A novel thiazole boron compound and its preparation method and application

Abstract

The present invention discloses an aminothiazole amide-boron difluoride compound and its preparation method and application. The compound is shown in formula I and is prepared according to the following method: a compound shown in formula II, boron trifluoride and a base are reacted in an organic solvent, and after the reaction is completed, an aminothiazole amide-boron difluoride compound shown in formula I is obtained. The raw materials of the method of the present invention are simple and easy to synthesize, the preparation process is concise, and the obtained aminothiazole amide-boron difluoride compound is easy to purify and separate, and has stable properties. The compound provided by the present invention has photophysical properties such as fluorescence and phosphorescence emission, and has broad application prospects.

Description

Technical Field

[0001] The invention relates to a novel thiazole boron compound and a preparation method and application thereof, belonging to the field of organic luminescent materials. Background Art

[0002] Room temperature phosphorescence has been widely studied because of its unique luminescence mechanism, long lifetime, and more red-shifted emission wavelength relative to fluorescence. In pure organic compound systems, it is difficult for molecular excited states to undergo intersystem crossing, and triplet excited states are more likely to undergo non-radiative transitions and are easily quenched by oxygen. The above characteristics are not conducive to the production of room temperature phosphorescence. Therefore, the preparation of pure organic compounds with room temperature phosphorescence properties has become a major research hotspot and difficulty (BZ Tang, Nat. Rev. Mater. 2020, 5, 869; W. Huang, Ann. Phys. (Berlin) 2019, 531, 1800482; B. Liu, Nat. Commun. 2019, 10, 2111.).

[0003] Fluorescent dye molecules containing boron centers have many advantages such as adjustable fluorescence emission spectra, good photostability, solubility and high fluorescence quantum yield (B. Gilroy, Angew. Chem. Int. Ed. 2019, 58, 1052; F. O'Shea, Chem. Soc. Rev. 2016, 45, 3846). They can be applied to many fields such as fluorescent probes (G. Yang, Nat. Commun. 2018, 9, 362), bioimaging (Nhu TNPhan, Angew. Chem. Int. Ed. 2019, 58, 3438), chemical sensing (G. Yang, Adv. Funct. Mater. 2013, 23, 340.), and ion detection (ZM Huiden, Angew. Chem. Int. Ed. 2018, 57, 3377.), and have attracted much attention. If boron-containing fluorescent dye molecules with room temperature phosphorescence properties can be developed, their various luminescence properties can be used to broaden their application range. At the same time, such compounds can also be used to further study their room temperature phosphorescence mechanism. Summary of the invention

[0004] The purpose of the present invention is to provide a novel aminothiazole amide-boron difluoride compound, which has photophysical properties such as fluorescence and phosphorescence emission and has broad application prospects.

[0005] The aminothiazole amide-boron difluoride compound provided by the present invention has a general structural formula as shown in Formula I:

[0006]

[0007] In Formula I, R 1 Any one selected from the following groups:

[0008]

[0009] Among them, R 3 Any one of the following groups: -H, -F, -Cl, -Br, -I, -NO2, -CF3, -N3, -R 5 、-OR 6 , R 5 and R 6 are all alkyl groups having 1 to 10 carbon atoms, preferably alkyl groups having 1 to 5 carbon atoms, and more preferably methyl groups;

[0010] R 4 Any one selected from the following groups:

[0011] R 2 Any one selected from the following groups:

[0012] - t Bu,

[0013] The aminothiazole amide-boron difluoride compound of the present invention is preferably any one of the following:

[0014]

[0015]

[0016] The present invention also provides a method for preparing the aminothiazole amide-boron difluoride compound, comprising the following steps:

[0017] In the presence of a base, the compound represented by formula II reacts with boron trifluoride in an organic solvent to obtain the product;

[0018]

[0019] In formula II, the definitions of the various groups are the same as in formula I.

[0020] In the above preparation method, the base can be at least one of diisopropylethylamine (DIPEA), triethylamine (TEA), pyridine, piperidine, 4-dimethylaminopyridine (DMAP), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,4-diazabicyclo[2.2.2]octane (DABCO), calcium carbonate, cesium carbonate and cesium fluoride, preferably DIPEA.

[0021] In the above preparation method, the organic solvent may be at least one of n-hexane, toluene, ether, dichloromethane, 1,2-dichloroethane, tetrahydrofuran, chloroform and acetonitrile, preferably chloroform.

[0022] In the above preparation method, the usage ratio of the compound represented by formula II, the base, the boron trifluoride and the organic solvent is: 0.20mmol:1.0-3.0mmol:1.0-3.0mmol:2.0-8.0mL, preferably 0.2mmol:0.2mmol:3mmol:2.0mL.

[0023] In the above preparation method, the reaction temperature can be from room temperature to the reflux temperature of the organic solvent, and the reaction time is 1.0 to 12.0 hours.

[0024] The aminothiazole amide-boron difluoride compound shown in formula I provided by the present invention has photophysical properties such as fluorescence and phosphorescence, and can therefore be used as a room temperature phosphorescent material and a room temperature fluorescent material.

[0025] The invention adopts a substrate that is easy to synthesize, a cheap and readily available base and boron trifluoride, and synthesizes a novel aminothiazole amide-boron difluoride compound through a simple coordination reaction. The reaction conditions are mild, and the obtained product is stable in the air and easy to separate and purify. At the same time, the product also exhibits excellent photophysical properties such as fluorescence and phosphorescence, and has broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 It is the emission spectrum of the compound represented by Formula Ie at room temperature. DETAILED DESCRIPTION

[0027] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0028] Unless otherwise specified, the materials and reagents used in the following examples can be obtained from commercial sources.

[0029] Example 1: Preparation of compound Ia (R 1 is phenyl, R 2 for- t Bu)

[0030] The reaction formula is as follows:

[0031]

[0032] 0.20mmol of the compound represented by formula IIa was placed in a 25mL Schlenk tube, protected by argon, and evacuated and replaced 3 times. 2.0mL of deoxygenated dry chloroform was injected into the system, and the solid was completely dissolved by stirring. 2.0mmol of DIPEA was injected into the system, and the mixture was stirred at room temperature for 15min. 3.0mmol of BF3·Et2O was injected into the system, and the mixture was stirred at room temperature for 15min. The system was then transferred to a preheated oil bath and heated to reflux, and the heating and stirring were continued for 2h. 4mL of H2O was added to the system to quench the reaction. The system was extracted with CH2Cl2 (5mL×3 times). The organic phases were combined and washed with saturated NaCl solution 3 times. The organic phase was separated, dried by adding Na2SO4, and allowed to stand. Na2SO4 was removed by filtration, the solvent was removed by rotary evaporation, and the mixture was separated by column chromatography (200-300 mesh silica gel, eluent was petroleum ether: ethyl acetate = 10:1). 64mg of compound Ia was obtained. The compound was a yellow solid with a yield of 84%.

[0033] MP:173℃.

[0034] 1 H NMR (500MHz, CDCl3): δ (ppm) 7.96 (dd, J = 7.3, 4.5Hz, 2H), 7.51-7.49 (m, 3H), 6.71 (br, 1H), 1.52 (s, 9H), 1.44 (s, 9H).

[0035] 13 C NMR (125MHz, CDCl3): δ (ppm) 162.8, 151.4, 145.0, 131.7, 129.5, 127.7, 127.6, 124.6, 53.4, 53.2, 28.6.

[0036] IR(KBr):υ(cm -1 )3316(m),2978(m),2966(m),1653(s),1586(s),1311(s),1132(s).

[0037] HRMS(ESI):m / z calcd.for C 18 H 25 BF2N3OS[M+H] + 380.1774; found 380.1769.

[0038] EA:calcd.for C 18 H 24BF2N3OS: C 57.00%, H 6.38%, N 11.08%; found: C 56.93%, H6.41%, N 11.06%.

[0039] It can be seen from the above that the structure of the above compound is correct and is the compound represented by formula Ia.

[0040] Among them, the preparation method of the compound represented by formula IIa as a reactant is as follows (J. Zhu, Angew. Chem. Int. Ed. 2017, 56, 6599):

[0041]

[0042] Take 2.50mmol of the compound represented by formula IIIa and 0.25mmol of Y(OTf)3 and add them into a 100mL two-necked bottle, protect with argon, and evacuate and replace three times. Inject 50mL of deoxygenated dry toluene into the system, and then inject 12.50mmol t BuNC. Heat the system in an 80°C oil bath, continue heating and stirring for 2 hours. Quench the reaction with a saturated NaHCO3 solution, separate the organic phase, and extract the aqueous phase with ethyl acetate (20 mL × 3 times). Combine the organic phases, and then wash with a saturated NaCl solution 3 times. Separate the organic phase, add Na2SO4 to dry, and let stand. Filter to remove Na2SO4, remove the solvent by rotary evaporation, and separate by column chromatography (200-300 mesh silica gel, eluent is petroleum ether: ethyl acetate = 40:1). 457 mg of the compound of formula IIa is obtained. The compound is a yellow solid with a yield of 69%.

