Aryl sulfur benzothiazole compound as well as preparation method and application thereof

Abstract

The invention discloses an aryl sulfur benzothiazole compound as well as a preparation method and application thereof. The aryl sulfur benzothiazole compound is characterized in that the structural formula is one of formulas (1)-(2): # imgabs0 #, in the formula, R1 is selected from one of-H,-Me,-OMe,-Cl and-Br, and R2 is selected from one of-H,-Me,-OMe,-t-Bu,-Cl and-Br. A series of aryl thiobenzothiazole compounds are synthesized, and the synthesis method has the advantages of easily available raw materials, simple operation, mild reaction conditions, wide substrate adaptability and the like, and has good application prospects in the aspects of synthesis research of photoelectric materials and antiviral drugs and the like.

Description

Technical Field

[0001] The invention relates to the technical field of organic synthesis, and in particular to a preparation method and application of an arylthiobenzothiazole compound. Background Art

[0002] It is well known that heteroaromatic compounds with thioorganic groups and their derivatives have important biological activities. These compounds have potential uses as anticancer, antibacterial, antiviral, antituberculosis, antihelminthic, antidiabetic, antifungal and antimicrobial agents (Singh, M., Singh, SK, Gangwar, M., Nath, G., Singh, SK RSC Adv. 2014, 4, 19013; Huang, ST, Hsei, IJ, Chen, C. Bioorg. Med. Chem. 2006, 14, 6106.). In particular, some 2-thiothioazoles, such as 2-arylthiobenzothiazoles, have attracted much attention due to their unique structures and their potential 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 C-S bonds by 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, VP Chem. 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 are used as active catalysts (Lee, CF, Liu, YC, Badsara, SS, Chem. Asian J. 2014, 9, 706.). Among them, Cu-catalyzed sarylation reaction of aryl thiols with aryl halides and aryl sources such as boric acid is a powerful tool for synthesizing asymmetric disulfides containing benzene rings (Lin, Y., Cai, M., Fang, Z., Zhao, H. Tetrahedron. 2016, 72, 3335.). However, the preparation of 2-arylthiobenzothiazoles by these methods is largely limited by the types of pre-made complex 2-halogenated benzothiazoles or 2-mercaptobenzothiazoles (Yonova, IM, Osborne, CA, Morrissette, NSJ 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 disadvantages, such as high reaction temperature, poor substrate universality, etc., and usually require the use of stoichiometric transition metals to catalyze the reaction.

[0004] As a class of efficient C1 synthons, isonitriles have rich chemical properties determined by their special valence bond structure. In recent years, isonitriles have been combined with various free radical precursors such as Togni reagents and phosphine oxides under photocatalysis to efficiently construct nitrogen-containing heterocyclic compounds with diverse structures (Wu, L., Yu, J., Cheng, Y. Angew. Chem. Int. Ed. 2022, 61, e202209293). Therefore, we have developed a new method for synthesizing arylthiobenzothiazole compounds, which uses isonitriles and aryl disulfides to undergo tandem cyclization under light conditions to construct 2-arylthiobenzothiazole derivatives in a green and efficient manner. This method has cheap and readily available raw materials, mild reaction conditions, simple operation, and a wide range of substrate applications, and has broad application prospects. Summary of the invention

[0005] The purpose of the present invention is to provide a method for preparing a class of arylthiobenzothiazole compounds in view of the shortcomings and deficiencies of the prior art.

[0006] The technical solution adopted by the present invention is:

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

[0008] Where R 1 is selected from one of -H, -Me, -OMe, -Cl, and -Br, R 2 One selected from -H, -Me, -OMe, -t-Bu, -Cl, -Br

[0009] A method for preparing an arylthiobenzothiazole compound comprises the following steps: The disulfide and the base are dispersed in a solvent, and the disulfide is One of

[0010] The reaction is carried out under the irradiation of visible light to obtain an arylthiobenzothiazole compound.

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

[0012] In the above method, 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 (DBU for short).

[0013] In the above method, the solvent is at least one of toluene, ethylene dichloride, methanol, dimethyl sulfoxide, tetrahydrofuran, acetonitrile and chloroform.

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

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

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

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

[0018] In the above method, the specific operations of separation and purification are: extracting the reaction solution with ethyl acetate for multiple times, combining the organic phases, drying with anhydrous sodium sulfate, filtering, taking the filtrate for vacuum distillation, and purifying the obtained crude product by column chromatography.

