WO2026007304A1 - 一种苯醌类化合物和氢醌的绿色联产方法 - Google Patents

一种苯醌类化合物和氢醌的绿色联产方法

Info

Publication number
WO2026007304A1
WO2026007304A1 PCT/CN2024/132645 CN2024132645W WO2026007304A1 WO 2026007304 A1 WO2026007304 A1 WO 2026007304A1 CN 2024132645 W CN2024132645 W CN 2024132645W WO 2026007304 A1 WO2026007304 A1 WO 2026007304A1
Authority
WO
WIPO (PCT)
Prior art keywords
water
hydroquinone
acid
benzoquinone
green
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/CN2024/132645
Other languages
English (en)
French (fr)
Inventor
李浩然
王永涛
余轲涵
徐洪斌
姚加
杨辉
梁赛赟
王会
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shandong Nhu Vitamin Co Ltd
Zhejiang University
Zhejiang NHU Co Ltd
Original Assignee
Shandong Nhu Vitamin Co Ltd
Zhejiang University
Zhejiang NHU Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shandong Nhu Vitamin Co Ltd, Zhejiang University, Zhejiang NHU Co Ltd filed Critical Shandong Nhu Vitamin Co Ltd
Publication of WO2026007304A1 publication Critical patent/WO2026007304A1/zh
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C46/00—Preparation of quinones
    • C07C46/02—Preparation of quinones by oxidation giving rise to quinoid structures
    • C07C46/06—Preparation of quinones by oxidation giving rise to quinoid structures of at least one hydroxy group on a six-membered aromatic ring

