CN109320507B

CN109320507B - Chiral fluorescent compound based on quinoline amide folder and preparation method and application thereof

Info

Publication number: CN109320507B
Application number: CN201811074784.7A
Authority: CN
Inventors: 江华; 郑丹
Original assignee: Beijing Normal University
Current assignee: Beijing Normal University
Priority date: 2018-09-14
Filing date: 2018-09-14
Publication date: 2020-05-22
Anticipated expiration: 2038-09-14
Also published as: CN109320507A

Abstract

The invention discloses a chiral fluorescent compound of a quinoline amide folder and a preparation method and application thereof. The structural general formula of the compound is shown as the following formula I or formula II,

the chiral fluorescent material has the characteristic of CPL luminescence, has good solubility in common organic solvents, and has yellow solution and good stability. The CPL signal intensity and the luminous intensity can be regulated and controlled according to the chain length of the compound, and the purpose of changing the CPL intensity and the luminous intensity by changing the length of the spirochete is achieved. The compound has wide application prospect in the fields of preparing chiral organic luminescent dye with circular polarization luminescent property, preparing chiral fluorescent probe and identifying fluorescence.

Description

Chiral fluorescent compound based on quinoline amide folder and preparation method and application thereof

Technical Field

The invention relates to the field of materials and preparation, in particular to a quinoline amide foldate-based chiral fluorescent compound and a preparation method and application thereof.

Background

The chiral organic fluorescent material is an organic material which has both chiral and luminescent properties. Chiral molecules with circular polarization light emission (CPL) characteristics have attracted attention in recent years due to their broad application prospects in the fields of photochemical materials, chiral identification, display devices, optical storage devices, chiral light emitting diodes, CPL lasers, asymmetric photocatalytic reactions and the like.

At present, organic molecules in the field are hot spots in the field due to the characteristics of simple structure, easy derivation, various varieties and the like. But because a higher asymmetry factor (g) cannot be obtained_lum) And quantum yield, limits the applications in the field of fluorescent materials.

The quinoline amide folds are different from the traditional helicene which forms a helical structure based on the main pi-pi stacking effect, and the folding effect is mainly driven by the three-center hydrogen bond effect formed by the N atoms on adjacent quinoline rings and amide hydrogen between the adjacent quinoline rings. A chromophore and a chiral induction center are introduced into a quinoline amide folder, and the folder generates the characteristics of circular polarization luminescence.

Disclosure of Invention

The technical problem to be solved by the application is to provide a quinoline amide folder-based chiral fluorescent compound, which has good CPL luminescence characteristics, and the CPL signal intensity and the luminescence intensity of the compound can be regulated and controlled according to the chain length of the compound.

Another technical problem to be solved by the present application is to provide a preparation method of a chiral fluorescent compound based on a quinoline amide foldate.

Another technical problem to be solved by the present application is to provide an application of a chiral fluorescent compound based on a quinoline amide foldate.

In order to solve the first technical problem, the invention adopts the following technical scheme:

a chiral fluorescent compound based on a quinoline amide folder is disclosed, wherein the structural general formula of the compound is shown as the following formula I or formula II,

in the formula I or formula II, R₁Independently selected from alkyl, carbazolyl, aromatic group or substituted aromatic group with 1-15 carbon atoms, carbazoloxy, R₂Independently selected from alkyl with 1-15 carbon atoms, carbazolyl, aryl, substituted aryl, carbazoloxy, aryloxy or substituted aryloxy, wherein the substituent of the substituted aryl is alkyl with 1-15 carbon atoms or alkenyl with 2-15 carbon atoms, R₃Independently selected from alkyl with 1-15 carbon atoms, alkoxy with 1-15 carbon atoms, carbazolyl, aryl, substituted aryl, carbazoloxy, aryloxy or substituted aryloxy, wherein the one or more substituents of the substituted aryl are alkyl with 1-15 carbon atoms, alkenyl with 2-15 carbon atoms, alkynyl with 2-15 carbon atoms and alkoxy with 1-10 carbon atoms, R₁、R₂And R₃Equal to or different from each other, n is an integer greater than 1.

As a further improvement in the technical solution, the compound comprises S-type enantiomer and R-type enantiomer; wherein,

the structural formula of the S-type enantiomer is shown as the following formula S-I or formula S-II,

the structural formula of the R enantiomer is shown as the following formula R-I or R-II,

formula S-I, formula S-II, formula R-I or formula R-II wherein R₁Independently selected from alkyl, carbazolyl, aromatic group or substituted aromatic group with 1-15 carbon atoms, R₂Independently selected from alkyl with 1-15 carbon atoms, carbazolyl, aryl, substituted aryl, carbazoloxy, aryloxy or substituted aryloxy, wherein the substituent of the substituted aryl is alkyl with 1-15 carbon atoms or alkenyl with 2-15 carbon atoms, R₃Independently selected from alkyl with 1-15 carbon atoms, alkoxy with 1-15 carbon atoms, carbazolyl, aryl, substituted aryl, carbazoloxy, aryloxy or substituted aryloxy, wherein the one or more substituents of the substituted aryl are alkyl with 1-15 carbon atoms, alkenyl with 2-15 carbon atoms, alkynyl with 2-15 carbon atoms and alkoxy with 1-10 carbon atoms, R₁、R₂And R₃Equal to or different from each other, n is an integer greater than 1.

As a further improvement of the technical scheme, R is₁Selected from isobutyl, n is 4, 8 or 16, R₂Is methyl, said R₃Is a tert-butyl group.

A preparation method of a chiral fluorescent compound based on a quinoline amide folder, wherein the compound is shown as the formula I, and the preparation method comprises the following steps:

1) under the protection of argon, 4-substituted chiral 2- (2-aminophenyl) oxazole is dissolved in anhydrous dichloromethane, and N, N-diisopropylethylamine is added as alkali to obtain a solution a; dissolving carboxylic acid of the 4-isobutoxy-8-amino-2-carboxyl quinoline amide polymer in anhydrous dichloromethane to obtain a solution b; mixing the solution a and the solution b and stirring to obtain a single chiral quinoline amide polymer;

2) dissolving the single-chiral quinoline amide polymer obtained in the step 1) and 10% palladium-carbon in ethyl acetate in a hydrogen atmosphere, and heating and stirring to obtain amine of the single-chiral quinoline amide polymer;

3) under the protection of argon, anhydrous dichloromethane is used as a solvent, N, N-diisopropylethylamine is used as a base, and the amine of the single chiral quinoline amide polymer obtained in the step 2) and pivaloyl chloride are stirred at room temperature for 2-4 hours to obtain the compound shown in the formula I.

As a further improvement of the technical scheme, in the step 1), the ratio of acyl chloride of N, N-diisopropylethylamine and 4-isobutoxy-8-amino-2-carboxyl quinoline amide polymer to 4-substituted chiral 2- (2-aminophenyl) oxazole is 2-100: 1: 0.85-10;

in the step 2), the pressure of hydrogen is 0.8-1.5 MPa, the heating temperature is 40-60 ℃, the heating and stirring time is 6-15 hours, and the mass ratio of the single chiral quinoline amide polymer to 10% palladium-carbon is 10: 1-3;

in the step 3), the mass ratio of the pivaloyl to the amine of the single chiral quinoline amide polymer is 1-500: 1.

1) under the protection of argon, anhydrous dichloromethane is used as a solvent, N, N-diisopropylethylamine is used as a base, and the amine of the 4-isobutoxy-8-amino-2-carboxyl quinoline amide polymer and pivaloyl chloride are stirred at room temperature for 2-4 hours to obtain a fluorescence product pivaloyl quinoline amide polymer;

2) dissolving the pivaloyl quinoline amide polymer obtained in the step 1) in a mixed solvent of tetrahydrofuran and methanol, dissolving NaOH in deionized water, adding the dissolved NaOH, and heating and stirring for 1-4 h to obtain carboxylic acid of the pivaloyl quinoline amide polymer;

3) under the protection of argon, dissolving the carboxylic acid of the pivaloyl quinoline amide polymer obtained in the step 2) in anhydrous dichloromethane, adding oxalyl chloride, and stirring at room temperature to obtain acyl chloride of the pivaloyl quinoline amide polymer;

4) under the protection of argon, 4-substituted chiral 2- (2-aminophenyl) oxazole is dissolved in anhydrous dichloromethane, and N, N-diisopropylethylamine is added to obtain a solution c; dissolving acyl chloride of the pivaloyl quinoline amide polymer obtained in the step 3) in anhydrous dichloromethane to obtain a solution d, mixing the solutions c and d, and stirring to obtain the compound shown in the formula I.

As a further improvement of the technical solution,

in the step 1), the ratio of amine of N, N-diisopropylethylamine and 4-isobutoxy-8-amino-2-carboxyl quinoline amide polymer to pivaloyl chloride is 2-100: 1: 0.85-10;

in the step 2), the mass ratio of tetrahydrofuran, methanol and water is 5-100: 1-100: 0.1-50; the mass ratio of the pivaloyl quinoline amide polymer to the sodium hydroxide is 1: 10-1: 20;

in the step 3), the mass ratio of the carboxylic acid to the oxalyl chloride of the pivaloyl quinoline amide polymer is 1: 2-100;

in the step 4), the ratio of the acyl chloride of the pivaloyl quinoline amide polymer to the substance of 4-substituted chiral 2- (2-aminophenyl) oxazole is 1: 0.85-1.2.

A preparation method of a chiral fluorescent compound based on a quinoline amide folder, wherein the compound is shown as the formula II, and the preparation method comprises the following steps:

1) under the protection of argon, dissolving 4, 7-diisobutyl-1, 10-phenanthroline-2, 9-carboxylic acid in anhydrous dichloromethane, adding oxalyl chloride, and stirring at room temperature to obtain 4, 7-diisobutyl-1, 10-phenanthroline-2, 9-carboxylic acid chloride;

2) under the protection of argon, dissolving amine of the chiral quinoline amide polymer in anhydrous dichloromethane, and adding N, N-diisopropylethylamine to obtain a solution e; dissolving the 4, 7-diisobutyl-1, 10-phenanthroline-2, 9-carboxylic acid chloride obtained in the step 1) in anhydrous dichloromethane to obtain a solution f; and mixing and stirring the solution e and the solution f to obtain the compound shown in the formula II.

