Method for synthesizing dihydroxy compound based on double-acid catalytic system

Abstract

The invention relates to a double-acid catalytic system for catalytic synthesis of a dihydroxy compound and a method for catalytic synthesis of the dihydroxy compound. The double-acid catalytic system comprises a Lewis acid catalyst and a sulfydryl-containing protonic acid catalyst and is used for catalytically synthesizing the dihydroxy compound. Compared with a traditional catalytic method, the dihydroxy compound is synthesized by one-step reaction of a carbonyl compound and an aromatic hydroxy compound through a synergistic catalysis effect of a double-acid catalytic system selected in the invention. According to the method, a good catalytic effect can be obtained at a relatively low reaction temperature within a relatively short reaction time, the conversion rate of the carbonyl compound is greater than 40%, the selectivity of the product dihydroxy compound is greater than 40%, the use of strong inorganic acid is completely abandoned, the defects of high pollution, strong corrosivity and low selectivity of a traditional method are greatly avoided, and the method is suitable for industrial production. Good industrialization prospects are realized.

Description

Technical Field

[0001] The present application relates to a method for preparing a dihydroxy compound and a catalyst, belonging to the field of organic chemistry. Background Art

[0002] Diaryl compounds containing multiple benzene rings in their structures have special optical properties and can undergo polymerization reactions to prepare special optical materials, thus having important economic value. However, the currently widely used method for preparing the above dihydroxy compounds mainly uses concentrated sulfuric acid. A large amount of protons are first used to activate the carbonyl group, and then an alkylation reaction is carried out with an aromatic hydroxy compound to obtain the dihydroxy compound product. In patents CN104030899A, CN1696090A, CN105001027A, CN103058833A, and CN108863733A, different catalysts are respectively used to activate the carbonyl compound, so that it undergoes two addition reactions with an aromatic compound containing a hydroxyl group. However, the catalytic systems adopted in the above patents have the disadvantages of large catalyst consumption, strong corrosiveness, long reaction time, and difficult product separation, which limit the wide industrial application of such compounds.

[0003] In the papers Applied Catalysis A: General 354(2009)176–182, RSC Adv., 2014, 4, 33466, and Chemical Engineering Journal 298(2016)271–280, different catalysts are respectively used to activate the carbonyl compound, so that it undergoes two alkylation reactions with phenoxyethanol. Most of the catalysts adopted in these papers are acidic ionic liquids, and they still prepare dihydroxy compounds based on the principle of activating the carbonyl group by acid sites. Moreover, the used ionic liquid catalysts have the disadvantages of complex synthesis and high cost, which limit their large-scale application. Summary of the Invention

[0004] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a dual-acid catalytic system for catalytic synthesis of dihydroxylation and a method for catalytic synthesis of dihydroxy compounds. The dual-acid catalytic system has the advantages of high catalytic activity, low cost, low corrosiveness, etc., and is suitable for large-scale application.

[0005] One of the purposes of the present invention is to provide a dual-acid catalytic system for catalytic synthesis of dihydroxy compounds. The dual-acid catalytic system includes a Lewis acid catalyst and a protonic acid catalyst containing a mercapto group, and the dual-acid catalytic system is used for synthesizing dihydroxy compounds.

[0006] According to one aspect of the present application, a dual-acid catalytic system for preparing dihydroxy compounds is provided.

[0007] A dual-acid catalytic system for preparing a dihydroxy compound, the dual-acid catalytic system comprising catalyst 1 and catalyst 2;

[0008] Catalyst 1 is a Lewis acid;

[0009] Catalyst 2 is a protonic acidic compound containing a mercapto group.

[0010] Preferably, the Lewis acid is any one of BF3, SbF5, SO3, CaCl2, TiCl4, CrCl2, MnCl4, FeCl3, AlCl3, CoCl2, NiCl2, CuCl2, ZnCl2, SnCl4, CaBr2, TiBr4, CrBr2, MnBr4, FeBr3, CoBr2, NiBr2, CuBr2, ZnBr2, SnBr4, more preferably any one of BF3, SbF5, CaCl2, TiCl4, CrCl2, MnCl4, FeCl3, AlCl3, CuCl2, ZnCl2, SnCl4, CaBr2, TiBr4, CrBr2, MnBr4, FeBr3, CuBr2, ZnBr2, SnBr4, and even more preferably any one of BF3, SbF5, TiCl4, FeCl3, AlCl3, ZnCl2, SnCl4, TiBr4, FeBr3, ZnBr2, SnBr4.

[0011] Preferably, catalyst 2 has the structure represented by Formula 1-6:

[0012] HS-R-COOH Formula 1

[0013] HS-R-SO3H Formula 2

[0014] HS-R-SO2H Formula 3

[0015] HS-R-OSO2H Formula 4

[0016] HS-R-PO3H2 Formula 5

[0017] HS-R-PO2H Formula 6;

[0018] wherein R is any one of an alkyl group having 1 to C 16 alkyl, phenyl, pyrazinyl, pyridyl, thiazolyl, benzothiazolyl, imidazolyl, indolyl, and a polyethylene glycol group with n = 1-16.

