2-aminopyrrole compound, and preparation method and application thereof

Abstract

The application discloses a 2-amino pyrrole compound and a preparation method and application thereof. The 2-amino pyrrole compound has a structure shown in formula I: wherein R1 and R2 are independently selected from C1-C 13 alkyl, ester, carboxylic acid, amide, substituted amino, C1-C 13 alkoxy, C6-C 20 aryl, C2-C 20 heteroaryl, substituted C1-C 13 alkyl, substituted C6-C 20 aryl, substituted C2-C 20 heteroaryl. The 2-amino pyrrole compound has a diversified structure, can be highly functionalized with two aryl groups, and is convenient for subsequent coupling and assembly; the pyrrolopyrimidine compound has a diversified structure and solid fluorescent property; and the preparation method has the advantages of easy raw material, simple method, convenient operation and high yield.

Description

Technical Field

[0001] This application relates to a 2-aminopyrrole compound, its preparation method, and its application, belonging to the field of organic synthesis. Background Technology

[0002] Pyrrole compounds are widely found in plants and animals and have extensive applications in pharmaceuticals, natural products, and materials. Conjugated aromatic molecules with push-pull electron structures often exhibit luminescent properties and have wide applications in luminescent materials. Therefore, the synthesis methods and applications of pyrrole compounds have attracted considerable attention from organic synthetic chemists. Currently, there are several routes for preparing pyrrole: 1. Through classic organic named reaction methods such as the Hantzsch pyrrole synthesis, Paal-Knorr pyrrole synthesis, and Knorr pyrrole synthesis; 2. Using specific structural starting compounds such as 1,3-enyne, 1,4-acetylenes, and heterocycles, cyclization reactions are carried out under certain conditions to construct pyrrole compounds. The former method is mature and widely used, but the resulting pyrrole has a specific structure. The latter method is more targeted, requiring pre-designed substrate synthesis, and often has higher efficiency and more directly constructs specific pyrrole molecular structures.

[0003] 2-Aminopyrrole compounds are a class of compounds with an intramolecular push-pull electron structure of aminocyano groups, and the amino and cyano groups can undergo a wide variety of reactions. Summary of the Invention

[0004] According to one aspect of this application, a 2-aminopyrrole compound is provided.

[0005] The compound has two aryl groups that can be linked to various substituents, which also facilitates subsequent coupling and assembly.

[0006] A 2-aminopyrrole compound, and its polymorphs, solvates, or salts thereof, said 2-aminopyrrole compound having the structure shown in Formula I:

[0007]

[0008] Formula I;

[0009] Among them, R1 and R2 are independently selected from C1 to C2. 13 Alkyl, ester, carboxylic acid, amide, substituted amino, C1~C 13 Alkoxy, C6~C 20 Aryl, C2~C 20 heteroaryl, substituted C1~C 13 Alkyl, substituted C6~C 20 Aryl, substituted C2~C 20 Mixed aromatics;

[0010] Preferably, R1 and R2 are independently selected from C1-C7 alkyl, ester, carboxylic acid, amide, substituted amino, C1-C7 alkoxy, C6-C 10 Aryl, C2~C 10 Heteroaryl, substituted C1~C7 alkyl, substituted C6~C 10 Aryl, substituted C2~C 10 Mixed aromatic compounds.

[0011] Alternatively, C1~C can be replaced. 13 The alkyl substituent is R. a ;

[0012] The R a Selected from deuterium atoms, halogens, C1~C 13 Polyfluoroalkyl, C2~C 13 alkenyl, C2~C 13 alkynyl, C3~C6 cycloalkyl, C2~C 13 Heterocyclic groups, C1~C 13 Oxyalkyl, C6~C 13 Oxyaryl, borate, silyl, C1~C 13 Alkylphosphine, C6~C 13 At least one of arylphosphine, -CN, and -NO2.

[0013] Alternatively, C6~C can be replaced. 20 The substituent of the aryl group is R. b ;

[0014] The R b Selected from deuterium atoms, halogens, C1~C 13 Alkyl, C1~C 13 Polyfluoroalkyl, C2~C 13 alkenyl, C2~C 13 alkynyl, C3~C6 cycloalkyl, C2~C 20 heteroaryl, C2~C 20 Heterocyclic groups, C1~C 13 Oxyalkyl, C6~C 20 Oxyaryl, borate, silyl, C1~C 13 Alkylphosphine, C6~C 20 At least one of arylphosphine, thioalkyl, sulfone, -CN, and -NO2.

