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CN-121990993-A - Preparation method of high-purity ganbaolin

CN121990993ACN 121990993 ACN121990993 ACN 121990993ACN-121990993-A

Abstract

The invention discloses a preparation method of high-purity gamboge, and relates to the technical field of synthetic chemistry. The glycyl amine is prepared by reacting pinacolone with chlorine to obtain monochloropinacolone, reacting pinacolone with parachlorophenol to obtain ether ketone, chlorinating the ether ketone by a chlorinating reagent to obtain chlorinated ether ketone, reacting the chlorinated ether ketone with imidazole to obtain a glycyl amine crude product, and refining the glycyl amine crude product by activated carbon, filtering, crystallizing, centrifuging and drying. The chloridizing reagent and the proper adding mode used in the chloridizing stage of ether ketone improve the reaction selectivity, do not generate SO 2 by-products which pollute the environment, have high environmental protection, do not use extra catalyst in the reaction process of chloroether ketone and imidazole, use recoverable and regenerated active carbon in the purification of the crude product of the gamboge, reduce the preparation cost, and the gamboge prepared by the invention has high yield and high purity and is suitable for industrialized production.

Inventors

  • XU GUILONG
  • PENG RONGGUI

Assignees

  • 黑龙江邦普生物科技有限公司

Dates

Publication Date
20260508
Application Date
20260130

Claims (10)

  1. 1. The preparation method of the high-purity gamboge is characterized by comprising the following steps of: Mixing pinacolone and methanol, cooling, introducing chlorine, stirring and reacting to obtain a reaction solution containing pinacolone, heating and distilling the reaction solution containing pinacolone under reduced pressure, and collecting fractions to obtain pinacolone; Mixing toluene, p-chlorophenol and potassium carbonate, stirring and heating, then dropwise adding chloropinacolone, heating and refluxing and stirring, and then cooling and washing to obtain a reaction solution containing ether ketone; Adding a chlorinating reagent into a reaction solution containing ether ketone under stirring, heating and stirring to obtain a reaction solution containing chlorinated ether ketone, heating and distilling the reaction solution containing chlorinated ether ketone under reduced pressure, cooling, preserving heat, centrifuging to obtain a crude product of chlorinated ether ketone and a centrifugal mother solution 1, and drying the crude product of chlorinated ether ketone to obtain chlorinated ether ketone; Mixing toluene, imidazole, chloroetherketone and N, N-dimethylbenzylamide, heating, refluxing and stirring, adding alkali liquor to regulate pH, washing, cooling an organic phase, preserving heat, centrifuging to obtain a centrifugal mother liquor 2 and a crude product of the ruby, mixing the crude product of the ruby, toluene and active carbon, heating, refluxing and stirring, cooling, filtering, continuously cooling filtrate, preserving heat, centrifuging to obtain a refined product and a centrifugal mother liquor 3, heating, decompressing and distilling the centrifugal mother liquor 3, and drying the refined product to obtain the high-purity ruby.
  2. 2. The method for preparing high-purity ganbazole according to claim 1, wherein in the step (1), the dosage ratio of pinacolone to methanol is 52-53g:0.87-0.91g.
  3. 3. The method for producing high purity glycyl urea according to claim 1, wherein in the step (1), the chlorine is added in stages, wherein the chlorine is introduced at a rate of 0.8 to 1.0L/min at the initial stage, at a rate of 1.5 to 1.7L/min at the medium stage, and at a rate of 0.5 to 0.7L/min at the later stage.
  4. 4. The method for producing high-purity glycyl-L-form according to claim 3, wherein the ratio of the time of introducing chlorine gas in the initial stage, the medium stage and the later stage is 1:1.5:0.5.
  5. 5. The method for preparing high-purity ganbazole according to claim 1, wherein in the step (2), the dosage ratio of toluene, parachlorophenol, potassium carbonate and chloropinacolone is 1.9-2.1g:43.0-44.0g:23.3-23.8g:47.0-48.0g.
  6. 6. The process for preparing high purity glycyl-L-G according to claim 1, wherein in step (3), the chlorine is intermittently added at a rate of 0.8-1L/min for 30-35min, and the chlorine is stopped for 3-5min, and the total time of intermittent chlorine addition is 4.5-5h.
  7. 7. The method for preparing high-purity gamboge according to claim 1, wherein in the step (4), the dosage ratio of toluene, imidazole, chloroetherketone and N, N-dimethylbenzylamide is 2.3-2.5g:24.0-24.5g:91.5-92.5g:4.5-5g.
  8. 8. The method for preparing high-purity gamboge according to claim 1, wherein in the step (4), the dosage ratio of the gamboge crude product, toluene and active carbon is 1-1.5g:13-15g:75-85mg.
  9. 9. The method for preparing high-purity gambogin according to claim 1, which is characterized in that: the pressure used for the temperature-rising and pressure-reducing distillation in the step (1), the step (3) and the step (4) is between-0.1 MPa and-0.08 MPa.
  10. 10. The method for preparing high-purity glycal according to claim 1, wherein the reaction process for preparing high-purity glycal is as follows: 。