[0019] Preferably, the catalyst 2 is selected from at least one of mercaptoacetic acid, mercaptopropionic acid, mercaptobutyric acid, carboxy dodecyl mercaptan and its isomers, thiosalicylic acid, 2-carboxy-3-mercapto-pyrazine, 2-carboxy-6-mercapto-pyridine, 2-mercapto-thiazoline, 5-carboxy-benzothiazole, 2-mercapto-4-carboxyimidazole, 4-mercapto-5-carboxyindole, mercapto-(PEG) n -carboxylic acid, at least one of the substances obtained by replacing the carboxyl group in the above substances with a sulfonic acid group, a sulfuric acid group, a sulfinic acid group, a sulfurous acid group, a phosphoric acid group, a phosphorous acid group, more preferably any one of mercaptoacetic acid, mercaptopropionic acid, mercaptobutyric acid, carboxy dodecyl mercaptan and its isomers, thiosalicylic acid, 2-(acetylamino)-3-mercapto-3-methylbutyric acid and its isomers, and / or at least one of the substances obtained by replacing the carboxyl group in the above substances with a sulfonic acid group, a sulfuric acid group, a sulfinic acid group, a sulfurous acid group, a phosphoric acid group, a phosphorous acid group, more preferably any one of mercaptoacetic acid, mercaptopropionic acid, mercaptobutyric acid, carboxy dodecyl mercaptan and its isomers, thiosalicylic acid and its isomers, and / or any one of the substances obtained by replacing the carboxyl group in the above substances with a sulfonic acid group, a sulfuric acid group, a sulfinic acid group, a sulfurous acid group, a phosphoric acid group, a phosphorous acid group.

[0020] Preferably, the ratio of the catalyst 1 to the catalyst 2, in terms of molar ratio, is 1:(0.005 - 0.5), more preferably any value of 1:0.005, 1:0.01, 1:0.015, 1:0.02, 1:0.025, 1:0.03, 1:0.035, 1:0.04, 1:0.045, 1:0.05, 1:0.055, 1:0.06, 1:0.065, 1:0.07, 1:0.075, 1:0.08, 1:0.085, 1:0.09, 1:0.095, 1:0.1, 1:0.11, 1:0.12, 1:0.13, 1:0.14, 1:0.15, 1:0.16, 1:0.17, 1:0.18, 1:0.19, 1:0.2 or a range value formed by any two of these values.

[0021] Preferably, the ratio of the catalyst 1 to the catalyst 2 is 1:(0.01 - 0.1), more preferably any value of 1:0.01, 1:0.015, 1:0.02, 1:0.025, 1:0.03, 1:0.035, 1:0.04, 1:0.045, 1:0.05, 1:0.055, 1:0.06, 1:0.065, 1:0.07, 1:0.075, 1:0.08, 1:0.085, 1:0.09, 1:0.095, 1:0.1 or a range value formed by any two of these values.

[0022] The present invention selects a dual-acid catalytic system of a Lewis acid catalyst and a protonic acid catalyst containing a mercapto group to catalyze the synthesis of dihydroxy compounds. The purpose of selecting the Lewis acid catalyst is to utilize the complexation of its cation with the C=O group. After the carbonyl compound reacts with the Lewis acid catalyst, the C=O characteristic peak in the infrared spectrum undergoes an obvious red shift, which confirms the occurrence of complexation and also indicates an increase in the C=O bond length, reducing the energy required for the protonation of C=O. Compared with the traditional concentrated sulfuric acid-mercaptopropionic acid catalytic system, the pre-activation of C=O makes the subsequent protonation to form C + -OH process easier, so that only a low molar amount of the weak protonic acid mercapto compound is needed to initiate the protonation process, thus completely eliminating the use of concentrated sulfuric acid; subsequently, the mercapto group forms a C + -SH intermediate by substituting -OH in the C + -OH group, promoting the subsequent reaction of the carbonyl compound with the aromatic hydroxy compound, and finally obtaining the product. The relevant intermediate structures were monitored by mass spectrometry, further verifying the above mechanism. Generally speaking, through the synergistic catalytic effect of the two acidic catalysts, the efficient preparation of dihydroxy compounds is realized, and the use of a high dose of concentrated sulfuric acid in the traditional method is completely eliminated.

[0023] The second aspect of this application provides a method for preparing a dihydroxy compound.

