4,4'-((propane-2,2-diyl)bis(4-azidophenoxy))diphenyl synthesis

Abstract

The application relates to the technical field of photoresist initiator synthesis, and provides a synthesis method of 4,4'-(propane-2,2-diyl)bis((4-azidophenoxy)phenyl), which comprises the following steps: taking 2,2'-bis[4-(4-aminophenoxyphenyl)]propane as raw material, reacting with sodium nitrite under low-temperature acidic conditions to form a diazonium salt, then reacting the diazonium salt with sodium azide under low-temperature conditions, adding an extraction solvent into the reaction solution, then separating the liquid, pouring the extraction solution into a precipitation solvent to precipitate a solid, and thus obtaining a bis-azide compound 4,4'-(propane-2,2-diyl)bis((4-azidophenoxy)phenyl). The obtained solid is subjected to nuclear magnetic hydrogen spectrum identification and liquid chromatography detection, and the results show that the prepared product is 4,4'-(propane-2,2-diyl)bis((4-azidophenoxy)phenyl), and the purity can reach more than 99%.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of photoresist initiator synthesis, in particular to a synthesis method of a 4,4'-(propane-2,2-diyl)bis((4-azidophenoxy)phenyl) synthesis method. BACKGROUND

[0002] The 4,4'-(propane-2,2-diyl)bis((4-azidophenoxy)phenyl) is an aromatic bis-azide compound, which is sensitive to light, contains a rigid skeleton and two azide groups in the structure, the rigid skeleton is an aromatic structure, can be used as a crosslinking agent for organic electronic devices, and is also used in the composition of positive or negative photosensitive resin and applied to the liquid crystal field. The azide compound is added as a crosslinking agent in the liquid crystal display layer, so that a coating with high heat resistance, high mechanical strength and low thermal expansion coefficient can be prepared, the crosslinking temperature can be reduced, the mechanical strength of the material can be improved, and the flexible substrate of various electronic devices is suitable.

[0003]

[0004] The compound is a bis-azide compound, has poor stability, and has the risk of explosion in the treatment and purification process. The patent CN109478015A mentions a synthesis method of the compound, adopts a method of directly removing the solvent to discharge, and has the risk and is not suitable for industrial production. Therefore, the application provides a synthesis method of 4,4'-(propane-2,2-diyl)bis((4-azidophenoxy)phenyl), which avoids the distillation operation and is suitable for industrial production. SUMMARY

[0005] The application provides a synthesis method of 4,4'-(propane-2,2-diyl)bis((4-azidophenoxy)phenyl).

[0006] The application adopts the following technical scheme:

[0007] A synthesis method of 4,4'-(propane-2,2-diyl)bis((4-azidophenoxy)phenyl), characterized by the following steps: taking 2,2'-bis[4-(4-aminophenoxyphenyl)]propane as raw material, reacting with sodium nitrite under low-temperature acidic conditions to form a diazonium salt, then reacting the diazonium salt with sodium azide under low-temperature conditions, adding an extraction solvent to the reaction solution, then separating the liquid, pouring the extraction solution into the solvent to precipitate the solid, and obtaining the bis-azide compound 4,4'-(propane-2,2-diyl)bis((4-azidophenoxy)phenyl).

[0008] The acidic catalyst is concentrated hydrochloric acid with a mass concentration of 36-38 %, and the mass ratio of 2,2'-bis[4-(4-aminophenoxyphenyl)]propane to concentrated hydrochloric acid is 1:1.0-2.0;

[0009] The mass ratio of the sodium nitrite to 2,2'-bis[4-(4-aminophenoxyphenyl)]propane is 1:1.5-2.5, and the reaction temperature is -5℃-5℃.

[0010] The mass ratio of the sodium azide to 2,2'-bis[4-(4-aminophenoxyphenyl)]propane is 1:1.5-2.5, and the reaction temperature is -10℃-5℃, preferably 0℃-5℃.

[0011] The reaction solvent is water, and the mass ratio of the water to 2,2'-bis[4-(4-aminophenoxyphenyl)]propane is 5-8:1, preferably 5-7:1, and more preferably 5-6:1.