[0043] Example 2: Preparation of compound Ib (R 1 for R 2 for- t Bu)

[0044] The reaction formula is as follows:

[0045]

[0046] 0.20 mmol of the compound represented by formula IIb was placed in a 25 mL Schlenk tube, protected by argon, and evacuated and replaced 3 times. 2.0 mL of deoxygenated dry chloroform was injected into the system, and the solid was completely dissolved by stirring. 2.0 mmol of DIPEA was injected into the system, and the mixture was stirred at room temperature for 15 min. 3.0 mmol of BF3·Et2O was injected into the system, and the mixture was stirred at room temperature for 15 min. The system was then transferred to a preheated oil bath and heated to reflux, and the heating and stirring were continued for 2 h. 4 mL of H2O was added to the system to quench the reaction. The system was extracted with CH2Cl2 (5 mL × 3 times). The organic phases were combined and washed with saturated NaCl solution 3 times. The organic phase was separated, dried by adding Na2SO4, and allowed to stand. Na2SO4 was removed by filtration, the solvent was removed by rotary evaporation, and the mixture was separated by column chromatography (200-300 mesh silica gel, eluent was petroleum ether: ethyl acetate = 10:1). 44 mg of the compound represented by formula Ib was obtained. The compound was a yellow solid with a yield of 55%.

[0047] MP:178℃.

[0048] 1 H NMR (400MHz, CDCl3): δ (ppm) 7.97 (dd, J = 8.5, 5.0Hz, 2H), 7.19 (t, J = 8.5Hz, 2H), 6.69 (br, 1H), 1.52 (s, 9H), 1.44 (s, 9H).

[0049] 13 C NMR (100MHz, CDCl3): δ (ppm) 165.9, 163.4, 162.7, 150.1, 144.9, 130.0, 124.0, 117.0, 116.8, 53.5, 53.2, 28.6.

[0050] IR(KBr):υ(cm -1 )3317(m),2971(m),1653(s),1584(s),1332(s),1132(s).

[0051] HRMS(ESI):m / z calcd for C 18 H 24 BF3N3OS[M+H] + 398.1680; found 398.1679.

[0052] EA:calcd.for C 18 H 23BF3N3OS: C 54.42%, H 5.84%, N 10.58%; found: C 54.64%, H 5.77%, N 10.39%.

[0053] It can be seen from the above that the structure of the above compound is correct and is the compound shown in Formula Ib.

[0054] The preparation method of the compound represented by formula IIb as a reactant is as follows:

[0055]

[0056] Take 30.0mmol of the compound represented by formula Vb and put it into a 100mL single-mouth bottle, and then add 15mL SOCl2 to the system. Place the system in a preheated oil bath and heat it to reflux, continue heating and stirring for 2h. Remove the solvent by rotary evaporation to obtain the compound represented by formula IVb, which is a yellow transparent liquid. Slowly add the compound represented by formula IVb to the NaHS solution cooled in an ice-water bath (60mmol NaHS is ultrasonically dissolved in a mixture of 4mL H2O and 36mL EtOH). The system is continuously cooled and stirred in an ice-water bath for 40min. Slowly add dilute hydrochloric acid to the system to make the pH of the system ≈ 2.0. Use ethyl acetate to extract the aqueous phase (20mL×3 times). Combine the organic phases and wash them 3 times with a saturated NaCl solution. Separate the organic phase, add Na2SO4 to dry, and let it stand. Filter to remove Na2SO4, and remove the solvent by rotary evaporation to obtain 4.30g of the compound represented by formula IIIb, which is a yellow liquid with a yield of 92%.

[0057] Take 2.50mmol of the compound represented by formula IIIb and 0.25mmol of Y(OTf)3 and add them into a 100mL two-necked bottle, protect with argon, and evacuate and replace three times. Inject 50mL of deoxygenated dry toluene into the system, and then inject 12.50mmol t BuNC. Heat the system in an 80°C oil bath, continue heating and stirring for 2 hours. Quench the reaction with a saturated NaHCO3 solution, separate the organic phase, and extract the aqueous phase with ethyl acetate (20 mL × 3 times). Combine the organic phases, and then wash with a saturated NaCl solution 3 times. Separate the organic phase, add Na2SO4 to dry, and let stand. Filter to remove Na2SO4, remove the solvent by rotary evaporation, and separate by column chromatography (200-300 mesh silica gel, eluent is petroleum ether: ethyl acetate = 40:1). 664 mg of the compound shown in formula IIb was obtained. The compound is a yellow solid with a yield of 76%.

[0058] Example 3: Preparation of compound Ic (R 1 for R 2 for- t Bu)

[0059] The reaction formula is as follows:

[0060]

[0061] 0.20mmol of the compound represented by formula IIc was placed in a 25mL Schlenk tube, protected by argon, and evacuated and replaced 3 times. 2.0mL of deoxygenated dry chloroform was injected into the system, and the solid was completely dissolved by stirring. 2.0mmol of DIPEA was injected into the system, and the mixture was stirred at room temperature for 15min. 3.0mmol of BF3·Et2O was injected into the system, and the mixture was stirred at room temperature for 15min. The system was then transferred to a preheated oil bath and heated to reflux, and the heating and stirring were continued for 2h. 4mL of H2O was added to the system to quench the reaction. The system was extracted with CH2Cl2 (5mL×3 times). The organic phases were combined and washed with saturated NaCl solution 3 times. The organic phase was separated, dried by adding Na2SO4, and allowed to stand. Na2SO4 was removed by filtration, the solvent was removed by rotary evaporation, and the mixture was separated by column chromatography (200-300 mesh silica gel, eluent was petroleum ether: ethyl acetate = 10:1). 51mg of the compound represented by formula Ic was obtained. The compound was a yellow solid with a yield of 62%.

[0062] MP:180℃.

[0063] 1 H NMR (400MHz, CDCl3): δ (ppm) 7.89 (d, J = 8.6 Hz, 2H), 7.46 (d, J = 8.6 Hz, 2H), 6.73 (br, 1H), 1.55 (s, 9H), 1.44 (s, 9H).

[0064] 13 C NMR (100MHz, CDCl3): δ (ppm) 162.7, 149.5, 145.1, 138.0, 129.8, 128.8, 126.1, 124.6, 53.5, 53.2, 28.5.

[0065] IR(KBr):υ(cm -1 )3312(m),2970(m),1653(s),1582(s),1334(s),1135(s).

[0066] HRMS(ESI):m / z calcd for C 18 H 22 BClF2N3OS[MH] - 412.1239; found 412.1238.

[0067] EA:calcd.for C 18 H 23 BClF2N3OS: C 52.26%, H 5.60%, N 10.16%; found: C 52.27%, H 5.43%, N 10.19%.

[0068] It can be seen from the above that the structure of the above compound is correct and is the compound represented by formula Ic.

[0069] The preparation method of the compound represented by formula IIc as a reactant is as follows:

[0070]

[0071] Take 15.0mmol of the compound shown in formula IVc, and slowly add a NaHS solution cooled in an ice-water bath (30mmol NaHS is ultrasonically dissolved in a mixture of 2mL H2O and 18mL EtOH). The system is continuously cooled and stirred in an ice-water bath for 40min. Slowly add dilute hydrochloric acid to the system to make the pH of the system ≈ 2.0. Use ethyl acetate to extract the aqueous phase (20mL×3 times). Combine the organic phases and wash them 3 times with a saturated NaCl solution. Separate the organic phase, add Na2SO4 to dry, and let it stand. Filter to remove Na2SO4, and remove the solvent by rotary evaporation to obtain 1.19g of the compound shown in formula IIIb, which is a yellow-green solid with a yield of 46%.

[0072] Take 2.0mmol of the compound represented by formula IIIc and 0.20mmol of Y(OTf)3 and add them into a 100mL two-necked bottle, protect with argon, and evacuate and replace three times. Inject 40mL of deoxygenated dry toluene into the system, and then inject 10.0mmol t BuNC. The system was placed in an 80°C oil bath and heated, and the heating and stirring were continued for 2 hours. The reaction was quenched with a saturated NaHCO3 solution, the organic phase was separated, and the aqueous phase was extracted with ethyl acetate (20 mL × 3 times). The organic phases were combined and then washed 3 times with a saturated NaCl solution. The organic phase was separated, added with Na2SO4, dried, and allowed to stand. Na2SO4 was removed by filtration, the solvent was removed by rotary evaporation, and column chromatography was performed (200-300 mesh silica gel, the eluent was petroleum ether: ethyl acetate = 40:1). 527 mg of the compound shown in formula IIc was obtained. The compound was a yellow solid with a yield of 72%.

[0073] Example 4: Preparation of compound Id (R 1 for R 2 for- t Bu)

[0074] The reaction formula is as follows:

[0075]

[0076] 0.20 mmol of the compound represented by formula IId was placed in a 25 mL Schlenk tube, protected by argon, and evacuated and replaced 3 times. 2.0 mL of deoxygenated dry chloroform was injected into the system, and the solid was completely dissolved by stirring. 2.0 mmol of DIPEA was injected into the system, and the mixture was stirred at room temperature for 15 min. 3.0 mmol of BF3·Et2O was injected into the system, and the mixture was stirred at room temperature for 15 min. The system was then transferred to a preheated oil bath and heated to reflux, and the heating and stirring were continued for 2 h. 4 mL of H2O was added to the system to quench the reaction. The system was extracted with CH2Cl2 (5 mL × 3 times). The organic phases were combined and washed with saturated NaCl solution 3 times. The organic phase was separated, dried by adding Na2SO4, and allowed to stand. Na2SO4 was removed by filtration, the solvent was removed by rotary evaporation, and the mixture was separated by column chromatography (200-300 mesh silica gel, eluent was petroleum ether: ethyl acetate = 10:1). 46 mg of the compound represented by formula Id was obtained. The compound was a yellow solid with a yield of 50%.

