A method for preparing fluorenyl diol using sulfonic acid type ionic liquid catalysis

Abstract

The present invention proposes a method for preparing fluorenyl diol by catalysis of sulfonic acid type ionic liquid, which belongs to the technical field of catalysis and organic synthesis, and is used to solve the technical problems of strong corrosion, large pollution and low selectivity of the traditional sulfuric acid method. The method comprises: after mixing the fluorenone derivative with the aromatic compound, adding the co-catalyst thiol compound. After reacting at a certain temperature until the substrate is dissolved, adding the sulfonic acid type ionic liquid catalyst, continuing the reaction for a certain time, and obtaining the fluorenyl diol, the conversion rate of the fluorenone derivative can reach up to 100%, the yield of the fluorenyl diol can reach up to 99%, and the selectivity can reach up to 99%. The method of the present invention avoids the use of traditional strong acid catalysts, and the catalyst sulfonic acid type ionic liquid used is characterized by high catalytic activity, recyclability, non-volatile, and green environmental protection.

Description

Technical Field

[0001] The invention belongs to the technical field of catalysis and organic synthesis, and in particular relates to a method for preparing fluorenyl diol by catalysis of sulfonic acid type ionic liquid. Background Art

[0002] Fluorenyl diol contains a special Cardo ring structure and is a raw material for preparing high-molecular materials with high thermal stability and excellent optical properties such as polycarbonate, epoxy resin and acrylic resin. At present, fluorenyl diol is often prepared by a one-step reaction under high temperature conditions using fluorenone derivatives and aromatic alcohols as raw materials, strong acids as catalysts, and thiol compounds as co-catalysts. This preparation method has low cost, short process and high atomic utilization, and has broad application prospects. However, the catalyst used in this method is often a strong acid such as sulfuric acid, which not only corrodes the reactor and causes environmental pollution, but also easily causes side reactions. Therefore, the development of highly selective green catalysts is of great significance for the preparation of fluorenyl diol.

[0003] In view of the shortcomings of strong acid catalysts, supported catalysts and ionic liquid catalysts have been developed. In the paper Green Chem, 2000, 2, 157, titanium / montmorillonite was used to catalyze 9-fluorenone and phenoxyethanol to prepare 9,9-di(4-hydroxyethylphenyl)fluorene (BPEF). Under the conditions of reaction temperature of 170°C and reaction time of 4h, the conversion rate of 9-fluorenone can reach 100%, and the selectivity of BPEF can reach 82%. In addition, there are also reports on the preparation of fluorenyl diols using ionic liquid catalysis. However, the substrates are limited to substances with few substituents, low steric hindrance, and easier activation, such as fluorenone and phenol. The products are single, and there are few studies on ionic liquid catalysts with adaptability to different reaction substrates. In addition, the catalytic mechanism of ionic liquids is still in the speculation stage, the specific activation site is not clear, and the precise structure-activity relationship between the structure of ionic liquids and catalytic activity has not yet been established, which makes it difficult to use them as guidance for the structural design of ionic liquid catalysts. Summary of the invention

[0004] In view of the technical problems of strong corrosiveness, high pollution and low selectivity of the traditional sulfuric acid method, the present invention proposes a method for preparing fluorenyl diol using sulfonic acid ionic liquid as a catalyst. The method has the advantages of low catalyst dosage and recyclability, high yield and selectivity, simple method and low pollution.

[0005] In order to achieve the above object, the technical solution of the present invention is achieved as follows:

[0006] A method for preparing fluorenyl diol using sulfonic acid ionic liquid catalysis, characterized in that after a fluorenone derivative and an aromatic compound are mixed in a certain proportion, a thiol compound is added, and the reaction is stirred at a certain temperature until the substrate is dissolved; a sulfonic acid ionic liquid catalyst is added, the reaction is continued for a certain time, and the product fluorenyl diol is obtained through post-treatment.

[0007] Preferably, it is characterized in that the general structural formula of the fluorenone derivative is as follows:

[0008]

[0009] Wherein, R1-R8 is selected from -H, n is 1 to 10 -C n H 2n+1 , -SC n H 2n+1 , n is 1 to 3 -C 6n H 4n+1 , -SC 6n H 4n+1 .

[0010] Preferably, it is characterized in that the structural formula of the aromatic compound is as follows:

[0011]

[0012] Wherein, R9 is selected from -OH, n is 1 to 10 -OC n H 2n OH, -SC n H 2n OH.

[0013] Preferably, it is characterized in that the thiol compound is selected from 3-mercaptopropionic acid, thioglycolic acid, n-dodecyl mercaptan, and 2-mercaptothiazoline.

[0014] Preferably, it is characterized in that the sulfonic acid ionic liquid is composed of anions and cations, and the cations are selected from the following structures:

[0015]

[0016] Among them, R 10 , R 12 -H, -C where n is 1 to 10 n H 2n+1 , -C n H 2n OH, -C n H 2n COOH, -C n H 2n NH2, -C n H 2n CONH2, R 13-C selected from the group consisting of -C wherein n is 1 to 10 n H 2n SO3H; anions are selected from dimethyl phosphate anions, diethyl phosphate anions, dibutyl phosphate anions, phosphate anions, hydrogen sulfate anions, methanesulfonate anions, trifluoroacetic acid anions, trifluoromethanesulfonate anions, tetrafluoroborate anions, and p-toluenesulfonate anions.

[0017] Preferably, it is characterized in that the reaction time is 4 to 24 hours and the reaction temperature is 100 to 200°C.

[0018] Preferably, it is characterized in that the molar ratio of the fluorenone derivative to the aromatic compound is (6:1) to (1:6).

[0019] Preferably, it is characterized in that the molar ratio of the fluorenone derivative to the thiol compound is (1:0.01) to (1:0.1).