Definitions

  • This invention relates to the field of fine chemical synthesis technology, specifically to a green co-production method for benzoquinone compounds and hydroquinone.
  • Vitamin E is a collective term for tocopherols, which have received considerable attention since their discovery in 1922.
  • a key intermediate in the synthesis of vitamin E is 2,3,5-trimethylhydroquinone.
  • 2,3,5-Trimethylhydroquinone can be obtained by catalytic hydrogenation of trimethylbenzoquinone.
  • Trimethylbenzoquinone, or 2,3,5-trimethylbenzoquinone (TMBQ) is also an important pharmaceutical intermediate.
  • TMBQ 2,3,5-trimethylphenol
  • 2,3,6-trimethylphenol 2,3,6-trimethylphenol
  • pseudotrimethylbenzene There are three main raw materials for the synthesis of TMBQ: 2,3,5-trimethylphenol, 2,3,6-trimethylphenol, and pseudotrimethylbenzene.
  • 2,3,6-trimethylphenol is mainly chosen as the raw material for the synthesis of TMBQ both domestically and internationally
  • TMBQ The synthesis of TMBQ from 2,3,6-trimethylphenol mainly involves chemical oxidation and catalytic oxidation.
  • 2,3,6-trimethylphenol is sulfonated to obtain 4-sulfono-2,3,6-trimethylphenol, which is then oxidized with manganese dioxide to obtain TMBQ.
  • the advantages of this method are its simplicity and low equipment investment cost.
  • its disadvantages include the potential for environmental pollution, and the tendency of 4-sulfono-2,3,6-trimethylphenol to clump during the actual synthesis process, making the dissolution operation cumbersome.
  • H2O2 hydrogen peroxide
  • TMBQ titanium dioxide
  • ruthenium-based catalysts A yield of 83% for trimethylquinone can be achieved (Adv. Synth. Catal., DOI: 10.1002/adsc.201000137); furthermore, using CuCl2 -poly(4-vinylpyridine) as a catalyst, DMSO as a solvent, and oxygen as an oxygen source, the conversion of 2,3,6-trimethylphenol can reach 100%, and the selectivity can reach 95%.
  • Chinese patent CN96180478.5 discloses a method for oxidizing 2,3,6-trimethylphenol to TMBQ using a heteropolyacid catalytic system, which can achieve a TMBQ yield of 95% and a 2,3,6-trimethylphenol conversion of 100%;
  • Chinese patent CN201711037289.4 proposes a process for using metatetramethylbenzene as a raw material to reduce the generation of by-products and improve the yield of trimethylquinone.
  • These catalytic oxidation methods use oxygen or hydrogen peroxide as oxidants, which are relatively environmentally friendly, but their disadvantages include difficulty in controlling selectivity, the need for high oxygen pressure, high cost of high-pressure reaction equipment, and high price of the metal catalysts used.
  • Hydroquinone is another widely used chemical product. As of 2018, global demand for hydroquinone was approximately 70,000 tons, mainly imported from countries such as France, Italy, and the United States. Demand for hydroquinone is gradually increasing. Also known as hydroquinone hydroquinone, it is primarily used in the synthesis of hydrogen peroxide and is also widely used in the synthesis of intermediates such as photographic film, polymerization inhibitors, berberine, and adrenaline. There are more than ten synthetic techniques for hydroquinone.
  • the main process routes include the Reppe synthesis method, which uses acetylene and carbon monoxide as raw materials under high temperature and pressure, requiring expensive catalysts and presenting challenges in recovery; the aniline oxidation method, which uses aniline as a raw material and manganese dioxide as an oxidant under acidic conditions, but suffers from equipment corrosion problems; other methods include the p-diisopropylbenzene peroxidation method, the bisphenol A method, the phenol hydrogen peroxide hydroxylation method, and electrochemical methods.
  • the synthesis of hydroquinone often begins with the oxidation of phenol or aniline to produce p-benzoquinone.
  • hydroquinone is easily oxidized, and during oxidation, it is readily further oxidized to p-benzoquinone. Therefore, a reducing agent such as hydrogen is needed to reduce p-benzoquinone to obtain hydroquinone. Consequently, industrial methods for producing hydroquinone waste oxidizing agents and hydrogen, lacking atom economy.
  • the purpose of this invention is to provide a green co-production method for benzoquinone compounds and hydroquinone, which can simultaneously and efficiently prepare benzoquinone compounds and hydroquinone without the need for additional oxidizing and reducing agents.
  • a method for preparing benzoquinone compounds and hydroquinones by co-production comprising: a phenolic compound of formula (a) reacting with benzoquinones in a protic acid catalyst and a solvent to produce benzoquinone compounds of formula (b) and hydroquinones, the reaction formula being:
  • R1 , R2 , R3 , and R4 are independently selected from H, C1-10 alkyl, C1-10 alkoxy, Cl, F, Br, I, and C6 - C10 aryl, or R1 and R2 are cyclic with the carbon chain connecting R1 and R2 .
  • the solvent contains at least one of water or alcohol.
  • the C6 - C10 aryl group is further preferably phenyl or naphthyl; the C1-10 alkyl group is further preferably C1-6 alkyl; and the C1-10 alkoxy group is further preferably C1-6 alkoxy.
  • the alcohol solvent is further selected from one or more of methanol, ethanol, n-butanol, tert-butanol, isobutanol, n-propanol, isopropanol, pentanol, ethylene glycol, 1-hexanol, or hexafluoroisopropanol.
  • the other solvents are further selected from one or more combinations of acetonitrile, acetone, toluene, tetrahydrofuran, n-hexane, N,N-dimethylformamide, N,N-dimethylacetamide, 1-ethyl-3-methylimidazolium acetate, 1-ethylimidazolium, diethanolamide, and ethylene glycol methyl ether.
  • the other solvents should not contain oxidizing solvents, such as dimethyl sulfoxide.
  • This invention innovatively combines two industrial conversion processes for preparing quinone compounds and hydroquinone, eliminating the need for additional oxidants and reductants to achieve the co-production of quinone compounds and hydroquinone. Furthermore, this method uses inexpensive protic acids as catalysts, exhibiting high catalytic efficiency, high conversion rate, and good selectivity, which enhances the competitiveness of both quinone and hydroquinone synthesis.
  • TMBQ the key to this method lies in the activation of p-benzoquinone in water or alcohol solvents, thereby utilizing the oxygen in solvent molecules such as water for an oxygenation reaction to generate TMBQ.
  • one part 2,3,6-trimethylphenol reacts with two parts p-benzoquinone and one part water to produce one part TMBQ and two parts hydroquinone.
  • the protic acid catalyst used in this method activates benzoquinone, increasing its activity in activating water or alcohol solvents, avoiding the use of metal catalysts, making it environmentally friendly, low-cost, and exhibiting high atom economy.
  • the redox reaction is carried out in an atmosphere of one or more mixed gases selected from air, nitrogen, argon, and oxygen, with a nitrogen atmosphere being the most preferred.
  • R1 , R2 , R3 , and R4 are independently selected from H, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, hexyl, methoxy, ethoxy, isopropoxy, tert-butoxy, Cl, F, Br, I, and phenyl, or R1 and R2 form a five-membered ring or a six-membered ring with the carbon chain connecting R1 and R2.
  • the five-membered ring or the six-membered ring can be an aliphatic ring or an aromatic ring.