As a further improvement of the technical scheme, in the step 1), the mass ratio of the 4, 7-diisobutyl-1, 10-phenanthroline-2, 9-carboxylic acid to oxalyl chloride is 1: 5-1000; (ii) a

In the step 2), the ratio of the amounts of the acyl chloride of 4, 7-diisobutyl-1, 10-phenanthroline-2, 9-carboxylic acid, N-diisopropylethylamine and the 4-substituted chiral 2- (2-aminophenyl) oxazole is 1:5 to 1000:2 to 10.

The invention also discloses application of the quinoline amide foldamer-based chiral fluorescent compound in the fields of preparation of chiral organic luminescent materials, preparation of chiral fluorescent probes and fluorescent identification.

Any range recited herein is intended to include the endpoints and any number between the endpoints and any subrange subsumed therein or defined therein.

The starting materials of the present invention are commercially available, unless otherwise specified, and the equipment used in the present invention may be any equipment conventionally used in the art or may be any equipment known in the art.

Compared with the prior art, the invention has the following beneficial effects:

the invention provides chiral organic molecules with circular polarization luminescence and a preparation method thereof. The chiral fluorescent material provided by the invention has the characteristic of CPL luminescence, has good solubility in common organic solvents, and has yellow solution and good stability. The CPL signal intensity and the luminous intensity of the chiral fluorescent material can be regulated and controlled according to the chain length of a compound shown by a formula S-I, R-I, S-II or R-II. When the value of n is larger, the CPL signal is stronger, and the luminous intensity is increased, so that the purpose of changing the CPL intensity and the luminous intensity by changing the length of the spiral body is achieved. The compounds have wide application prospects in the fields of preparation of chiral organic luminescent dyes with circular polarization luminescent properties, chiral fluorescent probes and fluorescent identification.

Drawings

FIG. 1 is a circular dichroism spectrum of the compound prepared in example 1;

FIG. 2 is a circular dichroism spectrum of the compound prepared in example 2;

FIG. 3 is a chart of the circular dichroism spectrum of the compound prepared in example 3;

FIG. 4 is a chart of the circular dichroism spectrum of the compound prepared in example 4;

FIG. 5 is a chart of the circular dichroism spectrum of the compound prepared in example 5;

FIG. 6 is a circular dichroism spectrum of the compound prepared in example 6;

FIG. 7 is a circular polarized luminescence spectrum of the compound prepared in example 1;

FIG. 8 is a circularly polarized luminescence spectrum of the compound prepared in example 2;

FIG. 9 is a circularly polarized luminescence spectrum of the compound prepared in example 3;

FIG. 10 is a circularly polarized luminescence spectrum of the compound prepared in example 4;

FIG. 11 is a circularly polarized luminescence spectrum of the compound prepared in example 5;

FIG. 12 is a circularly polarized luminescence spectrum of the compound prepared in example 6;

FIG. 13 is a graph of asymmetry factor as a function of wavelength for the circularly polarized luminescence spectrum of the compound prepared in example 1;

FIG. 14 is a graph of asymmetry factor as a function of wavelength for the circularly polarized luminescence spectrum of the compound prepared in example 2;

FIG. 15 is a graph of asymmetry factor as a function of wavelength for the circularly polarized luminescence spectrum of the compound prepared in example 3;

FIG. 16 is a graph of the asymmetry factor as a function of wavelength for the circularly polarized luminescence spectrum of the compound prepared in example 4;

FIG. 17 is a graph of the asymmetry factor as a function of wavelength for the circularly polarized luminescence spectrum of the compound prepared in example 5;

FIG. 18 is a graph of asymmetry factor as a function of wavelength for the circularly polarized luminescence spectrum of the compound prepared in example 6.

Detailed Description

In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.

The application relates to a chiral fluorescent compound based on a quinoline amide folder, the structural general formula of a racemate of the compound is shown as the following formula I or formula II,

According to certain embodiments of the present application, the above compounds include the S enantiomer and the R enantiomer.

Wherein the structural formula of the S-type enantiomer is shown as the following formula S-I or formula S-II,

formula S-I, formula S-II, formula R-I or formula R-II wherein R₁Independently selected from alkyl, carbazolyl and aryl with 1-15 carbon atomsAn aryl or substituted aryl, carbazoloxy; r₂Independently selected from alkyl with 1-15 carbon atoms, carbazolyl, aryl, substituted aryl, carbazoloxy, aryloxy or substituted aryloxy, wherein the substituent of the substituted aryl is alkyl with 1-15 carbon atoms or alkenyl with 2-15 carbon atoms; r₃Independently selected from alkyl with 1-15 carbon atoms, alkoxy with 1-15 carbon atoms, carbazolyl, aryl, substituted aryl, carbazoloxy, aryloxy or substituted aryloxy, wherein the one or more substituents of the substituted aryl are alkyl with 1-15 carbon atoms, alkenyl with 2-15 carbon atoms, alkynyl with 2-15 carbon atoms and alkoxy with 1-10 carbon atoms, R₁、R₂And R₃Equal to or different from each other, n is an integer greater than 1.

According to certain embodiments of the present application, the compounds of formula S-I have the structures shown below as formulas S-I1 through S-I3:

in the above formulas S-I1 and S-I2, R₂Independently selected from methyl, isopropyl, phenyl or benzyl.

According to certain embodiments of the present application, the compounds of formula S-II have the following structures S-II1 through S-II 3:

according to certain embodiments of the present application, the compounds of formula R-I have the following structures R-I1 through R-I3:

according to certain embodiments of the present application, the compounds of formula R-II have the structure of formula R-II1 to

R-II 3:

still further, according to certain embodiments of the present application, the compounds of formula S-I1 are of the following formulae S-I1-a through S-I1-d:

the compounds shown in the formulas S-I1 are shown in the formulas S-I1-a to S-I1-d, chiral amine has chiral induction effect on quinoline amide folder, and the chiral induction is complete, so that the quinoline amide folder with optical activity has single chirality and shows circular polarization luminescence.

Still further, according to certain embodiments of the present application, the compounds of formula S-I2 are of the following formulae S-I2-a through S-I2-d:

the compounds shown in the formulas S-I1 are shown in the formulas S-I1-a to S-I1-d, chiral amine has chiral induction effect on quinoline amide folder, and the chiral induction is complete, so that the quinoline amide folder with optical activity has single chirality and shows circular polarization luminescence. Furthermore, the chiral induction effect is amplified due to the increased chain length of the quinoline amide fold, and the effect of circularly polarized luminescence is also amplified.

The application relates to a preparation method of a quinoline amide foldate-based chiral fluorescent compound, which is shown as the formula I and comprises the following steps:

2) dissolving the single-chiral quinoline amide polymer obtained in the step 1) and 10% palladium-carbon in ethyl acetate in a hydrogen atmosphere, and heating and stirring the mixture overnight to obtain amine of the single-chiral quinoline amide polymer;

According to certain embodiments of the present application, in step 1), the ratio of the acyl chloride of the N, N-diisopropylethylamine, 4-isobutoxy-8-amino-2-carboxyquinoline amide multimer to the 4-substituted chiral 2- (2-aminophenyl) oxazole is 2-100: 1: 0.85-10; the preferred ratio is 2:1: 0.9. The applicant finds that the compound is prepared by using an acyl chloride condensation method, the reaction steps are simple, and the yield is considerable.

According to some embodiments of the present application, in the step 2), the pressure of hydrogen is 0.8 to 1.5 mpa, preferably 1.0 mpa, the heating temperature is 40 to 60 ℃, the heating and stirring time is 6 to 15 hours, and the mass ratio of the single chiral quinoline amide polymer to 10% palladium-carbon is 10:1 to 3; preferably 10: 1. The applicant finds that the synthesis scheme is simple and rapid in operation and post-treatment, high in yield, low in cost and high in atom conversion rate.

According to some embodiments of the present application, in step 3), the ratio of the amount of the substance of pivaloyl to the amine of the single chiral quinolinamide multimer is 1-500: 1, preferably 1.2: 1. The technical scheme has the advantages of simple operation, easily obtained raw materials and higher yield.

The reaction formula of the preparation method is as follows:

another preparation method of a quinoline amide foldate-based chiral fluorescent compound, which is shown as the formula I above, comprises the following steps:

According to some embodiments of the present application, in step 1), the ratio of the amine of the N, N-diisopropylethylamine, 4-isobutoxy-8-amino-2-carboxyquinoline amide polymer to the pivaloyl chloride is 2-100: 1: 0.85-10; preferably 2:1: 1.2. The technical scheme has the advantages of simple operation, easily obtained raw materials and higher yield.

According to some embodiments of the present application, in the step 2), the ratio of the amounts of the tetrahydrofuran, the methanol and the water is 5 to 100:1 to 100:0.1 to 50; preferably 10:1: 1; the ratio of the amount of the pivaloyl quinoline amide polymer to the amount of the sodium hydroxide is 1:10 to 1: 20. The operation scheme is simple and easy to implement, the post-treatment purification is simple, and the yield is considerable.

According to certain embodiments of the present application, in step 3), the ratio of the mass of carboxylic acid to oxalyl chloride of the pivaloyl quinoline amide multimer is 1:2 to 100; preferably 1: 2. The applicant finds that the reaction of oxalyl chloride and carboxylic acid is simple in reaction operation and post-treatment and considerable in yield.

According to certain embodiments of the present application, in said step 4), the ratio of the amount of the acid chloride of the pivaloyl quinoline amide multimer to the amount of the substance of the 4-substituted chiral 2- (2-aminophenyl) oxazole is 1:0.85 to 1.2, preferably 1: 0.9. The applicant finds that the compound prepared by using the acyl chloride condensation method has high reaction activity, simple reaction steps and considerable yield.

The reaction formula of the preparation method is as follows:

the application relates to a preparation method of a quinoline amide foldate-based chiral fluorescent compound, which is shown as the formula II and comprises the following steps:

2) under the protection of argon, dissolving amine of the chiral quinoline amide polymer in anhydrous dichloromethane, and adding N, N-diisopropylethylamine to obtain a solution e; dissolving the 4, 7-diisobutyl-1, 10-phenanthroline-2, 9-carboxylic acid chloride obtained in the step 1) in anhydrous dichloromethane to obtain a solution f; and (4) mixing the solutions e and f, and stirring to obtain the compound shown in the formula II.