[0020] Preferably, it is characterized in that the molar ratio of the fluorenone derivative to the sulfonic acid type ionic liquid is (1:0.1) to (1:2).

[0021] Preferably, it is characterized in that the post-treatment method is to add an aqueous solution to dissolve, precipitate with methanol to obtain a crude product, and then separate by column chromatography to obtain a high-purity product.

[0022] Preferably, the sulfonic acid ionic liquid can be used 1 to 20 times.

[0023] Preferably, it is characterized in that the conversion rate of the fluorenone derivative is 95-100%, the yield of fluorenyl diol is 90-99%, and the selectivity is 90-99%.

[0024] Preferably, it is characterized in that the fluorenyl diol product has the following structural formula:

[0025]

[0026] Wherein, R1-R8 is selected from -H, n is 1 to 10 -C n H 2n+1 , -SC n H 2n+1 , n is 1 to 3 -C 6n H 4n+1 , -SC 6n H 4n+1 , R9 is selected from -OH, n is 1 to 10 -OC n H 2n OH, -SC n H 2n OH.

[0027] Beneficial effects of the present invention:

[0028] (1) The sulfonic acid ionic liquid catalyst described in the present application has hydrogen bonding, electrostatic and acidic sites. While activating the co-catalyst, it can form hydrogen bonding and electrostatic effects with the reaction substrate. Through synergistic strengthening, it can activate the reaction substrate containing oxygen, sulfur substitution and high steric hindrance, expand the types of fluorenyl diols, and provide new raw materials for the subsequent preparation of high-performance polymers.

[0029] (2) The method for preparing fluorenyl diol provided in the present application has the advantages of low catalyst dosage and recyclability, high yield and selectivity, simple method and low pollution. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0031] Figure 1 The BPEF prepared in Example 28 1 H NMR spectroscopy.

[0032] Figure 2 The BPEF prepared in Example 28 13 C NMR spectroscopy.

[0033] Figure 3 This is the reaction pathway diagram of condensation catalyzed by sulfonic acid ionic liquid. DETAILED DESCRIPTION

[0034] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0035] Embodiment 1:

[0036] Accurately weigh 0.01 mol of 9-fluorenone, 0.04 mol of phenol and 0.0006 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 150°C until the reactants are dissolved, add 0.01 mol of 1-methyl-3-sulfopropylimidazole dimethyl phosphate, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 1, and separate the crude product by column chromatography. The eluent is a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 to obtain a high-purity product. The conversion rate of 9-fluorenone is 95%, the yield of compound 1 is 92%, and the selectivity is 97%.

[0037]

[0038] Embodiment 2:

[0039] Accurately weigh 0.01 mol of 9-fluorenone, 0.04 mol of phenol and 0.0006 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 150°C until the reactants are dissolved, add 0.01 mol of 1-methyl-3-sulfopropylimidazole dibutyl phosphate, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 1, and separate the crude product by column chromatography. The eluent is a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 to obtain a high-purity product. The conversion rate of 9-fluorenone is 95%, the yield of compound 1 is 94%, and the selectivity is 99%.

[0040] Embodiment 3:

[0041] Accurately weigh 0.01 mol of 9-fluorenone, 0.04 mol of phenol and 0.0006 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 150°C until the reactants are dissolved, add 0.01 mol of 1-methyl-3-sulfopropyl imidazole phosphate, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 1, and separate the crude product by column chromatography. The eluent is a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 to obtain a high-purity product. The conversion rate of 9-fluorenone is 95%, the yield of compound 1 is 90%, and the selectivity is 95%.

[0042] Embodiment 4:

[0043] Accurately weigh 0.01 mol of 9-fluorenone, 0.04 mol of phenol and 0.0006 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 150°C until the reactants are dissolved, add 0.01 mol of 1-methyl-3-sulfopropylimidazole hydrogen sulfate, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 1, and separate the crude product by column chromatography. The eluent is a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 to obtain a high-purity product. The conversion rate of 9-fluorenone is 95%, the yield of compound 1 is 91%, and the selectivity is 96%.

[0044] Embodiment 5:

[0045] Accurately weigh 0.01 mol of 9-fluorenone, 0.04 mol of phenol and 0.0006 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 150°C until the reactants are dissolved, add 0.01 mol of 1-methyl-3-sulfopropylimidazole methanesulfonate, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 1, and separate the crude product by column chromatography. The eluent is a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 to obtain a high-purity product. The conversion rate of 9-fluorenone is 96%, the yield of compound 1 is 94%, and the selectivity is 98%.

[0046] Embodiment 6:

[0047] Accurately weigh 0.01 mol of 9-fluorenone, 0.04 mol of phenol and 0.0006 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 150°C until the reactants are dissolved, add 0.01 mol of 1-methyl-3-sulfopropylimidazole trifluoroacetate, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 1, and separate the crude product by column chromatography. The eluent is a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 to obtain a high-purity product. The conversion rate of 9-fluorenone is 95%, the yield of compound 1 is 90%, and the selectivity is 95%.

[0048] Embodiment 7:

[0049] Accurately weigh 0.01 mol of 9-fluorenone, 0.04 mol of phenol and 0.0006 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 150°C until the reactants are dissolved, add 0.01 mol of 1-methyl-3-sulfopropylimidazole trifluoromethanesulfonate, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 1, and separate the crude product by column chromatography, using a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 as the eluent to obtain a high-purity product, the conversion rate of 9-fluorenone is 100%, the yield of compound 1 is 99%, and the selectivity is 99%.

[0050] Embodiment 8:

[0051] Accurately weigh 0.01 mol of 9-fluorenone, 0.04 mol of phenol and 0.0006 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 150°C until the reactants are dissolved, add 0.01 mol of 1-methyl-3-sulfopropyl imidazole tetrafluoroborate, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 1, and separate the crude product by column chromatography, using a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 as the eluent to obtain a high-purity product, with a conversion rate of 9-fluorenone of 95%, a yield of compound 1 of 90%, and a selectivity of 95%.

