A class of arylthiobenzothiazole compounds, their preparation methods and applications

Abstract

This invention discloses a class of arylthiobenzothiazole compounds, their preparation methods, and applications. A class of arylthiobenzothiazole compounds, characterized in that they have a structural formula of one of formulas (1) to (2): where R... 1 Selected from one of -H, -Me, -OMe, -Cl, -Br, R 2 The compounds are selected from one of -H, -Me, -OMe, -t-Bu, -Cl, and -Br. This invention synthesizes a series of arylthiobenzothiazole compounds, and its synthesis method has the advantages of readily available raw materials, simple operation, mild reaction conditions, and wide substrate adaptability, and has good application prospects in the synthesis and research of optoelectronic materials and antiviral drugs.

Description

Technical Field

[0001] This invention relates to the field of organic synthesis technology, specifically to a method for preparing and applying a class of arylthiobenzothiazole compounds. Background Technology

[0002] It is well known that heteroaromatic compounds and their derivatives with thiolated organic groups have important biological activities. These compounds have potential uses as anticancer, antibacterial, antiviral, antituberculosis, antiworm, antidiabetic, antifungal and antimicrobial agents (Singh, M., Singh, SK, Gangwar, M., Nath, G., Singh, SKRSC Adv. 2014, 4, 19013; Huang, ST, Hsei, IJ, Chen, C. Bioorg. Med. Chem. 2006, 14, 6106.). In particular, some 2-thiomercaptoazoles, such as 2-arylthiobenzothiazole, have attracted much attention due to their unique structure and potential use as radioactive amyloid imaging and anticancer agents (Azam, MA, Suresh, B. Sci. Pharm. 2012, 80, 789; Pejin, B., Iodice, C., Tommonaro, G., De Rosa, SJ Nat. Prod. 2008, 71, 1850.).

[0003] The construction of CS bonds via transition metal-catalyzed cross-coupling reactions is one of the most important tools in organic synthesis because it is widely applicable to the preparation of a variety of biologically active compounds (Beletskaya, IP, Ananikov, VPChem.Rev., 2011, 111, 1596; Bhunia, S., Pawar, GG, Kumar, SV, Jiang, Y., Ma, D. Angew. Chem. Int. Ed. 2017, 56, 16136.). In these reactions, various transition metals such as Pd, Cu, Ni, Fe, Mn, Co, In, Au, and Rh have been used as active catalysts (Lee, CF, Liu, YC, Badsara, SS, Chem. Asian J. 2014, 9, 706.). Cu-catalyzed sarylation reactions of aryl thiols with aryl halides and aryl sources such as boric acid are powerful tools for synthesizing asymmetric binary sulfides containing benzene rings (Lin, Y., Cai, M., Fang, Z., Zhao, H. Tetrahedron. 2016, 72, 3335.). However, the preparation of 2-arylthiobenzothiazoles using these methods is largely limited by the types of complex 2-halobenzothiazoles or 2-mercaptobenzothiazoles prepared beforehand (Yonova, IM, Osborne, CA, Morrissette, NSG J Org. Chem. 2014, 79, 1947; Badsara, SS, Chan, CC, Lee, CFA Asian J Org. Chem. 2014, 3, 1197.). Moreover, these transition metal-mediated reactions have many drawbacks, such as excessively high reaction temperatures and poor substrate universality, and usually require the use of stoichiometric transition metals for catalysis.

[0004] Isonitriles, as a class of highly efficient C1 synthons, possess a rich array of chemical properties determined by their unique valence structure. In recent years, photocatalytic synthesis of isonitriles with various free radical precursors, such as Togni reagents and phosphine oxides, has yielded diverse nitrogen-containing heterocyclic compounds (Wu, L., Yu, J., Cheng, Y. Angew. Chem. Int. Ed. 2022, 61, e202209293). Therefore, we have developed a novel method for synthesizing arylthiobenzothiazole compounds. This method utilizes the tandem cyclization of isonitriles and aryl disulfides under photoluminescence to construct 2-arylthiobenzothiazole derivatives in a green and efficient manner. The method employs inexpensive and readily available raw materials, mild reaction conditions, simple operation, and a wide range of applicable substrates, demonstrating broad application prospects. Summary of the Invention

[0005] The purpose of this invention is to address the shortcomings and deficiencies of existing technologies by providing a method for preparing a class of arylthiobenzothiazole compounds.

