Synthesis method of photoinduced aryl dithiocarbamate

Abstract

The invention discloses a method for synthesizing an aryl dithiocarbamate compound through light induction. Under purple light irradiation, aryl triazene is used as an aryl and amido bifunctional reagent, and green and efficient synthesis of the aryl dithiocarbamate compound is realized through nitrogen removal of the aryl triazene and insertion of carbon disulfide. The method has the advantages that raw materials are stable and easy to obtain, conditions are mild, operation is simple, reaction time is short, and any metal, photosensitizer and other additives do not need to be used.

Description

Technical Field

[0001] The invention relates to the field of organic synthesis, and in particular to a method for realizing efficient and green synthesis of aryl dithiocarbamate derivatives by light induction, using aryl triazene as a bifunctional reagent of aryl and amine, and inserting carbon disulfide through denitrogenation of aryl triazene. Background Art

[0002] Dithiocarbamates are one of the most important sulfur-containing organic frameworks and exhibit various biological activities such as anticancer, anti-infective, antibacterial and antitumor properties. (W.Huang,Y.Ding,Y.Miao,et al.,Synthesis and AntitumorActivity of Novel Dithiocarbamate Substituted Chromones.Eur.J.Med.Chem.44(2009)3687-3696.X.Hou,Z.Ge,T.Wang,et al.,Dithiocarbamic Acid Esters as Anticancer Agent.Part 1:4-Substituted-Piperazine-1-Carbodithioic Acid 3-Cyano-3,3-Diphenyl-Propyl Esters.Bioorg.Med.Chem.Lett.16(2006)4214-4219.G.Brahemi,FRKona,A.Fiasella,et al.,Exploring the StructuralRequirements for Inhibition of the Ubiquitin E3 Ligase Breast CancerAssociated Protein 2(BCA2)as a Treatment for Breast Cancer.J.Med.Chem.53(2010)2757-2765.M.Ayman,SMEl-Messery,EEHabib,et al.,Targeting MicrobialResistance:Synthesis,Antibacterial Evaluation,DNABinding and Modeling StudyofNew Chalcone-Based Dithiocarbamate Derivatives. Bioorg. Chem. 85 (2019) 282-292. V. Bala, G. Gupta, LV Sharma, Chemical and Medicinal Versatility of Dithiocarbamates: An Overview. Mini-Rev. Med. Chem. 14 (2014) 1021-1032.).Methods for constructing aryl dithiocarbamates by transition metal-catalyzed carbon-hydrogen bond activation and other methods have been reported, mainly using aryl halides, aryl boronic acids, aryl diazonium salts, diaryl iodonium trifluorides, aryl thianthrene salts, etc. as arylation reagents, and preparing them by three-component reaction with carbon disulfide and amines (MY Gao, W. Xu, SB Zhang, et al., Synthesis of Phenyl Dithiocarbamates Starting from Sodium Dialkyldithiocarbamates and Aryl Boronic Acids: A Copper Catalyzed S-Arylation. Eur. J. Org. Chem. 2018 (2018) 6693-6698; Y. Liu, W. Bao, A New Method for the Synthesis of Dithiocarbamates by CuI-Catalyzed Coupling Reaction. Tetrahedron Lett.48(2007)4785-4788; ZBDong, Q.Cao, HYPeng, et al., A Highly Efficient CuCl. 2 -Catalyzed C-SCoupling ofAryl Iodides with Tetraalkylthiuram Disulfides:Synthesis ofArylDithiocarbamates.Synthesis50(2018)1527-1534; W.Xu,F.Gao,ZBDong,Copper-Catalyzed S-Arylation Starting fromArylboronic Acids and Tetraalkylthiuram Disulfide.Eur.J.Org.Chem.2018(2018)821-828;MTZeng,W.Xu,X.Liu,et al.,Copper-Catalyzed S-Arylation ofTetraalkylthiuram Disulfides by Using DiaryliodoniumSalts.Eur.J.Org.Chem.2017(2017)6060-6066; ZBDong,X.Liu,C.Bolm,Copper-Catalyzed C(sp 2)-S Coupling Reactions for the Synthesis ofArylDithiocarbamates with Thiuram Disulfide Reagents.Org.Lett.19(2017)5916-5919;B.B.Touré,D.G.Hall,Natural Product Synthesis Using Multicomponent ReactionStrategies.Chem.Rev.109(2009)4439-4486;S.Bhadra,A.Saha,B.C.Ranu,One-PotCopper Nanoparticle-Catalyzed Synthesis of S-aryl and S-VinylDithiocarbamates in Water:High Diastereoselectivity Achieved for VinylDithiocarbamates.Green Chem.10(2008)1224-1230;C.Qi,T.Guo,W.Xiong,Copper-Mediated Coupling ofBoronicAcids,Amines,and CarbonDisulfide:AnApproach toOrganic Dithiocarbamates.Synlett.27(2016)2626-2630;S.K.Parida,S.Jaiswal,P.Singh,et al.,Multicomponent Synthesis ofBiologically Relevant S-ArylDithiocarbamates Using Diaryliodonium Salts.Org.Lett.23(2021)6401-6406;H.Xu,X.Li,J.Ma,D.S.Yang,et al.,An Electron Donor-Acceptor Photoactivation Strategyfor the Synthesis of S-Aryl Dithiocarbamates using Thianthrenium Salts underMildAqueous Micellar Conditions.Chinese Chemical Letters 34(2023)108403.)。

[0003] The present invention adopts aryl triazene, which is often used as a substitute for aryl diazonium salt due to its good stability, easy preparation and multiple reaction sites. In addition, the aryl triazene itself has aryl and amine fragments and can be decomposed under light conditions to participate in the reaction as an aryl and amine bifunctional reagent, and can induce the insertion of carbon disulfide to synthesize dithiocarbamate derivatives in a green and efficient manner.