Description

Preparation method of high-purity ganbaolin Technical Field The invention relates to the technical field of synthetic chemistry, in particular to a preparation method of high-purity gambogin. Background The glycal, also known as 1- (4-chlorophenoxy) -1- ((1-imidazolyl) -3, 3-dimethyl-2-butanone, is widely applied to conditioning washing and caring products such as antipruritic and anti-dandruff shampoo, hair conditioner and the like by virtue of broad-spectrum sterilization performance, and also can be applied to high-grade washing products such as antibacterial perfumed soap, bath lotion, medicinal toothpaste, mouthwash and the like, the pure gamboge is white or off-white crystal, and if the purity is not high, gamboge has the problems of poor color and peculiar smell, and the quality of daily chemical products is adversely affected. The preparation method of the ganbazole generally comprises the steps of firstly chlorinating pinacolone to obtain monochloropinacolone, then reacting the monochloropinacolone with parachlorophenol to obtain etherketone, chlorinating the etherketone to obtain chlorinated etherketone, and finally reacting the chlorinated etherketone with imidazole to obtain the ganbazole. The sulfuryl chloride (SO 2Cl2) is used as a chlorinating agent, but a byproduct SO 2 generated by the ether ketone chlorination reaction pollutes the environment and is not suitable for industrial production, and the obtained ganbazole is high in purity but insufficient in yield, which means that more raw materials are wasted or converted into byproducts, the raw material cost is increased, the actual yield is far lower than expected after the amplified production, and the economic benefit is adversely affected. Therefore, how to develop a proper ether ketone chlorination method, reduce environmental pollution, solve the problem of insufficient yield of the gamboge, and obtain gamboge with high purity and high yield, which is worthy of further exploration. Disclosure of Invention In order to solve the technical problems, the invention provides a preparation method of high-purity gambogin. The aim of the invention can be achieved by the following technical scheme: a preparation method of high-purity gambogin comprises the following steps: Mixing pinacolone and methanol, cooling, introducing chlorine, stirring and reacting to obtain a reaction solution containing pinacolone, heating and distilling the reaction solution containing pinacolone under reduced pressure, and collecting fractions to obtain pinacolone; Mixing toluene, p-chlorophenol and potassium carbonate, stirring and heating, then dropwise adding chloropinacolone, heating and refluxing and stirring, and then cooling and washing to obtain a reaction solution containing ether ketone; adding a chlorinating reagent into the reaction solution containing the ether ketone under stirring, heating and stirring to obtain the reaction solution containing the chlorinated ether ketone, heating and distilling the reaction solution containing the chlorinated ether ketone under reduced pressure, cooling, preserving heat, centrifuging to obtain a crude product of the chlorinated ether ketone and a centrifugal mother solution 1, and drying the crude product of the chlorinated ether ketone to obtain the chlorinated ether ketone; Mixing toluene, imidazole, chloroetherketone and N, N-dimethylbenzylamide, heating, refluxing and stirring, adding alkali liquor to regulate pH, washing, cooling an organic phase, preserving heat, centrifuging to obtain a centrifugal mother liquor 2 and a crude product of the ruby, mixing the crude product of the ruby, toluene and active carbon, heating, refluxing and stirring, cooling, filtering, continuously cooling filtrate, preserving heat, centrifuging to obtain a refined product and a centrifugal mother liquor 3, and drying the refined product to obtain the high-purity ruby. A preparation method of high-purity gambogin comprises the following specific steps: Mixing pinacolone and methanol, cooling to 0 ℃, introducing chlorine, reacting for 15-16 hours at 0-5 ℃ to obtain a reaction solution containing pinacolone, heating and distilling the reaction solution containing pinacolone under reduced pressure, collecting distillate at 40-55 ℃ for sealing, and collecting fraction at 80-82 ℃ to obtain pinacolone; further, the dosage ratio of pinacolone to methanol is 52-53g:0.87-0.91g; The method comprises the steps of adding chlorine gas in a staged mode, wherein the staged addition is that the chlorine gas is added at a speed of 0.8-1.0L/min at the initial stage, the chlorine gas is added at a speed of 1.5-1.7L/min at the middle stage, the chlorine gas is added at a speed of 0.5-0.7L/min at the later stage, the time ratio of the chlorine gas to the chlorine gas is 1:1.5:0.5 at the initial stage, the chlorine gas is added at the middle stage and the chlorine gas is added at the later stage, and the total time of the chlorine gas is the time of reac