[0006] The technical solution adopted in this invention is:

[0007] A class of arylthiobenzothiazole compounds, the structural formula of which is one of formulas (1) to (2):

[0008] In the formula R 1 Selected from one of -H, -Me, -OMe, -Cl, -Br, R 2 Selected from -H, -Me, -OMe, -t-Bu, -Cl, -Br

[0009] A method for preparing a class of arylthiobenzothiazole compounds includes the following steps: [The text abruptly ends here, so the translation stops.] Disulfide and alkali are dispersed in a solvent, and disulfide is... One of them,

[0010] The reaction is carried out under visible light to obtain arylthiobenzothiazole compounds.

[0011] In the above method, the The molar ratio of disulfide to alkali is 1:1 to 3:1 to 2.

[0012] In the above method, the alkali is at least one of sodium carbonate, sodium hydroxide, potassium carbonate, cesium carbonate, triethylamine, and 1,8-diazabicyclo[5.4.0]undec-7-ene (abbreviated as DBU).

[0013] In the above method, the solvent is at least one selected from toluene, dichloroethane, methanol, dimethyl sulfoxide, tetrahydrofuran, acetonitrile, and chloroform.

[0014] In the above method, the reaction is carried out at a temperature of 10–80°C for a reaction time of 8–16 h.

[0015] In the above method, the reaction is carried out under a stirring speed of 300 rpm to 700 rpm.

[0016] In the above method, the visible light band includes at least one of 380nm-390nm, 440nm-445nm, 450nm-455nm, and 515nm-525nm.

[0017] In the above method, the reaction products are separated and purified after the reaction is completed.

[0018] In the above method, the specific operations of separation and purification are as follows: the reaction solution is extracted multiple times with ethyl acetate, the combined organic phases are dried with anhydrous sodium sulfate, filtered, the filtrate is subjected to vacuum distillation, and the crude product is purified by column chromatography.

[0019] In the above method, the eluent used in the column chromatography is composed of petroleum ether and ethyl acetate in a volume ratio of 10:1 to 50:1.

[0020] The principle of this invention: This invention uses 2-methylthioarylisocyanate and aryl disulfide as raw materials, and reacts them under visible light irradiation and the action of an alkali. Through free radical tandem cyclization reaction, intermolecular coupling and intramolecular cyclization are achieved, and finally, arylthiobenzothiazole compounds are obtained.

[0021] The beneficial effects of this invention are: this invention synthesizes a series of arylthiobenzothiazole compounds, and its synthesis method has the advantages of readily available raw materials, simple operation, mild reaction conditions, and wide substrate adaptability, and has good application prospects in drug application, bioactive molecules, and the synthesis research of other analogs. Attached Figure Description

[0022] Figure 1 The image shows the 1H NMR spectrum of the arylthiobenzothiazole compound from Example 1.

[0023] Figure 2 The image shows the carbon NMR spectrum of the arylthiobenzothiazole compound from Example 1.

[0024] Figure 3 The image shows the 1H NMR spectrum of the arylthiobenzothiazole compound from Example 2.

[0025] Figure 4 The image shows the carbon NMR spectrum of the arylthiobenzothiazole compound from Example 2.

[0026] Figure 5 The image shows the 1H NMR spectrum of the arylthiobenzothiazole compound from Example 3.

[0027] Figure 6 The image shows the carbon NMR spectrum of the arylthiobenzothiazole compound from Example 3.

[0028] Figure 7 The image shows the 1H NMR spectrum of the arylthiobenzothiazole compound from Example 4.

[0029] Figure 8 The image shows the carbon NMR spectrum of the arylthiobenzothiazole compound from Example 4.

[0030] Figure 9 The image shows the 1H NMR spectrum of the arylthiobenzothiazole compound from Example 5.

[0031] Figure 10 The image shows the carbon NMR spectrum of the arylthiobenzothiazole compound from Example 5.

[0032] Figure 11 The image shows the 1H NMR spectrum of the arylthiobenzothiazole compound from Example 6.

[0033] Figure 12 The image shows the carbon NMR spectrum of the arylthiobenzothiazole compound from Example 6.

[0034] Figure 13 The image shows the 1H NMR spectrum of the arylthiobenzothiazole compound from Example 7.

[0035] Figure 14 The image shows the carbon NMR spectrum of the arylthiobenzothiazole compound from Example 7.

[0036] Figure 15 The image shows the 1H NMR spectrum of the arylthiobenzothiazole compound from Example 8.

[0037] Figure 16 The image shows the carbon NMR spectrum of the arylthiobenzothiazole compound from Example 8.

[0038] Figure 17 The image shows the 1H NMR spectrum of the arylthiobenzothiazole compound from Example 9.

[0039] Figure 18 The image shows the carbon NMR spectrum of the arylthiobenzothiazole compound from Example 9.

[0040] Figure 19 The image shows the 1H NMR spectrum of the arylthiobenzothiazole compound from Example 10.