[0004] This reaction does not require any metal, photocatalyst or other additives, and the reaction conditions are green and mild. Summary of the invention

[0005] The present invention aims to provide a method for synthesizing a series of aromatic dithiocarbamate compounds by using aromatic triazene as a simple and readily available aromatic and amine bifunctional reagent, realizing the denitrogenation of aromatic triazene and inserting carbon disulfide under the induction of ultraviolet light. In order to achieve the above object, the technical scheme of the present invention is as follows:

[0006] Using aryl triazene 1 and carbon disulfide 2 as reaction substrates, aryl dithiocarbamate 3 was obtained under the induction of violet light; the synthesis route is shown in the following reaction formula:

[0007]

[0008] In the present invention, R 1 represents one or more substituents at the ortho, meta, para, etc. positions of the benzene ring, which may specifically be one or more of C1-C10 alkyl, C1-C10 alkoxy, halogen, and benzyl; preferably one or more of methyl, ethyl, isopropyl, tert-butyl, methoxy, ethoxy, methylthio, benzyl, fluorine, chlorine, and bromine;

[0009] R 2 means One or more of the above, wherein the wavy line represents a connection point.

[0010] In the present invention, the reaction solvent is one or more of acetonitrile, methanol, ethanol, toluene, acetone, 1,1-dichloroethane, N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide, N-methylpyrrolidone and 1,4-dioxane. Preferably, the reaction solvent is acetonitrile.

[0011] In the present invention, the reaction temperature is 20-50°C, and the best reaction effect is 25-28°C.

[0012] In the present invention, when the aryl triazene 1 reacts with carbon disulfide 2 in the reaction, the molar ratio of the aryl triazene 1 to the carbon disulfide 2 is in the range of 1:1 to 1:20, preferably 1:10 to 20, and most preferably 1:15 to 20.

[0013] In the present invention, the reaction time is 0.5 to 3 hours, preferably 1 to 2 hours, and most preferably 1 to 1.2 hours.

[0014] In the present invention, the wavelength of the ultraviolet light used is 390 to 395 nanometers.

[0015] The synthesis reaction of the present invention comprises the following steps:

[0016] Synthesis of aryl dithiocarbamate compound 3: aryl triazene 1 (X mmol), carbon disulfide 2 (Y mmol) and solvent CH 3 CN (ZmL), stirred for 0.5-3h at a temperature of 20-50°C and irradiated with violet light (390-395nm), to obtain the above-mentioned reaction product, aryl dithiocarbamate compound 3. The present invention overcomes many disadvantages of aryl triazene activation, such as the need for an equivalent amount of acid as a promoter, and the drawback of poor atom economy when aryl triazene is only used as an arylation agent, and only under light conditions, the denitrogenation of aryl triazene and the insertion of carbon disulfide are realized greenly and efficiently. All raw materials used in the present invention are industrial commodities, and the raw materials are cheap, easy to obtain, and widely available; the present invention only requires violet light irradiation, the reaction is green, the operation is simple, and no metal, photocatalyst or other additives are required.

[0017] The synthesis reaction of the present invention comprises the following steps:

[0018] Synthesis of aryl triazene 1:

[0019]

[0020] According to previous literature reports (J. Gao, Q. Song, L. Zhang, et al., Pd-Catalyzed C-7 Arylation of Indolines with Aryltriazenes under Mild Conditions. J. Org. Chem., 2023, 88(15): 11056-11068.), substituted aniline (10 mmol) was added to a 100 mL round-bottom flask, and then (36-38%) concentrated hydrochloric acid (2 mL) was added to the above aniline at 0°C, and an aqueous solution (5 mL) of sodium nitrite (11 mmol) was prepared and added dropwise to the hydrochloric acid solution of aniline. The obtained diazonium salt solution was continuously stirred in an ice bath for about 15 min, and then added into a cold solution containing 10 mL of an aqueous solution of potassium carbonate (1.2 mol / L) and amine (10 mmol) at one time. The reaction mixture was continuously stirred at room temperature for about 30 min. After the reaction was completed by monitoring by thin layer chromatography, the obtained product was recrystallized from ethanol or purified by column chromatography to obtain aryl triazene 1, which was confirmed to be the target product by nuclear magnetic resonance and high-resolution mass spectrometry. The aryl triazenes 1 synthesized in the present invention were all known substances.