  • the molar ratio of the phenolic compound to the p-benzoquinone is 1:0.05 to 15. More preferably, the molar ratio of the phenolic compound to the p-benzoquinone is 1:1 to 8. Even more preferably, the molar ratio of the phenolic compound to the p-benzoquinone is 1:2 to 6.
  • the reaction temperature of the redox reaction is 20-160°C, and more preferably 50-90°C.
  • the mass ratio of the non-aqueous solvent to the water in the solvent is 1:0-15, and does not include 0. Further, the mass ratio of the non-aqueous solvent to the water is 1:0.1-10; even further, the mass ratio of the non-aqueous solvent to the water is 1:0.1-8.
  • the solvent is a binary mixed solvent of methanol/water, ethanol/water, tert-butanol/water, n-butanol/water, 1-butanol/water, acetonitrile/water, isopropanol/water, 1-hexanol/water, dimethylacetamide/water, tetrahydrofuran/water, hexafluoroisopropanol/water, n-hexane/water, acetone/water, ethylene glycol dimethyl ether/water, or ethylene glycol methyl ether/water.
  • the amount of mixed solvent used there are no particularly strict requirements on the amount of mixed solvent used, as long as it can fully dissolve the reaction raw materials.
  • the total amount of solvent used for 1 mmol of phenolic compound is about 2 to 6 g.
  • the reaction is carried out at a pressure of 0.1-1 MPa.
  • the reaction time of the redox reaction is 0.5-96 h.
  • the phenolic compound represented by formula (a) is selected from 2,3,6-trimethylphenol, 2,3,5-trimethylphenol, o-cresol, m-cresol, 2,6-dimethylphenol, 2,3-dimethylphenol, 2,5-dimethylphenol, 3,5-dimethylphenol, thymol, 5-isopropyl-2-methylphenol, 5-isopropoxy-2-methylphenol, 2-methyl-1-naphthol, 2,3,5,6-tetramethylphenol, 2-methyl- One or more combinations of 5-chlorophenol, 2-chloro-3,5-dimethylphenol, 3-bromo-2,5-dimethylphenol, 2,6-dimethoxyphenol, 3-methoxyphenol, 2,3-dihydro-1H-4-indanol, 2,4-dimethyl-[1,1'-biphenyl]-3-phenol, 4-methyl-[1,1'-biphenyl]-3-phenol, 3,5-dimethyl-2-methoxyphenol, and 3,5-dimethyl-2
  • the protic acid catalyst is selected from one or more combinations of methanesulfonic acid, trifluoromethanesulfonic acid, hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, benzoic acid, nitric acid, acetic acid, trifluoroacetic acid, nitric acid, hydrobromic acid, and phosphoric acid; further, the protic acid catalyst is preferably one or more combinations of methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, hydrochloric acid, acetic acid, trifluoroacetic acid, and hydrochloric acid. Further, the molar ratio of the protic acid catalyst to the phenolic compound is 0.001–4 :1, preferably 0.001–1 :1, and more preferably 0.05–0.2:1.
  • This invention couples the production of trimethylbenzoquinone, which originally required oxidation with an oxidant, and the production of hydroquinone, which required reduction with hydrogen, in a cost-effective manner.
  • acid as a catalyst for redox reactions, two important chemical products can be obtained simultaneously.
  • the catalytic efficiency is high and the co-production yield is high, which helps to reduce the production cost of trimethylbenzoquinone and hydroquinone and reduce environmental pollution.
  • Figure 1 shows the GC-MS results of 2,3,5-trimethylbenzoquinone in Example 3. The positions of 2,3,5-trimethylbenzoquinone are marked in the figure, and the accurate molecular weight is given.
  • Figures 2 and 3 are the NMR spectra of 2,3,5-trimethylbenzoquinone and hydroquinone separated by column chromatography in Example 10, respectively.
  • FIG. 4 shows the QTOF results of the TMBQ column separation products in Example 10.
  • FIG. 5 shows the QTOF results of the hydroquinone column separation product in Example 10.
  • Figure 6 shows the GC-MS results of 2,6-dimethyl-1,4-p-benzodiquinone in Example 14, with the positions of 2,6-dimethyl-1,4-p-benzodiquinone marked in the figure;
  • Figure 7 shows the GC-MS results of tetramethyl-1,4-p-benzoquinone in Example 19, with the positions of tetramethyl-1,4-p-benzoquinone marked in the figure.
  • This comparative example provides a production process for the co-production of TMBQ and hydroquinone, which adopts the following synthetic route:
  • the method includes the following steps: In a 20 mL reaction flask, 0.5 mmol of 2,3,6-trimethylphenol, 1.5 mmol of 1,4-p-benzoquinone, 1.4 g of methanol, and 0.6 g of water are added. A magnetic stir bar is added, and after evacuation, a nitrogen gas bag (0.1 MPa) is connected. The reaction is carried out at 70 °C for 24 hours.
  • the conversion rate of 2,3,6-trimethylphenol is 100%
  • the TMBQ selectivity is 70.9%
  • the conversion rate of 1,4-p-benzoquinone is 86.9%
  • the selectivity of hydroquinone is 41.3%.
  • This embodiment provides a production process for the co-production of TMBQ and hydroquinone, which adopts the following synthetic route:
  • the method includes the following steps: In a 20 mL reaction flask, 0.5 mmol of 2,3,6-trimethylphenol, 1.5 mmol of 1,4-p-benzoquinone, 1.4 g of methanol, 0.6 g of water, and 0.1 mmol of hydrochloric acid solution (37% by mass) are added. A magnetic stir bar is added, and after evacuation, a nitrogen gas bag (0.1 MPa) is connected. The reaction is carried out at 70 °C for 2 hours. Samples are taken and analyzed by gas chromatography.
  • This embodiment provides a production process for the co-production of TMBQ and hydroquinone.
  • the difference between this embodiment and Example 1 is that 0.1 mmol of hydrochloric acid is replaced with 0.1 mmol of trifluoroacetic acid during the reaction.
  • the analytical results show that the conversion rate of 2,3,6-trimethylphenol is 94.6%, the selectivity of TMBQ is 96.0%, the conversion rate of 1,4-p-benzoquinone is 77.8%, and the selectivity of hydroquinone is 60.8%.
  • This embodiment provides a production process for the co-production of TMBQ and hydroquinone.
  • the difference between this embodiment and Example 1 is that 0.1 mmol of hydrochloric acid is replaced with 0.1 mmol of trifluoromethanesulfonic acid during the reaction.
  • the analytical results show that the conversion rate of 2,3,6-trimethylphenol is 93.3%, the selectivity of TMBQ is 100%, the conversion rate of 1,4-p-benzoquinone is 75.8%, and the selectivity of hydroquinone is 66.6%.
  • the gas chromatogram is shown in Figure 1, where the gas phase position of TMBQ is marked.
  • This embodiment provides a production process for the co-production of TMBQ and hydroquinone.
  • the difference between this embodiment and Example 3 is that the molar amount of trifluoromethanesulfonic acid is 0.05 mmol for the reaction.
  • the analytical results show that the conversion rate of 2,3,6-trimethylphenol is 93.2%, the selectivity of TMBQ is 93.9%, the conversion rate of 1,4-p-benzoquinone is 72.1%, and the selectivity of hydroquinone is 65.8%.
  • This example provides a production process for the co-production of TMBQ and hydroquinone.
  • the difference between this example and Example 3 is that the molar amount of trifluoromethanesulfonic acid is 0.5 mmol for the reaction.
  • the analytical results show that the conversion rate of 2,3,6-trimethylphenol is 95.0%, the selectivity of TMBQ is 100%, the conversion rate of 1,4-p-benzoquinone is 91.7%, and the selectivity of hydroquinone is 44.9%.
  • This example provides a process for the co-production of TMBQ and hydroquinone.
  • the difference between this example and Example 3 is that the molar amount of trifluoromethanesulfonic acid is 2 mmol for the reaction.
  • the analytical results show that the conversion rate of 2,3,6-trimethylphenol is 89.6%, the selectivity of TMBQ is 70.8%, the conversion rate of 1,4-p-benzoquinone is 66.4%, and the selectivity of hydroquinone is 79.2%.