According to certain embodiments of the present application, in step 1), the mass ratio of 4, 7-diisobutyl-1, 10-phenanthroline-2, 9-carboxylic acid to oxalyl chloride is 1:5 to 1000, preferably 1: 5. The applicant finds that the reaction of oxalyl chloride and a phenanthroline dicarboxylic acid compound has high reaction activity, simple reaction steps and considerable yield.

According to certain embodiments of the present application, in the step 2), the ratio of the amounts of the 4, 7-diisobutyl-1, 10-phenanthroline-2, 9-carboxylic acid chloride, N-diisopropylethylamine and the 4-substituted chiral 2- (2-aminophenyl) oxazole in the substance is 1:5 to 1000:2 to 10, preferably 1:5: 2. The applicant finds that the compound prepared by using the acyl chloride condensation method has high reaction activity, simple reaction steps and considerable yield.

The reaction formula of the preparation method is as follows:

the chiral fluorescent compound based on the quinoline amide folder has wide application prospects in the fields of preparation of chiral organic luminescent materials, preparation of chiral fluorescent probes and fluorescent identification.

The following examples further illustrate the invention. The reagents used in the examples of the present invention are commercially available unless otherwise specified.

Example 1

Preparation of Compounds of formula S-I1 and formula R-I1

The reaction formula is as follows:

the preparation process comprises the following steps:

1) 254mg of A was placed in a 50mL two-necked flask, and the above-mentioned compound was dissolved in 10mL of anhydrous dichloromethane under an argon atmosphere, and 31. mu.L of N, N-diisopropylethylamine and 25. mu.L of pivaloyl chloride were slowly added in this order by means of a syringe, followed by stirring at room temperature for 3 hours. The product was isolated by column chromatography as yellow powder product B in 93% yield;

2) dissolving 200mg of B in a mixed solvent of 10mL of tetrahydrofuran and 2mL of methanol in a 50mL eggplant-shaped bottle, dissolving 72mg of NaOH solid in 2mL of deionized water, slowly dropwise adding the obtained NaOH solution into the solution of B, heating the mixed solution in an oil bath at 40 ℃ for 2 hours, completely hydrolyzing the compound B, dropwise adding 1mol/L of dilute hydrochloric acid into the reacted solution, and reducing the pH of the reaction solution to 4-5; then extracting with a large amount of dichloromethane and deionized water, and using anhydrous NaSO for an organic phase₄Drying, distilling under reduced pressure to remove the organic solvent to obtain a yellow solid, namely a product C, wherein the yield is 82%;

3) dissolving 200mg of C in 10mL of anhydrous dichloromethane in a 50mL two-mouth bottle under the protection of argon, adding 15 mu L of oxalyl chloride by using an injector, stirring at room temperature for two hours, distilling under reduced pressure to remove an organic solvent, continuously vacuumizing on a vacuum pump for two hours, and dissolving in 3mL of anhydrous dichloromethane under the protection of argon for later use; an amount of 0.9 equivalents of 4-R-yl-2- (2-aminophenyl) oxazole or R-4-R-2- (2-aminophenyl) oxazole in a 50mL two-necked flask was dissolved in anhydrous dichloromethane under argon and 31 μ L N, N-diisopropylethylamine was added, after which the above acid chloride solution was slowly added by syringe and stirred at room temperature overnight. Separating the product by column chromatography to obtain the compound of formula S-I1 or R-I1. The yield is 62-85%.

When the chiral aminophenyl oxazole is S-4-methyl-2- (2-aminophenyl) oxazole, the resulting product is a compound of formula S-I1-a in 62% yield. The structure detection structure of the compound is as follows:¹H NMR(400 MHz,CDCl₃)δ13.18(s,1H),12.21(s,1H),11.81(s,1H),11.33(s,1H),9.14(s,1H), 8.77(d,1H),8.69(d,1H),8.63(d,1H),8.15(d,1H),8.09(d,1H),8.02(d,1H),7.97 (dd,2H),7.91(d,1H),7.67(dd,1H),7.61(dd,2H),7.52(dd,1H),7.34(m,2H),7.27 (d,1H),7.18(dd,1H),6.90(s,1H),6.81(s,1H),4.46(m,1H),4.36(m,1H), 4.14～4.21(m,2H),3.87～3.97(m,4H),3.06(t,1H),2.57(m,2H),2.46(m,1H), 2.20～2.37(m,4H),2.02(m,1H),1.19～1.35(m,24H),0.81(s,9H),0.48(d,3H).¹³C NMR(151MHz,CDCl₃)δ176.40,163.53,163.03,162.87,162.52,162.48,162.19, 150.43,150.33,149.61,149.06,139.24,138.48,137.91,137.79,137.03,134.21, 134.10,133.72,131.75,129.66,128.41,128.05,127.47,127.00,126.74,126.69, 125.30,122.95,122.55,122.47,122.01,121.60,120.10,117.45,116.99,116.78, 116.46,116.39,116.16,116.11,115.85,114.09,100.05,99.90,98.70,98.09,75.50, 75.33,75.20,69.73,67.43,42.40,39.77,29.77,28.37,28.28,28.24,27.06,19.57, 19.40,19.33.MS(ESI)calculated for C₇₁H₇₆N₁₀O₁₀[M+H]⁺1229.5824, found 1229.5442; the results of the detection revealed that the above compound had a correct structure.

When the chiral aminophenyl oxazole is S-4-phenyl-2- (2-aminophenyl) oxazole, the resulting product is a compound of formula S-I1-b in yieldThe content was 85%. The structure detection structure of the compound is as follows:¹H NMR(600 MHz,CDCl₃)δ13.12(s,1H),12.18(s,1H),11.53(s,1H),11.28(s,1H),9.13(s,1H), 8.70(d,1H),8.68(d,1H),8.63(d,1H),8.12(d,1H),8.07(d,1H),8.00(d,1H),7.99 (d,1H),7.95(d,1H),7.91(d,1H),7.64-7.66(m,2H),7.59(dd,1H),7.54(td,1H), 7.27-7.34(m,4H),7.20(t,1H),6.91(s,1H),6.84(s,1H),6.64-6.47(m,2H),6.42(s, 1H),6.41(s,1H),6.34(t,1H),4.44(dd,1H),4.37(dd,1H),4.13-4.19(m,2H),3.95 (d,2H),3.90(d,1H),3.24(dd,1H),2.50-2.55(m,2H),2.30-2.40(m,3H),2.14(t, 1H),2.10(dd,1H),1.98(dd,1H),1.19-1.33(m,36H),0.80(s,11H).¹³C NMR(101 MHz,)δ176.41,163.64,163.56,163.37,163.17,162.72,162.56,162.34,161.95, 160.92,150.43,150.39,149.65,149.14,141.24,139.06,138.36,137.96,137.87, 137.83,134.18,134.09,133.96,133.74,131.85,129.73,128.15,127.09,127.06, 126.72,125.79,123.07,122.56,122.52,121.87,121.68,120.29,117.11,117.03, 116.77,116.45,116.26,115.90,114.19,99.89,98.72,98.07,75.54,75.45,75.41, 75.16,72.29,69.23,39.79,29.78,28.38,28.34,28.26,27.09,19.57,19.53,19.47, 19.40.Yield:83％.MS(ESI)calculated for[M+H]⁺1291.5975, found 1291.5975; the results of the detection revealed that the above compound had a correct structure.

When the chiral aminophenyl oxazole is S-4-isobutyl-2- (2-aminophenyl) oxazole, the resulting product is a compound of formula S-I1-c in 68% yield.¹H NMR(400MHz,CDCl₃)δ13.26(s,1H), 12.23(s,1H),11.78(s,1H),11.35(s,1H),9.16(s,1H),8.74(d,1H),8.13(d,1H),8.63 (d,1H),8.14(d,1H),8.07(d,1H),8.01(d,1H),7.98(d,1H),7.97(d,1H),7.92(d, 1H),7.66(dd,1H),7.63(d,1H),7.62(d,1H),7.53(dd,1H),7.35(s,1H),7.34(d, 1H),7.32(s,1H),7.28(d,1H),7.19(dd,1H),6.91(s,1H),6.83(s,1H),4.43(dd,1H), 4.39(dd,1H)4.20(t,1H),4.16(t,1H),3.88-3.96(m,5H),3.20(t,1H),2.48-2.52(m, 2H),2.28-2.36(m,2H),2.22(dd,1H),1.90(dd,1H),1.20-1.33(m,50H),0.84(s,9H), 0.15(dd,6H).¹³C NMR(101MHz,CDCl₃)δ176.42,163.59,163.10,162.79,162.63, 162.13,162.01,161.08,150.47,150.39,149.93,148.98,139.17,138.42,137.92, 137.78,134.10,134.07,133.95,133.69,131.60,129.67,128.09,126.98,126.85, 126.75,122.95,122.49,121.98,121.61,120.00,117.26,116.97,116.48,116.40, 116.15,116.09,115.87,114.09,99.93,98.84,97.91,75.51,75.46,75.33,75.20,71.68, 68.21,39.78,32.88,32.00,29.77,29.44,28.42,28.36,28.27,27.23,27.07,22.77, 20.66,19.56,19.53,19.46,19.42,19.33,18.31,17.47,14.20.Yield:76％.MS(ESI) calculated for[M+H]⁺1257.6131, found 1257.6149; the results of the detection revealed that the above compound had a correct structure.

When the chiral aminophenyl oxazole is S-4-benzyl-2- (2-aminophenyl) oxazole, the resulting product is a compound of formula S-I1-d in 74% yield.¹H NMR(600MHz,CDCl₃)δ13.12(s,1H), 12.18(s,1H),11.53(s,1H),11.29(s,1H),9.13(s,1H),8.73(d,1H),8.67(d,1H), 8.64(d,1H),8.12(d,1H),8.07(d,1H),7.99(dd,2H),7.94(d,1H),7.89(d,1H),7.65 (m,3H),7.59(dd,1H),7.54(dd,1H),7.33(m,2H),7.29,(m,2H),7.20(dd,1H), 6.91(s,1H),6.84(s,1H),6.45(dd,2H),6.42(dd,2H),6.34(dd,1H),4.44(t,1H), 4.38(t,1H),4.16(m,2H),3.94(d,2H),3.94(d,2H),3.24(t,1H),2.53(m,2H), 2.34(m,4H),2.14(m,2H),1.98(dd,1H),1.19～1.32(m,24H),0.80(s,9H).¹³C NMR(151MHz,CDCl₃)δ176.39,163.54,163.05,162.86,162.55,162.49,162.20, 161.98,161.03,150.45,150.36,149.65,149.09,139.25,138.50,137.94,137.81, 137.04,134.22,134.14,133.74,131.73,129.65,128.40,128.04,127.48,126.99, 126.73,126.68,125.30,122.92,122.57,122.49,122.03,121.63,120.09,117.44, 117.00,116.77,116.49,116.38,116.19,116.09,115.83,114.11,100.06,99.90,98.73, 98.12,75.50,75.33,75.21,69.72,67.41,42.37,39.76,29.75,28.38,28.28,28.23, 27.05,19.54,19.51,19.45,19.37,19.31.MS(ESI)calculated for[M+H]⁺1305.6131, found 1305.6149; the results of the detection revealed that the above compound had a correct structure.