[0021] Where R 1 is one or more of methyl, ethyl, isopropyl, tert-butyl, methoxy, ethoxy, methylthio, benzyl, fluorine, chlorine, and bromine;

[0022] The amine is a primary amine or a secondary amine, R 2 =R 3 is one or more of methyl, ethyl, etc.; or R 2 ≠R 3 , R 2 = one or more of methyl, hydrogen, etc., R 3 = one or more of benzyl, cyclohexyl, etc.; or R 2 With R 3 They are connected to form one or two or more of a five-membered ring, a six-membered ring, and a six-membered heterocyclic ring.

[0023] Synthesis of aryl dithiocarbamate 3:

[0024]

[0025] Add aryl triazene 1 (0.2mmol, 1equiv.) and carbon disulfide 2 (4mmol, 20equiv.) to a 10mL reaction tube, then add solvent acetonitrile (1.5mL), put it into Shanghai Shanshi Technology Co., Ltd. AF1 parallel light reactor, adjust the light source to purple light (wavelength range 390-395nm), power to 10W, and reaction time to 1h. Then use silica gel column chromatography to separate (eluent is petroleum ether / ethyl acetate, v / v=5:1) to obtain the target product 3, which is confirmed to be the target product by nuclear magnetic resonance and high-resolution mass spectrometry.

[0026] The advantages of the present invention include: stable and readily available raw materials, mild conditions, simple operation, short reaction time, and no need to use any metal, photosensitizer or other additives. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 The hydrogen and carbon nuclear magnetic resonance spectra of Example 1 are shown in FIG.

[0028] Figure 2 The following are the hydrogen and carbon nuclear magnetic resonance spectra of Example 3.

[0029] Figure 3 The following are the hydrogen and carbon nuclear magnetic resonance spectra of Example 4.

[0030] Figure 4 The following are the hydrogen and carbon nuclear magnetic resonance spectra of Example 5.

[0031] Figure 5 The following are the hydrogen and carbon nuclear magnetic resonance spectra of Example 6.

[0032] Figure 6 The following are the hydrogen and carbon nuclear magnetic resonance spectra of Example 7.

[0033] Figure 7 The following are the hydrogen and carbon nuclear magnetic resonance spectra of Example 8.

[0034] Figure 8 The following are the hydrogen and carbon nuclear magnetic resonance spectra of Example 9.

[0035] Fig. 9 The following are the hydrogen and carbon nuclear magnetic resonance spectra of Example 10.

[0036] Fig.10 The following are the hydrogen and carbon nuclear magnetic resonance spectra of Example 11.

[0037] Fig.11 The following are the hydrogen and carbon nuclear magnetic resonance spectra of Example 12.

[0038] Fig.12 The following are the hydrogen and carbon nuclear magnetic resonance spectra of Example 13.

[0039] Fig.13 The following are the hydrogen and carbon nuclear magnetic resonance spectra of Example 14.

[0040] Fig.14 The following are the hydrogen and carbon nuclear magnetic resonance spectra of Example 15.

[0041] Fig.15 The following are the hydrogen and carbon nuclear magnetic resonance spectra of Example 16.

[0042] Fig.16 The following are the hydrogen and carbon nuclear magnetic resonance spectra of Example 17.

[0043] Fig.17 The following are the hydrogen and carbon nuclear magnetic resonance spectra of Example 18.

[0044] Fig.18 The following are the hydrogen and carbon nuclear magnetic resonance spectra of Example 19.

[0045] Fig.19 The following are the hydrogen and carbon nuclear magnetic resonance spectra of Example 20.

[0046] Fig. 20 These are the hydrogen and carbon nuclear magnetic resonance spectra of Example 21. DETAILED DESCRIPTION

[0047] The present invention is further described in detail in conjunction with the following specific examples, and the protection content of the present invention is not limited to the following examples. Without departing from the spirit and scope of the inventive concept, the changes and advantages that can be thought of by those skilled in the art are included in the present invention, and the attached claims are the scope of protection. The process, conditions, reagents, experimental methods, etc. for implementing the present invention, except for the contents specifically mentioned below, are all common knowledge and common common sense in the art, and the present invention has no special restrictions. The data given in the following examples include specific operations and reaction conditions and products. The purity of the product is identified by nuclear magnetic resonance and high-resolution mass spectrometry.

[0048] Example 1

[0049] Synthesis of aryl triazene 1a:

[0050]

[0051] According to previous literature reports (J. Gao, Q. Song, L. Zhang, et al., Pd-Catalyzed C-7 Arylation of Indolines with Aryltriazenes under Mild Conditions. J. Org. Chem., 2023, 88(15): 11056-11068.), p-methylaniline (10 mmol) was added to a 100 mL round-bottom flask, and then concentrated hydrochloric acid (2 mL) with a mass concentration of 36-38% was added to the above aniline at 0°C, and an aqueous solution (5 mL) of sodium nitrite (11 mmol) was prepared and added dropwise to the hydrochloric acid solution of aniline. The obtained diazonium salt solution was further stirred in an ice bath for 15 min, and then added all at once to a cold solution (0°C) containing 10 mL of an aqueous solution of potassium carbonate (1.2 mol / L) and tetrahydropyrrole (10 mmol). The reaction mixture was further stirred at room temperature for about 30 min. After the reaction was completed by monitoring by thin layer chromatography, the obtained product was recrystallized from ethanol or purified by column chromatography to obtain 1a, which was confirmed to be the known target product, aryl triazene 1a, by nuclear magnetic resonance and high-resolution mass spectrometry.