  • This embodiment provides a production process for the co-production of TMBQ and hydroquinone.
  • the difference between this embodiment and Example 3 is that the reaction temperature is 50°C.
  • the analytical results show that the conversion rate of 2,3,6-trimethylphenol is 87.3%, the selectivity of TMBQ is 93.2%, the conversion rate of 1,4-p-benzoquinone is 69.6%, and the selectivity of hydroquinone is 79.2%.
  • This embodiment provides a production process for the co-production of TMBQ and hydroquinone.
  • the difference between this embodiment and Example 3 is that the solvent conditions are changed to acetonitrile (1.4 g) and water (0.6 g).
  • the analytical results show that the conversion rate of 2,3,6-trimethylphenol is 82.1%, the selectivity of TMBQ is 79.3%, the conversion rate of 1,4-p-benzoquinone is 61.9%, and the selectivity of hydroquinone is 78.2%.
  • This embodiment provides a production process for the co-production of TMBQ and hydroquinone.
  • the difference between this embodiment and Example 3 is that the reaction temperature is 50°C and the reaction time is 6.5 hours.
  • the analytical results show that the conversion rate of 2,3,6-trimethylphenol is 93.3%, the selectivity of TMBQ is 83.5%, the conversion rate of 1,4-p-benzoquinone is 67.6%, and the selectivity of hydroquinone is 88.2%.
  • This embodiment provides a process for the co-production of TMBQ and hydroquinone.
  • the difference lies in the fact that the molar amounts of 2,3,6-trimethylphenol and 1,4-p-benzoquinone are increased by 10 times. 1 mmol of trifluoromethanesulfonic acid, 14 g of methanol, and 6 g of water are added, and the reaction is carried out for 24 hours. Gas chromatography analysis shows that the conversion rate of 2,3,6-trimethylphenol is 100%, the conversion rate of 1,4-p-benzoquinone is 82.1%, the selectivity of TMBQ is 95.9%, and the selectivity of hydroquinone is 77.7%.
  • This embodiment provides a production process for the co-production of TMBQ and hydroquinone.
  • the difference lies in the solvent conditions: dimethyl sulfoxide (1.4 g) and water (0.6 g) are used, and the reaction time is 24 hours.
  • the analytical results show that the conversion rate of 2,3,6-trimethylphenol is 99.7%, the selectivity of TMBQ is 25.7%, the conversion rate of 1,4-p-benzoquinone is 97.7%, and the selectivity of hydroquinone is 36.9%.
  • This embodiment provides a production process for the co-production of TMBQ and hydroquinone. Compared with Example 3, the difference is that the solvent is changed to methanol and water. The reaction is carried out under air conditions for 24 hours. The conversion rate of 2,3,6-trimethylphenol is 100%, the selectivity of TMBQ is 68.4%, the conversion rate of 1,4-p-benzoquinone is 95.5%, and the selectivity of hydroquinone is 42.4%.
  • Examples 11 and 12 indicate that the reaction results are poor when using the oxidizing solvent dimethyl sulfoxide or when the reaction atmosphere is air, which may be due to the oxidizing environment adversely interfering with the redox reaction.
  • This embodiment provides a production process for the co-production of TMBQ and hydroquinone.
  • the difference between this embodiment and Example 3 is that the solvent system is ethylene glycol monomethyl ether (1.4 g) and water (0.6 g), and the reaction time is 24 hours.
  • the analytical results show that the conversion rate of 2,3,6-trimethylphenol is 98.6%, the selectivity of TMBQ is 97.0%, the conversion rate of 1,4-p-benzoquinone is 86.6%, and the selectivity of hydroquinone is 71.3%.
  • This embodiment provides a process for the co-production of 2,6-dimethyl-1,4-p-benzodiquinone and hydroquinone.
  • the difference between this embodiment and Example 3 is that 0.5 mmol of 2,3,6-trimethylphenol is replaced with 0.5 mmol of 2,6-dimethylphenol, and the reaction time is 24 hours.
  • the analytical results show that the conversion rate of 2,6-dimethylphenol is 80.7%, the selectivity of 2,6-dimethyl-1,4-p-benzodiquinone is 46.1%, the conversion rate of 1,4-p-benzodiquinone is 82.9%, and the selectivity of hydroquinone is 53.9%.
  • the gas chromatogram is shown in Figure 6, where the gas phase position of 2,6-dimethyl-1,4-p-benzodiquinone is marked.
  • This embodiment provides a process for the co-production of 2,5-dimethyl-1,4-p-benzoquinone and hydroquinone.
  • the difference between this embodiment and Example 3 is that 0.5 mmol of 2,3,6-trimethylphenol is replaced with 0.5 mmol of 2,5-dimethylphenol, and the reaction time is 24 hours.
  • the analytical results show that the conversion rate of 2,5-dimethylphenol is 96.4%, the selectivity of 2,5-dimethyl-1,4-p-benzoquinone is 80.2%, the conversion rate of 1,4-p-benzoquinone is 93.4%, and the selectivity of hydroquinone is 58.4%.
  • This embodiment provides a production process for the co-production of thymol and hydroquinone.
  • the difference between this embodiment and Example 3 is that 0.5 mmol of 2,3,6-trimethylphenol is replaced with 0.5 mmol of thymol, and the reaction is carried out for 24 hours.
  • the analytical results show that the thymol conversion rate is 86.2%, the thymol selectivity is 48.9%, the 1,4-p-benzoquinone conversion rate is 92.1%, and the hydroquinone selectivity is 48.9%.
  • This embodiment provides a process for the co-production of 2,3-dimethyl-1,4-p-benzoquinone and hydroquinone.
  • the difference between this embodiment and Example 3 is that 0.5 mmol of 2,3,6-trimethylphenol is replaced with 0.5 mmol of 2,3-dimethylphenol, and the reaction time is 24 hours.
  • the analytical results show that the conversion rate of 2,3-dimethylphenol is 94.3%, the selectivity of 2,3-dimethyl-1,4-p-benzoquinone is 82.7%, the conversion rate of 1,4-p-benzoquinone is 90.4%, and the selectivity of hydroquinone is 49.0%.
  • This embodiment provides a production process for the co-production of thymequinone and hydroquinone.
  • the difference between this embodiment and Example 3 is that 0.5 mmol of 2,3,6-trimethylphenol is replaced with 0.5 mmol of 5-isopropyl-2-methylphenol, and the reaction is carried out for 24 hours.
  • the analytical results show that the conversion rate of 5-isopropyl-2-methylphenol is 83.0%, the selectivity of thymequinone is 87.1%, the conversion rate of 1,4-p-benzoquinone is 92.4%, and the selectivity of hydroquinone is 45.5%.
  • This embodiment provides a production process for the co-production of tetramethyl-1,4-p-benzoquinone and hydroquinone.
  • the difference is that 0.5 mmol of 2,3,6-trimethylphenol is replaced with 0.5 mmol of 2,3,5,6-tetramethylphenol and the reaction is carried out for 24 hours.
  • the conversion rate of 2,3,5,6-tetramethylphenol is 100%
  • the selectivity of tetramethyl-1,4-p-benzoquinone is 81.9%
  • the conversion rate of 1,4-p-benzoquinone is 94.6%
  • the selectivity of hydroquinone is 75.3%.
  • the gas chromatogram is shown in Figure 7, where the gas phase position of tetramethyl-1,4-p-benzoquinone is marked.
  • This example provides a production process for the co-production of TMBQ and hydroquinone.
  • the difference between this example and Example 3 is that 0.5 mmol of 2,3,6-trimethylphenol is replaced with 0.5 mmol of 2,3,5-trimethylphenol and the reaction is carried out for 24 hours.
  • the conversion rate of 2,3,5-trimethylphenol is 100%
  • the selectivity of TMBQ is 64.6%
  • the conversion rate of 1,4-p-benzoquinone is 88.4%
  • the selectivity of hydroquinone is 62.1%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

