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CN-119569659-B - Synthesis of 5-chloro-2, 4-diphenylpyrimidine

CN119569659BCN 119569659 BCN119569659 BCN 119569659BCN-119569659-B

Abstract

The invention relates to the technical field of organic chemistry, and particularly discloses a synthesis method of 5-chloro-2, 4-diphenyl pyrimidine, which comprises the steps of dissolving 5-amino-2, 4-diphenyl pyrimidine in a mixed solution of an organic solvent and water, adding acid, stirring, cooling, adding nitrite, stirring to form a first reaction system, then dropwise adding the first reaction system into an acidic salt solution of chloride to form a second reaction system, and reacting to obtain 5-chloro-2, 4-diphenyl pyrimidine. The yield and purity of the 5-chloro-2, 4-diphenyl pyrimidine are obviously improved, the performance of an organic electronic device constructed based on the organic light emitting technology is further optimized, and the method can be applied to the fields of display, illumination, optoelectronics and the like.

Inventors

  • HUANG JIALIANG
  • CHENG CHUNWEN
  • GUO CHAO
  • MA HONGBIN
  • ZHU YU
  • Ding Zongcang

Assignees

  • 奥盖尼克材料(苏州)有限公司
  • 江苏南大光电材料股份有限公司

Dates

Publication Date
20260512
Application Date
20241213

Claims (18)

  1. 1. The synthesis method of the 5-chloro-2, 4-diphenyl pyrimidine is characterized by comprising the following steps of: s1, adding 5-amino-2, 4-dichloropyrimidine, phenylboric acid, potassium carbonate and bis-triphenylphosphine palladium dichloride into a mixed solution of an organic solvent and water, and reacting under an inert gas atmosphere to obtain 5-amino-2, 4-diphenyl pyrimidine; S2, dissolving 5-amino-2, 4-diphenyl pyrimidine in a mixed solution of an organic solvent and water, adding acid, stirring, cooling, adding nitrite, stirring to form a first reaction system, and then dropwise adding the first reaction system into an acidic salt solution of chloride to form a second reaction system for reaction to obtain 5-chloro-2, 4-diphenyl pyrimidine; ; In the step S1, the feeding molar ratio of the 5-amino-2, 4-dichloropyrimidine to the phenylboronic acid is (142.5-162.5) (452.5-462.5), the feeding molar ratio of the potassium carbonate to the ditriphenylphosphorous palladium dichloride is (452.5-462.5) (2.5-3.5), the organic solvent is selected from one or a mixture of DMF, toluene, xylene, acetonitrile, acetic acid, NMP, alcohols and methylene dichloride, the inert gas atmosphere is one or a mixture of argon and nitrogen, and the reaction temperature is 60-100 ℃; In the step S2, the feeding molar ratio of the 5-amino-2, 4-diphenyl pyrimidine to the nitrite is (505-910) (555-1110), the feeding molar ratio of the acid to the nitrite is (2020-4040) (555-1110), the acid is selected from one or a mixture of hydrochloric acid, sulfuric acid and nitric acid, the nitrite is sodium nitrite, the acidic salt solution of the chloride is acidic cuprous chloride solution, the reaction temperature of the first reaction system is-10-0 ℃, and the reaction temperature of the second reaction system is 60-80 ℃.
  2. 2. The method for synthesizing 5-chloro-2, 4-diphenylpyrimidine according to claim 1, wherein the temperature of the reaction in step S1 is 80 ℃.
  3. 3. The method for synthesizing 5-chloro-2, 4-diphenylpyrimidine according to claim 1, wherein the reaction temperature of the first reaction system in step S2 is-5 ℃.
  4. 4. The method for synthesizing 5-chloro-2, 4-diphenylpyrimidine according to claim 1, wherein the reaction temperature of the second reaction system in step S2 is 70 ℃.
  5. 5. The method for synthesizing 5-chloro-2, 4-diphenylpyrimidine according to claim 1, wherein in step S2, the amount of 5-amino-2, 4-diphenylpyrimidine added per 1L of the organic solvent is 505-910 mmol.
  6. 6. The method for synthesizing 5-chloro-2, 4-diphenylpyrimidine according to claim 1, wherein in step S2, the amount of 5-amino-2, 4-diphenylpyrimidine added per 1L of the organic solvent is 505mmol.
  7. 7. The method for synthesizing 5-chloro-2, 4-diphenylpyrimidine according to claim 1, wherein in step S2, the amount of acid added per 1L of the organic solvent is 2020-40 mmol.
  8. 8. The method for synthesizing 5-chloro-2, 4-diphenylpyrimidine according to claim 1, wherein the amount of acid added per 1L of the organic solvent in step S2 is 2020mmol.
  9. 9. The method for synthesizing 5-chloro-2, 4-diphenylpyrimidine according to claim 1, wherein in the step S2, the amount of nitrite added in each 1L of the organic solvent is 555-1110 mmol.
  10. 10. The method for synthesizing 5-chloro-2, 4-diphenylpyrimidine according to claim 1, wherein in step S2, the amount of nitrite added per 1L of the organic solvent is 555mmol.
  11. 11. The method for synthesizing 5-chloro-2, 4-diphenylpyrimidine according to claim 1, wherein in step S1, the molar amount of 5-amino-2, 4-dichloropyrimidine added per 1L of the organic solvent is 142.5 to 162.5mmol.
  12. 12. The method for synthesizing 5-chloro-2, 4-diphenylpyrimidine according to claim 1, wherein in step S1, the molar amount of 5-amino-2, 4-dichloropyrimidine charged per 1L of the organic solvent is 152.5mmol.
  13. 13. The method for synthesizing 5-chloro-2, 4-diphenylpyrimidine according to claim 1, wherein in step S1, the molar amount of phenylboronic acid added per 1L of the organic solvent is 452.5-462.5 mmol.
  14. 14. The method for synthesizing 5-chloro-2, 4-diphenylpyrimidine according to claim 1, wherein in step S1, the molar amount of phenylboronic acid added per 1L of the organic solvent is 457.5mmol.
  15. 15. The method for synthesizing 5-chloro-2, 4-diphenylpyrimidine according to claim 1, wherein in step S1, the molar amount of potassium carbonate added per 1L of said organic solvent is 452.5 to 462.5mmol.
  16. 16. The method for synthesizing 5-chloro-2, 4-diphenylpyrimidine according to claim 1, wherein in step S1, the molar amount of potassium carbonate added per 1L of the organic solvent is 457.5mmol.
  17. 17. The method for synthesizing 5-chloro-2, 4-diphenylpyrimidine according to claim 1, wherein in step S1, the molar amount of bis-triphenylphosphine palladium dichloride added per 1L of the organic solvent is 2.5-3.5 mmol.
  18. 18. The method for synthesizing 5-chloro-2, 4-diphenylpyrimidine according to claim 1, wherein in step S1, the molar amount of ditriphenylphosphide dichloride charged per 1L of said organic solvent is 3.0mmol.