[0052] Synthesis of aryl dithiocarbamate 3a:

[0053]

[0054] Add aromatic triazene 1a (0.2 mmol, 1 equiv.) and carbon disulfide 2 (4 mmol, 20 equiv.) into a 25 mL reaction tube, then add solvent acetonitrile (1.5 mL), put it into a parallel light reactor, adjust the light source to purple light (390-395 nm), the power to 10 W, and the reaction time to 1 h. Then, the product was separated by silica gel column chromatography (eluent: petroleum ether / ethyl acetate, v / v=5:1) to obtain the target product 3a (known substance, SK Parida, S. Jaiswal, P. Singh, et al., Multicomponent Synthesis of Biologically Relevant S-Aryl Dithiocarbamates Using Diaryliodonium Salts. Org. Lett. 2021, 23, 16, 6401-6406.), which was confirmed as the target product by nuclear magnetic resonance and high-resolution mass spectrometry. The parameters of the obtained product were p-Tolyl pyrrolidine-1-carbodithioate (3a): yellow solid (33.7 mg, 71%), Melting point: 115-116°C. 1H NMR (600 MHz, CDCl 3 )δ7.53(d,J=8.1Hz,2H),7.10(d,J=8.0Hz,2H),3.96(t,J=7.0Hz,2H),3.74(t,J=6.9Hz,2H),2.31(s,3H),2.12-2.07(m,2H),2.00-1.96(m,2H). 13 CNMR (151MHz, CDCl 3 )δ191.83,138.60,132.85,130.66,129.80,56.97,50.66,26.68,24.28,21.27.

[0055] Example 2

[0056] The reaction steps and operating conditions were the same as those in Example 1, except that the reaction for synthesizing dithiocarbamate 3a was carried out without violet light irradiation. After the reaction was completed, only a trace amount of the target product 3a was obtained by the same post-treatment as above, with a yield of less than 5%, indicating that violet light irradiation is a necessary condition for the reaction.

[0057] Example 3

[0058] Synthesis of aryl triazene 1b:

[0059]

[0060] According to previous literature reports (J. Gao, Q. Song, L. Zhang, et al., Pd-Catalyzed C-7 Arylation of Indolines with Aryltriazenes under Mild Conditions. J. Org. Chem., 2023, 88(15): 11056-11068.), p-methylaniline (10 mmol) was added to a 100 mL round-bottom flask, and then concentrated hydrochloric acid (2 mL) with a mass concentration of 36-38% was added to the above aniline at 0°C, and an aqueous solution (5 mL) of sodium nitrite (11 mmol) was prepared and added dropwise to the hydrochloric acid solution of aniline. The obtained diazonium salt solution was further stirred in an ice bath for 15 min, and then added all at once to a cold solution (0°C) containing 10 mL of an aqueous solution of potassium carbonate (1.2 mol / L) and dimethylamine (10 mmol). The reaction mixture was further stirred at room temperature for about 30 min. After the reaction was completed by monitoring by thin layer chromatography, the obtained product was recrystallized from ethanol or purified by column chromatography to obtain 1b, which was confirmed to be the known target product, aryl triazene 1b, by nuclear magnetic resonance and high-resolution mass spectrometry.

[0061] Synthesis of aryl dithiocarbamate 3b:

[0062]

[0063] Add aryl triazene 1b (0.2 mmol, 1 equiv.) and carbon disulfide 2 (4 mmol, 20 equiv.) into a 25 mL reaction tube, then add solvent acetonitrile (1.5 mL), put it into a parallel light reactor, and irradiate it with 10 W purple light (390-395 nm) for 1 h. Then, the product was separated by silica gel column chromatography (eluent: petroleum ether / ethyl acetate, v / v=5:1) to obtain the target product 3b (known substance, T. Chatterjee, S. Bhadra, BCRanu, et al., Transition Metal-Free Procedure for the Synthesis of S-Aryl Dithiocarbamates Using Aryl Diazonium Fuoroborate in Water at Room Temperature. Green Chem., 2011, 13, 1837.), which was confirmed as the target product by nuclear magnetic resonance and high-resolution mass spectrometry. The parameters of the obtained product were p-tolyl dimethylcarbamodithioate (3b): white solid (30.4 mg, 72%), Melting point: 110-112°C. 1 H NMR (600 MHz, CDCl 3 )δ7.52-7.49(m,2H),7.10(d,J=8.0Hz,2H),3.59(s,4H),3.45(s,3H),2.31(s,3H). 13 CNMR (151MHz, CDCl 3 )δ196.41,138.6,132.68,130.5,129.8,47.50,41.72,21.27.