[0052] Embodiment 9:

[0053] Accurately weigh 0.01 mol of 9-fluorenone, 0.04 mol of phenol and 0.0006 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 150°C until the reactants are dissolved, add 0.01 mol of 1-methyl-3-sulfopropylimidazole p-toluenesulfonate, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 1, and separate the crude product by column chromatography. The eluent is a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 to obtain a high-purity product. The conversion rate of 9-fluorenone is 96%, the yield of compound 1 is 92%, and the selectivity is 96%.

[0054] Embodiment 10:

[0055] Accurately weigh 0.01 mol of 9-fluorenone, 0.04 mol of phenol and 0.0006 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 150°C until the reactants are dissolved, add 0.01 mol of 1,2-didecyl-3-sulfopropylimidazole trifluoromethanesulfonate, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 1, and separate the crude product by column chromatography. The eluent is a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 to obtain a high-purity product. The conversion rate of 9-fluorenone is 97%, the yield of compound 1 is 95%, and the selectivity is 98%.

[0056] Embodiment 11:

[0057] Accurately weigh 0.01 mol of 9-fluorenone, 0.04 mol of phenol and 0.0006 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 150°C until the reactants are dissolved, add 0.01 mol of 1,2-dihydroxyethyl-3-sulfopropylimidazole trifluoromethanesulfonate, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 1, and separate the crude product by column chromatography. The eluent is a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 to obtain a high-purity product. The conversion rate of 9-fluorenone is 100%, the yield of compound 1 is 98%, and the selectivity is 98%.

[0058] Embodiment 12:

[0059] Accurately weigh 0.01 mol of 9-fluorenone, 0.04 mol of phenol and 0.0006 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 150°C until the reactants are dissolved, add 0.01 mol of 1,2-diethylamino-3-sulfopropylimidazole trifluoromethanesulfonate, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 1, and separate the crude product by column chromatography. The eluent is a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 to obtain a high-purity product. The conversion rate of 9-fluorenone is 100%, the yield of compound 1 is 98%, and the selectivity is 98%.

[0060] Embodiment 13:

[0061] Accurately weigh 0.01 mol of 9-fluorenone, 0.04 mol of phenol and 0.0006 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 150°C until the reactants are dissolved, add 0.01 mol of 1,2-diacetamido-3-sulfopropylimidazole trifluoromethanesulfonate, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 1, and separate the crude product by column chromatography. The eluent is a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 to obtain a high-purity product. The conversion rate of 9-fluorenone is 98%, the yield of compound 1 is 96%, and the selectivity is 98%.

[0062] Embodiment 14:

[0063] Accurately weigh 0.01 mol of 9-fluorenone, 0.04 mol of phenol and 0.0006 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 150°C until the reactants are dissolved, add 0.01 mol of 1-methyl-2-sulfopropylpyrazole trifluoromethanesulfonate, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 1, and separate the crude product by column chromatography, using a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 as the eluent to obtain a high-purity product, the conversion rate of 9-fluorenone is 100%, the yield of compound 1 is 98%, and the selectivity is 98%.

[0064] Embodiment 15:

[0065] Accurately weigh 0.01 mol of 9-fluorenone, 0.04 mol of phenol and 0.0006 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 150°C until the reactants are dissolved, add 0.01 mol of 1,4-dimethyl-1,4-bis(sulfopropyl)piperazine trifluoromethanesulfonate, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 1, and separate the crude product by column chromatography, using a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 as the eluent to obtain a high-purity product, the conversion rate of 9-fluorenone is 100%, the yield of compound 1 is 99%, and the selectivity is 99%.

[0066] Embodiment 16:

[0067] Accurately weigh 0.01 mol of 9-fluorenone, 0.04 mol of phenol and 0.0006 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 150° C. until the reactants are dissolved, then add 0.01 mol of 1,4-bis(2-sulfoethyl)-1,4-diazabicyclo[2.2.2]octane-1,4-diimide trifluoromethanesulfonate, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, then add 20 ml of methanol to precipitate to obtain a crude product, compound 1, which is separated by column chromatography, and the eluent is a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 to obtain a high-purity product, the conversion rate of 9-fluorenone is 100%, the yield of compound 1 is 99%, and the selectivity is 99%.

[0068] Embodiment 17:

[0069] Accurately weigh 0.01 mol of 9-fluorenone, 0.04 mol of phenol and 0.0006 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 200°C until the reactants are dissolved, add 0.01 mol of 1-methyl-3-sulfopropylimidazole trifluoromethanesulfonate, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 1, and separate the crude product by column chromatography. The eluent is a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 to obtain a high-purity product. The conversion rate of 9-fluorenone is 97%, the yield of compound 1 is 90%, and the selectivity is 93%.

[0070] Embodiment 18:

[0071] Accurately weigh 0.01 mol of 9-fluorenone, 0.04 mol of phenol and 0.0006 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 200°C until the reactants are dissolved, add 0.01 mol of 1-methyl-3-sulfopropylimidazole trifluoromethanesulfonate, continue the reaction for 4 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 1, and separate the crude product by column chromatography. The eluent is a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 to obtain a high-purity product. The conversion rate of 9-fluorenone is 95%, the yield of compound 1 is 93%, and the selectivity is 98%.

[0072] Embodiment 19:

[0073] Accurately weigh 0.01 mol of 9-fluorenone, 0.04 mol of phenol and 0.0006 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 200°C until the reactants are dissolved, add 0.01 mol of 1-methyl-3-sulfopropylimidazole trifluoromethanesulfonate, continue the reaction for 24 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 1, and separate the crude product by column chromatography. The eluent is a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 to obtain a high-purity product. The conversion rate of 9-fluorenone is 98%, the yield of compound 1 is 90%, and the selectivity is 92%.