When the chiral aminophenyl oxazole is R-4-phenyl-2- (2-aminophenyl) oxazole, the resulting product is a compound of formula R-I1. The yield was 78%.¹H NMR(600MHz,CDCl₃)δ13.12(s,1H),12.18 (s,1H),11.53(s,1H),11.28(s,1H),9.13(s,1H),8.70(d,1H),8.68(d,1H),8.64(d, 1H),8.13(d,1H),8.07(d,1H),8.00(d,1H),7.99(d,1H),7.95(d,1H),7.90(d,1H), 7.64-7.66(m,2H),7.59(dd,1H),7.54(td,1H),7.27-7.34(m,4H),7.20(t,1H),6.91 (s,1H),6.84(s,1H),6.64-6.47(m,2H),6.42(s,1H),6.41(s,1H),6.34(t,1H),4.44 (dd,1H),4.37(dd,1H),4.13-4.19(m,2H),3.95(d,2H),3.90(d,1H),3.24(dd,1H), 2.50-2.55(m,2H),2.30-2.40(m,3H),2.14(t,1H),2.10(dd,1H),1.98(dd,1H), 1.19-1.33(m,36H),0.80(s,11H).¹³C NMR(101MHz,)δ176.41,163.64,163.56, 163.37,163.17,162.72,162.56,162.34,161.95,160.92,150.43,150.39,149.65, 149.14,141.24,139.06,138.36,137.96,137.87,137.83,134.18,134.09,133.96, 133.74,131.85,129.73,128.15,127.09,127.06,126.72,125.79,123.07,122.56, 122.52,121.87,121.68,120.29,117.11,117.03,116.77,116.45,116.26,115.90, 114.19,99.89,98.72,98.07,75.54,75.45,75.41,75.16,72.29,69.23,39.79,29.78, 28.38,28.34,28.26,27.09,19.57,19.53,19.47,19.40.Yield:78％.MS(ESI) calculated for[M+H]⁺1291.5975, found 1291.5993; the results of the detection revealed that the above compound had a correct structure.

Example 2

Preparation of Compounds of formula S-I2 or R-I2

The reaction formula is as follows:

the preparation process comprises the following steps:

1) 490mg of E was added to a 50mL two-necked flask, and the above-mentioned compound was dissolved in 10mL of anhydrous dichloromethane under an argon atmosphere, and 31. mu.L of N, N-diisopropylethylamine and 15. mu.L of pivaloyl were slowly added in this order by means of a syringe, and the mixture was stirred at room temperature for 3 hours. The product was isolated by column chromatography as yellow powder of product F in 71% yield;

2) dissolving 400mg of F in a mixed solvent of 10mL of tetrahydrofuran and 2mL of methanol in a 50mL eggplant-shaped bottle, dissolving 140mg of NaOH solid in 2mL of deionized water, slowly dropwise adding the obtained NaOH solution into the solution of F, heating the mixed solution in an oil bath at 40 ℃ for 4 hours, completely hydrolyzing the compound F, dropwise adding 1mol/L of dilute hydrochloric acid into the reacted solution, and reducing the pH of the reaction solution to 4-5. Then extracting with a large amount of dichloromethane and deionized waterAnhydrous NaSO for organic phase₄Drying, and distilling under reduced pressure to remove the organic solvent to obtain a yellow solid, namely a product G; the yield is 96%;

3) dissolving 300mg G in 10mL of anhydrous dichloromethane in a 50mL two-mouth bottle under the protection of argon, adding 10 mu L of oxalyl chloride by using an injector, stirring at room temperature for two hours, distilling under reduced pressure to remove an organic solvent, continuously vacuumizing on a vacuum pump for two hours, and dissolving in 3mL of anhydrous dichloromethane under the protection of argon for later use; the amount of substance 0.9 equivalents of 4-R-yl-2- (2-aminophenyl) oxazole was dissolved in anhydrous dichloromethane under argon in a 50mL two-necked flask and 31 μ L N, N-diisopropylethylamine was added, after which the above acid chloride solution was slowly added by syringe and stirred at room temperature overnight. The product of column chromatography is the compound of the formula S-I2 or R-I2. The yield is 64 to 71 percent.

When the chiral aminophenyl oxazole was S-4-methyl-2- (2-aminophenyl) oxazole, the resulting product was a compound of formula S-I2-a in 65% yield. The structure detection structure of the compound is as follows:¹H NMR(600 MHz,CDCl₃)δ12.61(s,1H),11.26(s,1H),11.20(s,1H),10.90(s,1H),10.84(s, 1H),10.72(s,1H),10.68(s,1H),8.62(s,1H),8.29(dd,1H),8.16(dd,1H),8.14 (dd,1H),8.02(dd,1H),7.90-7.94(m,5H),8.86(dd,1H),8.84(dd,1H),7.82(dd,1H), 7.81(dd,1H),7.72(dd,1H),7.71(dd,1H),7.69(dd,1H),7.65(dd,1H),7.35-3.38 (m,3H),7.27-7.34(m,4H),7.20(m,2H),7.16(dd,1H),7.07(dd,1H),7.04(dd,1H), 6.92(s,1H),6.89(dd,1H),6.85(s,1H),6.71(s,1H),6.65(s,1H),6.44(s,1H),6.31 (s,1H),6.29(s,1H),6.04(s,1H),4.15-4.18(m,1H),4.10-4.15(m,3H),4.00-4.07(m, 2H),3.78-3.96(m,13H),3.74(t,1H),3.66(t,1H),2.83(t,1H),2.33～2.51(m,10H), 2.21(m,2H),2.17(dd,1H),1.84(m,2H),1.11-1.34(m,50H),0.51(s,9H),0.22(d, 3H).¹³C NMR(151MHz,CDCl₃)δ176.00,163.09,162.96,162.74,162.64,162.49, 162.36,162.26,162.10,161.42,161.35,161.11,160.90,159.97,159.47,159.22, 158.85,149.78,149.71,149.55,149.18,148.78,148.74,148.57,148.31,138.45, 138.13,137.72,137.69,137.40,137.27,137.14,133.65,133.62,133.43,133.10, 133.00,132.93,132.56,131.19,128.91,127.40,126.64,126.52,126.39,126.15, 125.84,125.69,125.66,122.60,122.46,122.26,122.18,122.03,121.92,121.62, 121.40,119.88,117.20,116.96,116.79,116.71,116.61,116.23,116.18,116.03, 115.81,115.70,115.64,113.83,99.51,99.10,98.84,98.57,98.50,98.44,97.88,75.36, 75.21,75.17,75.14,75.06,75.03,74.90,71.11,60.69,39.42,29.75,28.25,28.20, 28.17,28.12,28.09,26.79,22.75,21.15,19.69,19.61,19.53,19.49,19.45,19.34, 19.32,19.27.MS(ESI)calculated for[M+2H]²⁺1099.5056, found 1099.5072; the results of the detection revealed that the above compound had a correct structure.

When the chiral aminophenyl oxazole is S-4-phenyl-2- (2-aminophenyl) oxazole, the resulting product is a compound of formula S-I2-b in 76% yield. The structure detection structure of the compound is as follows:¹H NMR(600 MHz,CDCl₃)δ12.51(s,1H),11.32(s,1H),11.21(s,1H),11.10(s,1H),10.86(s, 1H),10.72(s,1H),10.69(s,1H),8.62(s,1H),8.16(dd,1H),8.15(dd,1H),8.03(dd, 1H),7.95(dd,1H),7.94(dd,1H),7.90-7.92(m,4H),7.82(dd,1H),7.81(dd,1H), 7.76(dd,1H),7.74(dd,1H),7.72(dd,1H),7.70(dd,1H),7.65(dd,1H),7.40(dd, 1H),7.35(m,3H),7.29(m,4H),7.17(dd,1H),7.19(dd,1H),7.05(m,2H),6.93(dd, 1H)6.92(s,1H),6.85(s,1H),6.73(s,1H),6.61(dd,1H),6.60(s,1H),6.51(dd,1H), 6.40(s,1H),6.33(s,1H),6.33(s,1H),6.17(s,1H),6.03(s,1H),4.17(m,1H),4.12 (m,2H),4.07(m,3H),4.00(dd,2H),3.89-3.95(m,6H),3.82(m,2H),3.77(dd,1H), 3.71(t,1H),3.65(t,1H),3.14(t,1H),2.75(t,1H),2.62(dd,1H),2.33-2.46(m,8H),2.20 (m,1H),1.09-1.36(m,50H),0.51(s,9H).¹³C NMR(151MHz,CDCl₃)δ176.02, 163.11,162.98,162.80,162.75,162.51,162.20,161.44,160.91,160.69,160.04, 159.47,159.23,158.88,149.81,149.72,149.19,149.07,148.74,148.60,148.31, 141.03,138.50,137.97,137.76,137.67,137.44,137.29,137.15,133.66,133.45, 133.03,132.93,132.59,131.48,129.11,127.89,127.48,126.82,126.66,126.40, 126.15,125.88,125.72,125.63,125.55,122.58,122.27,122.04,121.91,121.44, 120.13,117.24,116.99,116.70,116.43,116.27,116.18,116.05,115.82,113.75,99.52, 99.10,98.80,98.43,97.97,75.37,75.24,75.19,75.11,75.03,74.87,71.92,68.80, 39.42,32.00,29.77,29.44,28.26,28.14,26.78,22.76,19.70,19.62,19.53,19.51, 19.45,19.34,19.32,19.27,14.19.MS(ESI)calculated for[M+2H]²⁺1130.5134, found 1130.5140; the results of the detection revealed that the above compound had a correct structure.