[0064] Example 4

[0065] Synthesis of aryl triazene 1c:

[0066]

[0067] According to previous literature reports (J. Gao, Q. Song, L. Zhang, et al., Pd-Catalyzed C-7 Arylation of Indolines with Aryltriazenes under Mild Conditions. J. Org. Chem., 2023, 88(15): 11056-11068.), p-methylaniline (10 mmol) was added to a 100 mL round-bottom flask, and then concentrated hydrochloric acid (2 mL) with a mass concentration of 36-38% was added to the above aniline at 0°C, and an aqueous solution (5 mL) of sodium nitrite (11 mmol) was prepared and added dropwise to the hydrochloric acid solution of aniline. The obtained diazonium salt solution was further stirred in an ice bath for 15 min, and then added all at once to a cold solution (0°C) containing 10 mL of an aqueous solution of potassium carbonate (1.2 mol / L) and diethylamine (10 mmol). The reaction mixture was further stirred at room temperature for about 30 min. After the reaction was completed by monitoring by thin layer chromatography, the obtained product was recrystallized from ethanol or purified by column chromatography to obtain 1c, which was confirmed to be the known target product, aryl triazene 1c, by nuclear magnetic resonance and high-resolution mass spectrometry.

[0068] Synthesis of aryl dithiocarbamate 3c:

[0069]

[0070] Add aryl triazene 1c (0.2 mmol, 1 equiv.) and carbon disulfide 2 (4 mmol, 20 equiv.) into a 25 mL reaction tube, then add solvent acetonitrile (1.5 mL), put it into a parallel light reactor, and irradiate it with 10 W purple light (390-395 nm) for 1 h. Then, the product was separated by silica gel column chromatography (eluent: petroleum ether / ethyl acetate, v / v=5:1) to obtain the target product 3c (known substance, T. Chatterjee, S. Bhadra, BCRanu, et al., Transition Metal-Free Procedure for the Synthesis of S-Aryl Dithiocarbamates Using Aryl Diazonium Fuoroborate in Water at Room Temperature. Green Chem., 2011, 13, 1837.), which was confirmed as the target product by nuclear magnetic resonance and high-resolution mass spectrometry. The parameters of the obtained product were p-tolyl diethylcarbamodithioate (3c): white solid (33.5 mg, 70%), Melting point: 75-76°C. 1HNMR (600MHz, CDCl 3 )δ7.49(d,J=8.2Hz,2H),7.10(d,J=8.0Hz,2H),4.05(d,J=6.5Hz,2H),3.82(d,J=6.6Hz,2H),2.31(s,3H),1.35-1.29(m,6H). 13 CNMR (151MHz, CDCl 3 )δ194.94,138.40,132.92,130.28,129.80,51.95,47.15,21.27,13.34,11.58.

[0071] Example 5

[0072] Synthesis of aryl triazene 1d:

[0073]

[0074] According to previous literature reports (J. Gao, Q. Song, L. Zhang, et al., Pd-Catalyzed C-7 Arylation of Indolines with Aryltriazenes under Mild Conditions. J. Org. Chem., 2023, 88(15): 11056-11068.), p-methylaniline (10 mmol) was added to a 100 mL round-bottom flask, and then concentrated hydrochloric acid (2 mL) with a mass concentration of 36-38% was added to the above aniline at 0°C, and an aqueous solution (5 mL) of sodium nitrite (11 mmol) was prepared and added dropwise to the hydrochloric acid solution of aniline. The obtained diazonium salt solution was further stirred in an ice bath for 15 min, and then added all at once to a cold solution (0°C) containing 10 mL of an aqueous solution of potassium carbonate (1.2 mol / L) and morpholine (10 mmol). The reaction mixture was further stirred at room temperature for about 30 min. After the reaction was completed by monitoring by thin layer chromatography, the obtained product was recrystallized from ethanol or separated and purified by column chromatography to obtain 1d, which was confirmed to be the known target product, aryl triazene 1d, by nuclear magnetic resonance and high-resolution mass spectrometry.

[0075] Synthesis of aryl dithiocarbamate 3d:

[0076]

[0077] Add aryl triazene 1d (0.2 mmol, 1 equiv.) and carbon disulfide 2 (4 mmol, 20 equiv.) into a 25 mL reaction tube, then add solvent acetonitrile (1.5 mL), put it into a parallel light reactor, and irradiate it with 10 W purple light (390-395 nm) for 1 h. Then, the product was separated by silica gel column chromatography (eluent: petroleum ether / ethyl acetate, v / v=5:1) to obtain the target product 3d (known substance, SK Parida, S. Jaiswal, P. Singh, et al., Multicomponent Synthesis of Biologically Relevant S-Aryl Dithiocarbamates Using Diaryliodonium Salts. Org. Lett. 2021, 23, 16, 6401-6406.), which was confirmed as the target product by nuclear magnetic resonance and high-resolution mass spectrometry. The parameters of the obtained product were p-tolyl morpholine-4-carbodithioate (3d): yellow solid (43 mg, 85%), Melting point: 136-137°C. 1 H NMR (600 MHz, CDCl 3 )δ7.50(d,J=8.2Hz,2H),7.11(d,J=8.0Hz,2H),4.29-4.08(m,4H),3.81-3.74(m,4H),2.32(s,3H). 13 C NMR (151 MHz, CDCl 3 )δ196.84,138.79,132.45,130.72,129.87,66.39,53.25,50.93,21.28.