[0074] Embodiment 20:

[0075] Accurately weigh 0.01 mol of 9-fluorenone, 0.04 mol of phenol and 0.0006 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 100°C until the reactants are dissolved, add 0.01 mol of 1-methyl-3-sulfopropylimidazole trifluoromethanesulfonate, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 1, and separate the crude product by column chromatography. The eluent is a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 to obtain a high-purity product. The conversion rate of 9-fluorenone is 95%, the yield of compound 1 is 91%, and the selectivity is 96%.

[0076] Embodiment 21:

[0077] Accurately weigh 0.06 mol of 9-fluorenone, 0.01 mol of phenol and 0.0006 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 150°C until the reactants are dissolved, add 0.01 mol of 1-methyl-3-sulfopropylimidazole trifluoromethanesulfonate, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 1, and separate the crude product by column chromatography. The eluent is a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 to obtain a high-purity product. The conversion rate of 9-fluorenone is 95%, the yield of compound 1 is 90%, and the selectivity is 95%.

[0078] Embodiment 22:

[0079] Accurately weigh 0.01 mol of 9-fluorenone, 0.06 mol of phenol and 0.0006 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 150°C until the reactants are dissolved, add 0.01 mol of 1-methyl-3-sulfopropylimidazole trifluoromethanesulfonate, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 1, and separate the crude product by column chromatography. The eluent is a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 to obtain a high-purity product. The conversion rate of 9-fluorenone is 95%, the yield of compound 1 is 90%, and the selectivity is 95%.

[0080] Embodiment 23:

[0081] Accurately weigh 0.01 mol of 9-fluorenone, 0.04 mol of phenol and 0.0006 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 150°C until the reactants are dissolved, add 0.001 mol of 1-methyl-3-sulfopropylimidazole trifluoromethanesulfonate, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 1, and separate the crude product by column chromatography. The eluent is a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 to obtain a high-purity product. The conversion rate of 9-fluorenone is 95%, the yield of compound 1 is 91%, and the selectivity is 96%.

[0082] Embodiment 24:

[0083] Accurately weigh 0.01 mol of 9-fluorenone, 0.04 mol of phenol and 0.0006 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 150°C until the reactants are dissolved, add 0.02 mol of 1-methyl-3-sulfopropylimidazole trifluoromethanesulfonate, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 1, and separate the crude product by column chromatography, using a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 as the eluent to obtain a high-purity product, with a conversion rate of 9-fluorenone of 95%, a yield of compound 1 of 90%, and a selectivity of 95%.

[0084] Embodiment 25:

[0085] Accurately weigh 0.01 mol of 9-fluorenone, 0.04 mol of phenol and 0.0006 mol of thioglycolic acid, mix them evenly, stir and react at 150°C until the reactants are dissolved, add 0.01 mol of 1-methyl-3-sulfopropylimidazole trifluoromethanesulfonate, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 1, and separate the crude product by column chromatography, using a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 as the eluent to obtain a high-purity product, with a conversion rate of 9-fluorenone of 97%, a yield of compound 1 of 95%, and a selectivity of 98%.

[0086] Embodiment 26:

[0087] Accurately weigh 0.01 mol of 9-fluorenone, 0.04 mol of phenol and 0.0006 mol of n-dodecyl mercaptan, mix them evenly, stir and react at 150° C. until the reactants are dissolved, add 0.01 mol of 1-methyl-3-sulfopropylimidazole trifluoromethanesulfonate, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 1, and separate the crude product by column chromatography. The eluent is a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 to obtain a high-purity product. The conversion rate of 9-fluorenone is 96%, the yield of compound 1 is 91%, and the selectivity is 95%.

[0088] Embodiment 27:

[0089] Accurately weigh 0.01 mol of 9-fluorenone, 0.04 mol of phenol and 0.0006 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 150° C. until the reactants are dissolved, then add 0.01 mol of 1-methyl-3-sulfopropylimidazole trifluoromethanesulfonate which has been recycled 20 times, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, and then add 20 ml of methanol to precipitate to obtain a crude product compound 1, which is separated by column chromatography, and the eluent is a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 to obtain a high-purity product, the conversion rate of 9-fluorenone is 95%, the yield of compound 1 is 90%, and the selectivity is 95%.

[0090] Embodiment 28:

[0091] Accurately weigh 0.01 mol of 9-fluorenone, 0.04 mol of phenoxyethanol and 0.0005 mol of 3-mercaptopropionic acid, mix well, stir and react at 150°C until the reactants are dissolved, add 0.01 mol of 1-methyl-2-sulfopropylimidazole trifluoromethanesulfonate, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 2 (BPEF), separate the crude product by column chromatography, and use a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 as the eluent to obtain a high-purity product. The conversion rate of 9-fluorenone is 99%, the yield of compound 2 is 98%, and the selectivity is 99%.

[0092] Compound 2 1 H NMR spectroscopy and 13 C NMR spectroscopy Figure 1 and 2 As shown, 1H NMR (600 MHz, DMSO-d6) δ7.90 (d, J = 7.5 Hz, 2H), 7.43–7.26 (m, 6H), 7.04–6.96 (m, 4H), 6.87–6.75 (m, 4H), 4.82 (t, J = 5.5 Hz, 2H), 3.91 (t, J = 5.1 Hz, 4H), 3.66 (q, J = 5.2 Hz, 4H). 13C NMR (151 MHz, DMSO-d6) δ157.87, 151.77, 139.84, 137.98, 129.17, 128.24, 127.94, 126.38, 120.92, 114.67, 69.90, 64.08, 60.03.