[0041] Figure 20 The image shows the carbon NMR spectrum of the arylthiobenzothiazole compound from Example 10.

[0042] Figure 21 The image shows the 1H NMR spectrum of the arylthiobenzothiazole compound from Example 11.

[0043] Figure 22 The image shows the carbon NMR spectrum of the arylthiobenzothiazole compound from Example 11.

[0044] Figure 23 The image shows the 1H NMR spectrum of the arylthiobenzothiazole compound from Example 12.

[0045] Figure 24 The image shows the carbon NMR spectrum of the arylthiobenzothiazole compound from Example 12.

[0046] Figure 25The image shows the 1H NMR spectrum of the arylthiobenzothiazole compound from Example 13.

[0047] Figure 26 The image shows the carbon NMR spectrum of the arylthiobenzothiazole compound from Example 13.

[0048] Figure 27 The image shows the fluorescence emission spectrum of the arylthiobenzothiazole compound from Example 1 after mixing with different ions.

[0049] Figure 28 The arylthiobenzothiazole compound of Example 1 was reacted with different concentrations of Au. 3+ Fluorescence emission spectrum after mixing. Detailed Implementation

[0050] The present invention will be further explained and described below with reference to specific embodiments.

[0051] Example 1

[0052] An arylthiobenzothiazole compound, the preparation method of which includes the following steps:

[0053] 0.1 mmol 0.2 mmol 0.2 mmol of 1,8-diazabicyclo[5.4.0]undec-7-ene (abbreviated as DBU) was dispersed in 2 mL of acetonitrile and reacted at room temperature for 12 h under visible light with a wavelength of 450 nm to 455 nm and a stirring speed of 500 rpm. The reaction solution was extracted three times with ethyl acetate, and the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the filtrate was subjected to vacuum distillation. The crude product was purified by column chromatography using petroleum ether and ethyl acetate in a volume ratio of 50:1 to obtain the arylthiobenzothiazole compound (yield: 98%).

[0054] The 1H NMR spectrum of the 2-arylthiobenzothiazole compound in this embodiment is shown below. Figure 1 As shown, the carbon NMR spectrum is as follows: Figure 2 As shown, the spectral data is as follows:

[0055] 1 H NMR (400MHz, CDCl3) δ7.88 (d, J = 8.0 Hz, 1H), 7.75–7.72 (m, 2H), 7.64 (d, J = 7. 6Hz, 1H), 7.54–7.45 (m, 3H), 7.42–7.38 (m, 1H), 7.26 (td, J = 8.0, 1.2Hz, 1H).

[0056] 13C NMR (101MHz, CDCl3): δ169.7,153.8,135.4,135.3,130.4,129.9,129.9,129.8,126.1,124.3,121.9,120.7.

[0057] The infrared test data of the 2-arylthiobenzothiazole compound in this embodiment are as follows:

[0058] IR(KBr) Vmax :3456,2922,2079,1638,1454,1307,1078,996,748,618cm -1 .

[0059] The mass spectrometry data of the 2-arylthiobenzothiazole compound in this embodiment are as follows:

[0060] HRMS (APCI) calcd for C 13 H 10 NS2[M+H] + :244.0249,Found:244.0244.

[0061] In summary, the structural formula of the arylthiobenzothiazole compound in this embodiment is as follows:

[0062] Example 2

[0063] An arylthiobenzothiazole compound, the preparation method of which includes the following steps:

[0064] 0.1 mmol 0.2 mmol 0.2 mmol of 1,8-diazabicyclo[5.4.0]undec-7-ene (abbreviated as DBU) was dispersed in 2 mL of acetonitrile and reacted at room temperature for 12 h under visible light with a wavelength of 450 nm to 455 nm and a stirring speed of 500 rpm. The reaction solution was extracted three times with ethyl acetate, and the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the filtrate was subjected to vacuum distillation. The crude product was purified by column chromatography using petroleum ether and ethyl acetate in a volume ratio of 50:1 to obtain the arylthiobenzothiazole compound (yield: 99%).

[0065] The 1H NMR spectrum of the arylthiobenzothiazole compound in this embodiment is as follows: Figure 3 As shown, the carbon NMR spectrum is as follows: Figure 4 As shown, the spectral data is as follows:

[0066] 1H NMR (400MHz, CDCl3): δ7.75 (d, J = 8.4Hz, 1H), 7.72–7.67 (m, 2H), 7.48–7.41 (m, 4H), 7.19 (d, J = 9.6Hz, 1H), 2.4 (s, 3H).