[0078] Example 6

[0079] Synthesis of aryl triazene 1e:

[0080]

[0081] According to previous literature reports (J. Gao, Q. Song, L. Zhang, et al., Pd-Catalyzed C-7 Arylation of Indolines with Aryltriazenes under Mild Conditions. J. Org. Chem., 2023, 88(15): 11056-11068.), p-methylaniline (10 mmol) was added to a 100 mL round-bottom flask, and then concentrated hydrochloric acid (2 mL) with a mass concentration of 36-38% was added to the above aniline at 0°C, and an aqueous solution (5 mL) of sodium nitrite (11 mmol) was prepared and added dropwise to the hydrochloric acid solution of aniline. The obtained diazonium salt solution was continuously stirred in an ice bath for 15 min, and then added all at once to a cold solution (0°C) containing 10 mL of an aqueous solution of potassium carbonate (1.2 mol / L) and thiomorpholine (10 mmol). The reaction mixture was continuously stirred at room temperature for about 30 min. After the reaction was completed by monitoring by thin layer chromatography, the obtained product was recrystallized from ethanol or purified by column chromatography to obtain 1e, which was confirmed to be the known target product, aryl triazene 1e, by nuclear magnetic resonance and high-resolution mass spectrometry.

[0082] Synthesis of aryl dithiocarbamate 3e:

[0083]

[0084] Add aryl triazene 1e (0.2mmol, 1equiv.) and carbon disulfide 2 (4mmol, 20equiv.) to a 25mL reaction tube, then add solvent acetonitrile (1.5mL), put it into a parallel light reactor, and irradiate it with 10W purple light (390-395nm) for 1h. Then separate it by silica gel column chromatography (eluent is petroleum ether / ethyl acetate, v / v=5:1) to obtain the target product 3e (unknown substance), which is confirmed to be the target product by nuclear magnetic resonance and high-resolution mass spectrometry. The parameters of the obtained product are p-tolylthiomorpholine-4-carbodithioate (3e): yellow oil (43.6mg, 81%). 1 H NMR (600 MHz, CDCl 3 )δ7.51-7.48(m,2H),7.11(d,J=8.0Hz,2H),4.57-4.40(m,4H),2.78(s,4H),2.32(s,3H). 13 CNMR (151MHz, CDCl 3)δ196.40,138.79,132.51,130.64,129.91,57.02,54.05,27.57,21.31.HRMS(ESI)m / z:[M+H] + Calcd for C 12 H 15 NS 3 :270.0439;Found:270.0438.

[0085] Example 7

[0086] Synthesis of aryl triazene 1f:

[0087]

[0088] According to previous literature reports (J. Gao, Q. Song, L. Zhang, et al., Pd-Catalyzed C-7 Arylation of Indolines with Aryltriazenes under Mild Conditions. J. Org. Chem., 2023, 88(15): 11056-11068.), p-methylaniline (10 mmol) was added to a 100 mL round-bottom flask, and then concentrated hydrochloric acid (2 mL) with a mass concentration of 36-38% was added to the above aniline at 0°C, and an aqueous solution (5 mL) of sodium nitrite (11 mmol) was prepared and added dropwise to the hydrochloric acid solution of aniline. The obtained diazonium salt solution was further stirred in an ice bath for 15 min, and then added all at once to a cold solution (0°C) containing 10 mL of an aqueous solution of potassium carbonate (1.2 mol / L) and piperidine (10 mmol). The reaction mixture was further stirred at room temperature for about 30 min. After the reaction was completed by monitoring by thin layer chromatography, the obtained product was recrystallized from ethanol or purified by column chromatography to obtain 1f, which was confirmed to be the known target product, aryl triazene 1f, by nuclear magnetic resonance and high-resolution mass spectrometry.

[0089] Synthesis of aryl dithiocarbamate 3f:

[0090]

[0091] Add aryl triazene 1f (0.2 mmol, 1 equiv.) and carbon disulfide 2 (4 mmol, 20 equiv.) into a 25 mL reaction tube, then add solvent acetonitrile (1.5 mL), put it into a parallel light reactor, and irradiate it with 10 W purple light (390-395 nm) for 1 h. Then, the product was separated by silica gel column chromatography (eluent: petroleum ether / ethyl acetate, v / v=5:1) to obtain the target product 3f (known substance, SK Parida, S. Jaiswal, P. Singh, et al., Multicomponent Synthesis of Biologically Relevant S-Aryl Dithiocarbamates Using Diaryliodonium Salts. Org. Lett. 2021, 23, 16, 6401-6406.), which was confirmed as the target product by nuclear magnetic resonance and high-resolution mass spectrometry. The parameters of the obtained product were p-tolyl piperidine-1-carbodithioate (3f): yellow solid (36.7 mg, 73%), Melting point: 131-132°C. 1 H NMR (600 MHz, CDCl 3 )δ7.49(d,J=8.2Hz,2H),7.10(d,J=8.0Hz,2H),4.29-3.97(m,4H),2.31(s,3H),1.72(s,6H). 13 C NMR (151 MHz, CDCl 3 )δ195.01,138.40,132.91,130.30,129.78,55.71,52.37,26.36,25.55,24.22,21.25.