[0077] MP:190℃.

[0078] 1 H NMR (400MHz, CDCl3): δ (ppm) 7.82 (d, J = 8.6 Hz, 2H), 7.62 (d, J = 8.6 Hz, 2H), 6.74 (br, 1H), 1.51 (s, 9H), 1.44 (s, 9H).

[0079] 13 C NMR (100MHz, CDCl3): δ (ppm) 162.7, 149.6, 145.1, 132.8, 128.9, 126.5, 126.4, 124.7, 53.5, 53.2, 28.5.

[0080] IR(KBr):υ(cm -1 )3312(m),2963(m),1656(s),1581(s),1308(s),1135(s).

[0081] HRMS(ESI):m / z calcd for C 18 H 22 BBrF2N3OS[MH] - 456.0734; found 456.0732.

[0082] EA:calcd.for C 18 H 23BBrF2N3OS: C 47.19%, H 5.06%, N 9.17%; found: C47.14%, H5.07%, N 8.96%.

[0083] It can be seen from the above that the structure of the above compound is correct and is the compound represented by formula Id.

[0084] The preparation method of the compound represented by formula IId as the reactant is as follows:

[0085]

[0086] Take 15.0mmol of the compound shown in formula Vd and put it into a 50mL single-mouth bottle, and then add 10mL SOCl2 to the system. Place the system in a preheated oil bath and heat it to reflux, continue heating and stirring for 2h. Rotary evaporation removes the solvent to obtain the compound shown in formula IVd, which is a nearly white solid. Slowly add the compound shown in formula IVd to the NaHS solution cooled in an ice-water bath (30mmol NaHS is ultrasonically dissolved in a mixture of 2mL H2O and 18mL EtOH). The system is continuously cooled and stirred in an ice-water bath for 50min. Filter to remove insoluble matter. Slowly add dilute hydrochloric acid to the filtrate to make the system pH≈2.0. A white precipitate is precipitated in the system, and 2.38g of the compound shown in formula IIId is filtered out. The compound is a white solid with a yield of 73%.

[0087] Take 2.0mmol of the compound represented by formula IIId and 0.2mmol of Y(OTf)3 and add them into a 100mL two-necked bottle, protect with argon, and evacuate and replace three times. Inject 40mL of deoxygenated dry toluene into the system, and then inject 10.0mmol t BuNC. Heat the system in an 80°C oil bath, continue heating and stirring for 2 hours. Quench the reaction with a saturated NaHCO3 solution, separate the organic phase, and extract the aqueous phase with ethyl acetate (20 mL × 3 times). Combine the organic phases, and then wash with a saturated NaCl solution 3 times. Separate the organic phase, add Na2SO4 to dry, and let stand. Filter to remove Na2SO4, remove the solvent by rotary evaporation, and separate by column chromatography (200-300 mesh silica gel, eluent is petroleum ether: ethyl acetate = 40:1). 396 mg of the compound shown in formula IId is obtained. The compound is a yellow oily substance with a yield of 48%.

[0088] Example 5: Preparation of compound Ie (R 1 for R 2 for- t Bu)

[0089] The reaction formula is as follows:

[0090]

[0091] 0.20 mmol of the compound represented by formula IIe was placed in a 25 mL Schlenk tube, protected by argon, and evacuated and replaced 3 times. 2.0 mL of deoxygenated dry chloroform was injected into the system, and the solid was completely dissolved by stirring. 2.0 mmol of DIPEA was injected into the system, and the mixture was stirred at room temperature for 15 min. 3.0 mmol of BF3·Et2O was injected into the system, and the mixture was stirred at room temperature for 15 min. The system was then transferred to a preheated oil bath and heated to reflux, and the heating and stirring were continued for 2 h. 4 mL of H2O was added to the system to quench the reaction. The system was extracted with CH2Cl2 (5 mL × 3 times). The organic phases were combined and washed with saturated NaCl solution 3 times. The organic phase was separated, dried by adding Na2SO4, and allowed to stand. Na2SO4 was removed by filtration, the solvent was removed by rotary evaporation, and the mixture was separated by column chromatography (200-300 mesh silica gel, eluent was petroleum ether: ethyl acetate = 10:1). 46 mg of the compound represented by formula Ie was obtained. The compound was a yellow solid with a yield of 46%.

[0092] MP:190℃.

[0093] 1 H NMR (500MHz, CDCl3): δ (ppm) 7.83 (d, J = 8.6 Hz, 2H), 7.67 (d, J = 8.6 Hz, 2H), 6.75 (br, 1H), 1.51 (s, 9H), 1.43 (s, 9H).

[0094] 13 C NMR (125MHz, CDCl3): δ (ppm) 162.7, 149.7, 145.1, 138.7, 128.8, 127.0, 124.7, 98.6, 53.5, 53.2, 28.6, 28.5.

[0095] IR(KBr):υ(cm -1 )3315(m),2968(m),1652(s),1587(s),1314(s),1138(s).

[0096] HRMS(ESI):m / z calcd for C 18 H 22 BF2IN3OS[MH] - 504.0595; found 504.0593.

[0097] EA:calcd.for C 18 H 23BF2IN3OS:C 42.80%, H 4.59%, N 8.32%; found: C42.89%, H4.44%, N 8.44%.

[0098] It can be seen from the above that the structure of the above compound is correct and is the compound represented by formula Ie.

[0099] The preparation method of the compound represented by formula IIe as a reactant is as follows:

[0100]

[0101] Take 30.0mmol of the compound represented by formula Ve and put it into a 100mL single-mouth bottle, and then add 15mL SOCl2 to the system. Place the system in a preheated oil bath and heat it to reflux, continue heating and stirring for 4h. Remove the solvent by rotary evaporation to obtain the compound represented by formula IVe as a white solid. Slowly add the compound represented by formula IVe to the NaHS solution cooled in an ice-water bath (60mmol NaHS is ultrasonically dissolved in a mixture of 4mL H2O and 36mL EtOH). The system is continuously cooled and stirred in an ice-water bath for 1h. Filter to remove insoluble matter. Slowly add dilute hydrochloric acid to the filtrate to make the system pH≈2.0. A white precipitate is precipitated in the system, and 6.67g of the compound represented by formula IIIe is obtained by filtration. The compound is a nearly white solid with a yield of 84%.

[0102] Take 2.50mmol of the compound represented by formula IIIe and 0.25mmol of Y(OTf)3 and add them into a 100mL two-necked bottle, protect with argon, and evacuate and replace three times. Inject 50mL of deoxygenated dry toluene into the system, and then inject 12.50mmol t BuNC. Heat the system in an 80°C oil bath, continue heating and stirring for 3 hours. Quench the reaction with a saturated NaHCO3 solution, separate the organic phase, and extract the aqueous phase with ethyl acetate (20 mL × 3 times). Combine the organic phases, and then wash with a saturated NaCl solution 3 times. Separate the organic phase, add Na2SO4 to dry, and let stand. Filter to remove Na2SO4, remove the solvent by rotary evaporation, and separate by column chromatography (200-300 mesh silica gel, eluent is petroleum ether: ethyl acetate = 40:1). 772 mg of the compound of formula IIe is obtained. The compound is a yellow solid with a yield of 68%.

[0103] Example 6: Preparation of the compound If(R 1 for R 2 for- t Bu)

[0104] The reaction formula is as follows:

[0105]

[0106] 0.20mmol of the compound represented by formula IIf was placed in a 25mL Schlenk tube, protected by argon, and evacuated and replaced 3 times. 2.0mL of deoxygenated dry chloroform was injected into the system, and the solid was completely dissolved by stirring. 2.0mmol of DIPEA was injected into the system, and the mixture was stirred at room temperature for 15min. 3.0mmol of BF3·Et2O was injected into the system, and the mixture was stirred at room temperature for 15min. The system was then transferred to a preheated oil bath and heated to reflux, and the heating and stirring were continued for 2h. 4mL of H2O was added to the system to quench the reaction. The system was extracted with CH2Cl2 (5mL×3 times). The organic phases were combined and washed with saturated NaCl solution 3 times. The organic phase was separated, dried by adding Na2SO4, and allowed to stand. Na2SO4 was removed by filtration, the solvent was removed by rotary evaporation, and the mixture was separated by column chromatography (200-300 mesh silica gel, eluent was petroleum ether: ethyl acetate = 10:1). 11mg of the compound represented by formula If was obtained. The compound was a yellow solid with a yield of 12%.

[0107] MP:179℃.

[0108] 1 H NMR (400MHz, CDCl3): δ (ppm) 8.08 (d, J = 8.3Hz, 2H), 7.74 (d, J = 8.3Hz, 2H), 6.85 (br, 1H), 1.51 (s, 9H), 1.46 (s, 9H).

[0109] 13 C NMR (100MHz, CDCl3): δ (ppm) 162.6, 148.1, 145.8, 133.0, 132.7, 130.8, 127.9, 126.5, 125.0, 124.8, 53.6, 53.3, 28.5.

[0110] IR(KBr):υ(cm -1 )3314(m),2969(m),1660(s),1581(s),1325(s),1132(s).

[0111] HRMS(ESI):m / z calcd.for C 19 H 22 BF5N3OS[MH] - 446.1502; found 446.1496.

[0112] EA:calcd.for C 19 H 23BF5N3OS: C 51.02%, H 5.18%, N 9.39%; found: C 51.26%, H5.15%, N 9.51%.