[0015] Alternatively, C2~C can be replaced. 20 The substituent of the heteroaryl group is R. c ;

[0016] The R c Independently selected from deuterium atoms, halogens, C1~C 13Alkyl, C1~C 13 Polyfluoroalkyl, C2~C 13 alkenyl, C2~C 13 alkynyl, C3~C6 cycloalkyl, C2~C 20 Heterocyclic groups, C1~C 13 Oxyalkyl, C6~C 20 Oxyaryl, borate, silyl, C1~C 13 Alkylphosphine, C6~C 20 At least one of arylphosphine, -CN, and -NO2.

[0017] Alternatively, the structural formula of the compound represented by Formula I is selected from the following compounds:

[0018] .

[0019] According to another aspect of this application, a method for preparing 2-aminopyrrole compounds is provided. This method involves preparing 2-aminopyrrole from α-β-unsaturated imines. The method is simple, synthesizing pyrrole from imines in a single step with high yield. The product is directly precipitated by adding water and filtering, eliminating the need for column chromatography.

[0020] A method for preparing a 2-aminopyrrole compound includes the following steps:

[0021] (S) A mixture containing an α-β-unsaturated imine compound, a base, an organic solvent, and a trimethylnitrile silane is reacted under an inert gas to give a 2-aminopyrrole compound.

[0022] ,

[0023] or

[0024] (A) A mixture containing α-β-unsaturated cyanosulfonamide, a base, an organic solvent, and trimethylnitrile silane is reacted under an inert gas to give a 2-aminopyrrole compound.

[0025] ;

[0026] Among them, R 1 Same as R1; R 2 Same as R2;

[0027] R3 is independently selected from C1~C 13 Alkyl, C3~C8 cycloalkyl, C6~C 20 Aryl, -NO2, -CF3, -OH, -NH2;

[0028] Optionally, C1~C 13 The alkyl group is not substituted or is replaced by one or more R groups. ASubstituent substitution, the R A Selected from halogens, cycloalkyl groups, aryl groups, -OH, -NH2, -CN, -NO2, -CF, and -CO2H;

[0029] The C3~C8 aryl groups are either not replaced or replaced by one or more R groups. B Substituent substitution, the R B Selected from halogens, alkyl groups, cycloalkyl groups, -OH, -NH2, -CN, -NO2, -CF, and -CO2H.

[0030] The above-mentioned 2-aminopyrrole compounds are selected from any of the 2-aminopyrrole compounds described above.

[0031] Optionally, the α-β-unsaturated cyanosulfonamide is obtained by addition reaction of an α-β-unsaturated imine compound with a 1,2-cyano group.

[0032] Optionally, in step (S), the base is selected from at least one of potassium carbonate, sodium carbonate, sodium tert-butoxide, potassium fluoride, triethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 4-dimethylaminopyridine, and triethylenediamine.

[0033] Optionally, the organic solvent is selected from at least one of acetonitrile, N,N-dimethylformamide, tetrahydrofuran, N-methylpyrrolidone, and 1,4-dioxane.

[0034] Optionally, the inactive gas is selected from nitrogen, argon, and helium.

[0035] Optionally, the mass-to-volume ratio of the α-β unsaturated imine compound to the organic solvent is 10 mg / mL to 100 mg / mL.

[0036] Optionally, the molar ratio of the α-β unsaturated imine compound to the base is 1:0.5 to 1:5;

[0037] Preferably, the molar ratio of the α-β unsaturated imine compound to the base is 1:1.5 to 1:2.5.

[0038] Preferably, the molar ratio of the α-β unsaturated imine compound to the trimethylnitrile silane is 1:2 to 1:2.2.

[0039] Alternatively, the reaction conditions are as follows:

[0040] Temperature range: 0℃ to 100℃;

[0041] The time ranges from 0.5 h to 24 h.

[0042] Optionally, in step (A), the base is selected from at least one of potassium carbonate, sodium carbonate, sodium tert-butoxide, potassium fluoride, triethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 4-dimethylaminopyridine, and triethylenediamine.