本发明公开了一种苯醌类化合物和氢醌的绿色联产方法，该方法将酚类化合物与苯醌在质子酸催化剂和溶剂中发生氧化还原反应生成苯醌类化合物和氢醌，所述溶剂包含水或醇溶剂中的至少一个。该方法将原本需要氧化剂氧化的三甲基苯醌生产和需要氢气还原的氢醌生产进行耦合，以廉价的(I)酸为催化剂进行氧化还原反应，同时获得两种重要化工产品，催化效率高，联产产率高，有利于降低三甲基苯醌和氢醌的生产成本，减少环境污染。

Description

一种苯醌类化合物和氢醌的绿色联产方法 技术领域
本发明涉及精细化工合成技术领域，具体涉及到一种苯醌类化合物和氢醌的绿色联产方法。
背景技术
维生素E是生育酚类化合物的总称，自1922年发现以后一直受到高度的关注，现如今维生素E在保健品领域非常重要，同时还在医药、食品、饲料、化妆品等多个领域有重要用途。维生素E合成的重要中间体是2,3,5-三甲基氢醌2,3,5-三甲基氢醌可以通过三甲基苯醌催化加氢得到。三甲基苯醌，即2,3,5-三甲基苯醌(简称TMBQ)，同样是一种重要的药物中间体，TMBQ的合成原料主要有三种：2,3,5-三甲基苯酚、2,3,6-三甲基苯酚和偏三甲苯，目前国内外主要选择2,3,6-三甲基苯酚作为原料合成TMBQ。
根据2,3,6-三甲基苯酚合成TMBQ主要有化学氧化法和催化氧化法。在化学氧化法中，2,3,6-三甲基苯酚经过磺化得到4-磺酸基-2,3,6-三甲基苯酚，再经过二氧化锰氧化得到TMBQ，这种方式优点在于合成简单、设备投资成本低，缺点在于易造成环境污染，且实际合成过程中4-磺酸基-2,3,6-三甲基苯酚容易结块，溶解操作繁琐。
在催化氧化法中，使用双氧水(H2O2)作为氧源，再经过脱水得到TMBQ。在实验室研究中，报道了多种催化剂的效果，使用了钌系催化剂可以实现三甲醌83％的产率(Adv.Synth.Catal，DOI:10.1002/adsc.201000137)；再者有以CuCl2-聚(4-乙烯吡啶)为催化剂，使用DMSO作为溶剂，氧气作为氧源，2,3,6-三甲基苯酚的转化率可以达到100％，选择性可以得到95％。中国专利CN96180478.5公开了一种杂多酸催化体系氧化2,3,6-三甲基苯酚得到TMBQ的方法，该方法可获得TMBQ收率达到95％，2,3,6-三甲基苯酚转化率达到100％；中国专利CN201711037289.4提出了使用偏四甲苯作为原料合成，减少副产物的生成，提高三甲基苯醌收率的工艺。这些催化氧化法使用氧气或双氧水作氧化剂，相对环境友好，但缺点是选择性难以控制、需要的氧气压力高、高压反应设备成本高，且所用的金属催化剂价格较高。
氢醌是另外一种广泛使用的化工产品，截至2018年氢醌的全球需求大约在7万吨左右，主要从法国、意大利、美国等国家进口，氢醌的需求正在逐渐提升。其又名对苯二酚，主要用于合成双氧水，也多用于摄影胶片、阻聚剂、黄连素、肾上腺素等中间体合成等用途。氢醌的合成技术有十余种，主要工艺路线包括Reppe合成法，以乙炔和一氧化碳为原料高温高压下反应，需要昂贵的催化剂同时存在难以回收的问题；苯胺氧化法以苯胺作为原料，酸性条件下以二氧化锰作为氧化剂，存在设备腐蚀的问题；除此以外还有对二异丙苯过氧化法、双酚A法、苯酚过氧化氢羟基化法、电化学法等。氢醌的合成过程中往往是先通过氧化苯酚、苯胺等方法生成对苯醌，原因是氢醌易被氧化，在氧化中易进一步氧化为对苯醌，因而需要通过氢气等还原剂还原对苯醌，从而得到氢醌。因此，工业生产氢醌的方法中浪费了氧化剂和氢气，缺乏原子经济性。
发明内容
本发明的目的是提供一种苯醌类化合物和氢醌的绿色联产方法，该方法能同时实现苯醌类化合物和氢醌的高效制备，并且不需要加入额外的氧化剂和还原剂。
为达到上述目的，本发明采用的技术方案是：
一种联产苯醌类化合物和氢醌的制备方法，该方法包括：式(a)所示的酚类化合物与苯醌在质子酸催化剂和溶剂中发生氧化还原反应生成式(b)所示的苯醌类化合物和氢醌，反应式为：
其中，R1、R2、R3、R4分别独立地选自H、C1-10烷基、C1-10烷氧基、Cl、F、Br、I、C6～C10芳基，或者R1、R2与连接R1、R2的碳链成环；
所述溶剂至少包含水或醇溶剂中的一个。
其中，所述的C6～C10芳基进一步优选为苯基或者萘基；所述的C1-10烷基进一步优选为C1-6烷基，所述的C1-10烷氧基进一步优选为C1-6烷氧基。
其中，“至少包含”表示所述溶剂还可以包含其他溶剂或者不包含其他溶剂，所述醇溶剂进一步选自甲醇、乙醇、正丁醇、叔丁醇、异丁醇、正丙醇、异丙醇、戊醇、乙二醇、1-己醇或六氟异丙醇中的一种或者多种；所述其他溶剂进一步选自乙腈、丙酮、甲苯、四氢呋喃、正己烷、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、1-乙基-3-甲基咪唑乙酸盐、1-乙基咪唑、二乙醇二甲醚、乙二醇甲醚中的一种或多种的组合。并且进一步地，所述其他溶剂不宜包含氧化性溶剂，例如二甲基亚砜。
本发明创新性地将制备醌类化合物和氢醌的两个工业转化过程结合，不需要加入其他氧化剂和还原剂，实现醌类化合物和氢醌的联产，同时该方法使用廉价的质子酸作为催化剂，催化效率高，转化率高、选择性好，有利于同时提高醌类化合物和氢醌合成的竞争力。以醌类化合物为TMBQ为例，该方法能够实现的关键在于对苯醌对水或醇溶剂的活化，从而将水等溶剂分子中的氧用来进行加氧反应生成TMBQ，理论上一份2,3,6-三甲基苯酚与两份对苯醌和一份水反应，生成一份TMBQ和两份氢醌。该方法使用的质子酸作为催化剂可以活化苯醌，使其活化水或醇溶剂的活性提高，避免的金属催化剂的使用，环境友好，成本低，反应具有较高的原子经济性。
作为优选，所述氧化还原反应在空气、氮气、氩气、氧气中的一种或多种混合气体氛围下进行，优选为氮气氛围。
作为优选，式(a)中R1、R2、R3、R4分别独立地选自H、甲基、乙基、丙基、异丙基、正丁基、异丁基、叔丁基、正戊基、异戊基、新戊基、己基、甲氧基、乙氧基、异丙氧基、叔丁氧基、Cl、F、Br、I、苯基，或者R1、R2与连接R1、R2的碳链形成五元环或者六元环，该五元环或六元环可以为脂肪环，也可以为芳香环。
作为优选，所述酚类化合物与所述对苯醌的投料摩尔比为1∶0.05～15。更进一步地，所述酚类化合物与所述对苯醌的投料摩尔比为1∶1～8。更进一步地，所述酚类化合物与所述对苯醌的投料摩尔比为1∶2～6。
作为优选，所述氧化还原反应的反应温度为20-160℃，优选为50-90℃。
作为优选，当溶剂条件为含水溶剂条件时，溶剂中所述非水溶剂和所述水质量比为1∶0-15，并且不包含0。进一步地，所述非水溶剂和所述水质量比为1∶0.1～10；更进一步地，所述非水溶剂和所述水质量比为1∶0.1-8。更进一步地，所述溶剂为甲醇/水、乙醇/水、叔丁醇/水、正丁醇/水、1-丁醇/水、乙腈/水、异丙醇/水、1-己醇/水、二甲基乙酰胺/水、四氢呋喃/水、六氟异丙醇/水、正己烷/水、丙酮/水、乙二醇二甲醚/水、乙二醇甲醚/水二元混合溶剂。
混合溶剂的用量无特别严格的要求，能将反应原料充分溶解即可，一般1mmol酚类化合物所采用的溶剂总量为2～6g左右。
作为优选，反应压力在0.1-1MPa压力下进行。
作为优选，所述氧化还原反应的反应时间为0.5-96h。
作为优选，式(a)所示的酚类化合物为选自2,3,6-三甲基苯酚、2,3,5-三甲基酚、邻甲酚、间甲酚、2,6-二甲基苯酚、2,3-二甲基酚、2,5-二甲基苯酚、3,5-二甲基酚、百里酚、5-异丙基-2-甲基苯酚、5-异丙氧基-2甲基苯酚、2-甲基-1-萘酚、2,3,5,6-四甲基苯酚、2-甲基-5-氯苯酚、2-氯-3,5-二甲基苯酚、3-溴-2,5-二甲基苯酚、2,6-二甲氧基苯酚、3-甲氧基苯酚、2,3-二氢-1H-4-茚醇、2,4-二甲基-[1,1'-联苯]-3-酚、4-甲基-[1,1'-联苯]-3-酚、3,5-二甲基-2-甲氧基苯酚、3,5-二甲基-2-碘苯酚中的一种或多种的组合。
作为优选，所述质子酸催化剂选自甲磺酸、三氟甲磺酸、盐酸、硫酸、对甲苯磺酸、苯甲酸、硝酸、乙酸、三氟乙酸、硝酸、氢溴酸、磷酸中的一种或多种的组合；进一步地，所述质子酸催化剂优选为甲磺酸、三氟甲磺酸、对甲苯磺酸、盐酸、乙酸、三氟乙酸、盐酸中的一种或多种的组合。进一步地，所述质子酸催化剂与所述酚类化合物的投料摩尔比为0.001～4:1，优选为0.001～1:1，进一步优选为0.05～0.2：1。
同现有技术相比，本发明的有益效果体现在：
本发明将原本需要氧化剂氧化的三甲基苯醌生产和需要氢气还原的氢醌生产进行耦合，以廉价的酸为催化剂进行氧化还原反应，同时获得两种重要化工产品，催化效率高，联产产率高，有利于降低三甲基苯醌和氢醌的生产成本，减少环境污染。
附图说明
图1是实施例3中2,3,5-三甲基苯醌的GC-MS结果，图中标记了2,3,5-三甲基苯醌的位置，并给出了准确的分子量；
图2和图3分别是实施例10中过柱分离的2,3,5-三甲基苯醌和氢醌的核磁谱图。
图4是实施例10中TMBQ的过柱分离产物的QTOF结果；
图5是实施例10中氢醌的过柱分离产物的QTOF结果；
图6是实施例14中2,6-二甲基-1,4-对苯二醌的GC-MS结果，图中标记了2,6-二甲基-1,4-对苯二醌的位置；
图7是实施例19中四甲基-1,4-对苯醌的GC-MS结果，图中标记了四甲基-1,4-对苯醌的位置。
具体实施方式