[0012] The sodium nitrite in the form of an aqueous solution is dropped into the aqueous solution of 2,2'-bis[4-(4-aminophenoxyphenyl)]propane containing an acidic catalyst, and the dropping time of the sodium nitrite is 1-3h, preferably 1-2h.

[0013] The sodium azide in the form of an aqueous solution is dropped into the reaction solution, and the dropping time of the sodium azide is 1-6h, preferably 2-4h.

[0014] The extraction solvent is one or two or more of toluene, ethyl acetate, dichloromethane, and dichloroethane, and the mass ratio of the solvent to 2,2'-bis[4-(4-aminophenoxyphenyl)]propane is 2-5:1, preferably 2-4:1, and more preferably 2-3:1.

[0015] The precipitation solvent is one or two or more of weak polar solvents such as n-hexane, n-heptane, n-octane, cyclohexane, and petroleum ether, and the mass ratio of the precipitation solvent to the extraction solvent is 5-10:1, preferably 5-8:1, and more preferably 5-6:1.

[0016] The precipitated solid is suction filtered at 0-5℃ and dried at 20-60℃ to obtain the product.

[0017] The present application has the following beneficial effects:

[0018] The present application provides a synthesis method of 4,4'-(propane-2,2-diyl)bis((4-azidophenoxy)phenyl), which is simple in operation, mild in post-treatment conditions, safer in operation process, high in product purity, and more suitable for industrial production. BRIEF DESCRIPTION OF DRAWINGS

[0019] Figure 1 The figure is a nuclear magnetic hydrogen spectrum identification map;

[0020] Figure 2 The figure is a liquid phase detection map. DETAILED DESCRIPTION

[0021] The present invention will now be described in detail with reference to specific embodiments:

[0022] Example 1

[0023] Add 54g of 2,2'-bis[4-(4-aminophenoxyphenyl)]propane and 320g of water to a 1L three-necked flask, stir, and cool to 5°C. Add 96g of concentrated hydrochloric acid (36% by mass) (this is exothermic and can be added in 4 equal batches). Continue cooling to 0-5°C, and dropwise add a mixed solution of 28.8g of sodium nitrite and 70g of water, maintaining the temperature at 0-5°C, for 2-3 hours (2.5 hours in this case). After the addition is complete, stir the reaction at 0-5°C for 3 hours until the reaction solution becomes clear and transparent. The reaction solution was kept at 0-5℃. A mixed solution of 25.2g sodium azide and 100g water was added dropwise, and the addition was completed in about 4-6 hours (5 hours in this case). After the addition was completed, the mixture was stirred at 0-5℃ for 1 hour. 108g ethyl acetate was added for extraction. The aqueous layer was removed by separation. The extract was added dropwise to 540g n-hexane to precipitate. The mixture was filtered at 0-5℃ and dried under vacuum at 45℃ for 6 hours to obtain 59.6g of white crystals. The yield was 86.72% and the purity was 99.67%.

[0024] The results showed that its structure is 4,4'-(propane-2,2-diyl)bis((4-azidophenoxy)benzene). The 1H NMR spectroscopy identification results are shown below. Figure 1 As shown.

[0025] Subsequently, liquid chromatography was performed for detection, see Figure 2 As shown in the figure, the results indicate that the purity of 4,4'-(propane-2,2-diyl)bis((4-azidophenoxy)benzene) prepared by the present invention can reach over 99%.