[0043] Optionally, the organic solvent is selected from at least one of acetonitrile, N,N-dimethylformamide, tetrahydrofuran, N-methylpyrrolidone, and 1,4-dioxane.

[0044] Optionally, the inactive gas is selected from nitrogen, argon, and helium.

[0045] Optionally, the mass-to-volume ratio of the α-β-unsaturated cyanosulfonamide to the organic solvent is 11 mg / mL to 110 mg / mL.

[0046] Optionally, the molar ratio of the α-β unsaturated cyanosulfonamide to the base is 1:0.5 to 1:5;

[0047] Preferably, the molar ratio of the α-β unsaturated cyanosulfonamide to the base is 1:1.5 to 1:2.5.

[0048] Optionally, the molar ratio of the α-β-unsaturated cyanosulfonamide to the trimethylnitrile silane is 1:0.1 to 1:5;

[0049] Preferably, the molar ratio of the α-β unsaturated cyanosulfonamide to the trimethylnitrile silane is 1:0.5 to 1:1.3.

[0050] Alternatively, the reaction conditions are as follows:

[0051] Temperature range: 0℃ to 100℃;

[0052] The time ranges from 0.5 h to 24 h.

[0053] According to a third aspect of this application, a pyrrolopyrimidine compound is provided.

[0054] The 2-aminopyrrole compounds described above and / or the pyrrolopyrimidine compounds prepared by the 2-aminopyrrole compounds obtained by the preparation method described above, wherein the pyrrolopyrimidine compounds have the structure shown in Formula II:

[0055]

[0056] Formula II;

[0057] R4, R5, and R6 are independently selected from C1 to C2. 13 Alkyl, C6~C 20 Aryl, C2~C 20heteroaryl, substituted C1~C 13 Alkyl, substituted C6~C 20 Aryl, substituted C2~C 20 Mixed aromatics;

[0058] Preferably, R4, R5, and R6 are independently selected from C1-C7 alkyl groups and C6-C6 alkyl groups. 10 Aryl, C2~C 10 Heteroaryl, substituted C1~C7 alkyl, substituted C6~C 10 Aryl, substituted C2~C 10 Mixed aromatic compounds.

[0059] Alternatively, C1~C can be replaced. 13 The alkyl substituent is R. d ;

[0060] The R d Independently selected from deuterium atoms, halogens, C1~C 13 Polyfluoroalkyl, C2~C 13 alkenyl, C2~C 13 alkynyl, C3~C6 cycloalkyl, C2~C 13 Heterocyclic groups, C1~C 13 Oxyalkyl, C6~C 13 Oxyaryl, borate, silyl, C1~C 13 Alkylphosphine, C6~C 13 At least one of arylphosphine, -CN, and -NO2.

[0061] Alternatively, C6~C can be replaced. 20 The substituent of the aryl group is R. e ;

[0062] The R e Selected from deuterium atoms, halogens, C1~C 13 Alkyl, C1~C 13 Polyfluoroalkyl, C2~C 13 alkenyl, C2~C 13 alkynyl, C3~C6 cycloalkyl, C2~C 20 heteroaryl, C2~C 20 Heterocyclic groups, C1~C 13 Oxyalkyl, C6~C 20 Oxyaryl, borate, silyl, C1~C 13 Alkylphosphine, C6~C 20 At least one of arylphosphine, thioalkyl, sulfone, -CN, and -NO2.

[0063] Alternatively, C2~C can be replaced. 20 The substituent of the heteroaryl group is R. f ;

[0064] The R f Independently selected from deuterium atoms, halogens, C1~C 13 Alkyl, C1~C 13 Polyfluoroalkyl, C2~C 13 alkenyl, C2~C 13 alkynyl, C3~C6 cycloalkyl, C2~C 20 Heterocyclic groups, C1~C 13 Oxyalkyl, C6~C 20 Oxyaryl, borate, silyl, C1~C 13 Alkylphosphine, C6~C 20 At least one of arylphosphine, -CN, and -NO2.

[0065] Alternatively, the structural formula of the compound represented by Formula II is selected from the following compounds:

[0066] .