[0067] 13 C NMR (101MHz, CDCl3): δ167.9,151.9,135.7,135.1,134.4,130.2,130.1,129.8,127.6,121.4,120.5,21.4.

[0068] The infrared test data of the arylthiobenzothiazole compound in this embodiment are as follows:

[0069] IR(KBr) Vmax :3697,2919,1439,1005,813,748,692,495cm -1 .

[0070] The mass spectrometry data of the arylthiobenzothiazole compound in this embodiment are as follows:

[0071] HRMS (APCI) calcd for C 14 H 11 NS2[M+H] + :258.0406,Found:258.0402.

[0072] In summary, the structural formula of the arylthiobenzothiazole compound in this embodiment is as follows:

[0073] Example 3

[0074] An arylthiobenzothiazole compound, the preparation method of which includes the following steps:

[0075] 0.1 mmol 0.2 mmol 0.2 mmol of 1,8-diazabicyclo[5.4.0]undec-7-ene (abbreviated as DBU) was dispersed in 2 mL of acetonitrile and reacted at room temperature for 12 h under visible light with a wavelength of 450 nm to 455 nm and a stirring speed of 500 rpm. The reaction solution was extracted three times with ethyl acetate, and the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the filtrate was subjected to vacuum distillation. The crude product obtained by vacuum distillation was purified by column chromatography using petroleum ether and ethyl acetate in a volume ratio of 50:1 to obtain the arylthiobenzothiazole compound (yield: 70%).

[0076] The 1H NMR spectrum of the arylthiobenzothiazole compound in this embodiment is as follows: Figure 5 As shown, the carbon NMR spectrum is as follows: Figure 6 As shown, the spectral data is as follows:

[0077] 1 H NMR (400MHz, CDCl3): δ7.99 (d, J=1.6Hz, 1H), 7.77–7.68 (m, 2H), 7.55–7.45 (m, 4H), 7.34 (dd, J=8.8, 2.0Hz).

[0078] 13 C NMR (101MHz, CDCl3): δ172.2, 155.1, 135.6, 134.2, 130.8, 130.1, 129.4, 127.3, 124.7, 121.8, 119.8.

[0079] The infrared test data of the arylthiobenzothiazole compound in this embodiment are as follows:

[0080] IR(KBr) Vmax :3700,2922,2362,1576,1423,1147,890,748,620,696cm -1 .

[0081] The mass spectrometry data of the arylthiobenzothiazole compound in this embodiment are as follows:

[0082] HRMS (APCI) calcd for C 13 H8BrNS2[M+H] + :321.9355,Found:321.9349.

[0083] In summary, the structural formula of the arylthiobenzothiazole compound in this embodiment is as follows:

[0084] Example 4

[0085] An arylthiobenzothiazole compound, the preparation method of which includes the following steps:

[0086] 0.1 mmol 0.2 mmol 0.2 mmol of 1,8-diazabicyclo[5.4.0]undec-7-ene (abbreviated as DBU) was dispersed in 2 mL of acetonitrile and reacted at room temperature for 12 h under visible light with a wavelength of 450 nm to 455 nm and a stirring speed of 500 rpm. The reaction solution was extracted three times with ethyl acetate, and the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the filtrate was subjected to vacuum distillation. The crude product was purified by column chromatography using petroleum ether and ethyl acetate in a volume ratio of 50:1 to obtain the arylthiobenzothiazole compound (yield: 98%).

[0087] The 1H NMR spectrum of the arylthiobenzothiazole compound in this embodiment is as follows: Figure 7 As shown, the carbon NMR spectrum is as follows: Figure 8 As shown, the spectral data is as follows:

[0088] 1 H NMR (400MHz, CDCl3) δ7.77 (d, J = 8.8 Hz, 1H), 7.71–7.67 (m, 3H), 7.12 (d, J = 2.4 Hz, 1H), 7.00 (dd, J = 9.2, 2.8 Hz, 1H), 3.80 (s, 3H).

[0089] 13 C NMR (101MHz, CDCl3) δ165.6,157.1,148.3,137.1,134.8,130.4,130.1,129.8,122.5,114.9,103.9,55.7.

[0090] The infrared test data of the arylthiobenzothiazole compound in this embodiment are as follows:

[0091] IR(KBr) Vmax :3452,3063,2924,2114,1636,1435,1221,889,748,612cm -1 .

[0092] The mass spectrometry data of the arylthiobenzothiazole compound in this embodiment are as follows:

[0093] HRMS (APCI) calcd for C 14 H 11 NOS2[M+H] + :274.0355,Found:274.0350.