When the chiral aminophenyl oxazole was S-4-isopropyl-2- (2-aminophenyl) oxazole, the resulting product was a compound of formula S-I2-c in 67% yield. The structure detection structure of the compound is as follows:¹H NMR(400 MHz,CDCl₃)δ12.68(s,1H),11.27(s,2H),11.22(s,1H),10.90(s,1H),10.87(s, 1H),10.73(s,1H),10.69(s,1H),8.63(s,1H),8.24(d,1H),8.17(dd,1H),8.03(dd, 1H),7.90-7.93(m,4H),7.88(d,1H),7.80-7.87(m,4H),7.75(d,1H),7.71(d, 1H),7.65(d,1H),7.39(d,1H),7.38(d,1H),7.29-7.35(m,5H),7.14-7.24(m,3H), 7.04(dd,1H),7.03(dd,1H),6.91(s,1H),6.90(dd,1H),6.85(s,1H),6.73(s,1H), 6.66(s,1H),6.46(s,1H),6.31(s,1H),6.27(s,1H),6.03(s,1H),4.09-4.18(m,6H), 3.87-4.05(m,11H),3.77-3.83(m,5H),3.37(t,1H),3.65(t,1H),2.97(t,1H), 2.34-2.53(m,11H),2.22(t,2H),1.64(t,1H)0.96-1.43(m110H),0.88(s,9H),-0.07 (d,3H),-0.12(d,3H).¹³C NMR(101MHz,CDCl₃)δ176.02,163.09,162.95,162.71, 162.51,162.32,162.27,162.22,161.43,160.89,159.88,159.49,159.26,158.88, 149.79,149.71,149.52,149.23,148.94,148.70,148.57,148.31,138.63,138.04, 137.74,137.71,137.42,137.37,137.27,137.15,133.61,133.43,133.09,133.01, 132.93,132.57,131.23,129.06,127.45,126.65,126.57,126.39,126.16,125.83, 125.69,122.60,122.46,122.26,122.17,122.01,121.92,121.56,121.43,119.74, 117.24,117.11,116.99,116.74,116.65,116.24,116.05,115.80,115.66,113.55,99.52, 99.11,98.84,98.54,98.47,98.41,97.83,75.36,75.21,75.06,74.91,71.27,67.85, 39.42,32.62,32.00,29.77,29.43,28.24,28.21,28.16,28.13,26.78,22.76,19.69, 19.61,19.56,19.53,19.45,19.34,19.28,18.04,17.21,14.19.MS(ESI)calculated for [M+2H]²⁺1113.5212, found 1130.5235; the results of the detection revealed that the above compound had a correct structure.

When the chiral aminophenyl oxazole is S-4-benzyl-2- (2-aminophenyl) oxazole, the resulting product is a compound of formula S-I2-d in 64% yield. The structure detection structure of the compound is as follows:¹H NMR(600 MHz,CDCl₃)δ12.53(s,1H),11.22(s,1H),11.19(s,1H),10.98(s,1H),10.83(s, 1H),10.83(s,1H),10.72(s,1H),10.67(s,1H),8.62(s,1H),8.19(m,3H),8.01(dd, 1H),7.89-7.93(m,4H),7.79-7.83(m,4H),7.75(dd,1H),7.71(dd,1H),7.69(dd, 1H),7.64(dd,1H),7.37(dd,1H),7.35(dd,1H),7.33(dd,1H),7.27-7.31(m,3H),7.21 (dd,1H),7.19(dd,1H),7.16(dd,1H),7.05(dd,1H),7.03(dd,1H),6.91(dd,1H),6.90 (dd,1H),6.84(s,1H),6.73(s,1H),6.66(s,1H),6.43(s,1H),6.32(s,1H),6.31(s,1H), 6.28(s,1H),6.25(s,1H),6.23(dd,1H),6.20(s,1H),6.19(s,1H),6.01(s,1H),4.16(t, 1H),4.10-4.17(m3H),4.02(t,1H),3.93-3.98(m,4H),3.77-3.91(m,10H),3.64(t, 1H),3.00(t,1H),2.22-2.52(m,8H),1.95(t,1H),1.83-1.87(dd,2H),1.15-1.35(m, 73H),0.50(s,9H).¹³C NMR(151MHz,CDCl₃)δ176.01,163.09,162.96,162.66, 162.62,162.48,162.33,162.27,162.13,161.91,161.43,160.90,160.87,159.91, 159.47,159.23,158.88,149.79,149.71,149.20,149.02,148.63,148.55,148.31, 138.68,138.11,137.71,137.43,137.42,137.36,137.27,137.14,136.91,133.69, 133.64,133.61,133.44,133.11,133.02,132.94,132.61,131.38,129.06,128.21, 127.40,127.34,126.64,126.44,126.38,126.13,125.85,125.71,125.68,125.16, 122.64,122.48,122.26,122.18,122.01,121.98,121.92,121.60,121.41,119.86, 117.30,117.19,116.96,116.72,116.63,116.52,116.26,116.22,116.19,116.06, 115.80,115.70,115.63,113.55,99.52,99.49,99.24,98.82,98.46,98.40,98.05,75.38, 75.36,75.19,75.05,75.02,74.92,69.35,67.08,42.16,39.42,29.77,29.39,28.26, 28.25,28.20,28.16,28.13,28.09,27.29,26.78,22.76,19.70,19.68,19.65,19.54, 19.52,19.51,19.48,19.45,19.42,19.37,19.33,19.31,19.27,19.26,14.18,0.06.MS (ESI)calculated for[M+2H]²⁺1137.5212, found 1137.5234; the results of the detection revealed that the above compound had a correct structure.

When the chiral aminophenyl oxazole is R-4-phenyl-2- (2-aminophenyl) oxazole, the resulting product is a compound of formula R-I2 in 76% yield. The structure detection structure of the compound is as follows:¹H NMR(600 MHz,CDCl₃)δ12.51(s,1H),11.33(s,1H),11.21(s,1H),11.10(s,1H),10.86(s, 1H),10.72(s,1H),10.69(s,1H),8.62(s,1H),8.16(dd,1H),8.15(dd,1H),8.03(dd, 1H),8.14(dd,1H),7.96(dd,1H),7.94(dd,1H),7.90-7.92(m,4H),7.81(dd,1H), 7.81(dd,1H),7.77(dd,1H),7.75(dd,1H),7.72(dd,1H),7.70(dd,1H),7.65(dd, 1H),7.40(dd,1H),7.35(m,3H),7.29(m,4H),7.17(dd,1H),7.19(dd,1H),7.05(m, 2H),6.93(dd,1H)6.92(s,1H),6.85(s,1H),6.73(s,1H),6.61(dd,1H),6.60(s,1H), 6.51(dd,1H),6.40(s,1H),6.33(s,1H),6.33(s,1H),6.17(s,1H),6.03(s,1H),4.17 (m,1H),4.12(m,2H),4.07(m,3H),4.00(dd,2H),3.89-3.95(m,6H),3.82(m,2H), 3.76(t,1H),3.71(t,1H),3.65(t,1H),3.14(t,1H),2.75(t,1H),2.62(dd,1H), 2.33-2.46(m,8H),2.20(m,1H),1.09-1.36(m,50H),0.51(s,9H).¹³C NMR(151MHz,CDCl₃)δ176.03,163.11,162.98,162.80,162.75,162.51,162.41,162.27,162.20,162.14,161.44,160.91,160.69,160.04,159.47,159.23,158.88,149.81,149.71,149.18,149.07,148.74,148.60,148.30,141.02,138.50,137.97,137.76,137.67,137.44,137.29,137.14,133.66,133.45,133.03,132.93,132.58,131.49,130.97,129.11,128.91,127.89,127.48,126.82,126.66,126.48,126.40,126.15,125.89,125.73,125.64,125.55,122.58,122.27,122.21,122.03,121.91,121.44,120.13,117.24,116.99,116.90,116.75,116.70,116.43,116.27,116.18,116.05,115.83,115.75,115.65,113.75,99.52,99.10,98.80,98.53,98.42,97.96,75.35,75.24,75.19,75.11,75.03,74.87,71.92,68.80,65.64,39.42,32.00,30.66,29.77,29.44,28.26,28.16,28.12,26.79,22.77,19.68,19.62,19.53,19.51,19.46,19.34,19.33,19.27,14.19,13.80.MS(ESI)calculated for[M+2H]²⁺1130.5134, found 1130.5148; the results of the detection revealed that the above compound had a correct structure.

Example 3

Preparation of Compounds of formula S-I3 or R-I3

The reaction formula is as follows:

the preparation process comprises the following steps:

1) dissolving 200mg L of the mixture in a 50mL two-mouth bottle under the protection of argon in 3mL of anhydrous dichloromethane, adding 5 mu L of oxalyl chloride by using an injector, stirring at room temperature for two hours, distilling under reduced pressure to remove an organic solvent, continuing vacuumizing on a vacuum pump for two hours, and dissolving in 1mL of anhydrous dichloromethane under the protection of argon for later use; the amount of substance 0.9 equivalents of 4-R-yl-2- (2-aminophenyl) oxazole was dissolved in anhydrous dichloromethane under argon in a 50mL two-necked flask and 11 μ L N, N-diisopropylethylamine was added, after which the above acid chloride solution was slowly added by syringe and stirred at room temperature overnight. Separating the product by column chromatography to obtain the compound M with the yield of 61-63 percent.

2) Mixing 150mg of compound M with 15mg of 10% palladium-carbon solid, dissolving in 5mL of ethyl acetate, and heating and stirring the solution in 1.0 MPa hydrogen overnight under the pressure of the solution; preferably, the reaction temperature is 60 ℃; and cooling the reaction solution, filtering out palladium-carbon solid after reaction through diatomite, and distilling the obtained filtrate under reduced pressure to remove the solvent to obtain yellow solid, namely the compound N. The yield is 89-95%;

3) 490mg of N is added into a 25mL two-port bottle, argon is used as protective gas, the compound is dissolved into 10mL of anhydrous dichloromethane, 10 mu L of N, N-diisopropylethylamine and 8 mu L of pivaloyl chloride are slowly added by a syringe, and stirring is carried out for 3 hours at room temperature; separating the yellow powdery product O of the product by column chromatography to obtain the compound shown as S-I3 or R-I3. The yield is 64-71%.