以下结合具体实施例对上述方案做进一步说明；应理解，这些实施例是用于说明本发明的基本原理、主要特征和优点，而本发明不受以下实施例的范围限制；实施例中采用的实施条件可以根据具体要求做进一步调整，未注明的实施条件通常为常规实验中的条件。
下述实施例中未作特殊说明，所有原料均来自于商购或通过本领域的常规方法制备而得。
下述中，所有反应转化率和产率使用气相色谱测定(使用商业渠道购买的原料和产物定标准曲线)。
对比例1
本对比例提供一种联产TMBQ和氢醌的生产工艺，该方法采用如下合成路径：
该方法包括如下步骤，在20mL的反应瓶中，加入0.5mmol 2,3,6-三甲基苯酚、1.5mmol 1,4-对苯醌、1.4g甲醇、0.6g水，加入磁子，抽真空后接入氮气气囊(0.1MPa)，在70℃下反应24小时，2,3,6-三甲基苯酚转化率为100％，TMBQ选择性为70.9％，1,4-对苯醌转化率为86.9％，氢醌的选择性为41.3％。
实施例1
本实施例提供一种联产TMBQ和氢醌的生产工艺，该方法采用如下合成路径：
该方法包括如下步骤，在20mL的反应瓶中，加入0.5mmol 2,3,6-三甲基苯酚、1.5mmol 1,4-对苯醌、1.4g甲醇、0.6g水、0.1mmol盐酸溶液(质量浓度37％)，加入磁子，抽真空后接入氮气气囊(0.1MPa)，在70℃下反应2小时，取样，进行气相色谱分析，结果为：2,3,6-三甲基苯酚转化率为100％，TMBQ选择性为97.5％，1,4-对苯醌转化率为83.7％，氢醌的选择性为40.5％。
实施例2
本实施例提供一种联产TMBQ和氢醌的生产工艺，该实施例与实施例1相比，区别之处在于，将0.1mmol盐酸替换为0.1mmol三氟乙酸，进行反应。分析结果为，2,3,6-三甲基苯酚转化率为94.6％，TMBQ选择性为96.0％，1,4-对苯醌转化率为77.8％，氢醌的选择性为60.8％。
实施例3
本实施例提供一种联产TMBQ和氢醌的生产工艺，该实施例与实施例1相比，区别之处在于，将0.1mmol盐酸替换为0.1mmol三氟甲磺酸，进行反应。分析结果为，2,3,6-三甲基苯酚转化率为93.3％，TMBQ选择性为100％，1,4-对苯醌转化率为75.8％，氢醌的选择性为66.6％，气相色谱图见图1，其中标注了TMBQ气相位置。
实施例4
本实施例提供一种联产TMBQ和氢醌的生产工艺，该实施例与实施例3相比，区别之处在于，三氟甲磺酸摩尔量为0.05mmol，进行反应。分析结果为，2,3,6-三甲基苯酚转化率为93.2％，TMBQ选择性为93.9％，1,4-对苯醌转化率为72.1％，氢醌的选择性为65.8％。
实施例5
本例提供一种联产TMBQ和氢醌的生产工艺，该实施例与实施例3相比，区别之处在于，三氟甲磺酸摩尔量为0.5mmol，进行反应。分析结果为，2,3,6-三甲基苯酚转化率为95.0％，TMBQ选择性为100％，1,4-对苯醌转化率为91.7％，氢醌的选择性为44.9％。
实施例6
本例提供一种联产TMBQ和氢醌的生产工艺，该例与实施例3相比，区别之处在于，三氟甲磺酸的摩尔量为2mmol，进行反应。分析结果为，2,3,6-三甲基苯酚转化率为89.6％，TMBQ选择性为70.8％，1,4-对苯醌转化率为66.4％，氢醌的选择性为79.2％。
实施例7
本实施例提供一种联产TMBQ和氢醌的生产工艺，该实施例与实施例3相比，区别之处在于，反应温度为50℃。分析结果为，2,3,6-三甲基苯酚转化率为87.3％，TMBQ选择性为93.2％，1,4-对苯醌转化率为69.6％，氢醌的选择性为79.2％。
实施例8
本实施例提供一种联产TMBQ和氢醌的生产工艺，该实施例与实施例3相比，区别之处在于，溶剂条件改为乙腈(1.4g)和水(0.6g)。分析结果为，2,3,6-三甲基苯酚转化率为82.1％，TMBQ选择性为79.3％，1,4-对苯醌转化率为61.9％，氢醌的选择性为78.2％。
实施例9
本实施例提供一种联产TMBQ和氢醌的生产工艺，该实施例与实施例3相比，区别之处在于，反应温度为50℃，反应6.5小时。分析结果为，2,3,6-三甲基苯酚转化率为93.3％，TMBQ选择性为83.5％，1,4-对苯醌转化率为67.6％，氢醌的选择性为88.2％。
实施例10
本实施例提供一种联产TMBQ和氢醌的生产工艺，该实施例与实施例3相比，区别之处在于，2,3,6-三甲基苯酚和1,4-对苯醌摩尔量放大10倍，加入三氟甲磺酸1mmol，14g甲醇、6g水，反应24小时，气相检测2,3,6-三甲基苯酚转化率为100％，1,4-对苯醌转化率为82.1％，TMBQ选择性为95.9％，氢醌的选择性为77.7％。后续加入适量硅胶，旋干以后进行柱层析色谱分离得到两个产物，干燥后再将产物分别进行质谱检测。最终TMBQ收率为93.1％，氢醌的收率为62.3％；图2和3分别为过柱分离得到的TMBQ和氢醌的核磁图谱，图4和5分别为过柱分离得到的TMBQ和氢醌的QTOF结果。
实施例11
本实施例提供一种联产TMBQ和氢醌的生产工艺，该实施例与实施例3相比，区别之处在于，溶剂条件改为二甲基亚砜(1.4g)和水(0.6g)，反应24小时。分析结果为，2,3,6-三甲基苯酚转化率为99.7％，TMBQ选择性为25.7％，1,4-对苯醌转化率为97.7％，氢醌的选择性为36.9％。
实施例12
本实施例提供一种联产TMBQ和氢醌的生产工艺，该实施例与实施例3相比，区别之处在于，溶剂种类改为甲醇和水，在空气条件下反应24小时，2,3,6-三甲基苯酚转化率为100％，TMBQ选择性为68.4％，1,4-对苯醌转化率为95.5％，氢醌的选择性为42.4％。
实施例11和实施例12的结果表明，采用氧化性溶剂二甲基亚砜，或者反应氛围为空气，反应结果较差，可能氧化性环境会对氧化还原反应产生不利的干扰。
实施例13
本实施例提供一种联产TMBQ和氢醌的生产工艺，该实施例与实施例3相比，区别之处在于，溶剂体系为乙二醇单甲醚(1.4g)和水(0.6g)，反应24小时。分析结果为，2,3,6-三甲基苯酚转化率为98.6％，TMBQ选择性为97.0％，1,4-对苯醌转化率为86.6％，氢醌的选择性为71.3％。
实施例14
本实施例提供一种联产2,6-二甲基-1,4-对苯二醌和氢醌的生产工艺，该实施例与实施例3相比，区别之处在于，将0.5mmol的2,3,6-三甲基苯酚替换为0.5mmol的2,6-二甲基苯酚，反应24小时。分析结果为，2,6-二甲基酚转化率为80.7％，2,6-二甲基-1,4-对苯二醌选择性为46.1％，1,4-对苯醌转化率为82.9％，氢醌的选择性为53.9％；气相色谱图见图6，其中标注了2,6-二甲基-1,4-对苯二醌气相位置。
实施例15
本实施例提供一种联产2,5-二甲基-1,4-对苯醌和氢醌的生产工艺，该实施例与实施例3相比，区别之处在于，将0.5mmol的2,3,6-三甲基苯酚替换为0.5mmol的2,5-二甲基苯酚，反应24小时。分析结果为，2,5-二甲基苯酚转化率为96.4％，2,5-二甲基-1,4-对苯醌选择性为80.2％，1,4-对苯醌转化率为93.4％，氢醌的选择性为58.4％。
实施例16
本实施例提供一种联产百里醌和氢醌的生产工艺，该实施例与实施例3相比，区别之处在于，将0.5mmol的2,3,6-三甲基苯酚替换为0.5mmol的百里酚反应24小时。分析结果为，百里酚转化率为86.2％，百里醌选择性为48.9％，1,4-对苯醌转化率为92.1％，氢醌的选择性为48.9％。
实施例17
本实施例提供一种联产2,3-二甲基-1,4-对苯醌和氢醌的生产工艺，该实施例与实施例3相比，区别之处在于，将0.5mmol的2,3,6-三甲基苯酚替换为0.5mmol的2,3-二甲基苯酚反应24小时。分析结果为，2,3-二甲基苯酚转化率为94.3％，2,3-二甲基-1,4-对苯醌选择性为82.7％，1,4-对苯醌转化率为90.4％，氢醌的选择性为49.0％。
实施例18
本实施例提供一种联产百里醌和氢醌的生产工艺，该实施例与实施例3相比，区别之处在于，将0.5mmol的2,3,6-三甲基苯酚替换为0.5mmol的5-异丙基-2-甲基苯酚反应24小时。分析结果为，5-异丙基-2-甲基苯酚转化率为83.0％，百里醌选择性为87.1％，1,4-对苯醌转化率为92.4％，氢醌的选择性为45.5％。
实施例19
本实施例提供一种联产四甲基-1,4-对苯醌和氢醌的生产工艺，该实施例与实施例3相比，区别之处在于，将0.5mmol的2,3,6-三甲基苯酚替换为0.5mmol的2,3,5,6-四甲基苯酚反应24小时，2,3,5,6-四甲基苯酚转化率为100％，四甲基-1,4-对苯醌选择性为81.9％，1,4-对苯醌转化率为94.6％，氢醌的选择性为75.3％；气相色谱图见图7，其中标注了四甲基-1,4-对苯醌气相位置。
实施例20
本例提供一种联产TMBQ和氢醌的生产工艺，该例与实施例3相比，区别之处在于，将0.5mmol的2,3,6-三甲基苯酚替换为0.5mmol的2,3,5-三甲基苯酚反应24小时，2,3,5-三甲基苯酚转化率为100％，TMBQ选择性为64.6％，1,4-对苯醌转化率为88.4％，氢醌的选择性为62.1％。
上述实施例只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围之内。
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。