[0113] From the above, it can be seen that the structure of the above compound is correct and is the compound represented by formula If.

[0114] The preparation method of the compound represented by formula IIf as a reactant is as follows:

[0115]

[0116] Take 30.0mmol of the compound represented by formula Vf and put it into a 100mL single-mouth bottle, and then add 15mL SOCl2 to the system. Place the system in a preheated oil bath and heat it to reflux, continue heating and stirring for 2h. Remove the solvent by rotary evaporation to obtain the compound represented by formula IVf, which is a dark gray liquid. Slowly add the compound represented by formula IVf to the NaHS solution cooled in an ice-water bath (60mmol NaHS is ultrasonically dissolved in a mixture of 4mL H2O and 36mL EtOH). The system is continuously cooled and stirred in an ice-water bath for 70min. Slowly add dilute hydrochloric acid to the system to make the pH of the system ≈ 2.0. Use ethyl acetate to extract the aqueous phase (20mL×3 times). Combine the organic phases and wash them 3 times with a saturated NaCl solution. Separate the organic phase, add Na2SO4 to dry, and let it stand. Filter to remove Na2SO4, and remove the solvent by rotary evaporation to obtain 5.83g of the compound represented by formula IIIf, which is a yellow liquid with a yield of 94%.

[0117] Take 3.0mmol of the compound represented by formula IIIf and 0.30mmol of Y(OTf)3 and add them into a 100mL two-necked bottle, protect with argon, and evacuate and replace three times. Inject 60mL of deoxygenated dry toluene into the system, and then inject 15.0mmol t BuNC. Heat the system in an 80°C oil bath, continue heating and stirring for 2 hours. Quench the reaction with a saturated NaHCO3 solution, separate the organic phase, and extract the aqueous phase with ethyl acetate (20 mL × 3 times). Combine the organic phases, and then wash with a saturated NaCl solution 3 times. Separate the organic phase, add Na2SO4 to dry, and let stand. Filter to remove Na2SO4, remove the solvent by rotary evaporation, and separate by column chromatography (200-300 mesh silica gel, eluent is petroleum ether: ethyl acetate = 40:1). 323 mg of the compound shown in formula IIf was obtained. The compound is a yellow solid with a yield of 27%.

[0118] Example 7: Preparation of compound Ig (R 1 for R 2 for- t Bu)

[0119] The reaction formula is as follows:

[0120]

[0121] 0.20 mmol of the compound represented by formula IIg was placed in a 25 mL Schlenk tube, protected by argon, and evacuated and replaced 3 times. 2.0 mL of deoxygenated dry chloroform was injected into the system, and the solid was completely dissolved by stirring. 2.0 mmol of DIPEA was injected into the system, and the mixture was stirred at room temperature for 15 min. 3.0 mmol of BF3·Et2O was injected into the system, and the mixture was stirred at room temperature for 15 min. The system was then transferred to a preheated oil bath and heated to reflux, and the heating and stirring were continued for 2 h. 4 mL of H2O was added to the system to quench the reaction. The system was extracted with CH2Cl2 (5 mL × 3 times). The organic phases were combined and washed with saturated NaCl solution 3 times. The organic phase was separated, dried by adding Na2SO4, and allowed to stand. Na2SO4 was removed by filtration, the solvent was removed by rotary evaporation, and column chromatography was performed (200-300 mesh silica gel, eluent was petroleum ether: ethyl acetate = 10:1). 32 mg of the compound represented by formula Ig was obtained. The compound was a yellow solid with a yield of 41%.

[0122] MP:184℃.

[0123] 1 H NMR (500MHz, CDCl3): δ (ppm) 7.84 (d, J = 8.2Hz, 2H), 7.28 (d, J = 8.2Hz, 2H), 6.65 (br, 1H), 2.41 (s, 3H), 1.52 (s, 9H), 1.43 (s, 9H).

[0124] 13 C NMR (125MHz, CDCl3): δ (ppm) 162.8, 152.0, 144.6, 142.5, 130.2, 127.6, 124.9, 124.4, 53.4, 53.1, 28.7, 28.6, 21.6.

[0125] IR(KBr):υ(cm -1 )3307(m),2962(m),1653(s),1588(s),1311(s),1126(s).

[0126] HRMS(ESI):m / z calcd for C 19 H 27 BF2N3OS[M+H] + 394.1936; found 394.1934.

[0127] EA:calcd.for C 19 H 26 BF2N3OS: C 58.02%, H 6.66%, N 10.68%; found: C58.14%, H6.73%, N 10.54%.

[0128] It can be seen from the above that the structure of the above compound is correct and is the compound represented by formula Ig.

[0129] The preparation method of the compound shown in formula IIg as the reactant is as follows:

[0130]

[0131] Take 40.0mmol of the compound represented by formula Vg and put it into a 100mL single-mouth bottle, and then add 15mL SOCl2 to the system. Place the system in a preheated oil bath and heat it to reflux, continue heating and stirring for 3.5h. Remove the solvent by rotary evaporation to obtain the compound represented by formula IVg, which is a nearly colorless liquid. Slowly add the compound represented by formula IVg to the NaHS solution cooled in an ice-water bath (80mmol NaHS is ultrasonically dissolved in a mixture of 4mL H2O and 36mL EtOH). The system is continuously cooled and stirred in an ice-water bath for 30min. Slowly add dilute hydrochloric acid to the system to make the pH of the system ≈ 2.0. Use ethyl acetate to extract the aqueous phase (20mL×3 times). Combine the organic phases and wash them 3 times with a saturated NaCl solution. Separate the organic phase, add Na2SO4 to dry, and let it stand. Filter to remove Na2SO4, and remove the solvent by rotary evaporation to obtain 5.85g of the compound represented by formula IIIg, which is a yellow liquid with a yield of 96%.

[0132] Take 2.50mmol of the compound represented by formula IIIg and 0.25mmol of Y(OTf)3 and add them into a 100mL two-necked bottle, protect with argon, and evacuate and replace three times. Inject 50mL of deoxygenated dry toluene into the system, and then inject 12.50mmol t BuNC. Heat the system in an 80°C oil bath, continue heating and stirring for 2 hours. Quench the reaction with a saturated NaHCO3 solution, separate the organic phase, and extract the aqueous phase with ethyl acetate (20 mL × 3 times). Combine the organic phases, and then wash with a saturated NaCl solution 3 times. Separate the organic phase, add Na2SO4 to dry, and let stand. Filter to remove Na2SO4, remove the solvent by rotary evaporation, and separate by column chromatography (200-300 mesh silica gel, eluent is petroleum ether: ethyl acetate = 40:1). 512 mg of the compound shown in formula IIg is obtained. The compound is a yellow solid with a yield of 59%.

[0133] Example 8: Preparation of compound Ih (R1 for R 2 for- t Bu)

[0134] The reaction formula is as follows:

[0135]

[0136] 0.20 mmol of the compound represented by formula IIh was placed in a 25 mL Schlenk tube, protected by argon, and evacuated and replaced 3 times. 2.0 mL of deoxygenated dry chloroform was injected into the system and stirred to completely dissolve the solid. 2.0 mmol of DIPEA was injected into the system and stirred at room temperature for 15 min. 3.0 mmol of BF3·Et2O was injected into the system and continued to stir at room temperature for 15 min. The system was then transferred to a preheated oil bath and heated to reflux, and continued heating and stirring for 2 h. 4 mL of H2O was added to the system to quench the reaction. The system was extracted with CH2Cl2 (5 mL × 3 times). The organic phases were combined and washed with saturated NaCl solution 3 times. The organic phase was separated, dried by adding Na2SO4, and allowed to stand. Na2SO4 was removed by filtration, the solvent was removed by rotary evaporation, and column chromatography was performed (200–300 mesh silica gel, eluent was petroleum ether: ethyl acetate = 10:1). 43 mg of the compound represented by formula Ih was obtained. The compound was a yellow solid with a yield of 52%.

[0137] MP:181℃.

[0138] 1 H NMR (500MHz, CDCl3): δ (ppm) 7.91 (d, J = 8.8 Hz, 2H), 6.98 (d, J = 8.8 Hz, 2H), 6.58 (br, 1H), 3.86 (s, 3H), 1.52 (s, 9H), 1.42 (s, 9H).

[0139] 13 C NMR (125MHz, CDCl3): δ (ppm) 162.8, 162.4, 152.2, 144.1, 129.6, 124.2, 120.2, 114.9, 55.5, 53.4, 53.1, 28.7, 28.6.

[0140] IR(KBr):υ(cm -1 )3306(m),2967(m),1659(s),1589(s),1309(s),1132(s).

[0141] HRMS(ESI):m / z calcd for C 19 H 27BF2N3O2S[M+H] + 410.1880; found 410.1883.

[0142] EA:calcd.for C 19 H 26 BF2N3O2S: C 55.76%, H 6.40%, N 10.27%; found: C 55.78%, H6.54%, N 10.30%.

[0143] It can be seen from the above that the structure of the above compound is correct and is the compound shown in formula Ih.