[0024] A method for preparing a dihydroxy compound, the method comprising the following steps:

[0025] Mix a carbonyl compound, an aromatic hydroxy compound, and a dual-acid catalyst system, and react to obtain the dihydroxy compound;

[0026] The dual-acid catalyst system is the above catalyst combination;

[0027] The carbonyl compound has the structure described by Formula I - Formula III below:

[0028]

[0029]

[0030]

[0031] Wherein, X1 is selected from any one of C, S, O, N, and C=O;

[0032] X2 or X3 is independently selected from one of C or N;

[0033] When X2 and / or X3 is N, there is no R group connected to X2 and X3, and the remaining R groups are each independently selected from hydrogen, halogen, hydroxyl, ester group, cyano group, amino group, mercapto group, substituted or unsubstituted alkyl with 1-6 carbon atoms, substituted or unsubstituted cycloalkyl with 3-10 carbon atoms, substituted or unsubstituted alkenyl with 2-6 carbon atoms, substituted or unsubstituted cycloalkyl with 1-6 carbon atoms, alkoxy group, substituted or unsubstituted phenyl or condensed phenyl with 6-30 carbon atoms, substituted or unsubstituted heteroaryl or condensed heteroaryl with 6-30 carbon atoms, or an atom or atomic group capable of substituting the above groups;

[0034] When X2 or X3 is C, R is each independently selected from hydrogen, halogen, hydroxyl, ester group, cyano group, amino group, mercapto group, substituted or unsubstituted alkyl with 1-6 carbon atoms, substituted or unsubstituted cycloalkyl with 3-10 carbon atoms, substituted or unsubstituted alkenyl with 2-6 carbon atoms, substituted or unsubstituted cycloalkyl with 1-6 carbon atoms, alkoxy group, substituted or unsubstituted phenyl or condensed phenyl with 6-30 carbon atoms, substituted or unsubstituted heteroaryl or condensed heteroaryl with 6-30 carbon atoms, or an atom or atomic group capable of substituting the above groups.

[0035] Preferably, the aromatic hydroxy compound is selected from phenol or a compound having a structure shown in Formula 1 - Formula 5 below:

[0036]

[0037] Among them, X4 is selected from any one of O, S, and N;

[0038] R2 is selected from any straight-chain or branched-chain alkane with 1-8 carbon atoms, any straight-chain or branched-chain alkene with 1-8 carbon atoms, any substituted or unsubstituted straight-chain or branched-chain alkane with 1-8 carbon atoms, any substituted or unsubstituted straight-chain or branched-chain alkene with 2-8 carbon atoms, an alkoxy group with 1-6 carbon atoms, a cycloalkyl with 3-10 carbon atoms, a substituted or unsubstituted phenyl or condensed phenyl with 6-30 carbon atoms, a substituted or unsubstituted heteroaryl or condensed heteroaryl with 6-30 carbon atoms.

[0039] Since the carbonyl condensation reaction described in the present invention is essentially an addition of the para-carbon of the aryl substituent to the carbonyl group, in fact, this reaction is not limited to the above several compounds with a hydroxyl group at the end group, and groups such as halogen, alkyl, and alkenyl can also cause this reaction to occur.

[0040] More preferably, the aromatic hydroxy compound is selected from any one of the following substances:

[0041] Preferably, the molar ratio of the carbonyl compound, aromatic hydroxy compound, catalyst 1, and catalyst 2 is 1:2-4:0.5-8:0.0025-4, such as 1:2:0.5:0.0025, 1:3:0.5:0.0025, 1:4:0.5:0.0025, 1:2:1:0.0025, 1:2:1.5:0.0025, 1:2:2:0.0025, 1:2.5:2.5:0.0025, 1:2:3:0.0025, 1:2:3.5:0.0025, 1:2:4:0.0025, 1:2:4.5:0.0025, 1:2:5:0.0025, 1:2:5.5:0.0025, 1:2:6:0.0025, 1:2:6.5:0.0025, 1:2:7:0.0025, 1:2:7.5:0.0025, 1:2:8:0.0025, 1:2:0.5:0.005, 1:2:0.5:0.05, 1:2:0.5:0.5, 1:2:0.5:1, 1:2:0.5:1.5, 1:2:0.5:2, 1:2:0.5:2.5, 1:2:0.5:3, 1:2:0.5:3.5, 1:2:0.5:4, etc.

[0042] Preferably, the temperature of the reaction is 60°C - 170°C, such as 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, etc.

[0043] Preferably, the reaction time is 1 min - 8 h, such as 1 min, 5 min, 10 min, 15 min, 20 min, 25 min, 30 min, 35 min, 40 min, 45 min, 50 min, 55 min, 1 h, 1.5 h, 2 h, 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h, 5 h, 5.5 h, 6 h, 6.5 h, 7 h, 7.5 h, 8 h, etc.

[0044] In the third aspect of the present application, there is provided an application of a dihydroxy compound as a polymer monomer.

[0045] An application of a dihydroxy compound as a polymer monomer, wherein the polymer monomer is obtained using the above catalyst combination and / or the above preparation method. Description of the Drawings

[0046] Figure 1 For the weak interaction phenomenon of ZnCl2 with the carbonyl compound in Example 1 of the present application, the FT-IR spectrum shows that Zn 2+ The mixture with fluorenone has a 4 cm red shift phenomenon, indicating that Zn 2+ Promotes the reduction of the bond energy of C=O;

[0047] Figure 2 This is the mass spectrum of the product after the reaction in Example 1 of this application, indicating that the reaction in Example 1 can detect the diphenylated product of the target carbonyl compound (denoted by D in the figure);

[0048] Figure 3 This is the NMR spectrum of the product after the reaction in Example 1 of this application, indicating that the sample obtained according to Example 1 has no other interaction forces, showing that the chemical structure of the obtained product is consistent with the structure of the target product. Detailed implementation manners

[0049] The present application will be described in detail below with reference to examples, but the present application is not limited to these examples.