[0026] Example 2

[0027] 3L three-necked flask was charged with 2,2'-bis[4-(4-aminophenoxyphenyl)]propane 54 g, water 320 g, and stirring was started. The temperature was lowered to -5°C, and concentrated hydrochloric acid (36% by mass) 54 g was added. The temperature was lowered to -5°C, and a mixture of sodium nitrite 21.6 g and water 70 g was added dropwise at a temperature of -5-5°C over 1-2 h (1.5 h in this case). After the dropwise addition, the reaction was stirred at a temperature of -5-5°C for 3 h. The reaction solution was clear and transparent. The temperature of the reaction solution was lowered to -5-5°C, and a mixture of sodium azide 36 g and water 100 g was added dropwise at a temperature of 0-5°C over 1-2 h (1.5 h in this case). After the dropwise addition, the reaction was stirred at a temperature of 0-5°C for 1 h. Ethyl acetate 270 g was added to extract the reaction solution. The water layer was removed by separation, and the extract was added dropwise to n-hexane 2700 g to precipitate the product. The precipitate was collected by filtration at a temperature of 0-5°C, and dried at 45°C under reduced pressure for 6 h to obtain a white crystalline product 50.3 g (yield: 73.2%, 99.52%). The white product was identified by1H NMR and liquid chromatography. The results showed that the structure of the product was 4,4'-(propane-2,2-diyl)bis((4-azidophenoxy)benzene).

[0028] Example 3

[0029] 2L three-necked flask was charged with 2,2'-bis[4-(4-aminophenoxyphenyl)]propane 54 g, water 320 g, and stirring was started. The temperature was lowered to -5°C, and concentrated hydrochloric acid (36% by mass) 54 g was added. The temperature was lowered to -5°C, and a mixture of sodium nitrite 21.6 g and water 70 g was added dropwise at a temperature of -5-5°C over 1-2 h (1.5 h in this case). After the dropwise addition, the reaction was stirred at a temperature of -5-5°C for 3 h. The reaction solution was clear and transparent. The temperature of the reaction solution was lowered to -5-5°C, and a mixture of sodium azide 36 g and water 100 g was added dropwise at a temperature of 0-5°C over 1-2 h (1.5 h in this case). After the dropwise addition, the reaction was stirred at a temperature of 0-5°C for 1 h. Ethyl acetate 270 g was added to extract the reaction solution. The water layer was removed by separation, and the extract was added dropwise to n-hexane 2700 g to precipitate the product. The precipitate was collected by filtration at a temperature of 0-5°C, and dried at 45°C under reduced pressure for 6 h to obtain a white crystalline product 50.3 g (yield: 73.2%, 99.52%). The white product was identified by1H NMR and liquid chromatography. The results showed that the structure of the product was 4,4'-(propane-2,2-diyl)bis((4-azidophenoxy)benzene).

[0030] Examples 4-8

[0031] Examples 4-8 were obtained according to the following table. The amount of 2,2'-bis[4-(4-aminophenoxyphenyl)]propane used was 54 g, and the differences from Example 1 are shown in the table. The conditions and procedures were the same as in Example 1, except that different extraction solvents and precipitating solvents were used.

[0032] Group Extraction solvent Precipitation solvent Product weight g Yield Purity Example 4 Methylene chloride 108 g n-Hexane 540 g 56.9 82.85％ 99.65％ Example 5 Dichloroethane 108 g n-Heptane 540 g 56.09 81.64％ 99.76％ Example 6 Toluene 162 g Petroleum ether 810 g 55.4 80.65％ 99.19％ Example 7 Toluene 108 g Petroleum ether 540 g 54.2 78.89％ 99.47％ Example 8 Ethyl acetate 216 n-Octane 1296 g 53.9 78.45％ 99.37％

[0033] Comparative Example 1

[0034] Into a 1L three-necked flask was added 2,2'-bis[4-(4-aminophenoxyphenyl)]propane 54 g, water 320 g, and stirring, and the temperature was lowered to 5°C. Concentrated hydrochloric acid with a mass concentration of 36% 96 g was added (exothermic phenomenon, and the hydrochloric acid can be added in four batches), and the temperature was lowered to 0-5°C. A mixture of 28.8 g of sodium nitrite and 70 g of water was added dropwise, and the temperature was controlled at 0-5°C, and the dropwise addition was completed in 2-3 h (2.5 h in this case). After the dropwise addition was completed, the reaction was stirred at 0-5°C for 3 h, and the reaction solution was clear and transparent. The temperature of the reaction solution was 0-5°C, and a mixture of 25.2 g of sodium azide and 100 g of water was added dropwise, and the temperature was controlled at 0-5°C, and the dropwise addition was completed in about 4-6 h (5 h in this case), and the reaction was stirred at 0-5°C for 1 h after the dropwise addition was completed. Ethyl acetate 108 g was added for extraction, and the aqueous layer was removed by liquid-liquid separation. The extraction solution was added dropwise into 540 g of methyl tert-butyl ether to precipitate, and the precipitate was filtered at 0-5°C, and dried at 45°C under vacuum for 6 h to obtain 26.6 g of white crystals, with a yield of 38.7% and a purity of 99.05%. The white solid obtained was subjected to nuclear magnetic resonance hydrogen spectrum identification and liquid chromatography detection, and the results showed that the structure was 4,4'-(propane-2,2-diyl)bis((4-azidophenoxy)phenyl).