[0144] The preparation method of the compound represented by formula IIh as a reactant is as follows:

[0145]

[0146] Take 30.0mmol of the compound shown in formula Vh and put it into a 100mL single-mouth bottle, and then add 15mL SOCl2 to the system. Place the system in a preheated oil bath and heat it to reflux, continue heating and stirring for 1h. Rotary evaporation removes the solvent to obtain the compound shown in formula IVh as a white solid. Slowly add the compound shown in formula IVh to the NaHS solution cooled in an ice-water bath (60mmol NaHS is ultrasonically dissolved in a mixture of 4mL H2O and 36mL EtOH). The system is continuously cooled and stirred in an ice-water bath for 45min. Filter to remove insoluble matter. Slowly add dilute hydrochloric acid to the filtrate to make the system pH≈2.0, and a white precipitate is precipitated in the system to obtain 4.57g of the compound shown in formula IIIh, which is a white solid with a yield of 91%.

[0147] Take 2.50mmol of the compound represented by formula IIIh and 0.25mmol of Y(OTf)3 and add them into a 100mL two-necked bottle, protect with argon, and evacuate and replace three times. Inject 50mL of deoxygenated dry toluene into the system, and then inject 12.50mmol t BuNC. Heat the system in an 80°C oil bath, continue heating and stirring for 2 hours. Quench the reaction with a saturated NaHCO3 solution, separate the organic phase, and extract the aqueous phase with ethyl acetate (20 mL × 3 times). Combine the organic phases, and then wash with a saturated NaCl solution 3 times. Separate the organic phase, add Na2SO4 to dry, and let stand. Filter to remove Na2SO4, remove the solvent by rotary evaporation, and separate by column chromatography (200-300 mesh silica gel, eluent is petroleum ether: ethyl acetate = 40:1). 569 mg of the compound shown in formula IIh is obtained. The compound is a yellow solid with a yield of 63%.

[0148] Example 9: Preparation of compound Ii (R1 for R 2 for- t Bu)

[0149] The reaction formula is as follows:

[0150]

[0151] 0.20mmol of the compound represented by formula IIi was placed in a 25mL Schlenk tube, protected by argon, and evacuated and replaced 3 times. 2.0mL of deoxygenated dry chloroform was injected into the system and stirred to completely dissolve the solid. 2.0mmol of DIPEA was injected into the system and stirred at room temperature for 15min. 3.0mmol of BF3·Et2O was injected into the system and continued to stir at room temperature for 15min. The system was then transferred to a preheated oil bath and heated to reflux, and continued heating and stirring for 2h. 4mL of H2O was added to the system to quench the reaction. The system was extracted with CH2Cl2 (5mL×3 times). The organic phases were combined and washed with saturated NaCl solution 3 times. The organic phase was separated, dried by adding Na2SO4, and allowed to stand. Na2SO4 was removed by filtration, the solvent was removed by rotary evaporation, and column chromatography was performed (200–300 mesh silica gel, eluent was petroleum ether: ethyl acetate = 10:1). 29mg of the compound represented by formula Ii was obtained. The compound was a yellow solid with a yield of 35%.

[0152] MP:157℃.

[0153] 1 H NMR (500MHz, CDCl3): δ (ppm) 7.62 (s, 1H), 7.43 (d, J = 7.8Hz, 2H), 7.36 (t, J = 8.1Hz, 1H ),7.04(dd,J=8.1,1.8Hz,1H),6.70(br,1H),3.88(s,3H),1.52(s,9H),1.43(s,9H).

[0154] 13 C NMR (125MHz, CDCl3): δ (ppm) 162.8, 160.2, 151.2, 145.0, 130.4, 128.7, 124.5, 120.0, 118.2, 112.3, 111.4, 55.6, 53.4, 53.1, 28.6.

[0155] IR(KBr):υ(cm -1 )3328(m),2969(m),1652(s),1581(s),1312(s),1134(s).

[0156] HRMS(ESI):m / z calcd for C 19 H 27 BF2N3O2S[M+H] + 410.1880; found 410.1881.

[0157] EA:calcd.for C 19 H 26 BF2N3O2S: C 55.76%, H 6.40%, N 10.27%; found: C55.89%, H6.55%, N 10.14%.

[0158] It can be seen from the above that the structure of the above compound is correct and is the compound represented by formula Ii.

[0159] The preparation method of the compound represented by formula IIi as the reactant is as follows:

[0160]

[0161] Take 30.0mmol of the compound represented by formula Vi and put it into a 100mL single-mouth bottle, and then add 15mL SOCl2 to the system. Place the system in a preheated oil bath and heat it to reflux, continue heating and stirring for 2h. Remove the solvent by rotary evaporation to obtain the compound represented by formula IVi, which is a colorless liquid. Slowly add the compound represented by formula IVi to the NaHS solution cooled in an ice-water bath (60mmol NaHS is ultrasonically dissolved in a mixture of 4mL H2O and 36mL EtOH). The system is continuously cooled and stirred in an ice-water bath for 40min. Slowly add dilute hydrochloric acid to the system to make the pH of the system ≈ 2.0. Use ethyl acetate to extract the aqueous phase (20mL×3 times). Combine the organic phases and wash them 3 times with a saturated NaCl solution. Separate the organic phase, add Na2SO4 to dry, and let it stand. Filter to remove Na2SO4, and remove the solvent by rotary evaporation to obtain 4.91g of the compound represented by formula IIIi, which is a brown-yellow liquid with a yield of 97%.

[0162] Take 4.0mmol of the compound represented by formula IIIi and 0.40mmol of Y(OTf)3 and add them into a 100mL two-necked bottle, protect with argon, and evacuate and replace three times. Inject 80mL of deoxygenated dry toluene into the system, and then inject 20.0mmol tBuNC. Heat the system in an 80°C oil bath, continue heating and stirring for 2 hours. Quench the reaction with a saturated NaHCO3 solution, separate the organic phase, and extract the aqueous phase with ethyl acetate (20 mL × 3 times). Combine the organic phases, and then wash with a saturated NaCl solution 3 times. Separate the organic phase, add Na2SO4 to dry, and let stand. Filter to remove Na2SO4, remove the solvent by rotary evaporation, and separate by column chromatography (200-300 mesh silica gel, eluent is petroleum ether: ethyl acetate = 40:1). Obtain 713 mg of the compound shown in formula IIi. The compound is a brown-yellow oily substance with a yield of 49%.

[0163] Example 10: Preparation of compound Ij (R 1 for R 2 for- t Bu)

[0164] The reaction formula is as follows:

[0165]

[0166] 0.20mmol of the compound represented by formula IIi was placed in a 25mL Schlenk tube, protected by argon, and evacuated and replaced 3 times. 2.0mL of deoxygenated dry chloroform was injected into the system, and the solid was completely dissolved by stirring. 2.0mmol of DIPEA was injected into the system, and the mixture was stirred at room temperature for 15min. 3.0mmol of BF3·Et2O was injected into the system, and the mixture was stirred at room temperature for 15min. The system was then transferred to a preheated oil bath and heated to reflux, and the heating and stirring were continued for 2h. 4mL of H2O was added to the system to quench the reaction. The system was extracted with CH2Cl2 (5mL×3 times). The organic phases were combined and washed with saturated NaCl solution 3 times. The organic phase was separated, dried by adding Na2SO4, and allowed to stand. Na2SO4 was removed by filtration, the solvent was removed by rotary evaporation, and the mixture was separated by column chromatography (200-300 mesh silica gel, eluent was petroleum ether: ethyl acetate = 10:1). 44mg of the compound represented by formula Ij was obtained. The compound was a yellow solid with a yield of 59%.

[0167] MP:128℃.

[0168] 1 H NMR (500MHz, CDCl3): δ (ppm) 7.53 (d, J = 1.4Hz, 1H), 7.45 (d, J = 3.7Hz, 1H), 6.62 (dd, J = 3.6, 1.7Hz, 1H), 6.49 (br, 1H), 1.52 (s, 9H), 1.42 (s, 9H).

[0169] 13C NMR (125MHz, CDCl3): δ (ppm) 162.7, 145.3, 144.4, 142.9, 139.7, 123.2, 114.5, 113.8, 53.5, 53.1, 28.6, 28.5.

[0170] IR(KBr):υ(cm -1 )3327(m),2975(m),2954(m),1658(s),1584(s),1307(s),1132(s).

[0171] HRMS(ESI):m / z calcd for C 16 H 23 BF2N3O2S[M+H] + 370.1567; found 370.1570.

[0172] EA:calcd.for C 16 H 22 BF2N3O2S: C 52.05%, H 6.01%, N 11.38%; found: C52.12%, H6.11%, N 11.31%.

[0173] It can be seen from the above that the structure of the above compound is correct and is the compound shown in formula Ij.

[0174] The preparation method of the compound represented by formula IIj as the reactant is as follows:

[0175]

[0176] Take 15.0mmol of the compound represented by formula Vj and put it into a 50mL single-mouth bottle, and then add 10mL SOCl2 to the system. Place the system in a preheated oil bath and heat it to reflux, continue heating and stirring for 5h. Remove the solvent by rotary evaporation to obtain the compound represented by formula IVj, which is a light pink liquid. Slowly add the compound represented by formula IVj to the NaHS solution cooled in an ice-water bath (30mmol NaHS is ultrasonically dissolved in a mixture of 2mL H2O and 18mL EtOH). The system is continuously cooled and stirred in an ice-water bath for 30min. Slowly add dilute hydrochloric acid to the system to make the pH of the system ≈ 2.0. Use ethyl acetate to extract the aqueous phase (20mL×3 times). Combine the organic phases and wash them 3 times with a saturated NaCl solution. Separate the organic phase, add Na2SO4 to dry, and let it stand. Filter to remove Na2SO4, and remove the solvent by rotary evaporation to obtain 1.57g of the compound represented by formula IIIj, which is a yellow solid with a yield of 82%.