[0050] Unless otherwise specified, the raw materials and catalysts in the examples of this application are purchased through commercial channels. Among them, the carbonyl compounds and aromatic hydroxyl compounds are all purchased from Aladdin, the metal salts and proton acids are all purchased from Sinopharm, and the compounds containing -SH groups are all purchased from Macklin.

[0051] The analysis methods in the examples of this application are as follows:

[0052] The reaction materials after the reaction are analyzed by high performance liquid chromatography, and the conversion rate of the carbonyl compound and the selectivity of the diphenylated product are calculated using the peak area.

[0053] The calculation of the conversion rate and selectivity in the examples of this application is as follows:

[0054] In the examples of this application, the conversion rate of the carbonyl compound and the selectivity of the dihydroxy compound are both calculated based on the following formula.

[0055] Conversion rate = 100% × (1 - remaining amount of carbonyl compound / total amount of carbonyl compound)

[0056] Among them, the remaining amount and total amount of the carbonyl compound are calculated using the peak area measured by high performance liquid chromatography.

[0057] Selectivity = 100% × (total amount of target product / total amount of product)

[0058] Among them, the total amount of the dihydroxy compound and the total amount of the product are calculated using the peak area measured by high performance liquid chromatography.

[0059] Example 1

[0060] Mix 1 mol of fluorenone, 2.5 mol of phenol, 2 mol of ZnCl2, and 0.01 mol of mercaptopropionic acid, add them to a reaction vessel, heat up to 110 °C, and react for 2 h to obtain a dark red solid substance. Add ethanol to the reaction vessel after the reaction, stir it with the obtained dark red solid substance to obtain a dark red homogeneous solution, transfer the solution into a beaker, and evaporate to obtain a white target product.

[0061] The yield and selectivity of the product were determined by high performance liquid chromatography. Add acetonitrile to the reaction vessel with the dark red solid substance for dissolution, and then dilute it with acetonitrile. The diluted solution was injected into the high performance liquid chromatography for determination. The conversion rate of fluorenone was 95.4%, and the selectivity of the target product was 97.2%.

[0062] The structural formula of the product obtained in this example is:

[0063] Example 2

[0064] Mix 1 mol of fluorenone, 2.5 mol of phenoxyethanol, 2 mol of ZnCl2, and 0.01 mol of mercaptopropionic acid, add them to a reaction vessel, heat up to 110 °C, and react for 2 h to obtain a dark red solid substance. Add ethanol to the reaction vessel after the reaction, stir it with the obtained dark red solid substance to obtain a dark red homogeneous solution, transfer the solution into a beaker, and evaporate to obtain a white target product.

[0065] The yield and selectivity of the product were determined by high performance liquid chromatography. Add acetonitrile to the reaction vessel with the dark red solid substance for dissolution, and then dilute it with acetonitrile. The diluted solution was injected into the high performance liquid chromatography for determination. The conversion rate of fluorenone was 91.4%, and the selectivity of the target product was 96.3%.

[0066] The structural formula of the product obtained in this example is:

[0067] Example 3

[0068] Mix 1 mol of fluorenone, 2.5 mol of phenoxyisopropanol, 2 mol of ZnCl2, and 0.01 mol of mercaptopropionic acid, add them to a reaction vessel, heat up to 110 °C, and react for 2 h to obtain a dark red solid substance. Add ethanol to the reaction vessel after the reaction, stir it with the obtained dark red solid substance to obtain a dark red homogeneous solution, transfer the solution into a beaker, and evaporate to obtain a white target product.

[0069] The yield and selectivity of the product were determined by high performance liquid chromatography. Acetonitrile was added to the reaction vessel with dark red solid material for dissolution, and then diluted with acetonitrile. The diluted solution was injected into the high performance liquid chromatography for determination. The conversion rate of fluorenone was 90.5%, and the selectivity of the target product was 93.8%.

[0070] The structural formula of the product obtained in this example is:

[0071] Example 4

[0072] 1 mol of fluorenone, 2.5 mol of phenoxybutanediol, 2 mol of ZnCl2, and 0.01 mol of mercaptopropionic acid were mixed and added to a reaction vessel. The temperature was raised to 110 °C and the reaction was carried out for 2 h to obtain a dark red solid material. Ethanol was added to the reaction vessel and stirred with the obtained dark red solid material to obtain a dark red homogeneous solution. The solution was transferred to a beaker and evaporated to obtain a white target product.

[0073] The yield and selectivity of the product were determined by high performance liquid chromatography. Acetonitrile was added to the reaction vessel with dark red solid material for dissolution, and then diluted with acetonitrile. The diluted solution was injected into the high performance liquid chromatography for determination. The conversion rate of fluorenone was 93.4%, and the selectivity of the target product was 96.7%.