[0093] Taking this example as an example, the mechanism analysis of the preparation of fluorenyl diol by sulfonic acid ionic liquid catalysis is further analyzed. Figure 3 As shown, first, the H +The carbonyl group of 9-fluorenone is activated to form a carbon-positive intermediate (I), which attracts the attack of nucleophiles to react. Since the hydroxyl group on the intermediate (I) is difficult to dissociate, and the weak nucleophilicity of the positive (o-) or para (p-) carbon of phenoxyethanol makes it difficult for phenoxyethanol to react directly with the intermediate (I). Therefore, it is necessary to add a strongly nucleophilic -SH thiol compound to assist in catalysis. The fluorine atoms in the ionic liquid accelerate the nucleophilic substitution reaction of the thiol compound due to their own strong electronegativity and electron-withdrawing ability. Since the nucleophilicity of the -SH group is stronger than that of the positive (o-) or para (p-) carbon of phenoxyethanol, the intermediate (I) is converted into the thiosalt intermediate (II). Due to the resistance of the chemical structure site, phenoxyethanol acts as a nucleophile at the main p-carbon position, attacks the intermediate (II) and converts it into the tertiary carbon positive intermediate (III), which may also be one of the reasons for the relatively high selectivity of the reaction, and the thiol co-catalyst is released back into the reaction system. Finally, the tertiary carbocation intermediate III combines with another phenoxyethanol molecule to give the final BPEF, while releasing back a proton and recruiting the ionic liquid catalyst.

[0094] In summary, the nucleophilic addition reaction of phenoxyethanol to the sulfonate intermediate is the rate-determining step in the synthesis of BPEF, and its energy barrier is 38.6 Kcal·mol -1 In addition, ionic liquid and 3-mercaptopropionic acid were used as raw materials and phenoxyethanol as H + The acceptor and donor play an important role in the synthesis of BPEF. Therefore, the reaction mechanism of BPEF synthesis is that the ionic liquid activates the thiol compound and the reactant as well as the synergistic catalysis of the thiol compound, so that the reaction proceeds smoothly.

[0095]

[0096] Embodiment 29:

[0097] Accurately weigh 0.01 mol of 9-fluorenone, 0.04 mol of phenoxyethanol and 0.0005 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 150°C until the reactants are dissolved, add 0.01 mol of 1,4-dihydroxy-1,4-bis(sulfopropyl)piperazine hydrogen sulfate, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 2, and separate the crude product by column chromatography. The eluent is a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 to obtain a high-purity product. The conversion rate of 9-fluorenone is 99%, the yield of compound 2 is 98%, and the selectivity is 99%.

[0098] Embodiment 30:

[0099] Accurately weigh 0.01 mol of 9-fluorenone, 0.04 mol of phenoxyethanol and 0.0005 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 150°C until the reactants are dissolved, add 0.01 mol of 1,4-bis(2-sulfoethyl)-1,4-diazabicyclo[2.2.2]octane-1,4-diimide hydrogen sulfate, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 2, and separate the crude product by column chromatography, using a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 as the eluent to obtain a high-purity product, with a conversion rate of 9-fluorenone of 99%, a yield of compound 2 of 97%, and a selectivity of 98%.

[0100] Embodiment 31:

[0101] Accurately weigh 0.01 mol of 1,2,3,4,5,6,7,8-octamethyl-9-fluorenone, 0.04 mol of phenoxyethanol and 0.0005 mol of 3-mercaptopropionic acid, mix well, stir and react at 150°C until the reactants are dissolved, add 0.01 mol of 1-methyl-3-sulfopropylimidazole trifluoromethanesulfonate, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 2, and separate the crude product by column chromatography, using a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 as the eluent to obtain a high-purity product, the conversion rate of 1,2,3,4,5,6,7,8-octamethyl-9-fluorenone is 96%, the yield of compound 3 is 93%, and the selectivity is 97%.

[0102]

[0103] Embodiment 32:

[0104] Accurately weigh 0.01 mol of 1,2,3,4,5,6,7,8-octamethyl-9-fluorenone, 0.04 mol of phenoxyethanol and 0.0005 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 150°C until the reactants are dissolved, add 0.01 mol of 1,4-dihydroxy-1,4-bis(sulfopropyl)piperazine hydrogen sulfate, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 2, and separate the crude product by column chromatography, using a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 as the eluent to obtain a high-purity product, the conversion rate of 1,2,3,4,5,6,7,8-octamethyl-9-fluorenone is 99%, the yield of compound 3 is 97%, and the selectivity is 98%.

[0105] Embodiment 33:

[0106] Accurately weigh 0.01 mol of 1,2,3,4,5,6,7,8-octamethyl-9-fluorenone, 0.04 mol of phenoxyethanol and 0.0005 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 150°C until the reactants are dissolved, add 0.01 mol of 1,4-bis(2-sulfoethyl)-1,4-diazabicyclo[2.2.2]octane-1,4-diimide hydrogen sulfate, continue to react for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 2, and separate the crude product by column chromatography, using a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 as the eluent to obtain a high-purity product, the conversion rate of 1,2,3,4,5,6,7,8-octamethyl-9-fluorenone is 98%, the yield of compound 3 is 96%, and the selectivity is 98%.

[0107] Embodiment 34:

[0108] Accurately weigh 0.01 mol of 1,2,3,4,5,6,7,8-octadecyl-9-fluorenone, 0.04 mol of phenol and 0.0005 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 150° C. until the reactants are dissolved, add 0.01 mol of 1-methyl-3-sulfopropylimidazole trifluoromethanesulfonate, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 2, and separate the crude product by column chromatography, using a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 as the eluent to obtain a high-purity product 1,2,3,4,5,6,7,8-octadecyl-9-fluorenone with a conversion rate of 95%, a yield of compound 4 of 90%, and a selectivity of 95%.