[0177] Take 4.0mmol of the compound represented by formula IIIj and 0.40mmol of Y(OTf)3 and add them into a 100mL two-necked bottle, protect with argon, and evacuate and replace three times. Inject 80mL of deoxygenated dry toluene into the system, and then inject 20.0mmol t BuNC. Heat the system in an 80°C oil bath, continue heating and stirring for 2.5h. Quench the reaction with a saturated NaHCO3 solution, separate the organic phase, and extract the aqueous phase with ethyl acetate (20mL×3 times). Combine the organic phases, and then wash with a saturated NaCl solution 3 times. Separate the organic phase, add Na2SO4 to dry, and let stand. Filter to remove Na2SO4, remove the solvent by rotary evaporation, and separate by column chromatography (200-300 mesh silica gel, eluent is petroleum ether: ethyl acetate = 40:1). 125 mg of the compound shown in formula IIj was obtained. The compound is a yellow solid with a yield of 10%.

[0178] Example 11: Preparation of compound Ik (R 1 for R 2 for- t Bu)

[0179] The reaction formula is as follows:

[0180]

[0181] 0.20 mmol of the compound represented by formula IIk was placed in a 25 mL Schlenk tube, protected by argon, and evacuated and replaced 3 times. 2.0 mL of deoxygenated dry chloroform was injected into the system, and the solid was completely dissolved by stirring. 2.0 mmol of DIPEA was injected into the system, and the mixture was stirred at room temperature for 15 min. 3.0 mmol of BF3·Et2O was injected into the system, and the mixture was stirred at room temperature for 15 min. The system was then transferred to a preheated oil bath and heated to reflux, and the heating and stirring were continued for 2 h. 4 mL of H2O was added to the system to quench the reaction. The system was extracted with CH2Cl2 (5 mL × 3 times). The organic phases were combined and washed with saturated NaCl solution 3 times. The organic phase was separated, dried by adding Na2SO4, and allowed to stand. Na2SO4 was removed by filtration, the solvent was removed by rotary evaporation, and the mixture was separated by column chromatography (200-300 mesh silica gel, eluent was petroleum ether: ethyl acetate = 10:1). 59 mg of the compound represented by formula Ik was obtained. The compound was a yellow solid with a yield of 76%.

[0182] MP:171℃.

[0183] 1H NMR (400MHz, CDCl3): δ (ppm) 7.86 (d, J = 3.8Hz, 1H), 7.53 (d, J = 5.0Hz, 1H), 7.15 (t, J = 4.4Hz, 1H), 6.58 (br, 1H), 1.52 (s, 9H), 1.42 (s, 9H).

[0184] 13 C NMR (100MHz, CDCl3): δ (ppm) 162.7, 144.5, 144.1, 130.9, 130.6, 129.1, 128.9, 123.5, 53.5, 53.2, 28.6.

[0185] IR(KBr):υ(cm -1 )3302(s),2967(s),1652(s),1586(s),1307(s),1133(s).

[0186] HRMS(ESI):m / z calcd for C 16 H 22 BF2N3OS2[MH] - 384.1193; found 384.1191.

[0187] EA:calcd.for C 16 H 22 BF2N3OS2:C 49.88%, H 5.76%, N 10.91%; found: C50.00%, H5.76%, N 10.95%.

[0188] It can be seen from the above that the structure of the above compound is correct and is the compound shown in formula Ik.

[0189] The preparation method of the compound represented by formula IIk as the reactant is as follows:

[0190]

[0191] Take 15.0mmol of the compound represented by formula Vk and put it into a 50mL single-mouth bottle, and then add 10mL SOCl2 to the system. Place the system in a preheated oil bath and heat it to reflux, continue heating and stirring for 5h. Remove the solvent by rotary evaporation to obtain the compound represented by formula IVk, which is a brown liquid. Slowly add the compound represented by formula IVk to the NaHS solution cooled in an ice-water bath (30mmol NaHS is ultrasonically dissolved in a mixture of 2mL H2O and 18mL EtOH). The system is continuously cooled and stirred in an ice-water bath for 35min. Slowly add dilute hydrochloric acid to the system to make the pH of the system ≈ 2.0. Use ethyl acetate to extract the aqueous phase (20mL×3 times). Combine the organic phases and wash them 3 times with a saturated NaCl solution. Separate the organic phase, add Na2SO4 to dry, and let it stand. Filter to remove Na2SO4, and remove the solvent by rotary evaporation to obtain 1.93g of the compound represented by formula IIIk, which is a yellow liquid with a yield of 89%.

[0192] Take 2.0mmol of the compound represented by formula IIIk and 0.20mmol of Y(OTf)3 and add them into a 100mL two-necked bottle, protect with argon, and evacuate and replace three times. Inject 40mL of deoxygenated dry toluene into the system, and then inject 10.0mmol t BuNC. Heat the system in an 80°C oil bath, continue heating and stirring for 2 hours. Quench the reaction with a saturated NaHCO3 solution, separate the organic phase, and extract the aqueous phase with ethyl acetate (20 mL × 3 times). Combine the organic phases, and then wash with a saturated NaCl solution 3 times. Separate the organic phase, add Na2SO4 to dry, and let stand. Filter to remove Na2SO4, remove the solvent by rotary evaporation, and separate by column chromatography (200-300 mesh silica gel, eluent is petroleum ether: ethyl acetate = 40:1). 352 mg of the compound shown in formula IIk is obtained. The compound is a yellow solid with a yield of 52%.

[0193] Example 12: Preparation of Compound I1 (R 1 for R 2 for- t Bu)

[0194] The reaction formula is as follows:

[0195]

[0196] 0.20mmol of the compound shown in formula II1 was placed in a 25mL Schlenk tube, protected by argon, and evacuated and replaced 3 times. 2.0mL of deoxygenated dry chloroform was injected into the system and stirred to completely dissolve the solid. 2.0mmol of DIPEA was injected into the system and stirred at room temperature for 15min. 3.0mmol of BF3·Et2O was injected into the system and continued to stir at room temperature for 15min. The system was then transferred to a preheated oil bath and heated to reflux, and continued heating and stirring for 2h. 4mL of H2O was added to the system to quench the reaction. The system was extracted with CH2Cl2 (5mL×3 times). The organic phases were combined and washed with saturated NaCl solution 3 times. The organic phase was separated, dried by adding Na2SO4, and allowed to stand. Na2SO4 was removed by filtration, the solvent was removed by rotary evaporation, and column chromatography was performed (200–300 mesh silica gel, eluent was petroleum ether: ethyl acetate = 10:1). 37mg of the compound shown in formula I1 was obtained. The compound was a yellow solid with a yield of 46%.

[0197] MP:168℃.

[0198] 1 H NMR (500MHz, CDCl3): δ (ppm) 7.53 (d, J = 7.5Hz, 2H), 7.40-7.38 (m, 3H), 7.24 (d, J=16.3Hz,1H),7.17(d,J=16.3Hz,1H),6.56(br,1H),1.52(s,9H),1.43(s,9H).

[0199] 13 C NMR (125MHz, CDCl3): δ (ppm) 162.8, 148.5, 144.3, 137.5, 134.4, 130.2, 129.1, 127.7, 122.7, 115.0, 53.6, 53.1, 28.6.

[0200] IR(KBr):υ(cm -1 )3319(m),2964(m),1662(s),1582(s),1304(s),1122(s).

[0201] HRMS(ESI):m / z calcd for C 20 H 27 BF2N3OS[M+H] + 406.1931; found 406.1934.

[0202] EA:calcd.for C 20 H 26BF2N3OS:C 59.27%, H 6.47%, N 10.37%; found: C59.20%, H6.60%, N 10.43%.

[0203] It can be seen from the above that the structure of the above compound is correct and is the compound shown in formula I1.

[0204] The preparation method of the compound shown in formula II1 as the reactant is as follows:

[0205]

[0206] Take 4.0mmol of the compound represented by formula V1 and 2.20mmol of Lawesson's reagent and add them to a 100mL two-necked bottle. Protect with argon gas, and evacuate and replace three times. Inject 80mL of deoxygenated dry toluene into the system, heat the system to reflux, continue heating and stirring for 3h. Cool slightly, and inject 20.0mmol t Add 0.40mmol Y(OTf)3 after BuNC. Heat the system in an oil bath at 80℃, continue heating and stirring for 2h. Quench the reaction with saturated NaHCO3 solution, separate the organic phase, and extract the aqueous phase with ethyl acetate (20mL×3 times). Combine the organic phases, and then wash with saturated NaCl solution 3 times. Separate the organic phase, add Na2SO4 to dry, and let stand. Filter to remove Na2SO4, remove the solvent by rotary evaporation, and separate by column chromatography (200-300 mesh silica gel, eluent is petroleum ether: ethyl acetate = 40:1). 323mg of the compound shown in formula II1 is obtained. The compound is a brown-yellow oily substance with a yield of 23%.