[0094] In summary, the structural formula of the arylthiobenzothiazole compound in this embodiment is as follows:

[0095] Example 5

[0096] An arylthiobenzothiazole compound, the preparation method of which includes the following steps:

[0097] 0.1 mmol 0.2 mmol 0.2 mmol of 1,8-diazabicyclo[5.4.0]undec-7-ene (abbreviated as DBU) was dispersed in 2 mL of acetonitrile and reacted at room temperature for 12 h under visible light with a wavelength of 450 nm to 455 nm and a stirring speed of 500 rpm. The reaction solution was extracted three times with ethyl acetate, and the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the filtrate was subjected to vacuum distillation. The crude product was purified by column chromatography using petroleum ether and ethyl acetate in a volume ratio of 50:1 to obtain the arylthiobenzothiazole compound (yield: 79%).

[0098] The 1H NMR spectrum of the arylthiobenzothiazole compound in this embodiment is as follows: Figure 9 As shown, the carbon NMR spectrum is as follows: Figure 10 As shown, the spectral data is as follows: 1 H NMR (400MHz, CDCl3): δ7.85 (d, J=2.0Hz, 1H), 7.76–7.71 (m, 2H), 7.57–7.48 (m, 4H), 7.25–7.22 (m, 1H).

[0099] 13 C NMR (101MHz, CDCl3): δ172.4,154.7,135.6,133.6,132.1,130.8,130.0,129.3,124.6,121.7,121.4.

[0100] The infrared test data of the arylthiobenzothiazole compound in this embodiment are as follows:

[0101] IR(KBr) Vmax :3699,3483,2922,2362,1545,1296,1067,865,798,614cm -1 .

[0102] The mass spectrometry data of the arylthiobenzothiazole compound in this embodiment are as follows:

[0103] HRMS (APCI) calcd for C 13 H8ClNS2[M+H] + :277.9860,Found:277.9854.

[0104] In summary, the structural formula of the arylthiobenzothiazole compound in this embodiment is as follows:

[0105] Example 6

[0106] An arylthiobenzothiazole compound, the preparation method of which includes the following steps:

[0107] 0.1 mmol 0.2 mmol 0.2 mmol of 1,8-diazabicyclo[5.4.0]undec-7-ene (abbreviated as DBU) was dispersed in 2 mL of acetonitrile and reacted at room temperature for 12 h under visible light with a wavelength of 450 nm to 455 nm and a stirring speed of 500 rpm. The reaction solution was extracted three times with ethyl acetate, and the combined organic phases were dried over anhydrous sodium sulfate, filtered, and the filtrate was subjected to vacuum distillation. The crude product was purified by column chromatography using petroleum ether and ethyl acetate in a volume ratio of 50:1 to obtain the arylthiobenzothiazole compound (yield: 97%).

[0108] The 1H NMR spectrum of the arylthiobenzothiazole compound in this embodiment is as follows: Figure 11 As shown, the carbon NMR spectrum is as follows: Figure 12 As shown, the spectral data is as follows:

[0109] 1 H NMR (400MHz, CDCl3): δ7.86 (d, J = 8.4Hz, 1H), 7.64–7.61 (m, 3H), 7.41–7.37 (m, 1H), 7.30–7.22 (m, 3H), 2.43 (s, 3H).

[0110] 13 C NMR (101MHz, CDCl3): δ170.8,153.9,141.1,135.5,135.4,130.7,126.2,126.1,124.1,121.8,120.7,21.4.

[0111] The infrared test data of the arylthiobenzothiazole compound in this embodiment are as follows:

[0112] IR(KBr) Vmax :3475,2921,2078,1638,1422,1087,999,805,752,617cm -1 .

[0113] The mass spectrometry data of the arylthiobenzothiazole compound in this embodiment are as follows:

[0114] HRMS (APCI) calcd for C 14 H 11 NS2[M+H] + :258.0406,Found:258.0401.

[0115] In summary, the structural formula of the arylthiobenzothiazole compound in this embodiment is as follows:

[0116] Example 7

[0117] An arylthiobenzothiazole compound, in addition to Replace with Except for the preparation process, it is exactly the same as in Example 6.

[0118] The yield of the arylthiobenzothiazole compound in this embodiment was 98%.

[0119] The 1H NMR spectrum of the arylthiobenzothiazole compound in this embodiment is as follows: Figure 13 As shown, the carbon NMR spectrum is as follows: Figure 14 As shown, the spectral data is as follows:

[0120] 1 H NMR (400MHz, CDCl3): δ7.85 (d, J=8.0Hz, 1H), 7.63 (dd, J=12.8, 8.8Hz, 3H), 7. 37(t,J=7.6Hz,1H), 7.22(t,J=7.6Hz,1H), 6.98(d,J=8.4Hz,1H), 3.85(s,3H).

