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CN-116836100-B - 2-Aminopyrrole compound and preparation method and application thereof

CN116836100BCN 116836100 BCN116836100 BCN 116836100BCN-116836100-B

Abstract

The application discloses a 2-aminopyrrole compound, a preparation method and application thereof. A 2-aminopyrrole compound, wherein the 2-aminopyrrole compound has a structure shown in a formula I: wherein R 1 and R 2 are independently selected from C 1 ～C 13 alkyl, ester, carboxylic acid, amide, substituted amino, C 1 ～C 13 alkoxy, C 6 ～C 20 aryl, C 2 ～C 20 heteroaryl, substituted C 1 ～C 13 alkyl, substituted C 6 ～C 20 aryl, substituted C 2 ～C 20 heteroaryl. The 2-aminopyrrole compound has various structures, two aryl groups can be highly functionalized, the subsequent coupling and the assembly are convenient, the pyrrolopyrimidine compound has various structures and solid fluorescence property, and the preparation method has the advantages of easily available raw materials, simple method, convenient operation and higher yield.

Inventors

  • BAO HONGLI
  • LI TAIAN
  • YE CHANGQING
  • LI YAJUN
  • ZHU NENGBO

Assignees

  • 闽都创新实验室
  • 中国科学院福建物质结构研究所

Dates

Publication Date
20260512
Application Date
20220324

Claims (9)

  1. 1. The preparation method of the 2-aminopyrrole compound is characterized by comprising the following steps of: (S) reacting a mixture containing an alpha-beta unsaturated imine compound, alkali, an organic solvent and trimethylnitrile silane under an inactive gas to obtain a 2-aminopyrrole compound; The structural formula of the alpha-beta unsaturated imine compound is as follows: ; The 2-aminopyrrole compound has a structure shown in a formula I: A formula I; Wherein R 1 is the same as R 1 , R 2 is the same as R 2 ; R 1 is independently selected from C 6 ～C 20 aryl, C 2 ～C 20 heteroaryl, R 2 is independently selected from C 6 ～C 20 aryl, C 2 ～C 20 heteroaryl; r 3 is independently selected from C 1 ~C 13 alkyl, C 3 ~C 8 cycloalkyl, C 6 ~C 20 aryl, -NO 2 、-CF 3 、-OH、-NH 2 .
  2. 2. The method according to claim 1, wherein in the step (S), the base is at least one selected from the group consisting of potassium carbonate, sodium t-butoxide, potassium fluoride, triethylamine, 1, 8-diazabicyclo [5.4.0] undec-7-ene, 4-dimethylaminopyridine and triethylenediamine.
  3. 3. The method according to claim 1, wherein the organic solvent is at least one selected from acetonitrile, N-dimethylformamide, tetrahydrofuran, N-methylpyrrolidone, and 1, 4-dioxane.
  4. 4. The method according to claim 1, wherein the inert gas is one selected from nitrogen, argon and helium.
  5. 5. The method according to claim 1, wherein the mass to volume ratio of the α - β unsaturated imine compound to the organic solvent is 10 mg/mL to 100 mg/mL.
  6. 6. The method according to claim 1, wherein the mass ratio of the α - β unsaturated imine compound to the base is 1:0.5 to 1:5.
  7. 7. The method according to claim 6, wherein the mass ratio of the α - β unsaturated imine compound to the base is 1:1.5 to 1:2.5.
  8. 8. The method according to claim 1, wherein the mass ratio of the α - β unsaturated imine compound to the trimethylnitrile silane is 1:2 to 1:2.2.
  9. 9. The preparation method according to claim 1, wherein the reaction conditions are as follows: The temperature is 0-100 ℃; The time is 0.5 h-24 h.