[0207] Example 13: Preparation of the compound Im(R 1 for R 2 for- t Bu)

[0208] The reaction formula is as follows:

[0209]

[0210] 0.20mmol of the compound represented by formula IIm was placed in a 25mL Schlenk tube, protected by argon, and evacuated and replaced 3 times. 2.0mL of deoxygenated dry chloroform was injected into the system, and the solid was completely dissolved by stirring. 2.0mmol of DIPEA was injected into the system, and the mixture was stirred at room temperature for 15min. 3.0mmol of BF3·Et2O was injected into the system, and the mixture was stirred at room temperature for 15min. The system was then transferred to a preheated oil bath and heated to reflux, and the heating and stirring were continued for 2h. 4mL of H2O was added to the system to quench the reaction. The system was extracted with CH2Cl2 (5mL×3 times). The organic phases were combined and washed with saturated NaCl solution 3 times. The organic phase was separated, dried by adding Na2SO4, and allowed to stand. Na2SO4 was removed by filtration, the solvent was removed by rotary evaporation, and column chromatography was performed (200-300 mesh silica gel, eluent was petroleum ether: ethyl acetate = 10:1). 29mg of the compound represented by formula Im was obtained. The compound was a yellow solid with a yield of 37%.

[0211] MP:174℃.

[0212] 1 H NMR (500MHz, CDCl3): δ (ppm) 7.5 (s, 1H), 7.10 (d, J = 16.0Hz, 1H), 7.02 (d, J = 16.0Hz, 1H), 6 .61(d,J=3.4Hz,1H),6.53(s,1H),6.49(dd,J=2.9,1.4Hz,1H),1.51(s,9H),1.41(s,9H).

[0213] 13 C NMR (125MHz, CDCl3): δ (ppm) 162.7, 150.8, 148.3, 145.0, 144.1, 123.9, 122.9, 114.4, 112.7, 112.6, 53.6, 53.1, 28.6.

[0214] IR(KBr):υ(cm -1 )3338(m),2978(m),1661(s),1574(s),1304(s),1106(s).

[0215] HRMS(ESI):m / z calcd for C 18 H 25 BF2N3O2S[M+H] + 396.1723; found 396.1728.

[0216] EA:calcd.for C 18 H 24BF2N3O2S: C 54.70%, H 6.12%, N 10.63%; found: C54.51%, H6.26%, N 10.60%.

[0217] It can be seen from the above that the structure of the above compound is correct and is the compound shown in Formula Im.

[0218] The preparation method of the compound shown in Formula IIm as the reactant is as follows:

[0219]

[0220] Take 85.0mmol of malonic acid and add it to a 50mL two-necked bottle, then add 5mL of pyridine and 0.5mL of piperidine in sequence. Heat the system to 85°C. During the heating process, slowly inject 50mmol of the compound represented by formula Vj. Continue heating and stirring for 6h. Place the system in an ice water bath to cool, slowly add 10% hydrochloric acid to it, a brown precipitate will precipitate in the system, and continue to add 10% hydrochloric acid until the precipitation is complete. Filter and recrystallize the precipitate in ethanol to obtain 2.84g of the compound represented by formula Vm, which is a brown solid with a yield of 41%.

[0221] Take 2.0mmol of the compound represented by formula Vm and 1.10mmol of Lawesson's reagent and add them to a 100mL two-necked bottle. Protect with argon gas, and evacuate and replace three times. Inject 40mL of deoxygenated dry toluene into the system, heat the system to reflux, continue heating and stirring for 2.5h. Cool slightly, add 0.20mmol of Y(OTf)3 into the system, and then inject 10.0mmol t BuNC. Heat the system in an 80°C oil bath, continue heating and stirring for 2 hours. Quench the reaction with a saturated NaHCO3 solution, separate the organic phase, and extract the aqueous phase with ethyl acetate (20 mL × 3 times). Combine the organic phases, and then wash with a saturated NaCl solution 3 times. Separate the organic phase, add Na2SO4 to dry, and let stand. Filter to remove Na2SO4, remove the solvent by rotary evaporation, and separate by column chromatography (200-300 mesh silica gel, eluent is petroleum ether: ethyl acetate = 40:1). 153 mg of the compound shown in formula IIm was obtained. The compound is a brown oily substance with a yield of 22%.

[0222] Example 14: Preparation of the compound In(R 1 for R 2 for- t Bu)

[0223] The reaction formula is as follows:

[0224]

[0225] 0.20mmol of the compound represented by formula IIn was placed in a 25mL Schlenk tube, protected by argon, and evacuated and replaced 3 times. 2.0mL of deoxygenated dry chloroform was injected into the system, and the solid was completely dissolved by stirring. 2.0mmol of DIPEA was injected into the system, and it was stirred at room temperature for 15min. 3.0mmol of BF3·Et2O was injected into the system, and it was continued to stir at room temperature for 15min. The system was then transferred to a preheated oil bath and heated to reflux, and the heating and stirring were continued for 2h. 4mL of H2O was added to the system to quench the reaction. The system was extracted with CH2Cl2 (5mL×3 times). The organic phases were combined and washed with saturated NaCl solution 3 times. The organic phase was separated, dried by adding Na2SO4, and allowed to stand. Na2SO4 was removed by filtration, the solvent was removed by rotary evaporation, and column chromatography was performed (200-300 mesh silica gel, eluent was petroleum ether: ethyl acetate = 10:1). 35mg of the compound represented by formula In was obtained. The compound was a yellow solid with a yield of 42%.

[0226] MP:178℃.

[0227] 1 H NMR (500MHz, CDCl3): δ (ppm) 7.40 (d, J = 4.9 Hz, 1H), 7.34 (d, J = 16.0 Hz, 1H), 7.25 (S, 1 H),7.07-7.05(m,1H),6.99(d,J=16.0Hz,1H),6.53(s,1H),1.51(s,9H),1.42(s,9H).

[0228] 13 C NMR (125MHz, CDCl3): δ (ppm) 162.7, 148.2, 144.0, 139.8, 130.2, 128.8, 128.3, 122.8, 113.7, 53.6, 53.1, 28.6.

[0229] IR(KBr):υ(cm -1 )3323(s),2978(s),1662(s),1572(s),1303(s),1106(s).

[0230] HRMS(ESI):m / z calcd for C 18 H 25 BF2N3OS2[M+H] + 412.1495; found 412.1499.

[0231] EA:calcd.for C 18 H 24BF2N3OS2:C 52.56%, H 5.88%, N 10.22%; found: C52.50%, H5.95%, N 10.21%.

[0232] From the above, it can be seen that the structure of the above compound is correct and is the compound represented by formula In.

[0233] The preparation method of the compound represented by formula IIn as a reactant is as follows:

[0234]

[0235] Take 85.0mmol of malonic acid and add it to a 50mL two-necked bottle, then add 5mL of pyridine and 0.5mL of piperidine in sequence. Heat the system to 85°C. During the heating process, slowly inject 50mmol of the compound represented by formula Vk. Continue heating and stirring for 6h. Place the system in an ice water bath to cool, slowly add 10% hydrochloric acid to it, a white precipitate will precipitate in the system, and continue to add 10% hydrochloric acid until the precipitation is complete. Filter and recrystallize the precipitate in ethanol to obtain 5.79g of the compound represented by formula Vn, which is a white solid with a yield of 75%.

[0236] Take 2.0mmol of the compound represented by formula Vn and 1.10mmol of Lawesson's reagent and add them to a 100mL two-necked bottle. Protect with argon gas, and evacuate and replace three times. Inject 40mL of deoxygenated dry toluene into the system, heat the system to reflux, continue heating and stirring for 5h. Cool slightly, add 0.20mmol of Y(OTf)3 into the system, and then inject 10.0mmol t BuNC. Heat the system in an 80°C oil bath, continue heating and stirring for 1h. Quench the reaction with a saturated NaHCO3 solution, separate the organic phase, and extract the aqueous phase with ethyl acetate (20mL×3 times). Combine the organic phases, and then wash with a saturated NaCl solution 3 times. Separate the organic phase, add Na2SO4 to dry, and let stand. Filter to remove Na2SO4, remove the solvent by rotary evaporation, and separate by column chromatography (200-300 mesh silica gel, eluent is petroleum ether: ethyl acetate = 40:1). 204 mg of the compound represented by formula IIn is obtained. The compound is a yellow solid with a yield of 28%.

[0237] Example 15: Preparation of compound Io (R1 is R2 is - t Bu)

[0238] The reaction formula is as follows:

[0239]

[0240] 0.20mmol of the compound represented by formula IIo was placed in a 25mL Schlenk tube, protected by argon, and evacuated and replaced three times. 2.0mL of deoxygenated dry chloroform was injected into the system, and the solid was completely dissolved by stirring. 2.0mmol of DIPEA was injected into the system, and the mixture was stirred at room temperature for 15min. 4.0mmol of BF3·Et2O was injected into the system, and the mixture was stirred at room temperature for 15min. The system was then transferred to a preheated oil bath and heated to reflux, and the heating and stirring were continued for 2h. 4mL of H2O was added to the system to quench the reaction. The system was extracted with CH2Cl2 (5mL×3 times). The organic phases were combined and washed with saturated NaCl solution for 3 times. The organic phase was separated, dried by adding Na2SO4, and allowed to stand. Na2SO4 was removed by filtration, the solvent was removed by rotary evaporation, and the mixture was separated by column chromatography (200-300 mesh silica gel, the eluent was petroleum ether:ethyl acetate = 15:1, and 0.2% (volume fraction) of ammonia water was added to the eluent). 23 mg of the compound represented by formula Io was obtained. The compound was a yellow solid, and the yield was 24%.