[0121] 13 C NMR (101MHz, CDCl3): δ171.8,161.6,154.1,137.5,135.3,126.0,124.0,121.6,120.7,120.1,115.4,55.4.

[0122] The infrared test data of the arylthiobenzothiazole compound in this embodiment are as follows:

[0123] IR(KBr) Vmax :3478,2361,1489,1420,1288,1243,1098,823,751,618cm -1 .

[0124] The mass spectrometry data of the arylthiobenzothiazole compound in this embodiment are as follows:

[0125] HRMS (APCI) calcd for C 14 H11 NOS2[M+H] + :274.0355,Found:274.0349.

[0126] In summary, the structural formula of the arylthiobenzothiazole compound in this embodiment is as follows:

[0127] Example 8

[0128] An arylthiobenzothiazole compound, in addition to Replace with Except for the preparation process, it is exactly the same as in Example 6.

[0129] The yield of the arylthiobenzothiazole compound in this embodiment was 91%.

[0130] The 1H NMR spectrum of the arylthiobenzothiazole compound in this embodiment is as follows: Figure 15 As shown, the carbon NMR spectrum is as follows: Figure 16 As shown, the spectral data is as follows:

[0131] 1 H NMR (400MHz, CDCl3): δ7.87(d,J=8.0Hz,1H),7.65(t,J=8.4Hz,3H),7.50–7.47(m,2H),7.41–7.37(m,1H),7.27–7.23(m,1H),1.36(s,9H).

[0132] 13 C NMR (101MHz, CDCl3): δ170.7,154.2,154.1,135.5,135.2,127.1,126.3,126.1,124.2,121.9,120.8,35.0,31.2.

[0133] The infrared test data of the arylthiobenzothiazole compound in this embodiment are as follows:

[0134] IR(KBr) Vmax :3742,3532,2959,2360,1457,1115,1004,830,755,618cm -1 .

[0135] The mass spectrometry data of the arylthiobenzothiazole compound in this embodiment are as follows:

[0136] HRMS (APCI) calcd for C 17 H 17 NS2[M+H] +:300.0875,Found:300.0869.

[0137] In summary, the structural formula of the arylthiobenzothiazole compound in this embodiment is as follows:

[0138] Example 9

[0139] An arylthiobenzothiazole compound, in addition to Replace with Except for the preparation process, it is exactly the same as in Example 6.

[0140] The yield of the arylthiobenzothiazole compound in this embodiment was 91%.

[0141] The 1H NMR spectrum of the arylthiobenzothiazole compound in this embodiment is as follows: Figure 17 As shown, the carbon NMR spectrum is as follows: Figure 18 As shown, the spectral data is as follows:

[0142] 1 H NMR (400MHz, CDCl3): δ7.87 (d, J = 8.4Hz, 1H), 7.66 (d, J = 8.0Hz, 1H), 7.60–7.54 (m, 4H), 7.40 (t, J = 8.0Hz, 1H), 7.27 (t, J = 8.0Hz, 1H).

[0143] 13 C NMR (101MHz, CDCl3): δ167.9,153.7,136.4,135.5,133.0,128.9,126.2,125.1,124.5,122.0,120.8.

[0144] The infrared test data of the arylthiobenzothiazole compound in this embodiment are as follows:

[0145] IR(KBr) Vmax :3537,3489,2078,1643,1460,1234,1076,1000,753,618cm -1 .

[0146] The mass spectrometry data of the arylthiobenzothiazole compound in this embodiment are as follows:

[0147] HRMS (APCI) calcd for C 13 H8BrNS2[M+H] + :321.9355,Found:321.9348.

[0148] In summary, the structural formula of the arylthiobenzothiazole compound in this embodiment is as follows: Example 10

[0149] An arylthiobenzothiazole compound, in addition to Replace with Except for the preparation process, it is exactly the same as in Example 6.

[0150] The yield of the arylthiobenzothiazole compound in this embodiment was 90%.

[0151] The 1H NMR spectrum of the arylthiobenzothiazole compound in this embodiment is as follows: Figure 19 As shown, the carbon NMR spectrum is as follows: Figure 20 As shown, the spectral data is as follows:

[0152] 1 H NMR (400MHz, CDCl3): δ7.88 (d, J=8.0Hz, 1H), 7.69–7.65 (m, 3H), 7.46–7.40 (m, 3H), 7.32–7.27 (m, 1H).

[0153] 13 C NMR (101MHz, CDCl3): δ168.4,153.8,137.0,136.5,135.6,130.2,128.4,126.3,124.6,122.1,120.9.