Description

2-Aminopyrrole compound and preparation method and application thereof Technical Field The application relates to a 2-aminopyrrole compound, a preparation method and application thereof, belonging to the field of organic synthesis. Background Pyrrole compounds exist widely in animals and plants, and are widely applied to the fields of medicines, natural products and materials. Conjugated aromatic molecules with push-pull electronic structures often have luminescent properties and have wide application in the field of luminescent materials, so that the synthesis method of pyrrole compounds and application research thereof are concerned by organic synthesis chemists. The prior method for preparing pyrrole is rich in 1, by classical organic name reaction Hantzsch pyrrole synthesis method, paal-Knorr pyrrole synthesis method, knorr pyrrole synthesis method and the like, and 2, by utilizing raw material compounds with specific structures such as 1, 3-eneyne, 1, 4-alkynylamine, heterocycle and the like, cyclizing reaction is carried out under certain conditions, so as to construct the pyrrole compound. The former method is mature and is widely applied, but the obtained product pyrrole is of a specific structure. The latter has higher purpose, needs to carry out pre-designed synthesis on the substrate, and the latter has higher efficiency and builds a certain pyrrole molecular structure more directly. The 2-aminopyrrole compound is a compound with an amino cyano group intramolecular push-pull electronic structure, and amino and cyano groups can perform various reactions. Disclosure of Invention According to one aspect of the present application, there is provided a 2-aminopyrrole compound. The compound has two aryl groups which can be connected with various substituents, and is convenient for subsequent coupling and assembly. A 2-aminopyrrole compound, its polymorphs, solvates or salts thereof, the 2-aminopyrrole compound having a structure of formula I: A formula I; wherein R 1 and R 2 are independently selected from C 1~C13 alkyl, ester, carboxylic acid, amide, substituted amino, C 1~C13 alkoxy, C 6~C20 aryl, C 2~C20 heteroaryl, substituted C 1~C13 alkyl, substituted C 6~C20 aryl, substituted C 2~C20 heteroaryl; Preferably, R 1 and R 2 are independently selected from C 1~C7 alkyl, ester, carboxylic acid, amide, substituted amino, C 1~C7 alkoxy, C 6~C10 aryl, C 2~C10 heteroaryl, substituted C 1~C7 alkyl, substituted C 6~C10 aryl, substituted C 2~C10 heteroaryl. Optionally, the substituent of the substituted C 1~C13 alkyl is R a; The R a is selected from at least one of deuterium atom, halogen, C 1~C13 polyfluoroalkyl, C 2~C13 alkenyl, C 2~C13 alkynyl, C 3~C6 cycloalkyl, C 2~C13 heterocyclyl, C 1~C13 oxo alkyl, C 6~C13 oxo aryl, boric acid group, silane group, C 1~C13 alkyl phosphine, C 6~C13 aryl phosphine, -CN and-NO 2. Optionally, the substituent of the substituted C 6~C20 aryl is R b; The R b is selected from at least one of deuterium atom, halogen, C 1~C13 alkyl, C 1~C13 polyfluoroalkyl, C 2~C13 alkenyl, C 2~C13 alkynyl, C 3~C6 cycloalkyl, C 2~C20 heteroaryl, C 2~C20 heterocyclic group, C 1~C13 oxo alkyl, C 6~C20 oxo aryl, boric acid group, silane group, C 1~C13 alkyl phosphine, C 6~C20 aryl phosphine, thioalkyl, sulfonyl, -CN and-NO 2. Optionally, the substituent of the substituted C 2~C20 heteroaryl is R c; the R c is independently selected from at least one of deuterium atom, halogen, C 1~C13 alkyl, C 1~C13 polyfluoroalkyl, C 2~C13 alkenyl, C 2~C13 alkynyl, C 3~C6 cycloalkyl, C 2~C20 heterocyclyl, C 1~C13 oxo alkyl, C 6~C20 oxo aryl, boric acid group, silane group, C 1~C13 alkylphosphine, C 6~C20 arylphosphine, -CN, and-NO 2. Alternatively, the structural formula of the compound represented by formula I is selected from the following compounds: 。 according to a further aspect of the present application, there is provided a process for the preparation of 2-aminopyrroles. The preparation method is a method for preparing 2-aminopyrrole from alpha-beta unsaturated imine. The method is simple, the pyrrole is synthesized from imine in one step, and the yield is high. The product treatment method directly adds water to separate out and filter, and column chromatography is not needed. A preparation method of 2-aminopyrrole compounds comprises the following steps: (S) reacting a mixture containing an alpha-beta unsaturated imine compound, a base, an organic solvent and trimethylnitrile silane under an inert gas to obtain a 2-aminopyrrole compound , Or (b) (A) The mixture containing alpha-beta unsaturated cyano sulfonamide, alkali, organic solvent and trimethylnitrile silane is reacted under the condition of inactive gas to obtain the 2-aminopyrrole compound ; Wherein R 1 is the same as R 1, R 2 is the same as R 2; R 3 is independently selected from C 1~C13 alkyl, C 3~C8 cycloalkyl, C 6~C20 aryl, -NO 2、-CF3、-OH、-NH2; optionally, C 1~C13 alkyl is unsubstituted or substituted with one or even more R A substituents, sa