When the chiral aminophenyl oxazole is S-4-phenyl-2- (2-aminophenyl) oxazole, the resulting product is a compound of formula S-I3 in 71% yield. The structure detection structure of the compound is as follows:¹H NMR(600 MHz,CDCl₃)δ12.27(s,1H),10.92(s,1H),10.78(s,1H),10.77(s,1H),10.40(s, 1H),10.36(s,1H),10.25(s,1H),10.17(s,1H),10.14(s,1H),10.08(s,1H),10.06(s, 1H),10.02(s,1H),9.99(s,1H),9.96(s,1H),9.95(s,1H),9.92(s,1H),8.39(s,1H), 7.97(d,1H),7.92(d,1H),7.73-7.79(m,6H),7.68-7.71(m,5H),7.59-7.65(m,12H), 7.55(d,1H),7.50(d,1H),7.39(d,1H),7.31(d,1H),7.20(d,1H),7.18(d,1H), 7.07-7.12(m,3H),6.94-7.00(m,9H),6.92(d,1H),6.91(d,1H),6.90(d,1H),6.86(d, 1H),6.85(d,1H),6.75-6.81(7H),6.67(s,1H),6.65(s,1H),6.50(dd,1H),6.48(s, 1H),6.45(s,1H),6.41(d,1H),6.40(d,1H),6.27(dd,1H),6.06(s,1H),6.03(s,1H), 6.01(s,1H),6.00(s,1H),5.93(s,1H),5.90(s,1H),5.87(s,1H),5.79(s,1H),5.77(s, 1H),5.77(s,1H),5.74(s,1H),5.73(s,1H),5.73(s,1H),5.70(s,1H),3.95(m,2H), 3.83-3.87(m,2H),3.74-3.79(m,5H),3.63-3.71(m,16H),3.49-3.60(m,15H),3.00(t, 1H),2.52(t,1H),2.42(dd,1H),2.71-2.31(m,20H),1.25(s,104H),1.00-1.21(m, 144H),0.84-0.94(m,30H).MS(MALDI)calculated for C₂₄₄H₂₄₆N₃₄O₃₄[M+H]⁺4196.86, found 4196.13; the results of the detection revealed that the above compound had a correct structure.

When the chiral aminophenyl oxazole is R-4-phenyl-2- (2-aminophenyl) oxazole, the resulting product is a compound of formula R-I3 in 64% yield. The structure detection structure of the compound is as follows:¹H NMR(600 MHz,CDCl₃)δ12.27(s,1H),10.92(s,1H),10.78(s,1H),10.77(s,1H),10.40(s, 1H),10.36(s,1H),10.25(s,1H),10.17(s,1H),10.14(s,1H),10.08(s,1H),10.06(s, 1H),10.02(s,1H),9.99(s,1H),9.96(s,1H),9.95(s,1H),9.92(s,1H),8.39(s,1H), 7.97(d,1H),7.92(d,1H),7.73-7.79(m,6H),7.68-7.71(m,5H),7.59-7.65(m,12H), 7.55(d,1H),7.50(d,1H),7.39(d,1H),7.31(d,1H),7.20(d,1H),7.18(d,1H), 7.07-7.12(m,3H),6.94-7.00(m,9H),6.92(d,1H),6.91(d,1H),6.90(d,1H),6.86(d, 1H),6.85(d,1H),6.75-6.81(7H),6.67(s,1H),6.65(s,1H),6.50(dd,1H),6.48(s, 1H),6.45(s,1H),6.41(d,1H),6.40(d,1H),6.27(dd,1H),6.06(s,1H),6.03(s,1H), 6.01(s,1H),6.00(s,1H),5.93(s,1H),5.90(s,1H),5.87(s,1H),5.79(s,1H),5.77(s, 1H),5.77(s,1H),5.74(s,1H),5.73(s,1H),5.73(s,1H),5.70(s,1H),3.95(m,2H), 3.83-3.87(m,2H),3.74-3.79(m,5H),3.63-3.71(m,16H),3.49-3.60(m,15H),3.00(t, 1H),2.52(t,1H),2.42(dd,1H),2.71-2.31(m,20H),1.25(s,104H),1.00-1.21(m, 144H),0.84-0.94(m,30H).MS(MALDI)calculated for C₂₄₄H₂₄₆N₃₄O₃₄[M+H]⁺4196.86, found 4196.99; the results of the detection revealed that the above compound had a correct structure.

Example 4

Preparation of Compounds of formula S-II1 or R-II1

The reaction formula is as follows:

the preparation process comprises the following steps:

1) 200mg of compound I was dissolved in 5mL of anhydrous dichloromethane in a 50mL two-neck flask under argon protection, 34. mu.L of oxalyl chloride was added by a syringe, the mixture was stirred at room temperature for two hours, the organic solvent was distilled off under reduced pressure, vacuum was applied to a vacuum pump for two hours, and the mixture was dissolved in 1mL of anhydrous dichloromethane under argon protection for further use. Dissolving 4-R group-2- (2-aminophenyl) oxazole in an amount of 0.9 equivalent in anhydrous dichloromethane in a 50mL two-necked flask under the protection of argon, adding 65 mu L N of N-diisopropylethylamine, slowly adding the above acid chloride solution by using a syringe, and stirring at room temperature overnight; separating the product by column chromatography to obtain compound J; the yield is 71% -85%;

2) 200mg of Compound J was mixed with 20mg of a 10% palladium on carbon solid, and the mixture was dissolved in 10mL of ethyl acetate, and the solution was stirred overnight under heating under a hydrogen atmosphere. Filtering out the palladium-carbon solid after reaction by using kieselguhr, and distilling the obtained filtrate under reduced pressure to remove the solvent to obtain a yellow solid, namely the compound K; the yield is 91-95%;

3) 20mg of P is dissolved in 5mL of anhydrous dichloromethane in a 50mL two-neck flask under the protection of argon, 10 mu L of oxalyl chloride is added by a syringe, the mixture is stirred for two hours at room temperature, the organic solvent is removed by distillation under reduced pressure, the vacuum is continuously pumped on a vacuum pump for two hours, and the mixture is dissolved in 3mL of anhydrous dichloromethane under the protection of argon for standby. Dissolving a substance amount of 2.0 equivalents of compound K in anhydrous dichloromethane in a 50mL two-neck flask under the protection of argon, adding 21 mu L N of N-diisopropylethylamine, slowly adding the acyl chloride solution by using a syringe, and stirring at room temperature overnight; separating the product by column chromatography to obtain a compound represented by formula S-II1 or R-II 1; the yield is 41-51%.

When the chiral aminophenyl oxazole is S-4-phenyl-2- (2-aminophenyl) oxazole, the resulting product is a compound of formula S-II1 in 41% yield. The structure detection structure of the compound is as follows:¹H NMR(600 MHz,CDCl₃)δ12.35(s,2H),12.04(s,2H),11.03(s,2H),10.97(s,2H),10.81(s, 2H),8.10(dd,2H),8.09(dd,2H),8.00(d,2H),7.92(d,2H),7.80(d,2H),7.68 (d,1H),7.64(d,1H),7.56(d,1H),7.47(d,1H),7.47(s,1H),7.42(d,1H),7.33(d,1H), 7.04-7.19(m,6H),7.07(dd,2H),6.88(dd,2H),6.58(d,2H),6.54(s,2H),6.52(d,2H), 6.48(d,2H),6.43(s,2H),6.26(s,2H),6.14(s,2H),6.13(s,2H),6.11(s,2H),6.07 (s,2H),3.84-3.91(m,16H),3.73-3.79(m,6H),3.64-3.66(m,4H),3.09(t,2H),2.74 (dd,2H),2.36-2.50(m,10H),2.22-2.29(m,4H),2.12-2.15(m,2H),1.23-1.33(m, 160H).¹³C NMR(151MHz,CDCl₃)δ162.68,162.61,162.10,162.06,161.84,161.75, 161.58,160.53,159.78,159.74,159.55,148.90,148.81,148.48,148.21,147.43, 142.52,141.18,138.61,138.02,137.75,137.03,136.68,133.72,133.44,133.18, 133.10,131.21,129.18,127.85,127.32,126.73,126.45,126.22,125.54,122.26, 121.55,121.46,121.10,120.82,119.98,119.82,119.00,116.91,116.71,116.64, 116.21,115.98,115.04,113.68,99.63,98.41,98.13,97.56,75.28,75.17,75.04,74.81, 71.85,68.76,32.00,29.85,29.77,29.68,29.40,29.32,28.35,28.29,28.24,28.21, 28.08,27.29,25.61,22.76,19.80,19.75,19.68,19.59,19.55,19.42,19.31,14.18, 1.09,0.07.MS(ESI)calculated for C₁₆₄H₁₆₀N₂₂O₂₂[M+H]²⁺1395.6111, found 1395.6115; the results of the detection revealed that the above compound had a correct structure.

When the chiral aminophenyl oxazole is R-4-phenyl-2- (2-aminophenyl) oxazole, the resulting product is a compound of formula R-II1 in 51% yield. The structure detection structure of the compound is as follows:¹H NMR(400 MHz,CDCl₃)δ12.35(s,2H),12.04(s,2H),11.03(s,2H),10.97(s,2H),10.81(s, 2H),8.10(dd,2H),8.09(dd,2H),8.00(d,2H),7.92(d,2H),7.80(d,2H),7.68(d,1H), 7.64(d,1H),7.56(d,1H),7.47(d,1H),7.47(s,1H),7.42(d,1H),7.33(d,1H),7.04-7.19 (m,6H),7.07(dd,2H),6.88(dd,2H),6.58(d,2H),6.54(s,2H),6.52(d,2H),6.48 (d,2H),6.43(s,2H),6.26(s,2H),6.14(s,2H),6.13(s,2H),6.11(s,2H),6.07 (s,2H),3.84-3.91(m,16H),3.73-3.79(m,6H),3.64-3.66(m,4H),3.09(t,2H),2.74 (dd,2H),2.36-2.50(m,10H),2.22-2.29(m,4H),2.12-2.15(m,2H),1.23-1.33(m, 200H).¹³C NMR(151MHz,CDCl₃)δ163.30,163.20,163.13,163.04,162.62,162.53, 162.16,161.77,160.62,153.67,150.53,149.86,149.33,145.52,141.29,139.11, 138.98,138.45,138.23,135.45,133.93,133.92,131.79,129.64,128.73,128.09, 127.93,127.02,126.73,126.50,125.74,125.70,124.19,124.09,122.98,122.59, 122.04,121.92,120.47,117.66,117.09,116.71,116.50,115.26,100.36,99.97,99.00, 97.73,75.79,75.45,75.43,75.20,72.16,69.09,53.68,41.95,32.00,29.76,29.73, 29.43,29.39,28.38,28.36,28.30,28.24,22.76,19.53,19.51,19.46,19.43,19.40, 19.34,19.28,19.26,18.68,17.40,14.18,12.06.MS(ESI)calculated for C₁₆₄H₁₆₀N₂₂O₂₂[M+H]²⁺1395.6111, found 1395.6134; the results of the detection revealed that the above compound had a correct structure.