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

[0020] Principle of the invention: The invention uses 2-methylthioaryl isocyanate and aryl disulfide as raw materials, places them under visible light irradiation, reacts under the action of a base, realizes intermolecular coupling and intramolecular cyclization through a free radical tandem cyclization reaction, and finally obtains an arylthiobenzothiazole compound.

[0021] The beneficial effects of the present invention are as follows: a series of arylthiobenzothiazole compounds are synthesized by the present invention, and the synthesis method thereof has the advantages of readily available raw materials, simple operation, mild reaction conditions, wide substrate adaptability, etc., and has good application prospects in drug application, bioactive molecules, synthesis research of other analogs, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of the arylthiobenzothiazole compound of Example 1.

[0023] Figure 2 This is the carbon NMR spectrum of the arylthiobenzothiazole compound of Example 1.

[0024] Figure 3 This is the hydrogen nuclear magnetic resonance spectrum of the arylthiobenzothiazole compound of Example 2.

[0025] Figure 4 This is the carbon NMR spectrum of the arylthiobenzothiazole compound of Example 2.

[0026] Figure 5 This is the hydrogen nuclear magnetic resonance spectrum of the arylthiobenzothiazole compound of Example 3.

[0027] Figure 6 This is the carbon NMR spectrum of the arylthiobenzothiazole compound of Example 3.

[0028] Figure 7 This is the hydrogen nuclear magnetic resonance spectrum of the arylthiobenzothiazole compound of Example 4.

[0029] Figure 8 This is the carbon NMR spectrum of the arylthiobenzothiazole compound of Example 4.

[0030] Fig. 9 This is the hydrogen nuclear magnetic resonance spectrum of the arylthiobenzothiazole compound of Example 5.

[0031] Fig.10 This is the carbon NMR spectrum of the arylthiobenzothiazole compound of Example 5.

[0032] Fig.11 This is the hydrogen nuclear magnetic resonance spectrum of the arylthiobenzothiazole compound of Example 6.

[0033] Fig.12 This is the carbon NMR spectrum of the arylthiobenzothiazole compound of Example 6.

[0034] Fig.13 This is the hydrogen nuclear magnetic resonance spectrum of the arylthiobenzothiazole compound of Example 7.

[0035] Fig.14 This is the carbon NMR spectrum of the arylthiobenzothiazole compound of Example 7.

[0036] Fig.15 This is the hydrogen nuclear magnetic resonance spectrum of the arylthiobenzothiazole compound of Example 8.

[0037] Fig.16 This is the carbon NMR spectrum of the arylthiobenzothiazole compound of Example 8.

[0038] Fig.17 This is the hydrogen nuclear magnetic resonance spectrum of the arylthiobenzothiazole compound of Example 9.

[0039] Fig.18 This is the carbon NMR spectrum of the arylthiobenzothiazole compound of Example 9.

[0040] Fig.19 This is the hydrogen nuclear magnetic resonance spectrum of the arylthiobenzothiazole compound of Example 10.

[0041] Fig. 20 This is the carbon NMR spectrum of the arylthiobenzothiazole compound of Example 10.

[0042] Fig.21 This is the hydrogen nuclear magnetic resonance spectrum of the arylthiobenzothiazole compound of Example 11.

[0043] Fig. 22 This is the carbon NMR spectrum of the arylthiobenzothiazole compound of Example 11.

[0044] Fig.23 This is the hydrogen nuclear magnetic resonance spectrum of the arylthiobenzothiazole compound of Example 12.

[0045] Fig.24 This is the carbon NMR spectrum of the arylthiobenzothiazole compound of Example 12.

[0046] Fig.25This is the hydrogen nuclear magnetic resonance spectrum of the arylthiobenzothiazole compound of Example 13.

[0047] Fig.26 This is the carbon NMR spectrum of the arylthiobenzothiazole compound of Example 13.

[0048] Fig. 27 The fluorescence emission spectra of the arylthiobenzothiazole compound of Example 1 after mixing with different ions.

[0049] Fig.28 The arylthiobenzothiazole compound of Example 1 and Au with different concentrations 3+ Fluorescence emission spectra after mixing. DETAILED DESCRIPTION

[0050] The present invention will be further explained and illustrated below in conjunction with specific embodiments.