[0109]

[0110]

[0111] Embodiment 35:

[0112] Accurately weigh 0.01 mol of 1,2,3,4,5,6,7,8-octadecyl-9-fluorenone, 0.04 mol of phenol and 0.0005 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 150°C until the reactants are dissolved, add 0.01 mol of 1,4-dihydroxy-1,4-bis(sulfopropyl)piperazine hydrogen sulfate, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 2, and separate the crude product by column chromatography, using a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 as the eluent to obtain a high-purity product 1,2,3,4,5,6,7,8-octadecyl-9-fluorenone with a conversion rate of 98%, a yield of compound 4 of 96%, and a selectivity of 98%.

[0113] Embodiment 36:

[0114] Accurately weigh 0.01 mol of 1,2,3,4,5,6,7,8-octadecyl-9-fluorenone, 0.04 mol of phenol and 0.0005 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 150° C. until the reactants are dissolved, add 0.01 mol of 1,4-bis(2-sulfoethyl)-1,4-diazabicyclo[2.2.2]octane-1,4-diimide hydrogensulfate, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 2, and separate the crude product by column chromatography, using a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 as the eluent to obtain a high-purity product 1,2,3,4,5,6,7,8-octadecyl-9-fluorenone with a conversion rate of 95%, a yield of compound 4 of 93%, and a selectivity of 98%.

[0115] Embodiment 37:

[0116] Accurately weigh 0.01 mol of 9-fluorenone, 0.04 mol of 2-phenylthioethanol and 0.0005 mol of 3-mercaptopropionic acid, mix well, stir and react at 150°C until the reactants are dissolved, add 0.01 mol of 1-methyl-3-sulfopropylimidazole trifluoromethanesulfonate, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 5, and separate the crude product by column chromatography. The eluent is a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 to obtain a high-purity product. The conversion rate of 9-fluorenone is 96%, the yield of compound 5 is 94%, and the selectivity is 98%.

[0117]

[0118] Embodiment 38:

[0119] Accurately weigh 0.01 mol of 9-fluorenone, 0.04 mol of 2-phenylthioethanol and 0.0005 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 150°C until the reactants are dissolved, add 0.01 mol of 1,4-dihydroxy-1,4-bis(sulfopropyl)piperazine hydrogen sulfate, continue to react for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 5, and separate the crude product by column chromatography. The eluent is a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 to obtain a high-purity product. The conversion rate of 9-fluorenone is 98%, the yield of compound 5 is 97%, and the selectivity is 99%.

[0120] Embodiment 39:

[0121] Accurately weigh 0.01 mol of 9-fluorenone, 0.04 mol of 2-phenylthioethanol and 0.0005 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 150°C until the reactants are dissolved, then add 0.01 mol of 1,4-bis(2-sulfoethyl)-1,4-diazabicyclo[2.2.2]octane-1,4-diimide hydrogen sulfate, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, then add 20 ml of methanol to precipitate to obtain a crude product compound 5, and separate the crude product by column chromatography, using a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 as the eluent to obtain a high-purity product, with a conversion rate of 9-fluorenone of 95%, a yield of compound 5 of 93%, and a selectivity of 98%.

[0122] Embodiment 40:

[0123] Accurately weigh 0.01 mol of 2,7-dithiomethyl-9-fluorenone, 0.04 mol of 2-phenylthioethanol and 0.0005 mol of 3-mercaptopropionic acid, mix well, stir and react at 150°C until the reactants are dissolved, add 0.01 mol of 1-methyl-3-sulfopropylimidazole trifluoromethanesulfonate, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 5, and separate the crude product by column chromatography. The eluent is a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 to obtain a high-purity product. The conversion rate of 2,7-dithiomethyl-9-fluorenone is 97%, the yield of compound 6 is 95%, and the selectivity is 98%.

[0124]

[0125] Embodiment 41:

[0126] Accurately weigh 0.01 mol of 2,7-dithiomethyl-9-fluorenone, 0.04 mol of 2-phenylthioethanol and 0.0005 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 150°C until the reactants are dissolved, add 0.01 mol of 1,4-dihydroxy-1,4-bis(sulfopropyl)piperazine hydrogen sulfate, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 5, and separate the crude product by column chromatography. The eluent is a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 to obtain a high-purity product. The conversion rate of 2,7-dithiomethyl-9-fluorenone is 97%, the yield of compound 6 is 95%, and the selectivity is 98%.

[0127] Embodiment 42:

[0128] Accurately weigh 0.01 mol of 2,7-dithiomethyl-9-fluorenone, 0.04 mol of 2-phenylthioethanol and 0.0005 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 150° C. until the reactants are dissolved, then add 0.01 mol of 1,4-bis(2-sulfoethyl)-1,4-diazabicyclo[2.2.2]octane-1,4-diimide hydrogen sulfate, continue the reaction for 8 h, add 20 ml of aqueous solution to dissolve, then add 20 ml of methanol to precipitate to obtain a crude product compound 5, and separate the crude product by column chromatography, using a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 as the eluent to obtain a high-purity product, with a conversion rate of 2,7-dithiomethyl-9-fluorenone of 97%, a yield of compound 6 of 95%, and a selectivity of 98%.

[0129] Embodiment 43:

[0130] Accurately weigh 0.01 mol of 2,7-diphenyl-9-fluorenone, 0.04 mol of 2-phenylthioethanol and 0.0005 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 150°C until the reactants are dissolved, add 0.01 mol of 1-methyl-3-sulfopropylimidazole trifluoromethanesulfonate, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 5, and separate the crude product by column chromatography. The eluent is a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 to obtain a high-purity product. The conversion rate of 2,7-diphenyl-9-fluorenone is 95%, the yield of compound 7 is 91%, and the selectivity is 96%.