[0154] The infrared test data of the arylthiobenzothiazole compound in this embodiment are as follows:

[0155] IR(KBr) Vmax :3560,3359,2920,2360,1643,1459,1267,1005,752,619cm -1 .

[0156] The mass spectrometry data of the arylthiobenzothiazole compound in this embodiment are as follows:

[0157] HRMS (APCI) calcd for C 13 H8ClNS2[M+H] + :277.9860,Found:277.9855.

[0158] In summary, the structural formula of the arylthiobenzothiazole compound in this embodiment is as follows: Example 11

[0159] An arylthiobenzothiazole compound, in addition to Replace with Except for the preparation process, it is exactly the same as in Example 6.

[0160] The yield of the arylthiobenzothiazole compound in this embodiment was 90%.

[0161] The 1H NMR spectrum of the arylthiobenzothiazole compound in this embodiment is as follows: Figure 21 As shown, the carbon NMR spectrum is as follows: Figure 22 As shown, the spectral data is as follows:

[0162] 1 H NMR (400MHz, CDCl3): δ7.76–7.70(m,4H),7.54–7.47(m,4H).

[0163] 13 C NMR (101MHz, CDCl3): δ170.7,152.8,137.0,135.5,130.7,130.0,129.6,129.4,123.3,122.9,117.8.

[0164] The infrared test data of the arylthiobenzothiazole compound in this embodiment are as follows:

[0165] IR(KBr) Vmax :3562,3355,2081,1640,1425,1383,1242,1088,743,619cm -1 .

[0166] The mass spectrometry data of the arylthiobenzothiazole compound in this embodiment are as follows:

[0167] HRMS (APCI) calcd for C 13 H8BrNS2[M+H] + :321.9355,Found:321.9349.

[0168] In summary, the structural formula of the arylthiobenzothiazole compound in this embodiment is as follows: Example 12

[0169] An arylthiobenzothiazole compound, in addition to Replace with Except for the preparation process, it is exactly the same as in Example 6.

[0170] The yield of the arylthiobenzothiazole compound in this embodiment was 78%.

[0171] The 1H NMR spectrum of the arylthiobenzothiazole compound in this embodiment is as follows: Figure 23 As shown, the carbon NMR spectrum is as follows: Figure 24As shown, the spectral data is as follows:

[0172] 1 H NMR (400MHz, CDCl3): δ7.86(d,J=8.0Hz,1H),7.65(d,J=8.4Hz,1H),7.42–7.38(m,1H),7.35(dd,J=8. 4, 2.4Hz, 1H), 7.27–7.25 (m, 1H), 7.24–7.22 (m, 1H), 6.96 (d, J = 8.4Hz, 1H), 3.96 (s, 3H), 3.90 (s, 3H).

[0173] 13 C NMR (101MHz, CDCl3): δ171.6,154.1,151.3,149.7,135.4,129.2,126.1,124.1,121.7,120.7,120.2,118.2,111.8,56.1,56.0.

[0174] The infrared test data of the arylthiobenzothiazole compound in this embodiment are as follows:

[0175] IR(KBr) Vmax :3702,2923,1580,1500,1424,1131,756,617cm -1 .

[0176] The mass spectrometry data of the arylthiobenzothiazole compound in this embodiment are as follows:

[0177] HRMS (APCI) calcd for C 15 H 13 NO2S2[M+H] + :304.0461,Found:304.0454.

[0178] In summary, the structural formula of the arylthiobenzothiazole compound in this embodiment is as follows: Example 13

[0179] An arylthiobenzothiazole compound, in addition to Replace with Except for the preparation process, it is exactly the same as in Example 6.

[0180] The yield of the arylthiobenzothiazole compound in this embodiment was 80%.

[0181] The 1H NMR spectrum of the arylthiobenzothiazole compound in this embodiment is as follows: Figure 25 As shown, the carbon NMR spectrum is as follows: Figure 26 As shown, the spectral data is as follows:

[0182] 1 H NMR (400MHz, CDCl3): δ8.26 (s, 1H), 7.91–7.84 (m, 4H), 7.70 (dd, J = 8.4, 2.0Hz, 1H), 7.60–7.52 (m, 3H), 7.38 (t, J = 8.0Hz), 7.23 (t, J = 7.6Hz, 1H).

[0183] 13 C NMR (101MHz, CDCl3): δ169.5,153.9,135.6,135.4,133.7,133.7,131.1,129.7,128.1,127.8,127.7,127.0,127.0,126.1,124.3,121.9,120.8.

[0184] The infrared test data of the arylthiobenzothiazole compound in this embodiment are as follows:

[0185] IR(KBr) Vmax :3021,3056,2921,1585,1456,1127,855,813,751,618cm -1 .