[0051] Example 1

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

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

[0054] The hydrogen nuclear magnetic resonance spectrum of the 2-arylthiobenzothiazole compound of this example is as follows Figure 1 As shown, the carbon NMR spectrum is as follows Figure 2 As shown, the spectrum analysis data is as follows:

[0055] 1 H NMR (400 MHz, CDCl 3 )δ7.88(d,J=8.0Hz,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 (101 MHz, CDCl 3 ): 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 spectrum data of the 2-arylthiobenzothiazole compound in this example are as follows:

[0060] HRMS (APCI) calculation for C 13 H 10 NS 2 [M+H] + :244.0249,Found:244.0244.

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

[0062] Example 2

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

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

[0065] The hydrogen nuclear magnetic resonance spectrum of the arylthiobenzothiazole compound of this example is as follows Figure 3 As shown, the carbon NMR spectrum is as follows Figure 4 As shown, the spectrum analysis data is as follows:

[0066] 1 H NMR (400 MHz, CDCl 3 ): 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 (101 MHz, CDCl 3 ): 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 of this embodiment are as follows:

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

[0070] The mass spectrum data of the arylthiobenzothiazole compound of this example are as follows:

[0071] HRMS (APCI) calculation for C 14 H 11 NS 2 [M+H] + :258.0406,Found:258.0402.

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

[0073] Example 3

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

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

[0076] The hydrogen nuclear magnetic resonance spectrum of the arylthiobenzothiazole compound of this example is as follows Figure 5 As shown, the carbon NMR spectrum is as follows Figure 6 As shown, the spectrum analysis data is as follows:

[0077] 1 H NMR (400 MHz, CDCl 3 ): 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 (101 MHz, CDCl 3 ): 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 of this embodiment are as follows:

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

[0081] The mass spectrum data of the arylthiobenzothiazole compound of this example are as follows:

[0082] HRMS (APCI) calculation for C 13 H 8 BrNS 2 [M+H] + :321.9355,Found:321.9349.

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

[0084] Example 4

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

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

[0087] The hydrogen nuclear magnetic resonance spectrum of the arylthiobenzothiazole compound of this example is as follows Figure 7 As shown, the carbon NMR spectrum is as follows Figure 8 As shown, the spectrum analysis data is as follows:

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

[0089] 13 C NMR (101 MHz, CDCl 3 )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 of this embodiment are as follows:

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

[0092] The mass spectrum data of the arylthiobenzothiazole compound of this example are as follows:

[0093] HRMS (APCI) calculation for C 14 H 11 NOS 2 [M+H] + :274.0355,Found:274.0350.

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

[0095] Example 5

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

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

[0098] The hydrogen nuclear magnetic resonance spectrum of the arylthiobenzothiazole compound of this example is as follows Fig. 9 As shown, the carbon NMR spectrum is as follows Fig.10 As shown, the spectrum analysis data is as follows: 1 H NMR (400 MHz, CDCl 3 ): 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 (101 MHz, CDCl 3 ): 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 of this embodiment are as follows:

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

[0102] The mass spectrum data of the arylthiobenzothiazole compound of this example are as follows:

[0103] HRMS (APCI) calculation for C 13 H 8 ClNS 2 [M+H] + :277.9860,Found:277.9854.

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

[0105] Example 6

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

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

[0108] The hydrogen nuclear magnetic resonance spectrum of the arylthiobenzothiazole compound of this example is as follows Fig.11 As shown, the carbon NMR spectrum is as follows Fig.12 As shown, the spectrum analysis data is as follows:

[0109] 1 H NMR (400 MHz, CDCl 3 ): 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 (101 MHz, CDCl 3): 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 of this embodiment are as follows:

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

[0113] The mass spectrum data of the arylthiobenzothiazole compound of this example are as follows:

[0114] HRMS (APCI) calculation for C 14 H 11 NS 2 [M+H] + :258.0406,Found:258.0401.

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

[0116] Example 7

[0117] An arylthiobenzothiazole compound, except that Replace with Other than that, the preparation process is exactly the same as Example 6.

[0118] The yield of the arylthiobenzothiazole compound in this example is 98%.