Examples 5,

Preparation of Compounds of formula S-II2 or R-II2

The reaction formula is as follows:

the preparation process comprises the following steps:

1) dissolving 200mg of compound R in 3mL of anhydrous dichloromethane in a 50mL two-neck flask under the protection of argon, adding 17 mu L of oxalyl chloride by using an injector, stirring at room temperature for two hours, removing the organic solvent by reduced pressure distillation, continuously vacuumizing on a vacuum pump for two hours, and dissolving in 1mL of anhydrous dichloromethane under the protection of argon for later use; the amount of substance 0.9 equivalents of 4-R-yl-2- (2-aminophenyl) oxazole was dissolved in anhydrous dichloromethane under argon in a 50mL two-necked flask and 35 μ L N, N-diisopropylethylamine was added, after which the above acid chloride solution was slowly added by syringe and stirred at room temperature overnight. Separating the product by column chromatography to obtain compound S; the yield is 71% -85%;

2) mixing 200mg of compound S with 20mg of 10% palladium-carbon solid, dissolving in 10mL of ethyl acetate, and heating and stirring the solution overnight under the atmospheric pressure in a hydrogen atmosphere; filtering out the palladium-carbon solid after reaction by using kieselguhr, and distilling the obtained filtrate under reduced pressure to remove the solvent to obtain a yellow solid, namely the compound T; the yield is 91-95%;

3) 20mg of P is dissolved in 10mL of anhydrous dichloromethane in a 50mL two-neck flask under the protection of argon, 10 mu L of oxalyl chloride is added by a syringe, the mixture is stirred for two hours at room temperature, the organic solvent is removed by distillation under reduced pressure, the vacuum is continuously pumped on a vacuum pump for two hours, and the mixture is dissolved in 3mL of anhydrous dichloromethane under the protection of argon for standby. Dissolving a substance amount of 2.0 equivalents of compound T in anhydrous dichloromethane in a 50mL two-neck flask under the protection of argon, adding 21 mu L N of N-diisopropylethylamine, slowly adding the acyl chloride solution by using a syringe, and stirring at room temperature overnight; separating the product by column chromatography to obtain a compound of formula S-II2 or R-II 2; the yield is 28-33%.

When the chiral aminophenyl oxazole is S-4-phenyl-2- (2-aminophenyl) oxazole, the resulting product is a compound of formula S-II2 in 33% yield. The structure detection structure of the compound is as follows:¹H NMR(600 MHz,CDCl₃)δ12.41(s,1H),11.64(s,1H),11.14(s,1H),11.01(s,1H),10.95(s, 1H),10.68(s,1H),10.60(s,1H),10.58(s,1H),10.51(s,1H),8.11(d,1H),8.06(d, 1H),8.03(d,1H),7.97(d,1H),7.96(d,1H),7.92(d,1H),7.90(d,1H),7.87(d,1H), 7.82(d,1H),7.80(d,1H),7.76(d,1H),7.74(d,1H),7.72(d,1H),7.71(d,1H),7.62 (d,1H),7.56(d,1H),7.41(d,1H),7.28-7.32(m,6H),7.19-7.24(m,10H),7.15(dd, 1H),7.09-7.12(m,3H),7.03-7.08(m,4H),7.02(s,1H),6.92(s,1H),6.89(d,1H), 6.88(d,1H),6.59(s,1H),6.57(d,1H),6.57(s,1H),6.50(s,1H),6.48(d,1H),6.47 (d,1H),6.28(s,1H),6.28(s,1H),6.15(s,1H),6.12(s,1H),6.11(s,1H),6.10(s,1H), 5.93(s,1H),4.11(m,2H),3.99-4.04(m,2H),3.84-3.92(m,20H),3.68-3.79(m,20H), 3.58(t,1H),3.08(t,1H),2.67(t,1H),2.52(dd,1H),2.33-2.44(m,19H),0.81-1.35(m, 90H).¹³C NMR(101MHz,CDCl₃)δ162.56,162.35,161.99,161.91,161.68,161.21, 161.03,160.93,160.39,159.63,158.99,158.76,158.35,148.90,148.55,148.37, 148.31,148.20,147.57,147.31,146.66,141.81,140.94,138.28,137.73,137.42, 137.04,136.91,136.75,136.23,135.97,133.35,133.19,132.52,132.31,131.32, 128.91,127.73,127.20,126.65,126.30,125.94,125.62,125.41,125.15,122.41, 121.95,121.70,121.23,121.09,120.30,119.99,119.27,118.43,116.61,116.32, 115.38,114.62,113.53,99.34,98.48,98.22,98.07,97.82,97.61,74.88,74.70,72.29, 71.71,68.56,32.01,31.52,30.39,30.28,29.78,29.44,28.87,28.53,28.11,28.01, 27.89,27.80,22.78,21.99,21.45,19.69,19.61,19.56,19.47,19.38,19.34,19.24, 19.21,14.21,9.76.MS(MALDI)calculated for C₂₇₆H₂₇₄N₃₈O₃₈[M+H]⁺4729.0755, found 4729.51; the results of the detection revealed that the above compound had a correct structure.

When the chiral aminophenyl oxazole is R-4-phenyl-2- (2-aminophenyl) oxazole, the resulting product is a compound of formula R-II2 in 28% yield. The structure detection structure of the compound is as follows:¹H NMR(600 MHz,CDCl₃)δ12.41(s,1H),11.64(s,1H),11.14(s,1H),11.01(s,1H),10.95(s, 1H),10.68(s,1H),10.60(s,1H),10.58(s,1H),10.51(s,1H),8.11(d,1H),8.06(d, 1H),8.03(d,1H),7.97(d,1H),7.96(d,1H),7.92(d,1H),7.90(d,1H),7.87(d,1H), 7.82(d,1H),7.80(d,1H),7.76(d,1H),7.74(d,1H),7.72(d,1H),7.71(d,1H),7.62 (d,1H),7.56(d,1H),7.41(d,1H),7.28-7.32(m,6H),7.19-7.24(m,10H),7.15(dd, 1H),7.09-7.12(m,3H),7.03-7.08(m,4H),7.02(s,1H),6.92(s,1H),6.89(d,1H), 6.88(d,1H),6.59(s,1H),6.57(d,1H),6.57(s,1H),6.50(s,1H),6.48(d,1H),6.47 (d,1H),6.28(s,1H),6.28(s,1H),6.15(s,1H),6.12(s,1H),6.11(s,1H),6.10(s,1H), 5.93(s,1H),4.11(m,2H),3.99-4.04(m,2H),3.84-3.92(m,20H),3.68-3.79(m,20H), 3.58(t,1H),3.08(t,1H),2.67(t,1H),2.52(dd,1H),2.33-2.44(m,19H),0.81-1.35(m, 90H).¹³C NMR(101MHz,CDCl₃)δ162.56,162.35,161.99,161.91,161.68,161.21, 161.03,160.93,160.39,159.63,158.99,158.76,158.35,148.90,148.55,148.37, 148.31,148.20,147.57,147.31,146.66,141.81,140.94,138.28,137.73,137.42, 137.04,136.91,136.75,136.23,135.97,133.35,133.19,132.52,132.31,131.32, 128.91,127.73,127.20,126.65,126.30,125.94,125.62,125.41,125.15,122.41, 121.95,121.70,121.23,121.09,120.30,119.99,119.27,118.43,116.61,116.32, 115.38,114.62,113.53,99.34,98.48,98.22,98.07,97.82,97.61,74.88,74.70,72.29, 71.71,68.56,32.01,31.52,30.39,30.28,29.78,29.44,28.87,28.53,28.11,28.01, 27.89,27.80,22.78,21.99,21.45,19.69,19.61,19.56,19.47,19.38,19.34,19.24, 19.21,14.21,9.76.MS(ESI)calculated for C₂₇₆H₂₇₄N₃₈O₃₈[M+Na]⁺4751.0574, found 4750.69; from the results of the detection, the above-mentionedThe compound has correct structure.

Example 6

Preparation of Compounds of formula S-II3 or R-II3

The reaction formula is as follows:

the preparation process comprises the following steps:

1) dissolving 200mg L of the mixture in a 50mL two-mouth bottle under the protection of argon in 3mL of anhydrous dichloromethane, adding 5 mu L of oxalyl chloride by using an injector, stirring at room temperature for two hours, distilling under reduced pressure to remove an organic solvent, continuing vacuumizing on a vacuum pump for two hours, and dissolving in 1mL of anhydrous dichloromethane under the protection of argon for later use; the amount of substance 0.9 equivalents of 4-R-yl-2- (2-aminophenyl) oxazole was dissolved in anhydrous dichloromethane under argon in a 50mL two-necked flask and 11 μ L N, N-diisopropylethylamine was added, after which the above acid chloride solution was slowly added by syringe and stirred at room temperature overnight. Separating the product by column chromatography to obtain compound M; the yield is 61-63%;

2) mixing 150mg of compound M with 15mg of 10% palladium-carbon solid, dissolving in 5mL of ethyl acetate, and heating and stirring the solution in 1.0 MPa hydrogen overnight under the pressure of the solution; preferably, the reaction temperature is 60 ℃; then cooling the reaction solution, filtering out palladium-carbon solid after reaction through diatomite, and distilling the obtained filtrate under reduced pressure to remove the solvent, wherein the obtained yellow solid is the compound N; the yield is 89-95%;

3) dissolving 10mg of P in 10mL of anhydrous dichloromethane in a 50mL two-mouth bottle under the protection of argon, adding 5 mu L of oxalyl chloride by using an injector, stirring at room temperature for two hours, distilling under reduced pressure to remove an organic solvent, continuously vacuumizing on a vacuum pump for two hours, and dissolving in 3mL of anhydrous dichloromethane under the protection of argon for later use; dissolving a compound N with the amount of 2.0 equivalents in anhydrous dichloromethane in a 50mL two-neck flask under the protection of argon, adding 10 mu L N of N-diisopropylethylamine, slowly adding the acyl chloride solution by using a syringe, and stirring at room temperature overnight; separating the product by column chromatography to obtain a compound of formula S-II3 or R-II 3; the yield is 19-25%.