[0241] 1 H NMR (400MHz, CDCl3): δ (ppm) 7.95 (d, J = 8.4Hz, 2H), 7.61 (d, J = 8.0Hz, 2H), 7.5 6-7.54(m,2H),7.373-7.367(m,3H),6.76(br,1H),1.53(s,9H),1.44(s,9H).

[0242] 13 C NMR (100MHz, CDCl3): δ (ppm) 162.8, 150.1, 145.1, 132.5, 131.8, 128.9, 128.5, 127.4, 127.0, 126.8, 124.7, 122.6, 93.1, 88.5, 53.5, 53.2, 28.6.

[0243] HRMS(ESI):m / z calcd.for C 26 H 27 BF2N3OS[MH] - 478.1941, found 478.1936.

[0244] EA:calcd.for C 26 H 28 BF2N3OS: C 65.14%, H 5.89%, N 8.77%; found: C 64.67%, H 5.88% N 8.61%.

[0245] It can be seen from the above that the structure of the above compound is correct, and it is the compound represented by formula Io.

[0246] The preparation method of the compound represented by formula IIo as a reactant is as follows:

[0247]

[0248] Add 1.0 mmol of the compound represented by formula IIe, 0.05 mmol of Pd(PPh3)4, 0.05 mmol of CuI, and 2.0 mmol of DBU to a 25 mL two-necked bottle, seal the system, protect with argon, and evacuate and replace three times. Then inject 5.0 mL of deoxygenated and dried DMSO into the system and stir to mix the components evenly. Then inject a DMSO solution of phenylacetylene (1.3 mmol of phenylacetylene dissolved in 5.0 mL of deoxygenated and dried DMSO) into the system. Stir at room temperature for 25 min. Add 5.0 mL of H2O to the system to quench the reaction. Extract the system three times with ethyl acetate. Combine the organic phases, wash twice with H2O, and then wash once with a saturated NaCl solution. Separate the organic phase, add Na2SO4 to dry, and let stand. Filter to remove Na2SO4, remove the solvent by rotary evaporation, and separate by column chromatography (200-300 mesh silica gel, gradient elution from petroleum ether to petroleum ether: ethyl acetate = 10:1). 423 mg of the compound represented by formula IIo was obtained. The compound was a yellow solid, and the yield was 98%.

[0249] Example 16: Preparation of compound Ip(R 1 for R 2 for- t Bu)

[0250] The reaction formula is as follows:

[0251]

[0252] 0.20mmol of the compound represented by formula IIp was placed in a 25mL Schlenk tube, protected by argon, and evacuated and replaced 3 times. 2.0mL of deoxygenated dry chloroform was injected into the system, and the solid was completely dissolved by stirring. 2.0mmol of DIPEA was injected into the system, and the mixture was stirred at room temperature for 15min. 3.0mmol of BF3·Et2O was injected into the system, and the mixture was stirred at room temperature for 15min. The system was then transferred to a preheated oil bath and heated to reflux, and the heating and stirring were continued for 2h. 4mL of H2O was added to the system to quench the reaction. The system was extracted with CH2Cl2 (5mL×3 times). The organic phases were combined and washed with saturated NaCl solution 3 times. The organic phase was separated, dried by adding Na2SO4, and allowed to stand. Na2SO4 was removed by filtration, the solvent was removed by rotary evaporation, and the mixture was separated by column chromatography (200-300 mesh silica gel, eluent was petroleum ether: ethyl acetate = 10:1). 51mg of the compound represented by formula Ip was obtained. The compound was a yellow solid with a yield of 59%.

[0253] 1 H NMR (500MHz, CDCl3): δ (ppm) 8.46 (s, 1H), 8.03-8.01 (m, 1H), 7.96-7.92 (m, 2H), 7.87-7.85 (m, 1H), 7.60-7.55 (m, 2H), 1.55 (s, 9H), 1.46 (s, 9H).

[0254] 13 C NMR (125MHz, CDCl3): δ (ppm) 162.9, 151.4, 145.0, 134.4, 133.0, 129.4, 129.1, 128.3, 127.8, 127.4, 125.0, 124.8, 123.8, 53.5, 53.2, 28.6.

[0255] HRMS(ESI):m / z calcd.for C 22 H 25 BF2N3OS[MH] - 428.1785, found 428.1780.

[0256] EA:calcd.for C 22 H 26 BF2N3OS: C 61.55%, H 6.10%, N 9.79%; found: C 61.08%, H 6.09%, N 9.60%.

[0257] It can be seen from the above that the structure of the above compound is correct and is the compound represented by formula Ip.

[0258] The preparation method of the compound represented by formula IIp as a reactant is as follows:

[0259]

[0260] Take 5.0mmol of the compound represented by formula V1 and 2.75mmol of Lawesson's reagent and add them to a 250mL two-necked bottle. Protect with argon gas, and evacuate and replace three times. Inject 100mL of deoxygenated dry toluene into the system, heat the system to reflux, continue heating and stirring for 12h. Cool slightly, add 0.50mmol of Y(OTf)3 into the system, and then inject 25.0mmol t BuNC. The system was placed in an 80°C oil bath and heated, and the heating and stirring were continued for 5 hours. The reaction was quenched with a saturated NaHCO3 solution, the organic phase was separated, and the aqueous phase was extracted with ethyl acetate (20 mL × 3 times). The organic phases were combined, and then washed with a saturated NaCl solution for 3 times. The organic phase was separated, added with Na2SO4, and dried, and allowed to stand. Na2SO4 was removed by filtration, the solvent was removed by rotary evaporation, and column chromatography was performed (200-300 mesh silica gel, the eluent was petroleum ether: ethyl acetate = 40:1, and 0.2% (volume fraction) ammonia water was added to the eluent). 759 mg of the compound represented by formula IIp was obtained. The compound was a yellow solid with a yield of 40%.

[0261] Example 17: Fluorescence performance

[0262] The aminothiazole amide-boron difluoride compound prepared by the present invention has good fluorescence properties, as shown in Table 1. It can be seen that such aminothiazole-boron difluoride compound has the advantages of relatively stable chemical properties, high molar extinction coefficient, large Stokes shift, and adjustable emission wavelength with the change of substituents.

[0263] Table 1 Photophysical properties of the compound represented by formula I in toluene solution at room temperature

[0264]

[0265]

[0266] Example 18: Room temperature phosphorescence performance

[0267] The aminothiazole amide-boron difluoride compound prepared by the present invention also exhibits room temperature phosphorescence emission performance. Taking the compound represented by Formula Ie as an example, the emission spectrum at room temperature is as follows: Figure 1 As shown, it can be seen from the emission spectrum that the compound represented by Formula Ie exhibits obvious room temperature phosphorescence emission (658nm), and compared with its fluorescence emission (499nm), the emission wavelength is closer to the infrared region. The phosphorescence lifetime is tested to be 108μs.

Claims

1. An aminothiazole amide-boron difluoride compound, the general structural formula of which is shown in Formula I: Formula I In Formula I, R 1 Any one selected from the following groups: 、 、 、 、 、 、 、 、 、 ； in, R 3 Any one of the following groups: -H, -F, -Cl, -Br, -I, -NO2, -CF3, -N3, -R 5 、-OR 6 , R 5 and R 6 All are alkyl groups with 1 to 10 carbon atoms; R 4 Any one selected from the following groups: , , ; R 2 Any one selected from the following groups: - t This, 、 。 2. The aminothiazole amide-boron difluoride compound according to claim 1, characterized in that: In Formula I, R 5 and R 6 All of them are alkyl groups with 1 to 5 carbon atoms.

3. The method for preparing the aminothiazole amide-boron difluoride compound according to claim 1 or 2, comprising the following steps: In the presence of a base, the compound represented by formula II reacts with boron trifluoride in an organic solvent to obtain the product; Formula II In formula II, R 1 Any one selected from the following groups: 、 、 、 、 、 、 、 、 、 ； in, R 3 Any one of the following groups: -H, -F, -Cl, -Br, -I, -NO2, -CF3, -N3, -R 5 、-OR 6 , R 5 and R 6 All are alkyl groups with 1 to 10 carbon atoms; R 4 Any one selected from the following groups: , , ; R 2 Any one selected from the following groups: -tBu、 、 。 4. The preparation method according to claim 3, characterized in that: The base is at least one of diisopropylethylamine, triethylamine, pyridine, piperidine, 4-dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,4-diazabicyclo[2.2.2]octane, calcium carbonate, cesium carbonate and cesium fluoride.

5. The preparation method according to claim 3 or 4, characterized in that: The organic solvent is at least one of n-hexane, toluene, ether, dichloromethane, 1,2-dichloroethane, tetrahydrofuran, chloroform and acetonitrile.

6. The preparation method according to claim 3 or 4, characterized in that: The usage ratio of the compound represented by formula II, the base, the boron trifluoride and the organic solvent is: 0.20 mmol: 1.0~3.0 mmol: 1.0~3.0 mmol: 2.0~8.0 mL.

7. The preparation method according to claim 3 or 4, characterized in that: The reaction temperature is from room temperature to the reflux temperature of the organic solvent, and the reaction time is 1.0 to 12.0 hours.

8. Use of the aminothiazole amide-boron difluoride compound according to claim 1 or 2 in the preparation of or as a phosphorescent material.

9. Use of the aminothiazole amide-boron difluoride compound according to claim 1 or 2 in the preparation of or as a fluorescent material.

10. The use according to claim 8 or 9, characterized in that: The phosphorescent material is a room temperature phosphorescent material; The fluorescent material is a room temperature fluorescent material.

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