[0119] The hydrogen nuclear magnetic resonance spectrum of the arylthiobenzothiazole compound of this example is as follows Fig.13 As shown, the carbon NMR spectrum is as follows Fig.14 As shown, the spectrum analysis data is as follows:

[0120] 1 H NMR (400 MHz, CDCl 3 ): 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 (101 MHz, CDCl 3): 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 of this embodiment are as follows:

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

[0124] The mass spectrum data of the arylthiobenzothiazole compound of this example are as follows:

[0125] HRMS (APCI) calculation for C 14 H 11 NOS 2 [M+H] + :274.0355,Found:274.0349.

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

[0127] Example 8

[0128] An arylthiobenzothiazole compound, except that Replace with Other than that, the preparation process is exactly the same as Example 6.

[0129] The yield of the arylthiobenzothiazole compound in this example is 91%.

[0130] The hydrogen nuclear magnetic resonance spectrum of the arylthiobenzothiazole compound of this example is as follows Fig.15 As shown, the carbon NMR spectrum is as follows Fig.16 As shown, the spectrum analysis data is as follows:

[0131] 1 H NMR (400 MHz, CDCl 3 ): 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 (101 MHz, CDCl 3): 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 of this embodiment are as follows:

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

[0135] The mass spectrum data of the arylthiobenzothiazole compound of this example are as follows:

[0136] HRMS (APCI) calculation for C 17 H 17 NS 2 [M+H] + :300.0875,Found:300.0869.

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

[0138] Example 9

[0139] An arylthiobenzothiazole compound, except that Replace with Other than that, the preparation process is exactly the same as Example 6.

[0140] The yield of the arylthiobenzothiazole compound in this example is 91%.

[0141] The hydrogen nuclear magnetic resonance spectrum of the arylthiobenzothiazole compound of this example is as follows Fig.17 As shown, the carbon NMR spectrum is as follows Fig.18 As shown, the spectrum analysis data is as follows:

[0142] 1 H NMR (400 MHz, CDCl 3 ): 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 (101 MHz, CDCl 3): 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 of this embodiment are as follows:

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

[0146] The mass spectrum data of the arylthiobenzothiazole compound of this example are as follows:

[0147] HRMS (APCI) calculation for C 13 H 8 BrNS 2 [M+H] + :321.9355,Found:321.9348.

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

[0149] An arylthiobenzothiazole compound, except that Replace with Otherwise, the preparation process is exactly the same as in Example 6.

[0150] The yield of the arylthiobenzothiazole compound in this example is 90%.

[0151] The hydrogen nuclear magnetic resonance spectrum of the arylthiobenzothiazole compound of this example is as follows Fig.19 As shown, the carbon NMR spectrum is as follows Fig. 20 As shown, the spectrum analysis data is as follows:

[0152] 1 H NMR (400 MHz, CDCl 3 ): 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 (101 MHz, CDCl 3 ): 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 of this embodiment are as follows:

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

[0156] The mass spectrum data of the arylthiobenzothiazole compound of this example are as follows:

[0157] HRMS (APCI) calculation for C 13 H 8 ClNS 2 [M+H] + :277.9860,Found:277.9855.

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

[0159] An arylthiobenzothiazole compound, except that Replace with Other than that, the preparation process is exactly the same as Example 6.

[0160] The yield of the arylthiobenzothiazole compound in this example is 90%.

[0161] The hydrogen nuclear magnetic resonance spectrum of the arylthiobenzothiazole compound of this example is as follows Fig.21 As shown, the carbon NMR spectrum is as follows Fig. 22 As shown, the spectrum analysis data is as follows:

[0162] 1 H NMR (400 MHz, CDCl 3 ): δ7.76–7.70(m,4H),7.54–7.47(m,4H).

[0163] 13 C NMR (101 MHz, CDCl 3 ): 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 of this embodiment are as follows:

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

[0166] The mass spectrum data of the arylthiobenzothiazole compound of this example are as follows:

[0167] HRMS (APCI) calculation for C 13 H 8 BrNS 2 [M+H] + :321.9355,Found:321.9349.

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

[0169] An arylthiobenzothiazole compound, except that Replace with Other than that, the preparation process is exactly the same as Example 6.

[0170] The yield of the arylthiobenzothiazole compound in this example is 78%.

[0171] The hydrogen nuclear magnetic resonance spectrum of the arylthiobenzothiazole compound of this example is as follows Fig.23 As shown, the carbon NMR spectrum is as follows Fig.24 As shown, the spectrum analysis data is as follows:

[0172] 1 H NMR (400 MHz, CDCl 3 ): 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 (101 MHz, CDCl 3 ): 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 of this embodiment are as follows:

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

[0176] The mass spectrum data of the arylthiobenzothiazole compound of this example are as follows:

[0177] HRMS (APCI) calculation for C 15 H 13 NO 2 S 2 [M+H] + :304.0461,Found:304.0454.