[0067] Optionally, the above-mentioned pyrrolopyrimidine compounds are prepared from the 2-aminopyrrole compounds described above and / or the 2-aminopyrrole compounds obtained by the preparation method described above.

[0068] According to a fourth aspect of this application, a method for preparing pyrrolopyrimidine compounds is provided.

[0069] A method for preparing a pyrrolopyrimidine compound includes the following steps:

[0070] A mixture containing 2-aminopyrrole compounds, diketones, and solvents is reacted under an inert gas to yield pyrrolopyrimidine compounds.

[0071] .

[0072] Optionally, the diketone is selected from 2,6-dimethyl-3,5-heptadecane and acetylacetone.

[0073] Optionally, the solvent is selected from glacial acetic acid, a mixture of glacial acetic acid and water.

[0074] Optionally, the volume ratio of the mixture of glacial acetic acid and water is 1:1.

[0075] Optionally, the inactive gas is selected from nitrogen, argon, and helium.

[0076] Optionally, the mass ratio of 2-aminopyrrole compound to diketone is 1:1 to 1:10.

[0077] Alternatively, the reaction conditions are as follows:

[0078] The temperature ranges from 15 ℃ to 125 ℃;

[0079] The time ranges from 0.5 h to 48 h.

[0080] According to a fifth aspect of this application, an application of a 2-aminopyrrole compound is provided.

[0081] The application of the 2-aminopyrrole compounds described above and / or the 2-aminopyrrole compounds obtained by the preparation method described above in the preparation of pyrrolopyrimidine compounds.

[0082] According to the sixth aspect of this application, an application of a pyrrolopyrimidine compound is provided.

[0083] The pyrrolopyrimidine compounds described above and / or the pyrrolopyrimidine compounds prepared by the methods described above may be used as fluorescent molecules or in pharmaceuticals.

[0084] In this application, C1~C 13 C6~C 20 "etc." refers to the number of carbon atoms contained in the group.

[0085] In this application, the term "alkyl" refers to a group formed by the loss of any one hydrogen atom from an alkane molecule.

[0086] In this application, the term "alkene" refers to a group formed by the loss of any one hydrogen atom from an alkene compound molecule.

[0087] In this application, the term "alkynyl" refers to a group formed by the loss of any one hydrogen atom from a molecule of an alkyne compound.

[0088] In this application, the term "aryl" refers to a group formed by the loss of a hydrogen atom from an aromatic ring in an aromatic compound molecule; for example, p-tolyl formed by the loss of a hydrogen atom at the para-position of the methyl group on the benzene ring of toluene.

[0089] In this application, the term "halogen" refers to at least one of fluorine, chlorine, bromine, and iodine.

[0090] In this application, the term "heterocyclic group" refers to a group formed by losing any one hydrogen atom from an organic compound containing a heterocyclic structure in its molecule. In addition to carbon atoms, the atoms constituting the ring contain at least one heteroatom, including nitrogen, sulfur, and oxygen atoms.

[0091] In this application, the term "polyfluoroalkyl" refers to a group formed by replacing any number of hydrogen atoms on an alkyl compound molecule with fluorine atoms.

[0092] In this application, the term "substituted amino" refers to a group formed by replacing any one hydrogen atom on an amino compound molecule.

[0093] In this application, the term "substituted alkyl" refers to a group formed by replacing any one hydrogen atom on an alkyl compound molecule.

[0094] In this application, the term "substituted aryl" refers to a group formed by replacing any one hydrogen atom on an aryl compound molecule.

[0095] In this application, the term "substituted heteroaryl" refers to a group formed by replacing any one hydrogen atom on a heteroaryl compound molecule.

[0096] In this application, the term "cycloalkyl" refers to a group formed by the loss of any one hydrogen atom from a cycloalkane molecule.

[0097] In this application, the term "oxoalkyl" refers to a group formed by replacing any hydrogen atom on an alkane molecule with an oxo group.

[0098] In this application, the terms "ester group," "carboxylic acid group," and "amide group" refer to the following structural formulas:

[0099] ;

[0100] Among them, when "M" is "O", it is an "ester group"; when "M" is "OH", it is a "carboxylic acid group"; and when "M" is "NH", it is an "amide group".