[0074] The structural formula of the product obtained in this example is:

[0075] Example 5

[0076] 0.01 mol of fluorenone, 0.02 mol of ZnCl2, 0.0005 mol of mercaptoacetic acid, and 0.025 mol of benzenethiol were added to a reaction vessel. The temperature was raised to 110 °C and stirred for 2 h. After the reaction, acetonitrile was added to quench the reaction. The components of the product were quantitatively detected by the external standard method and high performance liquid chromatography. The conversion rate of fluorenone was measured to be 97.1%, and the selectivity of the product was 95.8%.

[0077] The structural formula of the product obtained in this example is:

[0078] Example 6

[0079] 0.01 mol of fluorenone, 0.02 mol of ZnCl2, 0.0005 mol of mercaptoacetic acid, and 0.025 mol of 1-phenylsulfanylmethanol were added to a reaction vessel. The temperature was raised to 110 °C and stirred for 2 h. After the reaction, acetonitrile was added to quench the reaction. The components of the product were quantitatively detected by the external standard method and high performance liquid chromatography. The conversion rate of fluorenone was measured to be 93.3%, and the selectivity of the product was 95.1%.

[0080] The structural formula of the product obtained in this example is:

[0081] Example 7

[0082] 0.01 mol of fluorenone, 0.02 mol of ZnCl2, 0.0005 mol of mercaptoacetic acid, and 0.025 mol of 2-phenyldiethanolamine were added to a reaction vessel, heated to 110 °C, stirred, and reacted for 2 h. After the reaction was completed, acetonitrile was added to quench the reaction. The components of the product were quantitatively detected by the external standard method and high performance liquid chromatography. The conversion rate of fluorenone was measured to be 91.7%, and the selectivity of the product was 95.1%.

[0083] The structural formula of the product obtained in this example is:

[0084] Example 8

[0085] 0.01 mol of fluorenone, 0.02 mol of ZnCl2, 0.0005 mol of mercaptoacetic acid, and 0.025 mol of phenoxyphenol were added to a reaction vessel, heated to 110 °C, stirred, and reacted for 2 h. After the reaction was completed, acetonitrile was added to quench the reaction. The components of the product were quantitatively detected by the external standard method and high performance liquid chromatography. The conversion rate of fluorenone was measured to be 90.1%, and the selectivity of the product was 95.7%.

[0086] The structural formula of the product obtained in this example is:

[0087] Example 9

[0088] 0.01 mol of fluorenone, 0.02 mol of ZnCl2, 0.0005 mol of mercaptoacetic acid, and 0.025 mol of phenylthiophenol were added to a reaction vessel, heated to 110 °C, stirred, and reacted for 2 h. After the reaction was completed, acetonitrile was added to quench the reaction. The components of the product were quantitatively detected by the external standard method and high performance liquid chromatography. The conversion rate of fluorenone was measured to be 90.8%, and the selectivity of the product was 96.2%.

[0089] The structural formula of the product obtained in this example is:

[0090] Example 10

[0091] 0.01 mol of fluorenone, 0.02 mol of ZnCl2, 0.0005 mol of mercaptoacetic acid, and 0.025 mol of phenoxy-β-naphthol were added to a reaction vessel, heated to 110 °C, stirred, and reacted for 2 h. After the reaction was completed, acetonitrile was added to quench the reaction. The components of the product were quantitatively detected by the external standard method and high performance liquid chromatography. The conversion rate of fluorenone was measured to be 89.3%, and the selectivity of the product was 93.2%.

[0092] The structural formula of the product obtained in this example is:

[0093] Example 11

[0094] 0.01 mol of fluorenone, 0.02 mol of ZnCl2, 0.0005 mol of mercaptoacetic acid, and 0.025 mol of 1-phenoxybutanol were added to a reaction vessel, heated to 110 °C, stirred, and reacted for 2 h. After the reaction was completed, acetonitrile was added to quench the reaction. The product components were quantitatively detected by the external standard method and high performance liquid chromatography. The conversion rate of fluorenone was measured to be 92.7%, and the selectivity of the product was 93.2%.

[0095] The structural formula of the product obtained in this example is:

[0096] Example 12

[0097] 0.01 mol of fluorenone, 0.02 mol of ZnCl2, 0.0005 mol of mercaptoacetic acid, and 0.025 mol of n-octyl phenyl ether were added to a reaction vessel, heated to 110 °C, stirred, and reacted for 2 h. After the reaction was completed, acetonitrile was added to quench the reaction. The product components were quantitatively detected by the external standard method and high performance liquid chromatography. The conversion rate of fluorenone was measured to be 90.4%, and the selectivity of the product was 94.2%.

[0098] The structural formula of the product obtained in this example is:

[0099] Example 13

[0100] 0.01 mol of fluorenone, 0.02 mol of ZnCl2, 0.0005 mol of mercaptoacetic acid, and 0.025 mol of α-anthrol were added to a reaction vessel, heated to 110 °C, stirred, and reacted for 2 h. After the reaction was completed, acetonitrile was added to quench the reaction. The product components were quantitatively detected by the external standard method and high performance liquid chromatography. The conversion rate of fluorenone was measured to be 48.4%, and the selectivity of the product was 51.2%.