Claims (10)

  1. 一种苯醌类化合物和氢醌的绿色联产方法，其特征在于，包括：
    式(a)所示的酚类化合物与苯醌在质子酸催化剂和溶剂中发生氧化还原反应生成式(b)所示苯醌类化合物和氢醌；
    反应如下：
    其中，R1、R2、R3、R4分别独立地选自H、C1-10烷基、C1-10烷氧基、Cl、F、Br、I或C6～C10芳基，或者R1、R2与连接R1、R2的碳链成环；
    所述溶剂至少包含水或醇溶剂中的一个。
  2. 根据权利要求1所述的苯醌类化合物和氢醌的绿色联产方法，其特征在于：所述酚类化合物和苯醌的投料摩尔比为1∶0.05～15。
  3. 根据权利要求1所述的苯醌类化合物和氢醌的绿色联产方法，其特征在于：所述质子酸催化剂与所述酚类化合物的投料摩尔比为0.001～4:1，优选为0.05～0.2：1。
  4. 根据权利要求1所述的苯醌类化合物和氢醌的绿色联产方法，其特征在于：所述氧化还原反应的反应温度为20～160℃，优选为50～90℃。
  5. 根据权利要求1所述的苯醌类化合物和氢醌的绿色联产方法，其特征在于：R1、R2、R3、R4分别独立地选自H、甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基、异戊基、新戊基、己基、甲氧基、乙氧基、异丙氧基、叔丁氧基、Cl、F、Br、I或苯基，或者R1、R2与连接R1、R2的碳链形成五元环或者六元环。
  6. 根据权利要求1所述的苯醌类化合物和氢醌的绿色联产方法，其特征在于：式(a)所示的酚类化合物选自2,3,6-三甲基苯酚、2,3,5-三甲基酚、邻甲酚、间甲酚、2,6-二甲基苯酚、2,3-二甲基苯酚、2,5-二甲基苯酚、3,5-二甲基苯酚、百里酚、5-异丙基-2-甲基苯酚、5-异丙氧基-2-甲基苯酚、2-甲基-1-萘酚、2,3,5,6-四甲基苯酚、2-甲基-5-氯苯酚、2-氯-3,5-二甲基苯酚、3-溴-2,5-二甲基苯酚、2,6-二甲氧基苯酚、3-甲氧基苯酚、2,3-二氢-1H-4-茚醇、2,4-二甲基-[1,1'-联苯]-3-酚、4-甲基-[1,1'-联苯]-3-酚、3,5-二甲基-2-甲氧基苯酚、3,5-二甲基-2-碘苯酚中的一种或多种的组合。
  7. 根据权利要求1所述的苯醌类化合物和氢醌的绿色联产方法，其特征在于：反应在空气、氮气、氩气、氧气中的一种或多种混合气体氛围下进行，优选为氮气氛围。
  8. 根据权利要求1所述的苯醌类化合物和氢醌的绿色联产方法，其特征在于：所述醇溶剂为甲醇、乙醇、正丁醇、叔丁醇、异丁醇、正丙醇、异丙醇、戊醇、乙二醇、1-己醇或六氟异丙醇中的一种或者多种。
  9. 根据权利要求1所述的苯醌类化合物和氢醌的绿色联产方法，其特征在于：所述溶剂为非水溶剂和水组成的二元混合溶剂，优选为甲醇/水、乙醇/水、叔丁醇/水、正丁醇/水、异丁醇/水、乙腈/水、异丙醇/水、1-己醇/水、N,N-二甲基甲酰胺/水、N,N-二甲基乙酰胺/水、四氢呋喃/水、六氟异丙醇/水、正己烷/水、丙酮/水、乙二醇二甲醚/水、乙二醇单甲醚/水二元混合溶剂，所述非水溶剂和所述水质量比为0.1～10:1。
  10. 根据权利要求1所述的苯醌类化合物和氢醌的绿色联产方法，其特征在于：所述质子酸催化剂选自甲磺酸、三氟甲磺酸、盐酸、硫酸、对甲苯磺酸、苯甲酸、乙酸、三氟乙酸、硝酸、氢溴酸、磷酸中的一种或多种的组合，优选为甲磺酸、三氟甲磺酸、对甲苯磺酸、盐酸、乙酸、三氟乙酸中的一种或多种的组合。
PCT/CN2024/132645 2024-07-05 2024-11-18 一种苯醌类化合物和氢醌的绿色联产方法 Pending WO2026007304A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202410898400.2A CN118666647B (zh) 2024-07-05 2024-07-05 一种苯醌类化合物和氢醌的绿色联产方法
CN202410898400.2 2024-07-05