[0101] The compounds described above and their NMR data are shown in the table below:

[0102]

[0103] The beneficial effects that this application can produce include:

[0104] 1) The 2-aminopyrrole compounds provided in this application have diverse structures, with two aryl groups that can be highly functionalized, and are also convenient for subsequent coupling and assembly.

[0105] 2) The pyrrolopyrimidine compounds provided in this application have diverse structures and solid-state fluorescence properties, making them a very useful class of fluorescent molecules.

[0106] 3) The preparation method provided in this application has the advantages of readily available raw materials and simple method; the one-step synthesis of pyrrole from imine has the advantage of high yield; the product processing method can directly add water to precipitate and filter, without the need for column chromatography, thus making the operation more convenient. Detailed Implementation

[0107] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.

[0108] Unless otherwise specified, all raw materials used in the embodiments of this application were purchased through commercial channels.

[0109] The analysis method in the embodiments of this application is as follows:

[0110] Nuclear magnetic resonance analysis was performed using a Bruker-BioSpin AVANCE III HD and a JEOL ECZ600R.

[0111] The yield calculation in the embodiments of this application is as follows:

[0112] In the embodiments of this application, the yield of 2-aminopyrrole compounds = mass of actual product / mass of theoretical product × 100%;

[0113] Yield of pyrrolopyrimidine compounds = (mass of actual product / mass of theoretical product) × 100%.

[0114] Synthesis of 2-aminopyrrole compounds

[0115] Example 1

[0116]

[0117] 180 mg of bisphenyl α-β-unsaturated p-toluenesulfonylimide and 138 mg of potassium carbonate were added to a reaction tube, and nitrogen gas was introduced. Then, 4 mL of acetonitrile was added as a solvent, followed by 55 μL of TMSCN (trimethylacrylonitrile silane). After reacting at 70 °C for 12 hours, the reaction solution was evaporated to dryness and purified by column chromatography to give compound 1 (56 mg, yield 43%).

[0118] The NMR detection data of the product are as follows:

[0119] 1 H NMR (600 MHz, DMSO- d 6) δ 11.40 (s, 1H), 7.68 (d, J= 7.5 Hz, 2H),7.49 – 7.41 (m, 4H), 7.37 (t, J = 7.7 Hz, 2H), 7.27 (t, J = 7.4 Hz, 1H), 7.18 (t, J = 7.3 Hz, 1H), 4.84 (s, 2H).

[0120] Example 2

[0121]

[0122] 160 mg of 4-chlorobenzene-phenyl α-β-unsaturated methanesulfonamide and 106 mg of sodium carbonate were added to a reaction tube, and nitrogen gas was introduced. Then, 4 mL of N,N-dimethylformamide (DMF) was added as a solvent, followed by 55 μL of TMSCN. After reacting at 20 °C for 1 hour, the reaction solution was evaporated to dryness and purified by column chromatography to give compound 6 (25 mg, yield 17%).

[0123] The NMR detection data of the product are as follows:

[0124] 1 H NMR (400 MHz, DMSO- d 6) δ 11.46 (s, 1H), 7.71 (d, J = 7.7 Hz, 2H),7.59 – 7.39 (m, 6H), 7.32 (t, J = 7.3 Hz, 1H), 4.97 (s, 2H).

[0125] Example 3

[0126]

[0127] 161 mg of thiophene-phenyl α-β-unsaturated nitrosulfonamide and 80 mg of sodium tert-butoxide were added to a reaction tube, and nitrogen gas was introduced. Then, 4 mL of tetrahydrofuran (THF) was added as a solvent, followed by 55 μL of TMSCN. After reacting at 60 °C for 2 hours, the reaction solution was evaporated to dryness and purified by column chromatography to give compound 17 (21 mg, yield 16%).

[0128] The NMR detection data of the product are as follows:

[0129] 1 H NMR (400 MHz, DMSO- d 6) δ 11.5 (s, 1H), 7.7 (d, J= 7.0 Hz, 2H), 7.5 –7.4 (m, 3H), 7.4 – 7.3 (m, 1H), 7.2 (s, 1H), 7.1 (s, 1H), 5.0 (s, 2H).