[0101] The structural formula of the product obtained in this example is:

[0102] Example 14

[0103] 0.01 mol of fluorenone, 0.02 mol of ZnCl2, 0.0005 mol of thioglycolic acid, and 0.025 mol of 9-phenanthrol were added to a reaction vessel, heated to 110 °C, stirred, and reacted for 2 h. After the reaction was completed, acetonitrile was added to quench the reaction. The components of the product were quantitatively detected by the external standard method and high performance liquid chromatography. The conversion rate of fluorenone was measured to be 42.1%, and the selectivity of the product was 58.1%.

[0104] The structural formula of the product obtained in this example is:

[0105] Example 15

[0106] 0.01 mol of fluorenone, 0.02 mol of ZnCl2, 0.0005 mol of thioglycolic acid, and 0.025 mol of o-phenylphenol were added to a reaction vessel, heated to 110 °C, stirred, and reacted for 2 h. After the reaction was completed, acetonitrile was added to quench the reaction. The components of the product were quantitatively detected by the external standard method and high performance liquid chromatography. The conversion rate of fluorenone was measured to be 92.3%, and the selectivity of the product was 62.2%.

[0107] The structural formula of the product obtained in this example is:

[0108] It can be seen from Examples 1-15 that the catalyst combination composed of ZnCl2 and thioglycolic acid has good catalytic ability for the above-mentioned several aromatic hydroxy compounds, and the conversion rate of fluorenone and the selectivity of the product decrease with the increase of the chain length of the benzene hetero group compound. The activity of the para-carbon of the phenolic hydroxyl group is the highest, so the selectivity and conversion rate are relatively high.

[0109] Examples 16-42 detected the alkylation reaction of different carbonyl compounds with phenol. The catalyst 1, catalyst 2, reaction conditions, and reactant ratio used were the same as those in Example 1. The values of the conversion rate and selectivity obtained from the product test are shown in Table 1.

[0110] Table 1

[0111]

[0112]

[0113]

[0114]

[0115] It can be seen from Examples 16-42 that the catalyst combination can effectively alkylate different carbonyl compounds with considerable yield and selectivity. When the reactants contain different multi-electron bodies, such as halogen elements, N, O, and S elements, the conversion rate and selectivity of the reactants are slightly lower, and it is suspected that other multi-electron bodies react with aromatic hydroxyl compounds.

[0116] Examples 43-54

[0117] This example group uses a different catalyst 1. Other than that, the reaction raw materials, catalyst 2, reaction conditions, post-treatment process and material ratio are the same as those of Example 1. The conversion rates and selectivities obtained by different catalysts 1 and the tests are shown in Table 2.

[0118] Table 2

[0119] Example number Selection of Catalyst 1 Conversion rate % Selectivity % 43 <![CDATA[ZnBr2]]> 98.7 93.6 44 <![CDATA[ZnI2]]> 93.7 99.6 45 <![CDATA[FeCl3]]> 96.2 96.6 46 <![CDATA[AlCl3]]> 97 99.3 47 <![CDATA[BF3]]> 98.1 97.4 48 <![CDATA[SbF5]]> 94.3 96.1 49 <![CDATA[TiBr4]]> 90.6 98.9 50 <![CDATA[CrBr2]]> 76.1 86.2 51 <![CDATA[MnBr4]]> 86.0 84.4 52 <![CDATA[CoCl2]]> 77.0 83.7 53 <![CDATA[NiCl2]]> 82.2 84.9 54 <![CDATA[Copper(II) chloride]]> 75.4 85.3

[0120] It can be seen from Examples 43-54 that the catalytic effect of Lewis acids with strong electron-withdrawing ability is stronger, and the catalytic effect of Lewis acid cations with weaker electron-withdrawing ability is poorer. However, it can be seen from Examples 33 and 34 that when the Lewis acid cations are the same, changing the anion type has little effect on the catalytic activity.

[0121] Examples 55-68

[0122] This example group uses a different catalyst 2. Other than that, the reaction raw materials, catalyst 1, reaction conditions, post-treatment process and material ratio are the same as those of Example 1. The conversion rates and selectivities obtained by different catalysts 2 and the tests are shown in Table 3.

[0123] Table 3

[0124]

[0125]

[0126] According to the results in Examples 55-68, it can be seen that catalyst 2 only needs to provide protons and thiol groups to produce a good catalytic reaction, and the catalytic effect is basically independent of other groups. The proton donor can be a strong acid group or a weak acid group, and the selection of strong acid groups and weak acid groups has little effect on the catalytic effect.