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

[0179] An arylthiobenzothiazole compound, except that Replace with Other than that, the preparation process is exactly the same as Example 6.

[0180] The yield of the arylthiobenzothiazole compound in this example is 80%.

[0181] The hydrogen nuclear magnetic resonance spectrum of the arylthiobenzothiazole compound of this example is as follows Fig.25 As shown, the carbon NMR spectrum is as follows Fig.26 As shown, the spectrum analysis data is as follows:

[0182] 1 H NMR (400 MHz, CDCl 3 ): 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 (101 MHz, CDCl 3 ): 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 of this embodiment are as follows:

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

[0186] The mass spectrum data of the arylthiobenzothiazole compound of this example are as follows:

[0187] HRMS (APCI) calculation for C 17 H 11 NS 2 [M+H] + :294.0406,Found:294.0399.

[0188] In summary, the structural formula of the arylthiobenzothiazole compound of 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 + 、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 - ), and use the arylthiobenzothiazole compound of Example 1 to prepare 10mL of a tetrahydrofuran solution of the arylthiobenzothiazole compound with a concentration of 0.0001mol / L, then take 2mL of the tetrahydrofuran solution of the arylthiobenzothiazole compound and mix it evenly with 20μL of the metal ion aqueous solution, and then perform a fluorescence test on the mixed solution, with the scanning wavelength range as the horizontal axis and the fluorescence intensity as the vertical axis. The fluorescence emission (PL) spectra of the arylthiobenzothiazole compound of Example 1 after mixing with different ions are as shown in the figure Fig. 27 shown.

[0191] Depend on Fig. 27 It can be seen that there are three ions (Fe 2+ 、Ag + and Au 3+ ) will lead to a decrease in fluorescence intensity, among which Au 3+Au is the only metal ion that causes a significant decrease in fluorescence intensity, while other metal ions have little effect on fluorescence intensity, indicating that Au 3+ It is the best ion to suppress the fluorescence intensity of arylthiobenzothiazole compounds.

[0192] 2) Prepare 10mL of 0.01mol / L Au 3+ Aqueous solution (the corresponding anion is Cl - ), and 10 mL of a tetrahydrofuran solution of the arylthiobenzothiazole compound with a concentration of 0.0001 mol / L was prepared with the arylthiobenzothiazole compound of Example 1, and 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 evenly, and then the mixed solution was subjected to fluorescence testing, with the scanning wavelength range as the abscissa and the fluorescence intensity as the ordinate, and the obtained arylthiobenzothiazole compound of Example 1 and different concentrations of Au 3+ The fluorescence emission (PL) spectrum after mixing is shown in Fig.28 shown.

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

[0194] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. A class of arylthiobenzothiazole compounds, characterized in that: The structural formula of the arylthiobenzothiazole compound is one of formula (1) to formula (2): In the formula, R 1 is selected from one of -H, -Me, -OMe, -Cl, and -Br, R 2 One selected from -H, -Me, -OMe, -t-Bu, -Cl, and -Br.

2. The method for preparing the arylthiobenzothiazole compound according to claim 1, characterized in that: The following steps are involved: Will The disulfide and the base are dispersed in a solvent and reacted under the irradiation of visible light to obtain an arylthiobenzothiazole compound.

3. The preparation method according to claim 2, characterized in that: The disulfide is One of them.

4. The preparation method according to claim 2, characterized in that: Said The molar ratio of disulfide to base is 1:1-3:1-2.

5. The preparation method according to claim 2, characterized in that: 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.

6. The preparation method according to claim 1, characterized in that: The solvent is at least one of toluene, ethylene dichloride, methanol, dimethyl sulfoxide, tetrahydrofuran, acetonitrile and chloroform.

7. The preparation method according to claim 2, characterized in that: The wavelength band of the visible light includes at least one of 380nm to 390nm, 440nm to 445nm, 450nm to 455nm, and 515nm to 525nm.

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

9. The preparation method according to claim 2, characterized in that: The reaction is carried out under the condition of a stirring speed of 300 rpm to 700 rpm.

10. The use according to claim 1, characterized in that: Used as Au 3+ Fluorescent probes.

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