Search

CN-122006718-A - 4-Ethyl guaiacol derivative and preparation method thereof

CN122006718ACN 122006718 ACN122006718 ACN 122006718ACN-122006718-A

Abstract

The invention discloses a 4-ethyl guaiacol derivative and a preparation method thereof, belonging to the technical field of organic compound synthesis. The application of lignite residue as a catalyst in preparing the 4-ethyl guaiacol derivative comprises the steps of mixing aryl diazo ester compounds and 4-ethyl guaiacol, adding acetonitrile, stirring, using lignite residue as a catalyst for catalytic reaction, standing for reaction at room temperature for 1 h ℃, heating to 80 ℃ for continuous reaction for 10-12: 12 h, detecting that the raw materials react completely through TLC, stopping the reaction, filtering the reacted raw materials, washing a filter cake with dichloromethane until the filter cake is colorless, concentrating the filtrate under reduced pressure to remove volatile components, and separating by adopting silica gel column chromatography to obtain the 4-ethyl guaiacol derivative. The invention adopts the lignite residues as the catalyst, can relieve the problem of difficult lignite residue treatment, can provide a new thought for the selection of the catalyst in the organic synthesis reaction, realizes the recycling of waste resources, and is suitable for the purposes of green chemistry and green environmental protection.

Inventors

  • ZHANG ZHIPENG
  • ZHANG DONG
  • GONG MINGFU

Assignees

  • 中国人民解放军陆军军医大学第二附属医院

Dates

Publication Date
20260512
Application Date
20260130

Claims (8)

  1. 1. The application of lignite residues as a catalyst in preparing 4-ethyl guaiacol derivatives.
  2. 2. The use according to claim 1, further comprising a process for preparing 4-ethylguaiacol derivatives, characterized in that it comprises the steps of, S1, mixing an aryl diazo ester compound and 4-ethyl guaiacol, adding acetonitrile, and stirring; S2, then lignite residues are used as catalysts for catalytic reaction, and after standing reaction is carried out for 1h under the room temperature condition, the lignite residues are heated to 80 ℃ for continuous reaction for 10-12 h; S3, stopping the reaction when the TLC detects that the raw materials are completely reacted; s4, filtering the reacted raw materials, washing a filter cake of the raw materials to be colorless by using dichloromethane, concentrating the filtrate under reduced pressure to remove volatile components, and separating by adopting silica gel column chromatography to obtain the 4-ethyl guaiacol derivative; the synthetic route of the reaction is shown below: 。
  3. 3. the method for preparing 4-ethyl guaiacol derivative as claimed in claim 2, wherein the aryl diazonium ester compound is any one of methyl p-chlorophenyl diazonium acetate, methyl m-chlorophenyl diazonium acetate, methyl o-chlorophenyl diazonium acetate, isopropyl phenyl diazonium acetate, methyl 2, 4-dichloro diazonium acetate and methyl 3, 4-dichloro diazonium acetate.
  4. 4. The method for producing a 4-ethylguaiacol derivative as claimed in claim 3, wherein in the step S1, the amount of 4-ethylguaiacol is 0.75 mmol, the amount of brown coal residue is 150 to 200 mg when the aryl diazonium ester is 0.5 mmol, and the amount of acetonitrile solvent is 5 mL.
  5. 5. The method for producing a 4-ethylguaiacol derivative as claimed in claim 4, wherein the stirring time after the addition of acetonitrile is 10 to 20 minutes.
  6. 6. The process for preparing 4-ethylguaiacol derivatives as claimed in any of claims 2 to 5, wherein the entire reaction is carried out in an air atmosphere without protection of nitrogen or other inert gases.
  7. 7. The method for preparing 4-ethyl guaiacol derivative as claimed in claim 2, wherein the eluent used in the silica gel column chromatography is petroleum ether and ethyl acetate in a volume ratio of 6:1, and the boiling point of petroleum ether is 60-90 ℃.
  8. 8. The method for producing a 4-ethylguaiacol derivative as defined in claim 2, wherein R 1 is one or more of hydrogen, methyl, ethyl, methoxy, nitro, acyl, halogen and trifluoromethyl, wherein said halogen is F, cl, br, I, and R 2 is methyl, ethyl, allyl, phenyl, benzyl or alkyl.