[0127] Examples 69-86

[0128] This example group uses different reaction conditions, namely, temperature, reaction time and material ratio. Other than that, the reaction raw materials, catalyst 1, catalyst 2 and post-treatment process are the same as those in Example 1. The conversion rate and selectivity obtained by different catalysts 2 and tests are shown in Table 4 (wherein the material ratio is M (羰基化合物) :M(芳香族羟基化合物) : M (催化剂1) : M (催化剂2) ):

[0129] Table 4

[0130]

[0131]

[0132] It can be seen from the results in Examples 69 - 86 that the higher the temperature, the lower the required reaction time, and the catalytic effect is optimal. When the temperature is lower than 100°C, the catalytic effect is poor. The dosage of aromatic hydroxy compound reaches the best effect at 2.5 times. A low dosage will make it difficult to promote the reaction, and a high dosage will dilute the catalyst. The dosage of Catalyst 1 is preferably 2 times, achieving the optimal conversion rate and selectivity. Further increasing the dosage of Catalyst 1 cannot improve the conversion rate and selectivity, so there is no need to further increase the dosage of Catalyst 1. For the dosage of Catalyst 2, within the range disclosed in the examples, it has no obvious effect on the reaction, and good catalytic effects are achieved.

[0133] Comparative Example 1

[0134] This method is the traditional concentrated sulfuric acid method in the literature. The carbonyl compound and aromatic hydroxy compound are the same as in Example 1. The Catalyst 1 used is 98% sulfuric acid, and the Catalyst 2 is mercaptopropionic acid. The reaction temperature is 110°C, the time is 5 h, and the molar ratio of 9 - fluorenone, sulfuric acid, phenoxyethanol to 3 - mercaptopropionic acid is 1:2:2.5:0.05. The post - treatment method is the same as in Example 1, and the conversion rate of 9 - fluorenone obtained is 90.2%, and the selectivity of BPEF is 85.0%.

[0135] As can be seen from Comparative Example 1, the catalysts commonly used in the traditional preparation of dihydroxy compounds are usually strong protonic acid and mercapto compound catalytic systems, such as concentrated sulfuric acid, hydrofluoric acid and mercaptoethanol, dodecyl mercaptan. According to the industrial method used in the comparative example, when concentrated sulfuric acid and mercaptoethanol are used for co - catalysis, 2 mol of concentrated sulfuric acid is required for every 1 mol of carbonyl compound. However, in the method adopted in the present invention, the use of concentrated sulfuric acid is completely abandoned, and its proton is only provided by a weakly acidic mercapto compound, and only 0.005 - 0.5 mol of mercapto compound is required for every 1 mol of carbonyl compound.

[0136] In addition, since the products of the reaction described in this application are all products of two - step addition as described in Examples 1 - 12, the products obtained in other examples also have similar structural formulas.

[0137] The above are only several embodiments of the present application and do not impose any form of limitation on the present application. Although the present application is disclosed above with preferred embodiments, it is not intended to limit the present application. Any person skilled in the relevant art can make some changes or modifications within the scope of the technical solution of the present application by using the disclosed technical content, which are equivalent to equivalent implementation cases and all fall within the scope of the technical solution.

Claims

1. A dual acid catalyst system for preparing dihydroxy compounds, characterized in that, The double acid catalyst system includes catalyst 1 and catalyst 2; Catalyst 1 is a Lewis acid; Catalyst 2 is a protonic acid catalyst containing a mercapto group.

2. The dual acid catalyst system according to claim 1, wherein Catalyst 1 is any one of BF3, SbF5, SO3, CaCl2, TiCl4, CrCl2, MnCl4, FeCl3, AlCl3, CoCl2, NiCl2, CuCl2, ZnCl2, SnCl4, CaBr2, TiBr4, CrBr2, MnBr4, FeBr3, CoBr2, NiBr2, CuBr2, ZnBr2, SnBr4, preferably any one of BF3, SbF5, CaCl2, TiCl4, CrCl2, MnCl4, FeCl3, AlCl3, CuCl2, ZnCl2, SnCl4, CaBr2, TiBr4, CrBr2, MnBr4, FeBr3, CuBr2, ZnBr2, SnBr4, and more preferably any one of BF3, SbF5, TiCl4, FeCl3, AlCl3, ZnCl2, SnCl4, TiBr4, FeBr3, ZnBr2, SnBr4.