[0035] Comparative Examples 2-5

[0036] Comparative Examples 2-5 were obtained according to the following table, and the amount of raw material 2,2'-bis[4-(4-aminophenoxyphenyl)]propane was 54 g. The differences between Comparative Example 1 and Comparative Examples 2-5 are shown in the table below, and the contents not mentioned in the table were kept the same as in Comparative Example 1 (process and conditions). Different extraction solvents and precipitation solvents were used.

[0037]

[0038] As can be seen from the examples and Comparative Examples 1-6, when the precipitation solvent is replaced with an ether solvent with slightly higher polarity and better solubility, the product yield is greatly reduced, and the purity changes little.

Claims

1. A method for synthesizing 4,4'-(propane-2,2-diyl)bis((4-azidophenoxy)benzene), comprising using 2,2'-bis[4-(4-aminophenoxyphenyl)]propane as a raw material, reacting it with sodium nitrite in the presence of an acidic catalyst to form a diazonium salt, and then reacting the diazonium salt with sodium azide to generate 4,4'-(propane-2,2-diyl)bis((4-azidophenoxy)benzene); characterized in that: After the reaction, an extraction solvent is added to the reaction solution, and then the mixture is separated. The solution obtained from the extraction is added to a precipitation solvent to precipitate a solid, thus obtaining the diazid compound 4,4'-(propane-2,2-diyl)bis((4-azidophenoxy)benzene); the precipitation solvent is one or more of n-hexane, n-heptane, n-octane, and petroleum ether, and the extraction solvent is one or more of toluene, ethyl acetate, dichloromethane, and dichloroethane.

2. The synthesis method according to claim 1, characterized in that, The acidic catalyst is concentrated hydrochloric acid with a mass concentration of 36-38%, and the mass ratio of 2,2'-bis[4-(4-aminophenoxyphenyl)]propane to concentrated hydrochloric acid is 1:1.0-2.0; The mass ratio of sodium nitrite to 2,2'-bis[4-(4-aminophenoxyphenyl)]propane is 1:1.5-2.5, and the reaction temperature is -5℃ to 5℃.

3. The synthesis method according to claim 1, characterized in that, The mass ratio of sodium azide to 2,2'-bis[4-(4-aminophenoxyphenyl)]propane is 1:1.5-2.5, and the reaction temperature is -10℃ to 5℃.

4. The synthesis method according to claim 1 or 2, characterized in that: The reaction solvent is water, and its mass ratio with 2,2'-bis[4-(4-aminophenoxyphenyl)]propane is 5-8:

1.

5. The synthesis method according to claim 1 or 2, characterized in that: Sodium nitrite is added dropwise in the form of an aqueous solution to an aqueous solution of 2,2'-bis[4-(4-aminophenoxyphenyl)]propane containing an acidic catalyst, and the addition time of sodium nitrite is 1-3 hours.

6. The synthesis method according to claim 1 or 3, characterized in that: Sodium azide is added dropwise to the reaction solution in the form of an aqueous solution over a period of 1-6 hours.

7. The synthesis method according to claim 1, characterized in that: The mass ratio of the extraction solvent to 2,2'-bis[4-(4-aminophenoxyphenyl)]propane is 2-5:

1.

8. The synthesis method according to claim 1, characterized in that: The mass ratio of the precipitation solvent to the extraction solvent is 5-10:

1.

9. The synthesis method according to claim 1, characterized in that: The precipitated solid was filtered at 0-5℃ and dried at 20-60℃ to obtain the product.

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