Description

Synthesis of 5-chloro-2, 4-diphenylpyrimidine Technical Field The invention relates to the technical field of organic chemistry, and particularly discloses a synthesis method of 5-chloro-2, 4-diphenyl pyrimidine. Background The organic light emitting technology is an electronic control light emitting technology which utilizes an organic material to release energy through electron and hole recombination under the action of an external electric field and radiate the energy in a light form, has the characteristics of simple preparation, low cost, high light emitting efficiency, good flexibility and the like, and is widely applied to the fields of display, illumination, optoelectronics and the like. An organic electronic device constructed based on organic light emitting technology has a structure comprising an anode, a cathode, and an organic material layer interposed therebetween. These organic material layers are often carefully chosen from a range of specific compounds that act as core components of the organic layer and play a decisive role in the performance of the device. For example, KR20190011463A and KR20180041482A each describe in detail an innovative organic electronic device, the organic layer of which is embedded with a specific compound, and 5-chloro-2, 4-diphenylpyrimidine is an essential starting material for the synthesis of this key compound. However, the current methods for synthesizing 5-chloro-2, 4-diphenylpyrimidine have several disadvantages of numerous steps, complex operation, increased production difficulty and cost and reliance on expensive raw materials. For example, patent KR2016065298 reports a synthetic pathway, but this approach suffers from problems of excessive reaction and selective coupling, resulting in low product purity and low synthesis efficiency. In view of the above-mentioned drawbacks of the prior art, the present invention aims to develop a new synthesis method which is more efficient, economical and easy to operate, and which increases the yield and purity of 5-chloro-2, 4-diphenylpyrimidine. Disclosure of Invention In order to solve the above problems, the first aspect of the present invention provides a synthesis method of 5-chloro-2, 4-diphenylpyrimidine, which comprises the following steps: dissolving 5-amino-2, 4-diphenyl pyrimidine in a mixed solution of an organic solvent and water, adding acid, stirring, cooling, adding nitrite, stirring to form a first reaction system, and then dropwise adding the first reaction system into an acidic salt solution of chloride to form a second reaction system for reaction to obtain 5-chloro-2, 4-diphenyl pyrimidine. In some embodiments of the first aspect, the 5-amino-2, 4-diphenylpyrimidine is dosed in an amount of 505 to 910mmol, preferably 505mmol, per 1L of organic solvent. In some embodiments of the first aspect, the amount of 5-amino-2, 4-diphenylpyrimidine added per 1L of organic solvent is 550mmol, in some embodiments of the first aspect, the amount of 5-amino-2, 4-diphenylpyrimidine added per 1L of organic solvent is 600mmol, in some embodiments of the first aspect, the amount of 5-amino-2, 4-diphenylpyrimidine added per 1L of organic solvent is 650mmol, in some embodiments of the first aspect, the amount of 5-amino-2, 4-diphenylpyrimidine added per 1L of organic solvent is 700mmol, in some embodiments of the first aspect, the amount of 5-amino-2, 4-diphenylpyrimidine added per 1L of organic solvent is 750mmol, in some embodiments of the first aspect, the amount of 5-amino-2, 4-diphenylpyrimidine added per 1L of organic solvent is 800mmol, in some embodiments of the first aspect, the amount of 5-amino-2, 4-diphenylpyrimidine added per 1L of organic solvent is 1 mmol, and the amount of 5-2, 4-diphenylpyrimidine added per 1L of the first aspect is 900mmol. In some embodiments of the first aspect, the acid is dosed in an amount of 2020 to 40mmol, preferably 2020mmol, per 1L of organic solvent. In some embodiments of the first aspect, the amount of acid in each 1L of the organic solvent is 2050mmol, in some embodiments of the first aspect, the amount of acid in each 1L of the organic solvent is 2100mmol, in some embodiments of the first aspect, the amount of acid in each 1L of the organic solvent is 2150mmol, in some embodiments of the first aspect, the amount of acid in each 1L of the organic solvent is 2200mmol, in some embodiments of the first aspect, the amount of acid in each 1L of the organic solvent is 2250mmol, in some embodiments of the first aspect, the amount of acid in each 1L of the organic solvent is 2300mmol, in some embodiments of the first aspect, the amount of acid in each 1L of the organic solvent is 235 mmol, in some embodiments of the first aspect, the amount of acid in each 1L of the organic solvent is 26 mmol, in each 1 mmol, in some embodiments of acid in each 1L of the first aspect, the amount of acid in each 1L of the organic solvent is 26 mmol, in each embodiment of the organic solvent is 270