[0130] Example 4

[0131]

[0132] 218 mg of pyrene-phenyl α-β-unsaturated cyclopropylsulfonamide and 58 mg of potassium fluoride (KF) were added to a reaction tube, and nitrogen gas was introduced. Then, 4 ml of toluene was added as a solvent, followed by 55 μL of TMSCN. After reacting at 50 °C for 4 hours, the reaction solution was evaporated to dryness and purified by column chromatography to give compound 16 (71 mg, yield 37%).

[0133] The NMR detection data of the product are as follows:

[0134] 1 H NMR (400 MHz, DMSO- d 6) δ 11.64 (s, 1H), 8.35 (d, J = 7.9 Hz, 1H),8.33 – 8.28 (m, 2H), 8.24 – 8.18 (m, 3H), 8.14 – 8.07 (m, 2H), 8.05 (d, J = 7.9Hz, 1H), 7.82 (d, J = 7.5 Hz, 2H), 7.51 (t, J = 7.8 Hz, 2H), 7.34 (t, J = 7.4 Hz, 1H), 4.73 (s, 2H).

[0135] Example 5

[0136]

[0137] 204 mg of 4-trifluoromethyl-phenyl α-β-unsaturated trifluoromethylsulfonamide imide and 101 mg of triethylamine (TEA) were added to a reaction tube, and nitrogen gas was introduced. Then, 4 mL of N-methylpyrrolidone (NMP) was added as a solvent, and 55 μL of TMSCN was added. After reacting at 90 °C for 8 hours, the reaction solution was evaporated to dryness and column chromatography was performed to give compound 7 (47 mg, yield 29%).

[0138] The NMR detection data of the product are as follows:

[0139] 1H NMR (400 MHz, DMSO- d 6) δ 11.53 (s, 1H), 7.79 – 7.67 (m, 6H), 7.49(t, J = 7.8 Hz, 2H), 7.34 (t, J = 7.4 Hz, 1H), 5.16 (s, 2H).

[0140] Example 6

[0141]

[0142] 242 mg of bis(4-methylthiophenyl)α-β-p-nitrobenzenesulfonamide and 152 mg of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) were added to a reaction tube, and nitrogen gas was introduced. Then, 4 mL of 1,4-dioxane was added as a solvent, followed by 55 μL of TMSCN. After reacting at 100 °C for 10 hours, the reaction solution was evaporated to dryness and column chromatography was performed to give compound 31 (49 mg, yield 28%).

[0143] The NMR detection data of the product are as follows:

[0144] 1 H NMR (400 MHz, DMSO- d 6) δ 11.37 (s, 1H), 7.65 (d, J = 8.4 Hz, 2H), 7.43 (d, J = 8.3 Hz, 2H), 7.39 – 7.26 (m, 4H), 4.85 (s, 2H), 2.50 (s, 6H).

[0145] Example 7

[0146]

[0147] 212 mg of phenyl-biphenyl α-β-unsaturated pyridinesulfonamide and 122 mg of 4-dimethylaminopyridine were added to a reaction tube, and nitrogen gas was introduced. Then, 4 ml of DMF was added as a solvent, followed by 55 μL of TMSCN. After reacting at 80 °C for 24 hours, the reaction solution was evaporated to dryness and purified by column chromatography to give compound 20 (72 mg, yield 43%).

[0148] The NMR detection data of the product are as follows:

[0149] 1 H NMR (400 MHz, DMSO- d6) δ 11.54 (s, 1H), 7.87 – 7.79 (m, 4H), 7.74(d, J = 7.3 Hz, 2H), 7.54 – 7.47 (m, 4H), 7.43 (t, J = 7.7 Hz, 2H), 7.38 (t, J =7.3 Hz, 1H), 7.23 (t, J = 7.3 Hz, 1H), 4.94 (s, 2H).

[0150] Example 8

[0151]

[0152] 183 mg of phenyl-4-methylsulfonylphenyl α-β-unsaturated hydroxysulfonamide and 122 mg of triethylenediamine were added to a reaction tube, and nitrogen gas was introduced. Then, 4 ml of DMSO was added as a solvent, followed by 55 μL of TMSCN. After reacting at 75 °C for 5 hours, the reaction solution was evaporated to dryness and purified by column chromatography to give compound 27 (74 mg, yield 44%).