[0186] The mass spectrometry data of the arylthiobenzothiazole compound in this embodiment are as follows:

[0187] HRMS (APCI) calcd for C 17 H 11 NS2[M+H] + :294.0406,Found:294.0399.

[0188] In summary, the structural formula of the arylthiobenzothiazole compound in this embodiment is as follows:

[0189] Application testing:

[0190] 1) Prepare 10 mL of 0.01 mol / L aqueous solutions of 11 metal ions (including Ag) respectively. + Al 3 + Au 3+ Co 2+ Cu 2+ Fe 2+ Ir 3+ La 3+ Li + Mg 2+ and Pd 2+The corresponding anion is OAc. - or Cl - A 10 mL tetrahydrofuran solution of the arylthiobenzothiazole compound with a concentration of 0.0001 mol / L was prepared using the arylthiobenzothiazole compound from Example 1. Then, 2 mL of the tetrahydrofuran solution of the arylthiobenzothiazole compound was mixed thoroughly with 20 μL of an aqueous solution of metal ions. The mixed solution was then subjected to fluorescence testing. The fluorescence emission (PL) spectra of the arylthiobenzothiazole compound from Example 1 mixed with different ions were obtained by plotting the scanning wavelength range on the x-axis and the fluorescence intensity on the y-axis. Figure 27 As shown.

[0191] Depend on Figure 27 It can be seen that there are three types of ions (Fe). 2+ Ag + and Au 3+ This will cause a decrease in fluorescence intensity, in which Au 3+ Au was the only metal ion that caused a significant decrease in fluorescence intensity, while other metal ions had little effect on fluorescence intensity, indicating that Au... 3+ It is the best ion for suppressing the fluorescence intensity of arylthiobenzothiazole compounds.

[0192] 2) Prepare 10 mL of Au solution with a concentration of 0.01 mol / L. 3+ Aqueous solution (corresponding anion is Cl) - ), and prepared 10 mL of a 0.0001 mol / L tetrahydrofuran solution of the arylthiobenzothiazole compound using the arylthiobenzothiazole compound from Example 1. Then, 2 mL of the tetrahydrofuran solution of the arylthiobenzothiazole compound was mixed with different volumes (20 μL, 30 μL, 40 μL, 50 μL, 60 μL, and 100 μL) of Au. 3+ The aqueous solution was mixed thoroughly, and then the mixed solution was subjected to fluorescence testing. The scanning wavelength range was plotted on the x-axis, and the fluorescence intensity on the y-axis. The arylthiobenzothiazole compound obtained in Example 1 was compared with different concentrations of Au. 3+ The mixed fluorescence emission (PL) spectrum is shown below. Figure 28 As shown.

[0193] Depend on Figure 28 It can be seen that: with Au 3+ As the concentration of [agent] increases, the fluorescence intensity near 400 nm gradually decreases, indicating that the arylthiobenzothiazole compound of Example 1 can act as an Au [resource]. 3+ Fluorescent probe.

[0194] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A method for preparing a class of arylthiobenzothiazole compounds, characterized in that, Includes the following steps: Will A disulfide and a base are dispersed in a solvent and reacted under visible light to obtain an arylthiobenzothiazole compound; the disulfide is... , One of the following; the base is at least one of sodium carbonate, sodium hydroxide, potassium carbonate, cesium carbonate, triethylamine, and 1,8-diazabicyclo[5.4.0]undec-7-ene; the visible light band includes at least one of 380 nm to 390 nm, 440 nm to 445 nm, 450 nm to 455 nm, and 515 nm to 525 nm; the arylthiobenzothiazole compound has a structural formula of one of formulas (1) to (2): In the formula, R 1 Selected from one of -H, -Me, -OMe, -Cl, -Br, R 2 Selected from -H, -Me, -OMe, - t One of -Bu, -Cl, and -Br.

2. The preparation method according to claim 1, characterized in that: The The molar ratio of disulfide and alkali is 1:1 to 3:1 to 2.

3. The preparation method according to claim 1, characterized in that: The solvent is at least one selected from toluene, dichloroethane, methanol, dimethyl sulfoxide, tetrahydrofuran, acetonitrile, and chloroform.

4. The preparation method according to claim 1, characterized in that: The reaction was carried out at a temperature of 10 to 80°C for a time of 8 to 16 hours.

5. The preparation method according to claim 1, characterized in that: The reaction was carried out at a stirring speed of 300 rpm to 700 rpm.

6. The application of the arylthiobenzothiazole compound obtained by the preparation method according to claim 1, characterized in that: Used as Au 3+ Fluorescent probe.

Images