[0092] Example 8

[0093] Synthesis of aryl triazene 1g:

[0094]

[0095] According to previous literature reports (J. Gao, Q. Song, L. Zhang, et al., Pd-Catalyzed C-7 Arylation of Indolines with Aryltriazenes under Mild Conditions. J. Org. Chem., 2023, 88(15): 11056-11068.), p-methylaniline (10 mmol) was added to a 100 mL round-bottom flask, and then concentrated hydrochloric acid (2 mL) with a mass concentration of 36-38% was added to the above aniline at 0°C, and an aqueous solution (5 mL) of sodium nitrite (11 mmol) was prepared and added dropwise to the hydrochloric acid solution of aniline. The obtained diazonium salt solution was continuously stirred in an ice bath for 15 min, and then added all at once to a cold solution (0°C) containing 10 mL of an aqueous solution of potassium carbonate (1.2 mol / L) and 4-methylpiperidine (10 mmol). The reaction mixture was continuously stirred at room temperature for about 30 min. After the reaction was completed by monitoring by thin layer chromatography, the obtained product was recrystallized from ethanol or purified by column chromatography to obtain 1 g, which was confirmed to be the known target product, aryl triazene 1 g, by nuclear magnetic resonance and high-resolution mass spectrometry.

[0096] Synthesis of aryl dithiocarbamate 3g:

[0097]

[0098] Add 1g (0.2mmol, 1equiv.) of aryl triazene and 2 (4mmol, 20equiv.) of carbon disulfide into a 25mL reaction tube, then add acetonitrile (1.5mL) as solvent, put it into a parallel light reactor, and irradiate it with 10W purple light (390-395nm) for 1h. Then separate it by silica gel column chromatography (eluent is petroleum ether / ethyl acetate, v / v=5:1), and obtain 3g of the target product (unknown substance), which is confirmed as the target product by nuclear magnetic resonance and high-resolution mass spectrometry. The parameters of the obtained product are p-tolyl 4-methylpiperidine-1-carbodithioate (3g): yellow oil (37.4mg, 73%). 1 H NMR (600 MHz, CDCl 3 )δ7.52-7.46(m,2H),7.10(d,J=8.0Hz,2H),5.43(s,1H),4.67(s,1H),3.22(s,2H ),2.31(s,3H),1.78(d,J=13.7Hz,2H),1.41-1.27(m,2H),0.98(d,J=6.3Hz,3H). 13 C NMR (151 MHz, CDCl 3)δ195.14,138.43,132.91,130.35,129.80,54.87,51.23,34.40,33.62,30.90,21.30(d,J=11.0Hz).HRMS(ESI)m / z:[M+H] + Calcd for C 14 H 19 NS 2 :266.1032;Found:266.1029.

[0099] Example 9

[0100] Synthesis of aryl triazene 1h:

[0101]

[0102] According to previous literature reports (J. Gao, Q. Song, L. Zhang, et al., Pd-Catalyzed C-7 Arylation of Indolines with Aryltriazenes under Mild Conditions. J. Org. Chem., 2023, 88(15): 11056-11068.), p-methylaniline (10 mmol) was added to a 100 mL round-bottom flask, and then concentrated hydrochloric acid (2 mL) with a mass concentration of 36-38% was added to the above aniline at 0°C, and an aqueous solution (5 mL) of sodium nitrite (11 mmol) was prepared and added dropwise to the hydrochloric acid solution of aniline. The obtained diazonium salt solution was continuously stirred in an ice bath for 15 min, and then added all at once to a cold solution (0°C) containing 10 mL of an aqueous solution of potassium carbonate (1.2 mol / L) and N-methyl-1-benzylamine (10 mmol). The reaction mixture was continuously stirred at room temperature for about 30 min. After the reaction was completed by monitoring by thin layer chromatography, the obtained product was recrystallized from ethanol or separated and purified by column chromatography to obtain 1h, which was confirmed to be the known target product, aryl triazene 1h, by nuclear magnetic resonance and high-resolution mass spectrometry.

[0103] Synthesis of aryl dithiocarbamate 3h:

[0104]

[0105] Add aryl triazene 1h (0.2mmol, 1equiv.) and carbon disulfide 2 (4mmol, 20equiv.) into a 25mL reaction tube, then add solvent acetonitrile (1.5mL), put it into a parallel light reactor, and irradiate it with 10W purple light (390-395nm) for 1h. Then, the product was separated by silica gel column chromatography (eluent: petroleum ether / ethyl acetate, v / v=5:1) to obtain the target product 3h (known substance, Z.Chen, Y.Jin, PJStang, Polyvalent Iodine in Synthesis.2.A New Method for the Preparation of Aryl Esters of Dithiocarbamic Acids.J.Org.Chem.1987,52,18,4117-4118), which was confirmed as the target product by nuclear magnetic resonance and high-resolution mass spectrometry. The parameters of the obtained product were p-tolylbenzyl(methyl)carbamodithioate(3h):yellow solid(29.3mg,51%), Melting point:65~66℃. 1 H NMR (600 MHz, CDCl 3 )δ7.58-7.47(m,2H),7.34(dd,J=14.5,8.0Hz,5H),7.12(d,J=5.3Hz,2H),5.39-5.07(m,2H),3.52-3.34(m,3H),2.33(s,3H). 13 C NMR (151 MHz, CDCl 3 )δ198.35,138.69,132.69,130.67,130.05,129.87,128.66(d,J=93.4Hz),128.34,128.29,128.06,127.23,62.05,29.83,21.31.