3. The dual acid catalyst system according to claim 1, wherein Catalyst 2 has any one of the structures represented by Formula 1-6: HS-R-COOH Formula 1 HS-R-SO3H Formula 2 HS-R-SO2H Formula 3 HS-R-OSO2H Formula 4 HS-R-PO3H2 Formula 5 HS-R-PO2H Formula 6; Wherein, the R is any one of C1-C 16 alkyl, phenyl, pyrazinyl, pyridyl, thiazolyl, benzothiazolyl, imidazolyl, indolyl, polyethylene glycol group with n = 1-16, preferably mercaptoacetic acid, mercaptopropionic acid, mercaptobutyric acid, carboxy dodecyl mercaptan and its isomers, thiosalicylic acid, 2-carboxy-3-mercapto-pyrazine, 2-carboxy-6-mercapto-pyridine, 2-mercapto-thiazoline, 5-carboxy-benzothiazole, 2-mercapto-4-carboxyimidazole, 4-mercapto-5-carboxyindole, mercapto-(PEG) n -carboxylic acid, 2-(acetamido)-3-mercapto-3-methylbutyric acid and its isomers, and / or at least one of the substances obtained by replacing the carboxyl group in the above substances with a sulfonic acid group, a sulfate group, a sulfinic acid group, a sulfite group, a phosphoric acid group, a phosphorous acid group, more preferably at least one of mercaptoacetic acid, mercaptopropionic acid, mercaptobutyric acid, carboxy dodecyl mercaptan and its isomers, thiosalicylic acid, 2-(acetamido)-3-mercapto-3-methylbutyric acid and its isomers, and / or at least one of the substances obtained by replacing the carboxyl group in the above substances with a sulfonic acid group, a sulfate group, a sulfinic acid group, a sulfite group, a phosphoric acid group, a phosphorous acid group, more preferably at least one of mercaptoacetic acid, mercaptopropionic acid, mercaptobutyric acid, carboxy dodecyl mercaptan and its isomers, thiosalicylic acid and its isomers, and / or at least one of the substances obtained by replacing the carboxyl group in the above substances with a sulfonic acid group, a sulfate group, a sulfinic acid group, a sulfite group, a phosphoric acid group, a phosphorous acid group.

4. The dual acid catalyst system according to claim 1, characterized in that, The ratio of catalyst 1 to catalyst 2, in terms of molar ratio, is 1:(0.005 - 0.5), preferably 1:(0.01 - 0.2).

5. A method for preparing a dihydroxy compound, characterized in that, The method includes the following steps: After mixing a carbonyl compound, an aromatic hydroxy compound, and the double acid catalyst system, reacting to obtain the dihydroxy compound; The double acid catalyst system is the catalyst combination described in any one of Claims 1-4; The carbonyl compound has the structures represented by the following Formula 1 - Formula 21: Wherein, X1 is selected from any one of C, S, O, N, C=O; X2 or X3 are each independently selected from one of C or N; When X2 and / or X3 is N, there is no R group connected to X2 and X3, and the remaining R groups are each independently selected from hydrogen, halogen, hydroxy, ester group, cyano group, amino group, mercapto group, substituted or unsubstituted alkyl group with 1-6 carbon atoms, substituted or unsubstituted cycloalkyl group with 3-10 carbon atoms, substituted or unsubstituted alkenyl group with 2-6 carbon atoms, substituted or unsubstituted cycloalkyl group with 1-6 carbon atoms, alkoxy group, substituted or unsubstituted phenyl or condensed phenyl group with 6-30 carbon atoms, substituted or unsubstituted heteroaryl or condensed heteroaryl group with 6-30 carbon atoms, or an atom or atomic group capable of substituting the above groups; When X2 or X3 is C, each R is independently selected from hydrogen, halogen, hydroxyl, ester group, cyano group, amino group, mercapto group, substituted or unsubstituted alkyl group with 1-6 carbon atoms, substituted or unsubstituted cycloalkyl group with 3-10 carbon atoms, substituted or unsubstituted alkenyl group with 2-6 carbon atoms, substituted or unsubstituted cycloalkyl group with 1-6 carbon atoms, alkoxy group, substituted or unsubstituted phenyl group or condensed ring phenyl group with 6-30 carbon atoms, substituted or unsubstituted heteroaryl group or condensed ring heteroaryl group with 6-30 carbon atoms, or an atom or atomic group capable of substituting the above groups.

6. The method according to claim 5, wherein The aromatic hydroxyl compound is selected from phenol or a compound having a structure shown in Formula 1 - Formula 5 below: wherein, X4 is selected from any one of O, S, and N; R2 is selected from any straight-chain or branched-chain alkane with 1-8 carbon atoms, any straight-chain or branched-chain alkene with 1-8 carbon atoms, any substituted or unsubstituted straight-chain or branched-chain alkane with 1-8 carbon atoms, any substituted or unsubstituted straight-chain or branched-chain alkene with 2-8 carbon atoms, alkoxy group with 1-6 carbon atoms, cycloalkyl group with 3-10 carbon atoms, substituted or unsubstituted phenyl group or condensed ring phenyl group with 6-30 carbon atoms, substituted or unsubstituted heteroaryl group or condensed ring heteroaryl group with 6-30 carbon atoms.

7. The method according to claim 6, characterized in that, The ratio of the carbonyl compound, aromatic hydroxyl compound, catalyst 1, and catalyst 2, in terms of molar ratio, is 1:2 - 4:0.5 - 8:0.0025 - 4.

8. The method according to claim 5, wherein The temperature of the reaction is 60°C - 170°C, and the reaction time is 1 min - 8 h; Preferably, the temperature of the reaction is 110°C - 150°C; Preferably, the reaction time is 5 min - 5 h.

9. Application of the dihydroxy compound obtained by using the double acid catalyst system according to any one of claims 1 - 5 and using the method according to any one of claims 6 - 8 as a polymer monomer.

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