Publications (1)

Publication Number Publication Date
WO2026007304A1 true WO2026007304A1 (zh) 2026-01-08

Family

ID=92724439

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2024/132645 Pending WO2026007304A1 (zh) 2024-07-05 2024-11-18 一种苯醌类化合物和氢醌的绿色联产方法

Country Status (2)

Country Link
CN (1) CN118666647B (zh)
WO (1) WO2026007304A1 (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118666647B (zh) * 2024-07-05 2025-09-16 浙江大学 一种苯醌类化合物和氢醌的绿色联产方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995004044A1 (en) * 1993-07-30 1995-02-09 Eisai Co., Ltd. Process for producing hydroquinone and benzoquinone derivative
US20050137380A1 (en) * 2003-12-18 2005-06-23 Mahalingam Rathinam J. Processes for preparing benzoquinones and hydroquinones
CN102219665A (zh) * 2011-04-27 2011-10-19 扬州大学 2,3,5-三甲基苯醌和2,3,5-三甲基氢醌的一种合成方法
CN118666647A (zh) * 2024-07-05 2024-09-20 浙江大学 一种苯醌类化合物和氢醌的绿色联产方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102633614B (zh) * 2012-04-01 2013-10-09 河南大学 一种2,3,5-三甲基苯醌的制备方法
WO2014199659A1 (ja) * 2013-06-14 2014-12-18 Dic株式会社 フェノール性水酸基含有化合物、フェノール樹脂、硬化性組成物、その硬化物、半導体封止材料、及びプリント配線基板
EP3133055B1 (de) * 2013-07-02 2023-10-18 Basf Se Verfahren zur herstellung von 2,3,5-trimethylbenzochinon durch oxidation von 2,3,6-trimethylphenol
CN111153785B (zh) * 2020-01-08 2022-04-26 南京工业大学 一种催化2，3，6-三甲基苯酚氧化制备2，3，5-三甲基-1，4-苯醌的方法
CN117402050B (zh) * 2022-07-06 2025-07-25 大连理工大学 一种钴催化2,3,6-三甲基苯酚合成2,3,5-三甲基苯醌的方法
CN116102414B (zh) * 2023-02-07 2025-02-11 浙江大学 一种苯醌类化合物及2-甲基-1,4-萘醌的制备方法
CN118108589A (zh) * 2024-01-16 2024-05-31 浙江新和成药业有限公司 一种维生素e中间体2,3,5-三甲基苯醌的制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995004044A1 (en) * 1993-07-30 1995-02-09 Eisai Co., Ltd. Process for producing hydroquinone and benzoquinone derivative
US20050137380A1 (en) * 2003-12-18 2005-06-23 Mahalingam Rathinam J. Processes for preparing benzoquinones and hydroquinones
CN102219665A (zh) * 2011-04-27 2011-10-19 扬州大学 2,3,5-三甲基苯醌和2,3,5-三甲基氢醌的一种合成方法
CN118666647A (zh) * 2024-07-05 2024-09-20 浙江大学 一种苯醌类化合物和氢醌的绿色联产方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HU YUCAI, HAN DEHONG, QI ZENGHONG, YIN PING, LIANG TAO: "Two-Step Process for Catalytic Oxidation of Phenol to Hydroquinone", HUAXUE FANYING GONGCHENG YU GONGYI - CHEMICAL REACTION ENGINEERING AND TECHNOLOGY, ZHEJIANG DAXUE XUEBAO BIANJIBU, HANGZHOU,, CN, vol. 22, no. 6, 25 December 2006 (2006-12-25), CN , pages 544 - 548, XP093384797, ISSN: 1001-7631 *
ZHANG TIANYONG, WANG MENGYING, LI BIN, LIU QIAN: "Research Progress on the Catalytic Oxidation of 2,3,6-trimethylphenol to 2,3,5-trimethybenzoquinone", CHEMICAL INDUSTRY AND ENGINEERING PROGRESS, BEIJING UNIVERSITY OF CHEMICAL TECHNOLOGY, MEMBER OF CHINESE ACADEMY OF ENGINEERING, PROFESSOR, CHINA, vol. 35, no. 2, 5 February 2016 (2016-02-05), pages 513 - 518, XP093384796, ISSN: 1000-6613, DOI: 10.16085/j.issn.1000-6613.2016.02.025 *

Also Published As

Publication number Publication date
CN118666647A (zh) 2024-09-20
CN118666647B (zh) 2025-09-16

Similar Documents

Publication Publication Date Title
CN107141248A (zh) 一种可见光催化合成3‑砜基螺环三烯酮化合物的方法
CN101306986A (zh) 一种由苯乙烯催化氧化制备苯甲醛的方法
CN102795999A (zh) 对乙酰氧基苯乙烯的制备方法及其中间体的制备方法
CN118666647B (zh) 一种苯醌类化合物和氢醌的绿色联产方法
CN108002968B (zh) 一种酮类化合物氧化断裂碳碳键制备羧酸类化合物的方法
CN105601490A (zh) 高效催化氧化α-异佛尔酮制备氧代异佛尔酮
US10815178B2 (en) Intermolecular reaction of propargyl ethers with dimethylfuran in the presence of gold(I) complexes
Zhu et al. Oxidation of primary and secondary alcohols to the corresponding carbonyl compounds with molecular oxygen using 1, 1-diphenyl-2-picrylhydrazyl and WO3/Al2O3 as catalysts
CN113651681B (zh) 一种c-c键断裂制备醛/酮的方法
CN104496749B (zh) 一种取代肉桂醇的制备方法
CN103360218B (zh) 一种苯羟基化反应方法
CN102731234A (zh) 一种co促进的分子氧直接氧化羟化芳烃化合物的方法
CN121698746A (zh) 一种四氢姜黄素及其中间体的制备方法
CN113999098B (zh) 一种合成2,3,5-三甲基苯醌的方法
CN105289730B (zh) 普鲁士蓝类配合物在催化缩醛/酮反应中的应用
CN107344904B (zh) 一种钯催化氧化烯烃生成甲基酮的方法
CN107033006B (zh) 一种二芳基酮的制备方法
CN118108589A (zh) 一种维生素e中间体2,3,5-三甲基苯醌的制备方法
CN102766038A (zh) 一种氧化环己烯的方法
CN109503533B (zh) 一种苯并呋喃酮类化合物及其高效催化合成方法
CN103204775B (zh) 一种苯乙酮的氧化方法
CN111662169A (zh) 一种采用多金属氧酸盐催化氧化苯甲醇制备苯甲醛的方法
CN111233802A (zh) 一种糠酸酯的制备方法
CN105859496A (zh) 一种缩醛或缩酮类化合物的绿色合成方法
CN100497282C (zh) 氧代异佛尔酮的制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 24946170

Country of ref document: EP

Kind code of ref document: A1