[0153] The NMR detection data of the product are as follows:

[0154] 1 H NMR (400 MHz, DMSO- d 6) δ 11.67 (s, 1H), 8.00 – 7.82 (m, 4H), 7.52 –7.35 (m, 4H), 7.26 – 7.13 (m, 1H), 5.06 (s, 2H), 3.19 (s, 3H).

[0155] Synthesis of pyrrolopyrimidine compounds

[0156] Example 9

[0157]

[0158] 130 mg of diphenyl-2-aminopyrrole and 156 mg of 2,6-dimethyl-3,5-heptadecane were added to a reaction tube, and nitrogen gas was introduced. Then 2 ml of glacial acetic acid was added as a solvent. After reacting for 6 hours, the organic phase was extracted and column chromatography was performed to give compound 37 (84 mg, yield 45%).

[0159] The NMR detection data of the product are as follows:

[0160] 1 H NMR (400 MHz, Chloroform-d ) δ 8.14 (d, J = 7.6 Hz, 2H), 7.53 – 7.41(m, 7H), 7.30 (t, J = 7.4 Hz, 1H), 6.50 (s, 1H), 3.12 – 2.93 (m, 2H), 1.33 (d, J = 6.9 Hz, 6H), 1.01 (d, J = 6.7 Hz, 6H).

[0161] Example 10

[0162]

[0163] 175 mg of bis(p-methylthiophenyl)-2-aminopyrrole and 500 mg of acetylacetone were added to a reaction tube, and nitrogen gas was introduced. Then, 10 ml of glacial acetic acid and water (1:1 volume ratio) were added as solvents. After reacting for 24 hours, the organic phase was extracted and column chromatography was performed to obtain compound 41 (109 mg, yield 53%).

[0164] The NMR detection data of the product are as follows:

[0165] 1 H NMR (400 MHz, Chloroform- d ) δ 7.98 (d, J = 8.3 Hz, 2H), 7.43 – 7.35(m, 4H), 7.31 (d, J = 8.2 Hz, 2H), 6.33 (s, 1H), 2.55 (s, 3H), 2.52 (s, 3H), 2.50 (s, 3H), 2.11 (s, 3H).

[0166] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A method for preparing a 2-aminopyrrole compound, characterized in that, Includes the following steps: (S) A mixture containing an α-β unsaturated imine compound, a base, an organic solvent, and a trimethylnitrile silane is reacted under an inert gas to give a 2-aminopyrrole compound; The structural formula of the α-β unsaturated imine compound is: ; The 2-aminopyrrole compounds have the structure shown in Formula I: Formula I; Among them, R1 and R 1 Same; R2 and R 2 same; R 1 Independently selected from C6 to C 20 Aryl, C2~C 20 heteroaryl; R 2 Independently selected from C6 to C 20 Aryl, C2~C 20 Mixed aromatics; R3 is independently selected from C1~C 13 Alkyl, C3~C8 cycloalkyl, C6~C 20 Aryl, -NO2, -CF3, -OH, -NH2.

2. The preparation method according to claim 1, characterized in that, In step (S), the base is selected from at least one of potassium carbonate, sodium carbonate, sodium tert-butoxide, potassium fluoride, triethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 4-dimethylaminopyridine, and triethylenediamine.

3. The preparation method according to claim 1, characterized in that, The organic solvent is selected from at least one of acetonitrile, N,N-dimethylformamide, tetrahydrofuran, N-methylpyrrolidone, and 1,4-dioxane.

4. The preparation method according to claim 1, characterized in that, The inactive gas is selected from nitrogen, argon, and helium.

5. The preparation method according to claim 1, characterized in that, 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. The preparation method according to claim 1, characterized in that, The molar ratio of the α-β unsaturated imine compound to the base is 1:0.5 to 1:

5.

7. The preparation method according to claim 6, characterized in that, The molar ratio of the α-β unsaturated imine compound to the base is 1:1.5 to 1:2.

5.

8. The preparation method according to claim 1, characterized in that, The molar ratio of the α-β unsaturated imine compound to the trimethylnitrile silane is 1:2 to 1:2.

2.

9. The preparation method according to claim 1, characterized in that, The reaction conditions are as follows: Temperature range: 0℃ to 100℃; The time ranges from 0.5 h to 24 h.

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