4, 4, 4apos; preparation method of-dibenzylidene bisphenol

Abstract

The invention provides a preparation method of 4, 4 '-dibenzylidene bisphenol, and belongs to the technical field of preparation of medicine and electronic material intermediates. The preparation method of the 4, 4 '-dibenzylidene bisphenol comprises the following step: carrying out Friedel-Crafts reaction on a compound shown in a formula II and phenol to obtain a compound shown in a formula III. The 4, 4 '-dibenzylidene bisphenol is obtained through the Friedel-Crafts reaction of the dimethoxydiphenylmethane and the phenol, the 4, 4'-dibenzylidene bisphenol is easy to purify, the product quality of the prepared 4, 4 '-dibenzylidene bisphenol is improved, and the yield of the 4, 4'-dibenzylidene bisphenol is improved.

Description

Technical Field

[0001] The present invention relates to the technical field of the preparation of pharmaceutical and electronic material intermediates, and particularly relates to a method for preparing 4,4'-diphenylmethylenebisphenol. Background Art

[0002] Compound 4,4'-diphenylmethylenebisphenol is an important intermediate for pharmaceuticals and electronic materials, and has the following chemical structural formula:

[0003] Currently, there are mainly two methods for synthesizing 4,4'-diphenylmethylenebisphenol: The first is the reaction of expensive dichlorodiphenylmethane and phenol under solvent-free conditions as disclosed in the literature "Macromolecules, 2004, vol. 37, #9, p. 3151–3158", and the reported yield of 4,4'-diphenylmethylenebisphenol is about 60%. The second is the synthesis of 4,4'-diphenylmethylenebisphenol from benzophenone and phenol in the presence of potassium hydroxide as disclosed in Patent US2858342; the reaction temperature of this synthesis reaction is 157-159 °C, the reaction time is 200 h, and the yield is 17%.

[0004] However, for the synthesis of 4,4'-diphenylmethylenebisphenol by the first method, expensive dichlorodiphenylmethane is used as the raw material, a large amount of hydrogen chloride gas is generated during the reaction, the product is severely solidified, and it is difficult to stir during the reaction, making it difficult to scale up industrially. For the synthesis of 4,4'-diphenylmethylenebisphenol by the second method, the reaction time is long, the reaction temperature is relatively harsh, the yield is low, and special high-temperature reaction vessels are required for industrial scale-up, resulting in high equipment costs and making it impossible to achieve industrial scale-up. Summary of the Invention

[0005] In view of this, the object of the present invention is to provide a method for preparing 4,4'-diphenylmethylenebisphenol, aiming to improve the product quality of 4,4'-diphenylmethylenebisphenol and increase the yield of 4,4'-diphenylmethylenebisphenol.

[0006] To achieve the above object, the present invention provides a method for preparing 4,4'-diphenylmethylenebisphenol, comprising the following steps:

[0007]

[0008] (1) The compound of formula II undergoes a Friedel-Crafts reaction with phenol to obtain the compound of formula III.

[0009] Preferably, step (1) includes:

[0010] Add the compound of formula II and the first acid reagent to the first solvent, heat to 70 - 140 °C, then add phenol, stir and react for 8 - 24 h, and then filter to obtain the first filter cake;

[0011] Add the second solvent to the first filter cake and make a slurry, then filter and dry to obtain the compound of formula III.

[0012] Preferably, the first acid reagent is selected from one of sulfuric acid, p-toluenesulfonic acid and anhydrous zinc chloride;

[0013] The first solvent is selected from one or more of toluene, chlorobenzene and xylene.

[0014] Preferably, the second solvent is selected from one or more of methanol, ethanol, isopropanol and acetonitrile;

[0015] The molar ratio of the compound of formula II to phenol is 1:2.2 - 5.

[0016] Preferably, before step (1), it further includes:

[0017]

[0018] (2) The compound of formula I undergoes an addition reaction to obtain the compound of formula II.

[0019] Preferably, step (2) includes:

[0020] The compound of formula I reacts with trimethyl orthoformate to obtain the compound of formula II.

[0021] Preferably, the step of reacting the compound of formula I with trimethyl orthoformate to obtain the compound of formula II includes:

[0022] Add the compound of formula I and the second acid reagent to the third solvent, then dropwise add trimethyl orthoformate to the third solvent, and stir and react at 20 - 40 °C for 6 - 20 h, and then filter to obtain the second filter cake;

[0023] Wash the second filter cake with the fourth solvent, and then dry under reduced pressure to obtain the compound of formula II.

[0024] Preferably, the second acid reagent is selected from one of sulfuric acid, p-toluenesulfonic acid and methylsulfonic acid.