Description

4-Ethyl guaiacol derivative and preparation method thereof Technical Field The invention belongs to the technical field of organic compound synthesis, and particularly relates to a 4-ethyl guaiacol derivative and a preparation method thereof. Background Lignite residues are the main residual substances after lignite refining, are rich in various metal ions and have large holding capacity (hydrodynamics, 2017, 168:141; fuel, 2017, 203:214), but the problem of post-treatment is always a problem which plagues domestic and foreign environmental protection organizations (J.Anal. Appl. Pyrol., 2019, 139:40; energy, 2022, 240:122796). The currently common treatments are as fertilizers （Sci. Total Environ., 2021, 773: 145631; Coke. Chem., 2021, 64: 31; J. Air. Waste Manage., 2021, 71: 1175）、 animal litter (Waste Manage, 2021, 136:113), adsorbents (MINE WATER Environ, 2019, 38:24) or degradants (J.Environ. Chem. Eng., 2021, 9: 104784; chem. Eng. J.,2025, 521: 166275), and the like. If the catalyst can be used as an organic synthesis catalyst, the problem of difficult treatment of lignite residues can be relieved, a new thought can be provided for the selection of the catalyst in the organic synthesis reaction, and the reutilization of waste resources can be realized, so that the catalyst meets the aims of green chemistry and green environmental protection. The 4-ethyl guaiacol is a natural phenol product, has the functions of resisting oxidation, resisting bacteria, eliminating phlegm and the like, and can be used as a spice or other medical intermediates （J. Phys. Chem. B., 2012, 116: 7129; J. Chin. Inst. Food Sci. Technol., 2015, 15: 1; RSCAdvances, 2017, 7: 46395）, in industry, so that the structural modification and the derivatization based on the 4-ethyl guaiacol have important research values. The construction of C-C bond is realized through the insertion reaction of 4-ethyl guaiacol C-H, and the 4-ethyl guaiacol derivative is generated through one-step reaction, which is one of the important means for realizing the derivatization and structural transformation of the natural product 4-ethyl guaiacol. The C-C bond, which is present in various types of organic compounds, is one of the important chemical bonds constituting various substances (Acc. Chem. Res. 2023, 56:2867; J. Am. chem. Soc., 2023, 145:17527). The C-C bond construction methods reported so far often require expensive transition metal catalysts or complex ligands (J. Am. chem. Soc., 2008, 130:1566; ACSCatal., 2025, 15:3636), and therefore, we have attempted to develop a simple and effective method of constructing C-C bonds. Diazo Compounds (Diazo Compounds, r1r2c=n2) are a class of highly reactive reaction intermediates that can participate in a variety of reactions to build C-X (x= O, N, C, S, P, si, B, etc.) bonds (chem. Soc. Rev., 2016, 45:506, nature rev. Chem., 2019, 3:347), wherein C-C bond build up with phenolic Compounds can be achieved by C-H insertion reactions (j. Am. chem. Soc., 2008, 130:1566; green chem., 2020,22:1594). Based on the method, metal ions in lignite residues are utilized to induce aryl diazo ester compounds and 4-ethyl guaiacol to construct C-C bonds through metal carbene C-H insertion reaction, so that the preparation of a natural product 4-ethyl guaiacol derivative is realized, and an effective strategy is provided for derivatization and drug research and development based on the natural product. Disclosure of Invention In view of the above, an object of the present invention is to provide a 4-ethyl guaiacol derivative and a method for producing the same. In order to achieve the above purpose, the present invention provides the following technical solutions: the invention provides application of lignite residues as a catalyst in preparation of 4-ethyl guaiacol derivatives. Further, the method for preparing the 4-ethyl guaiacol derivative is also disclosed, wherein S1, the aryl diazo ester compound and the 4-ethyl guaiacol are mixed, acetonitrile is added, and then the mixture is stirred; S2, then lignite residues are used as catalysts for catalytic reaction, and after standing reaction is carried out for 1h under the room temperature condition, the lignite residues are heated to 80 ℃ for continuous reaction for 10-12 h; S3, stopping the reaction when the TLC detects that the raw materials are completely reacted; s4, filtering the reacted raw materials, washing a filter cake of the raw materials to be colorless by using dichloromethane, concentrating the filtrate under reduced pressure to remove volatile components, and separating by adopting silica gel column chromatography to obtain the 4-ethyl guaiacol derivative; the synthetic route of the reaction is shown below: 。 Further, the aryl diazo ester compound is any one of methyl p-chlorophenyl diazoacetate, methyl m-chlorophenyl diazoacetate, methyl o-chlorophenyl diazoacetate, isopropyl phenyl diazoacetate, methyl 2, 4-dichloro diazoacetate and methyl 3, 4-dichloro diazo