[0131]

[0132] Embodiment 44:

[0133] Accurately weigh 0.01 mol of 2,7-diphenyl-9-fluorenone, 0.04 mol of 2-phenylthioethanol and 0.0005 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 150°C until the reactants are dissolved, add 0.01 mol of 1,4-dihydroxy-1,4-bis(sulfopropyl)piperazine hydrogen sulfate, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 5, and separate the crude product by column chromatography, using a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 as the eluent to obtain a high-purity product, with a conversion rate of 2,7-diphenyl-9-fluorenone of 95%, a yield of compound 7 of 90%, and a selectivity of 95%.

[0134] Embodiment 45:

[0135] Accurately weigh 0.01 mol of 2,7-diphenyl-9-fluorenone, 0.04 mol of 2-phenylthioethanol and 0.0005 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 150°C until the reactants are dissolved, add 0.01 mol of 1,4-bis(2-sulfoethyl)-1,4-diazabicyclo[2.2.2]octane-1,4-diimide hydrogen sulfate, continue to react for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 5, and separate the crude product by column chromatography, using a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 as the eluent to obtain a high-purity product, with a conversion rate of 2,7-diphenyl-9-fluorenone of 95%, a yield of compound 7 of 92%, and a selectivity of 97%.

[0136] Embodiment 46:

[0137] Accurately weigh 0.01 mol of 2,7-di(1,1':4'1"-terphenyl)-9-fluorenone, 0.04 mol of 2-phenylthioethanol and 0.0005 mol of 3-mercaptopropionic acid, mix well, stir and react at 150°C until the reactants are dissolved, add 0.01 mol of 1-methyl-3-sulfopropylimidazole trifluoromethanesulfonate, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 5, and separate the crude product by column chromatography. The eluent is a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 to obtain a high-purity product. The conversion rate of 2,7-diphenyl-9-fluorenone is 95%, the yield of compound 8 is 91%, and the selectivity is 96%.

[0138]

[0139] Embodiment 47:

[0140] Accurately weigh 0.01 mol of 2,7-di(1,1':4'1"-terphenyl)-9-fluorenone, 0.04 mol of 2-phenylthioethanol and 0.0005 mol of 3-mercaptopropionic acid, mix well, stir and react at 150°C until the reactants are dissolved, add 0.01 mol of 1,4-dihydroxy-1,4-bis(sulfopropyl)piperazine hydrogen sulfate, continue to react for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 5, and separate the crude product by column chromatography. The eluent is a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 to obtain a high-purity product. The conversion rate of 2,7-diphenyl-9-fluorenone is 95%, the yield of compound 8 is 91%, and the selectivity is 96%.

[0141] Embodiment 48:

[0142] 0.01 mol of 2,7-di(1,1':4'1"-terphenyl)-9-fluorenone, 0.04 mol of 2-phenylthioethanol and 0.0005 mol of 3-mercaptopropionic acid were accurately weighed and mixed evenly. After stirring at 150°C until the reactants were dissolved, 0.01 mol of 1,4-bis(2-sulfoethyl)-1,4-diazabicyclo[2.2.2]octane-1,4-diimide hydrogen sulfate was added. After continuing the reaction for 8 hours, 20 ml of aqueous solution was added to dissolve it, and 20 ml of methanol was added to precipitate to obtain a crude product compound 5. The crude product was separated by column chromatography, and the eluent was a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 to obtain a high-purity product. The conversion rate of 2,7-diphenyl-9-fluorenone was 95%, the yield of compound 8 was 91%, and the selectivity was 96%.

[0143] Embodiment 49:

[0144] Accurately weigh 0.01 mol of 9-fluorenone, 0.04 mol of 4-phenylphenol and 0.0005 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 150°C until the reactants are dissolved, then add 0.01 mol of 1,4-bis(2-sulfoethyl)-1,4-diazabicyclo[2.2.2]octane-1,4-diimide hydrogen sulfate, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, then add 20 ml of methanol to precipitate to obtain a crude product compound 5, and separate the crude product by column chromatography, using a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 as the eluent to obtain a high-purity product, with a conversion rate of 2,7-diphenyl-9-fluorenone of 96%, a yield of compound 9 of 94%, and a selectivity of 98%.

[0145]

[0146] Embodiment 50:

[0147] Accurately weigh 0.01 mol of 9-fluorenone, 0.04 mol of 1-naphthol and 0.0005 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 150°C until the reactants are dissolved, then add 0.01 mol of 1,4-bis(2-sulfoethyl)-1,4-diazabicyclo[2.2.2]octane-1,4-diimide hydrogen sulfate, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, then add 20 ml of methanol to precipitate to obtain a crude product compound 5, and separate the crude product by column chromatography, using a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 as the eluent to obtain a high-purity product, with a conversion rate of 2,7-diphenyl-9-fluorenone of 98%, a yield of compound 10 of 97%, and a selectivity of 99%.

[0148]

[0149] Embodiment 51:

[0150] Accurately weigh 0.01 mol of 9-fluorenone, 0.06 mol of 1-naphthol and 0.0001 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 100°C until the reactants are dissolved, then add 0.02 mol of 1,4-bis(2-sulfoethyl)-1,4-diazabicyclo[2.2.2]octane-1,4-diimide hydrogen sulfate, continue the reaction for 24 hours, add 20 ml of aqueous solution to dissolve, then add 20 ml of methanol to precipitate to obtain a crude product compound 5, and separate the crude product by column chromatography, using a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 as the eluent to obtain a high-purity product, with a conversion rate of 2,7-diphenyl-9-fluorenone of 95%, a yield of compound 10 of 93%, and a selectivity of 98%.