[0025] Preferably, the third solvent is selected from one or more of methanol, isopropanol and acetonitrile.

[0026] Preferably, the fourth solvent is selected from one or more of methanol, isopropanol and acetonitrile;

[0027] The molar ratio of the compound of formula I to trimethyl orthoformate is 1:1.2 - 3.

[0028] The present invention provides a method for preparing 4,4'-diphenylmethylenebisphenol, comprising the following steps: The compound of formula II and phenol are subjected to a Friedel-Crafts reaction to obtain the compound of formula III. Thus, in the present invention, 4,4'-diphenylmethylenebisphenol is obtained by the Friedel-Crafts reaction of dimethoxydiphenylmethane and phenol. 4,4'-Diphenylmethylenebisphenol is easy to purify, improving the product quality of the preparation of 4,4'-diphenylmethylenebisphenol and increasing the yield of 4,4'-diphenylmethylenebisphenol. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 It is the HPLC chromatogram of 4,4'-diphenylmethylenebisphenol of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0030] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention.

[0031] The present invention provides a method for preparing 4,4'-diphenylmethylenebisphenol, comprising the following steps:

[0032]

[0033] (1) The compound of formula II and phenol are subjected to a Friedel-Crafts reaction to obtain the compound of formula III.

[0034] Unless otherwise specified, the present invention has no special requirements for the sources of the raw materials used in the preparation, and commercially available products well-known to those skilled in the art can be used.

[0035] In the present invention, the step (1) includes:

[0036] The compound of formula II and the first acid reagent are added to the first solvent, and after heating to 70-140 °C, phenol is added, and after stirring and reacting for 8-24 h, filtration is carried out to obtain a first filter cake;

[0037] The second solvent is added to the first filter cake and slurried, and then filtered and dried to obtain the compound of formula III.

[0038] In the present invention, the first acid reagent is selected from one of sulfuric acid, p-toluenesulfonic acid and anhydrous zinc chloride;

[0039] In the present invention, the first solvent is selected from one or more of toluene, chlorobenzene and xylene.

[0040] In the present invention, the second solvent is selected from one or more of methanol, ethanol, isopropanol and acetonitrile;

[0041] In the present invention, the molar ratio of the compound of formula II to the phenol is 1:2.2-5.

[0042] In the present invention, before the step (1), it further includes:

[0043]

[0044] (2) The compound of formula I undergoes an addition reaction to obtain the compound of formula II.

[0045] In the present invention, step (2) may include:

[0046] The compound of formula I reacts with trimethyl orthoformate to obtain the compound of formula II.

[0047] In the present invention, the step in which the compound of formula I reacts with trimethyl orthoformate to obtain the compound of formula II includes:

[0048] After adding the compound of formula I and the second acid reagent to the third solvent, trimethyl orthoformate is added dropwise to the third solvent, and the mixture is stirred and reacted at 20 - 40 °C for 6 - 20 h and then filtered to obtain a second filter cake;

[0049] After washing the second filter cake with the fourth solvent, it is dried under reduced pressure to obtain the compound of formula II.

[0050] In the present invention, the second acid reagent is selected from one of sulfuric acid, p-toluenesulfonic acid, and methanesulfonic acid.

[0051] In the present invention, the third solvent is selected from one or more of methanol, isopropanol, and acetonitrile.

[0052] In the present invention, the fourth solvent is selected from one or more of methanol, isopropanol, and acetonitrile;

[0053] In the present invention, the molar ratio of the compound of formula I to the trimethyl orthoformate is 1:1.2 - 3.

[0054] Next, the technical solutions in the present invention will be clearly and completely described in conjunction with the examples in the present invention

[0055] Example 1

[0056] 1) Add benzophenone (18.2 g, 0.10 mol), methanol (95 mL), and concentrated sulfuric acid (5 mL) to a 250 mL three-necked flask; add trimethyl orthoformate (21.2 g, 0.2 mol) dropwise to the three-necked flask, and stir and react at 30 °C for 16 hours; after the reaction is completed, filter, wash the filter cake with methanol, and dry it under reduced pressure to obtain 21.0 g of white powdery dimethoxydiphenylmethane, with a purity of 98.2% and a yield of 92.0%.

[0057] 2) Add the dimethoxydiphenylmethane (20.0 g, 0.087 mol) prepared in the previous step, toluene (100 mL), and sulfuric acid (2.0 mL) into a 500 mL three-necked flask. Heat the mixture to 80 °C, then add phenol (24.5 g, 0.261 mol) and stir for reaction for 12 h. After the reaction is completed, filter. The filter cake is slurried with ethanol (100 mL), filtered, and dried in vacuo to obtain 27.7 g of a white solid 4,4'-diphenylmethylenebisphenol with a purity of 98.6% and a yield of 90.5%.

