation of α-oximinoacetophenone derivatives, and can solve the problems of unfavorable safety production, decreased content, low reaction conversion rate, etc.

Active Publication Date: 2021-08-20
泰兴强力先先电子新材料有限公司 +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0002] α-Hydroxyaminoacetophenone derivatives are used as an important intermediate raw material (such as photoinitiator preparation raw materials), and in the prior art, oximation (also known as different nitrosation) reaction is used to prepare α-oximinoacetophenone derivatives, but there are the following technical defects: a) ethyl acetate is usually used as a solvent, hydrochloric acid catalyzes, and the conversion rate is low, about 85%; b) water has a certain solubility in ethyl acetate at room temperature, and the dehydration process is complicated. The yield is low; c) ethyl acetate decomposes under acidic conditions, and the content decreases; d) in summary, the conversion rate is low on the one hand, and on the other hand, ethyl acetate needs to be dehydrated by secondary distillation after distillation and crystallization, otherwise it is difficult to apply mechanically; e ) Iso-nitrosating reagents are generally nitrite or nitrite, and the dripping method is mostly slow dripping. Nitrite is unstable when exposed to light and air, and will be decomposed by heat to produce toxic gas nitrogen oxides, which is not conducive to safe production.
The price of nitrite is far lower than that of nitrite, but nitrite is solid and insoluble in organic solvents, and the reaction conversion rate is low when it is made into an aqueous solution and added dropwise

Method used

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  • Preparation method of α-oximinoacetophenone derivative
  • Preparation method of α-oximinoacetophenone derivative
  • Preparation method of α-oximinoacetophenone derivative

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] Embodiment 1: the structural formula is The preparation method of the α-oximino acetophenone derivative, reaction equation is as follows:

[0029]

[0030] Put 190kg of 4-phenylthiophenyl-1-octanone, 1200kg of new ethyl acetate or recovered ethyl acetate, 252kg of hydrochloric acid into the reaction kettle, stir and inject 72kg of hydrogen chloride gas into the reaction kettle, 10-30℃ in batches Add 70kg of sodium nitrite, add 3kg of sodium nitrite each time, add once every 3 minutes, after the addition is complete, keep warm for 1 hour, wash with water, adjust the pH to neutral, distill ethyl acetate, and the distilled ethyl acetate can continue to be used for feeding. After the distillation is completed, cyclohexane is added to crystallize to obtain the product with a yield of 95% and a content greater than 99%.

Embodiment 2

[0031] Embodiment 2: the structural formula is The preparation method of the α-oximino acetophenone derivative, reaction equation is as follows:

[0032]

[0033] Drop into 2-(3-cyclohexylpropionyl) 9,9-dibutyl fluorene 203kg in the reaction kettle, new ethyl acetate or reclaim ethyl acetate 1000kg, hydrochloric acid 430kg, pass into 40kg hydrogen chloride gas after stirring and completely dissolving, maintain at Add 55kg of sodium nitrite in batches at 10-30°C, add 3kg of sodium nitrite each time, add once every 3 minutes, after the addition is completed, keep warm for 1 hour, wash with water, adjust the pH to neutral, distill ethyl acetate, and distill the acetic acid Ethyl ester can continue to be used for feeding, after the distillation is finished, methanol is added to crystallize to obtain the product with a yield of 91% and a content of more than 99%.

Embodiment 3

[0034] Embodiment 3: the structural formula is The preparation method of the α-oximino acetophenone derivative, reaction equation is as follows:

[0035]

[0036] Drop into 6-(3-cyclohexylpropionyl)-9-ethylcarbazol-3 base-1-octanone 180kg in the reactor, new ethyl acetate or reclaim ethyl acetate 1800kg, hydrochloric acid 630kg, stir and pass Add 90kg of hydrogen chloride, maintain the temperature at 10-30°C, add 60kg of sodium nitrite in batches, add 3kg of sodium nitrite each time, add once every 3 minutes, after the addition, keep warm for 1 hour, wash with water, adjust the pH to neutral, and distill ethyl acetate Ethyl acetate that evaporates can continue to be fed mechanically. After the distillation is completed, toluene is added to crystallize to obtain the product with a yield of 90% and a content greater than 98%.

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Abstract

The invention discloses a preparation method of α-oximino acetophenone derivatives. The steps include putting acetophenone derivatives, ethyl acetate and hydrochloric acid into a reaction kettle, stirring and dissolving them completely, introducing hydrogen chloride gas, and heating the mixture at 0-50°C , put in nitrite, after the addition, keep warm for 1-10 hours, then wash with water, adjust the pH to neutral, distill ethyl acetate, add cyclohexane to crystallize after the distillation, and obtain the α-oximinoacetophenone derivative thing. The preparation method of the α-oximinoacetophenone derivative of the present invention can realize the recycling of the solvent ethyl acetate, can significantly improve the yield (more than 90%), and the purity of the target substance can reach more than 98%; the reaction is green and safe, Raw material cost is low.

Description

technical field [0001] The invention belongs to the technical field of fine chemicals, relates to the preparation of organic intermediates containing isonitroso groups through oximation reactions, and specifically provides a preparation method of α-oximinoacetophenone derivatives. Background technique [0002] α-Hydroxyaminoacetophenone derivatives are used as an important intermediate raw material (such as photoinitiator preparation raw materials), and in the prior art, oximation (also known as different nitrosation) reaction is used to prepare α-oximinoacetophenone derivatives, but there are the following technical defects: a) ethyl acetate is usually used as a solvent, hydrochloric acid catalyzes, and the conversion rate is low, about 85%; b) water has a certain solubility in ethyl acetate at room temperature, and the dehydration process is complicated. The yield is low; c) ethyl acetate decomposes under acidic conditions, and the content decreases; d) in summary, the con...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C319/20C07C323/47C07C249/04C07C251/40C07D209/86
CPCC07C1/26C07C45/46C07C249/04C07C319/20C07D209/86C07C2601/14C07C2603/18C07C323/47C07C251/40C07C323/22C07C13/567C07C49/563
Inventor 朱文斌苏文昌王于峰杨志佳
Owner 泰兴强力先先电子新材料有限公司