When the chiral aminophenyl oxazole is S-4-phenyl-2- (2-aminophenyl) oxazole, the resulting product is a compound of formula S-II3 in 25% yield. The structure detection structure of the compound is as follows:¹H NMR(400 MHz,CDCl₃)δ12.27(s,1H),10.92(s,1H),10.78(s,1H),10.76(s,1H),10.40(s, 1H),10.36(s,1H),10.25(s,1H),10.17(s,1H),10.14(s,1H),10.08(s,1H),10.06(s, 1H),10.02(s,1H),9.99(s,1H),9.96(s,1H),9.95(s,1H),9.92(s,1H),8.39(s,1H), 7.97(d,1H),7.92(d,1H),7.59-7.79(m,25H),7.55(d,1H),7.49(d,1H),7.39(d,1H), 7.30(d,1H),7.17-7.21(m,3H),7.06-7.13(m,4H),6.93-7.02(m,12H),6.91(s,1H), 6.91(s,1H),6.89(d,1H),6.86(s,1H),6.75-6.84(m,8H),6.70(s,1H),6.65(s,1H), 6.51(d,1H),6.48(s,1H),6.45(s,1H),6.42(s,1H),6.40(d,1H),6.38(d,1H),6.06 (s,1H),6.03(s,1H),6.02(s,1H),6.00(s,1H),5.93(s,1H),5.90(s,1H),5.87(s,1H), 5.78(s,1H),5.77(s,1H),5.77(s,1H),5.74(s,1H),5.73(s,1H),5.72(s,1H),5.70(s, 1H),4.30(m,1H),3.94-3.98(m,2H),3.45-3.88(m,43H),3.37-.42(m,2H),3.00(dd, 1H),2.42(dd,1H),2.16-2.33(m,21H),2.11(dd,1H),1.39-1.49(m,6H),1.00-1.28 (m,222H),0.83-0.89(m,13H).MS(MALDI)calculated forC₅₀₀H₅₀₀N₇₀O₇₀[M+H]⁺8604.7795, found 8604.71; the results of the detection revealed that the above compound had a correct structure.

When the chiral aminophenyl oxazole is R-4-phenyl-2- (2-aminophenyl) oxazole, the resulting product is a compound of formula R-II3 in 19% yield. The structure detection structure of the compound is as follows:¹H NMR(400 MHz,CDCl₃)δ12.27(s,1H),10.92(s,1H),10.78(s,1H),10.76(s,1H),10.40(s, 1H),10.36(s,1H),10.25(s,1H),10.17(s,1H),10.14(s,1H),10.08(s,1H),10.06(s, 1H),10.02(s,1H),9.99(s,1H),9.96(s,1H),9.95(s,1H),9.92(s,1H),8.39(s,1H), 7.97(d,1H),7.92(d,1H),7.59-7.79(m,25H),7.55(d,1H),7.49(d,1H),7.39(d,1H), 7.30(d,1H),7.17-7.21(m,3H),7.06-7.13(m,4H),6.93-7.02(m,12H),6.91(s,1H), 6.91(s,1H),6.89(d,1H),6.86(s,1H),6.75-6.84(m,8H),6.70(s,1H),6.65(s,1H), 6.51(d,1H),6.48(s,1H),6.45(s,1H),6.42(s,1H),6.40(d,1H),6.38(d,1H),6.06 (s,1H),6.03(s,1H),6.02(s,1H),6.00(s,1H),5.93(s,1H),5.90(s,1H),5.87(s,1H), 5.78(s,1H),5.77(s,1H),5.77(s,1H),5.74(s,1H),5.73(s,1H),5.72(s,1H),5.70(s, 1H),4.30(m,1H),3.94-3.98(m,2H),3.45-3.88(m,43H),3.37-.42(m,2H),3.00(dd, 1H),2.42(dd,1H),2.16-2.33(m,21H),2.11(dd,1H),1.39-1.49(m,6H),1.00-1.28 (m,222H),0.83-0.89(m,13H).MS(MALDI)calculated forC₅₀₀H₅₀₀N₇₀O₇₀[M+H]⁺8604.7795, found 8604.63; the results of the detection revealed that the above compound had a correct structure.

Example 7,

The compounds prepared in examples 1 to 6 were subjected to measurement of ultraviolet-visible absorption spectrum, fluorescence spectrum, circular dichroism spectrum and circular polarized light emission spectrum as shown in table 1 using methylene chloride as a solvent, and circular dichroism spectrum and circular polarized light emission spectrum as shown in fig. 1 to 18.

As can be seen from table 1 and fig. 13 to 15, fig. 16 to 18, the g values of the circularly polarized luminescence and the quantum yields of the compounds prepared according to the present invention increased as the chain length of the compounds increased.

TABLE 1 optical Properties of the Compounds prepared in examples 1-6

It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. Not all embodiments are exhaustive. All obvious changes and modifications which are obvious to the technical scheme of the invention are covered by the protection scope of the invention.

Claims

1. A chiral fluorescent compound based on a quinoline amide foldate, which is characterized in that: the structural general formula of the compound is shown as the following formula I or formula II,

in the formula I or formula II, R₁Is an isobutyl group; r₂Is methyl, phenyl, isobutyl, benzyl or isopropyl; r₃Is tert-butyl and n is 4, 8 or 16.

2. The chiral fluorescent compound based on a quinoline amide fold according to claim 1, characterized in that:

the compound comprises an S enantiomer and an R enantiomer; wherein,

formula S-I, formula S-II, formula R-I or formula R-II wherein R₁Is an isobutyl group; r₂Is methyl, phenyl, isobutyl, benzyl or isopropyl; r₃Is tert-butyl and n is 4, 8 or 16.

3. A method for preparing a chiral fluorescent compound based on a quinoline amide foldate, wherein the compound is shown as formula I in claim 1, and the method comprises the following steps:

3) under the protection of argon, taking anhydrous dichloromethane as a solvent, taking N, N-diisopropylethylamine as a base, and stirring the amine of the single chiral quinoline amide polymer obtained in the step 2) and pivaloyl chloride at room temperature for 2-4 hours to obtain a compound shown in a formula I;

in the step 1), the structural formula of the 4-substituted chiral 2- (2-aminophenyl) oxazole is as follows:

wherein R is methyl, phenyl, isobutyl, benzyl or isopropyl;

in step 1), the carboxylic acid of the 4-isobutoxy-8-amino-2-carboxyquinoline amide multimer has the following structural formula:

in the step 1), the structural formula of the single chiral quinoline amide polymer is as follows:

wherein n is 4, 8, 16; r is methyl, phenyl, isobutyl, benzyl or isopropyl;

in the step 2), the amine of the chiral quinoline amide polymer has the following structural formula:

wherein R is methyl, phenyl, isobutyl, benzyl or isopropyl.

4. The method for preparing a chiral fluorescent compound based on a quinoline amide fold according to claim 3,

in the step 1), the ratio of the amount of the carboxylic acid of the N, N-diisopropylethylamine and 4-isobutoxy-8-amino-2-carboxyl quinoline amide polymer to the amount of the 4-substituted chiral 2- (2-aminophenyl) oxazole is 2-100: 1: 0.85-10;

in the step 3), the ratio of the amount of the pivaloyl chloride to the amount of the amine of the single chiral quinoline amide polymer is 1-500: 1.

5. A method for preparing a chiral fluorescent compound based on a quinoline amide foldate, wherein the compound is shown as formula I in claim 1, and the method comprises the following steps:

4) under the protection of argon, 4-substituted chiral 2- (2-aminophenyl) oxazole is dissolved in anhydrous dichloromethane, and N, N-diisopropylethylamine is added to obtain a solution c; dissolving acyl chloride of the pivaloyl quinoline amide polymer obtained in the step 3) in anhydrous dichloromethane to obtain a solution d, and mixing the solutions c and d to obtain a compound shown in the formula I;

in step 1), the amine of the 4-isobutoxy-8-amino-2-carboxyquinoline amide multimer has the following structural formula:

in the step 1), the structural formula of the pivaloyl quinoline amide polymer is as follows:

in step 2), the structural formula of the carboxylic acid of the pivaloyl quinoline amide polymer is as follows:

in the step 3), the structural formula of the acyl chloride of the pivaloyl quinoline amide polymer is as follows:

in the step 4), the structural formula of the 4-substituted chiral 2- (2-aminophenyl) oxazole is as follows:

wherein R is methyl, phenyl, isobutyl, benzyl or isopropyl.

6. The method of claim 5, wherein the chiral fluorescent compound is selected from the group consisting of:

in the step 1), the mass ratio of the amine of the N, N-diisopropylethylamine and 4-isobutoxy-8-amino-2-carboxyl quinoline amide polymer to the pivaloyl chloride is 2-100: 1: 0.85-10;

7. A method for preparing a chiral fluorescent compound based on a quinoline amide foldate, wherein the compound is shown as formula II in claim 1, and the method comprises the following steps:

2) under the protection of argon, dissolving amine of the chiral quinoline amide polymer in anhydrous dichloromethane, and adding N, N-diisopropylethylamine to obtain a solution e; dissolving the 4, 7-diisobutyl-1, 10-phenanthroline-2, 9-carboxylic acid chloride obtained in the step 1) in anhydrous dichloromethane to obtain a solution f; mixing the solution e and the solution f, and stirring to obtain a compound shown in a formula II;

wherein R is methyl, phenyl, isobutyl, benzyl or isopropyl.

8. The method for preparing a chiral fluorescent compound based on a quinoline amide fold according to claim 7,

in the step 1), the mass ratio of the 4, 7-diisobutyl-1, 10-phenanthroline-2, 9-carboxylic acid to oxalyl chloride is 1: 5-1000;

in the step 2), the mass ratio of the 4, 7-diisobutyl-1, 10-phenanthroline-2, 9-carboxylic acid chloride, N-diisopropylethylamine and the 4-substituted chiral 2- (2-aminophenyl) oxazole is 1: 5-1000: 2-10.

9. The use of a quinoline amide fold-based chiral fluorescent compound according to any one of claims 1 to 2 in the preparation of chiral organic light-emitting materials, in the preparation of chiral fluorescent probes.