[0058] Example 2

[0059] 1) Add benzophenone (18.2 g, 0.10 mol), acetonitrile (100 mL), and concentrated sulfuric acid (5 mL) into a 250 mL three-necked flask. Dropwise add trimethyl orthoformate (21.2 g, 0.2 mol) into the three-necked flask and stir for reaction at 35 °C for 12 h. After the reaction is completed, filter and wash the filter cake with acetonitrile, and dry it under reduced pressure to obtain 21.5 g of a white powdery product dimethoxydiphenylmethane with a purity of 98.5% and a yield of 94.3%.

[0060] 2) Add the dimethoxydiphenylmethane (20.0 g, 0.087 mol) prepared in the previous step, xylene (100 mL), and sulfuric acid (2.0 mL) into a 500 mL three-necked flask. Heat the mixture to 120 °C, then add phenol (24.5 g, 0.261 mol) and stir for reaction for 24 h. After the reaction is completed, filter. The filter cake is slurried with ethanol (100 mL), filtered, and dried in vacuo to obtain 28.2 g of a white solid 4,4'-diphenylmethylenebisphenol with a purity of 98.3% and a yield of 92.1%.

[0061] Example 3

[0062] 1) Add benzophenone (18.2 g, 0.10 mol), isopropanol (110 mL), and concentrated sulfuric acid (5 mL) into a 250 mL three-necked flask. Dropwise add trimethyl orthoformate (21.2 g, 0.2 mol) into the three-necked flask and stir for reaction at 20 °C for 10 h. After the reaction is completed, filter and wash the filter cake with isopropanol, and dry it under reduced pressure to obtain 22.0 g of a white powdery product dimethoxydiphenylmethane with a purity of 98.5% and a yield of 96.5%.

[0063] 2) Add the dimethoxydiphenylmethane (20.0 g, 0.087 mol) prepared in the previous step, chlorobenzene (120 mL), and sulfuric acid (2.0 mL) to a 500 mL three-necked flask. Heat the mixture to 140 °C, then add phenol (24.5 g, 0.261 mol) and stir for 8 h. After the reaction is completed, filter. The filter cake is slurried with ethanol (100 mL), filtered, and dried in vacuo to obtain 28.0 g of a white solid 4,4'-diphenylmethylenebisphenol with a purity of 98.7% and a yield of 91.5%.

[0064] Example 4

[0065] 1) Add benzophenone (18.2 g, 0.10 mol), methanol (95 mL), and p-toluenesulfonic acid (1.72 g, 0.01 mol) to a 250 mL three-necked flask. Dropwise add trimethyl orthoformate (21.2 g, 0.2 mol) to the three-necked flask and stir at 40 °C for 20 h. After the reaction is completed, filter and wash the filter cake with methanol, then dry under reduced pressure to obtain 20.8 g of a white powdery product dimethoxydiphenylmethane with a purity of 98.5% and a yield of 91.2%.

[0066] 2) Add the dimethoxydiphenylmethane (20.0 g, 0.087 mol) prepared in the previous step, toluene (100 mL), and anhydrous zinc chloride (2.32 g, 0.017 mol) to a 500 mL three-necked flask. Heat the mixture to 100 - 105 °C, then add phenol (24.5 g, 0.261 mol) and stir for 16 h. After the reaction is completed, filter. The filter cake is slurried with ethanol (100 mL), filtered, and dried in vacuo to obtain 28.3 g of a white solid 4,4'-diphenylmethylenebisphenol with a purity of 99.0% and a yield of 92.5%.

[0067] Example 5

[0068] 1) Add benzophenone (18.2 g, 0.10 mol), methanol (95 mL), and methanesulfonic acid (1.44 g, 0.015 mol) to a 250 mL three-necked flask. Dropwise add trimethyl orthoformate (21.2 g, 0.2 mol) to the three-necked flask and stir at 30 °C for 14 h. After the reaction is completed, filter and wash the filter cake with methanol, then dry under reduced pressure to obtain 21.8 g of a white powdery product dimethoxydiphenylmethane with a purity of 98.7% and a yield of 94.6%.

[0069] 2) Add the dimethoxydiphenylmethane (20.0 g, 0.087 mol), toluene (100 mL) and p-toluenesulfonic acid (2.92 g, 0.017 mol) prepared in the previous step into a 500 mL three-necked flask. Heat the mixture to 100 °C, then add phenol (24.5 g, 0.261 mol) and stir for reaction for 20 h. After the reaction is completed, filter. Add ethanol (100 ml) to the filter cake for pulping, filter, and dry under vacuum to obtain 28.7 g of off-white solid 4,4'-diphenylmethylenebisphenol, with a purity of 98.4% and a yield of 93.8%.