[0151] Embodiment 52:

[0152] Accurately weigh 0.06 mol of 9-fluorenone, 0.01 mol of 1-naphthol and 0.001 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 200°C until the reactants are dissolved, add 0.006 mol of 1,4-bis(2-sulfoethyl)-1,4-diazabicyclo[2.2.2]octane-1,4-diimide hydrogen sulfate, continue the reaction for 4 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 5, and separate the crude product by column chromatography. The eluent is a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 to obtain a high-purity product. The conversion rate of 2,7-diphenyl-9-fluorenone is 99%, the yield of compound 10 is 95%, and the selectivity is 96%.

[0153] Comparative Example 1:

[0154] Accurately weigh 0.01 mol of 9-fluorenone, 0.04 mol of phenol and 0.0006 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 150°C until the reactants are dissolved, add 0.02 mol of sulfuric acid, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 1, and separate the crude product by column chromatography. The eluent is a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 to obtain a high-purity product. The conversion rate of 9-fluorenone is 75%, the yield of compound 1 is 62%, and the selectivity is 83%.

[0155] Comparative Example 2:

[0156] Accurately weigh 0.01 mol of 9-fluorenone, 0.04 mol of phenol and 0.0006 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 150°C until the reactants are dissolved, add 0.01 mol of propanesulfonic acid pyridinium sulfate, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 1, and separate the crude product by column chromatography. The eluent is a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 to obtain a high-purity product. The conversion rate of 9-fluorenone is 80%, the yield of compound 1 is 70%, and the selectivity is 88%.

[0157] Comparative Example 3:

[0158] Accurately weigh 0.01 mol of 2,7-di(1,1':4'1"-terphenyl)-9-fluorenone, 0.04 mol of 2-phenylthioethanol and 0.0006 mol of 3-mercaptopropionic acid, mix well, stir and react at 150°C until the reactants are dissolved, add 0.01 mol of propanesulfonic acid pyridinium sulfate, continue to react for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 2, and separate the crude product by column chromatography. The eluent is a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 to obtain a high-purity product. The conversion rate of 9-fluorenone is 75%, the yield of compound 2 is 63%, and the selectivity is 84%.

[0159] Comparative Example 4:

[0160] Accurately weigh 0.01 mol of 9-fluorenone, 0.04 mol of 1-naphthol and 0.0006 mol of 3-mercaptopropionic acid, mix them evenly, stir and react at 150°C until the reactants are dissolved, add 0.01 mol of propanesulfonic acid pyridinium sulfate, continue the reaction for 8 hours, add 20 ml of aqueous solution to dissolve, add 20 ml of methanol to precipitate to obtain a crude product compound 5, and separate the crude product by column chromatography. The eluent is a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 8:2 to obtain a high-purity product. The conversion rate of 2,7-diphenyl-9-fluorenone is 84%, the yield of compound 10 is 73%, and the selectivity is 87%.

[0161] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing fluorenyl diol using sulfonic acid type ionic liquid as catalyst, characterized in that: The fluorenone derivative, the aromatic compound and the thiol compound are mixed and dissolved, a sulfonic acid type ionic liquid catalyst is added, the reaction is continued for a certain time, and the product fluorenyl diol is obtained through post-treatment; The thiol compound is selected from any one of 3-mercaptopropionic acid, thioglycolic acid, n-dodecyl mercaptan or 2-mercaptothiazoline; The sulfonic acid ionic liquid is composed of anions and cations, and the cations are selected from the following structures: Among them, R 10 and R 12 Selected from -H, or -C where n is 1 to 10 n H 2n+1 , -C n H 2n OH, -C n H 2n COOH, -C n H 2n NH2, -C n H 2n CONH2;R 13 -C selected from n is 1 to 10 n H 2n SO3H; anions are selected from dimethyl phosphate anions, diethyl phosphate anions, dibutyl phosphate anions, phosphate anions, hydrogen sulfate anions, methanesulfonate anions, trifluoroacetic acid anions, trifluoromethanesulfonate anions, tetrafluoroborate anions or p-toluenesulfonate anions; The general structural formula of the fluorenone derivative is as follows: Wherein, R1-R8 is selected from -H, or -C where n is 1 to 10 n H 2n+1 , -SC n H 2n+1 , or -C where n is 1 to 3 6n H 4n+1 , -SC 6n H 4n+1 ; The structural formula of the aromatic compound is shown below: Wherein, R9 is selected from -OH, or -OC where n is 1 to 10 n H 2n OH, -SC n H 2n OH; The molar ratio of the fluorenone derivative to the aromatic compound is (6:1) to (1:6); the molar ratio of the fluorenone derivative to the thiol compound is (1:0.01) to (1:0.1); and the molar ratio of the fluorenone derivative to the sulfonic acid type ionic liquid is (1:0.1) to (1:2).

2. The method for preparing fluorenyl diol using sulfonic acid type ionic liquid as catalyst according to claim 1, characterized in that: The reaction time is 4-24 h, and the reaction temperature is 100-200 °C.

3. The method for preparing fluorenyl diol using sulfonic acid type ionic liquid as catalyst according to claim 1, characterized in that: The post-treatment method comprises adding an aqueous solution to dissolve, precipitating with methanol to obtain a crude product, and then separating with column chromatography to obtain a high-purity product.

4. The method for preparing fluorenyl diol using sulfonic acid type ionic liquid as catalyst according to any one of claims 1 to 3, characterized in that: The conversion rate of the fluorenone derivative is 95-100%, the yield of the fluorenyl diol is 90-99%, and the selectivity is 90-99%.

5. The method for preparing fluorenyl diol using sulfonic acid type ionic liquid as catalyst according to claim 4, characterized in that: The fluorenyl diol product structural formula is shown below: Wherein, R1-R8 is selected from -H, or -C where n is 1 to 10 n H 2n+1 , -SC n H 2n+1 , or -C where n is 1 to 3 6n H 4n+1 , -SC 6n H 4n+1 ; R9 is selected from -OH, or -OC where n is 1 to 10 n H 2n OH, -SC n H 2n OH.

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