[0070] Thus, in the step of reacting dimethoxydiphenylmethane with phenol to obtain 4,4'-diphenylmethylenebisphenol, the purity of the 4,4'-diphenylmethylenebisphenol product is above 98.0%, and the yield of 4,4'-diphenylmethylenebisphenol is above 90%. In the present invention, 4,4'-diphenylmethylenebisphenol is obtained by the Friedel-Crafts reaction of dimethoxydiphenylmethane with phenol. The 4,4'-diphenylmethylenebisphenol is easy to purify, improving the product quality of the preparation of 4,4'-diphenylmethylenebisphenol and increasing the yield of 4,4'-diphenylmethylenebisphenol.

[0071] When the present invention prepares 4,4'-diphenylmethylenebisphenol, the purity of the 4,4'-diphenylmethylenebisphenol product is above 98.0%, and the total yield is above 84%. The present invention uses benzophenone as the starting material, and obtains 4,4'-diphenylmethylenebisphenol through two steps of addition reaction and phenol substitution, reducing the raw material cost of preparing 4,4'-diphenylmethylenebisphenol. The intermediate is easy to purify, improving the product quality of the preparation of 4,4'-diphenylmethylenebisphenol. Each reaction step for preparing the 4,4'-diphenylmethylenebisphenol compound in the present invention is simple to operate, without ultra-low temperature and ultra-high temperature reaction conditions, and is convenient for industrial scale-up.

[0072] Although the above embodiments have described the present invention in detail, they are only a part of the embodiments of the present invention rather than all embodiments. People can also obtain other embodiments according to this embodiment without creative efforts, and these embodiments all belong to the protection scope of the present invention.

Claims

1. A method for preparing 4,4'-diphenylmethylene bisphenol, characterized in that: The following steps are involved: (1) The compound of formula II is reacted with phenol through Friedel-Crafts reaction to obtain the compound of formula III.

2. The method for preparing 4,4'-dibenzylidene bisphenol according to claim 1, characterized in that: The step (1) comprises: Add the compound of formula II and the first acid reagent to the first solvent, heat to 70-140° C., add phenol, stir to react for 8-24 hours, and then filter to obtain a first filter cake; The second solvent is added to the first filter cake and the mixture is slurried, filtered and dried to obtain the compound of formula III.

3. The method for preparing 4,4'-dibenzylidene bisphenol according to claim 2, characterized in that: The first acid reagent is selected from one of sulfuric acid, p-toluenesulfonic acid and anhydrous zinc chloride; The first solvent is selected from one or more of toluene, chlorobenzene and xylene.

4. The method for preparing 4,4'-dibenzylidene bisphenol according to claim 2, characterized in that: The second solvent is selected from one or more of methanol, ethanol, isopropanol and acetonitrile; The molar ratio of the compound of formula II to phenol is 1:2.2-5.

5. The method for preparing 4,4'-dibenzylidene bisphenol according to any one of claims 1 to 4, characterized in that: Before step (1), the method further includes: (2) The compound of formula I is subjected to an addition reaction to obtain a compound of formula II.

6. The method for preparing 4,4'-dibenzylidene bisphenol according to claim 5, characterized in that: The step (2) comprises: The compound of formula I is reacted with trimethyl orthoformate to obtain the compound of formula II.

7. The method for preparing 4,4'-dibenzylidene bisphenol according to claim 6, characterized in that: The step of reacting the compound of formula I with trimethyl orthoformate to obtain the compound of formula II comprises: After adding the compound of formula I and the second acid reagent into the third solvent, trimethyl orthoformate is added dropwise into the third solvent, and the mixture is stirred at 20 to 40° C. for 6 to 20 hours and then filtered to obtain a second filter cake; The second filter cake is washed with the fourth solvent and then dried under reduced pressure to obtain a compound of formula II.

8. The method for preparing 4,4'-dibenzylidene bisphenol according to claim 7, characterized in that: The second acid reagent is selected from one of sulfuric acid, p-toluenesulfonic acid and methanesulfonic acid.

9. The method for preparing 4,4'-dibenzylidene bisphenol according to claim 7, characterized in that: The third solvent is selected from one or more of methanol, isopropanol and acetonitrile.

10. The method for preparing 4,4'-dibenzylidene bisphenol according to claim 7, characterized in that: The fourth solvent is selected from one or more of methanol, isopropanol and acetonitrile; The molar ratio of the compound I to the trimethyl orthoformate is 1:1.2-3.

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