[0106] Example 10

[0107] Synthesis of aryl triazene 1i:

[0108]

[0109] According to previous literature reports (J. Gao, Q. Song, L. Zhang, et al., Pd-Catalyzed C-7 Arylation of Indolines with Aryltriazenes under Mild Conditions. J. Org. Chem., 2023, 88(15): 11056-11068.), p-methylaniline (10 mmol) was added to a 100 mL round-bottom flask, and then concentrated hydrochloric acid (2 mL) with a mass concentration of 36-38% was added to the above aniline at 0°C, and an aqueous solution (5 mL) of sodium nitrite (11 mmol) was prepared and added dropwise to the hydrochloric acid solution of aniline. The obtained diazonium salt solution was continuously stirred in an ice bath for 15 min, and then added all at once to a cold solution (0°C) containing 10 mL of an aqueous solution of potassium carbonate (1.2 mol / L) and N-methylcyclohexylamine (10 mmol). The reaction mixture was continuously stirred at room temperature for about 30 min. After the reaction was completed by monitoring by thin layer chromatography, the obtained product was recrystallized from ethanol or purified by column chromatography to obtain 1i, which was confirmed to be the known target product, aryl triazene 1i, by nuclear magnetic resonance and high-resolution mass spectrometry.

[0110] Synthesis of aryl dithiocarbamate 3i:

[0111]

[0112] Add aryl triazene 1i (0.2mmol, 1equiv.) and carbon disulfide 2 (4mmol, 20equiv.) to a 25mL reaction tube, then add solvent acetonitrile (1.5mL), put it into a parallel light reactor, and irradiate it with 10W purple light (390-395nm) for 1h. Then separate it by silica gel column chromatography (eluent is petroleum ether / ethyl acetate, v / v=5:1) to obtain the target product 3i (unknown substance), which is confirmed to be the target product by nuclear magnetic resonance and high-resolution mass spectrometry. The parameters of the obtained product are p-tolylcyclohexyl(methyl)carbamodithioate(3i):yellow oil(16.8mg,30%). 1 H NMR (600 MHz, CDCl 3 )δ(600MHz,CDCl 3 )δ7.51(d,J=7.9Hz,2H),7.10(d,J=8.0Hz,2H),3.45-3.26(m,3H),2.31(s,3H),1. 86(t,J=19.7Hz,5H),1.70(d,J=11.1Hz,1H),1.63-1.51(m,2H),1.45-1.36(m,3H). 13C NMR (151 MHz, CDCl 3 )δ195.68,132.94,130.37,129.82,129.52,120.42,65.41,62.94,39.43,34.24,30.73,29.40,25.58,21.30.HRMS(ESI)m / z:[M+H] + Calcd for C 15 H 21 NS 2 :280.1188;Found:280.1186.

[0113] Embodiment 11

[0114] Synthesis of aryl triazene 1j:

[0115]

[0116] According to previous literature reports (J. Gao, Q. Song, L. Zhang, et al., Pd-Catalyzed C-7 Arylation of Indolines with Aryltriazenes under Mild Conditions. J. Org. Chem., 2023, 88(15): 11056-11068.), p-methoxyaniline (10 mmol) was added to a 100 mL round-bottom flask, and then concentrated hydrochloric acid (2 mL) with a mass concentration of 36-38% was added to the above aniline at 0°C, and an aqueous solution (5 mL) of sodium nitrite (11 mmol) was prepared and added dropwise to the hydrochloric acid solution of aniline. The obtained diazonium salt solution was continuously stirred in an ice bath for 15 min, and then added all at once into a cold solution (0°C) containing 10 mL of an aqueous solution of potassium carbonate (1.2 mol / L) and morpholine (10 mmol). The reaction mixture was continuously stirred at room temperature for about 30 min. After the completion of the reaction monitored by thin layer chromatography, the obtained product was recrystallized from ethanol or separated and purified by column chromatography to obtain 1j, which was confirmed to be the known target product, aryl triazene 1j, by nuclear magnetic resonance and high-resolution mass spectrometry.

[0117] Synthesis of aryl dithiocarbamate 3j:

[0118]

[0119] Add aryl triazene 1j (0.2 mmol, 1 equiv.) and carbon disulfide 2 (4 mmol, 20 equiv.) into a 25 mL reaction tube, then add solvent acetonitrile (1.5 mL), put it into a parallel light reactor, and irradiate it with 10 W purple light (390-395 nm) for 1 h. Then, the product was separated by silica gel column chromatography (eluent: petroleum ether / ethyl acetate, v / v=5:1) to obtain the target product 3j (known substance, T. Chatterjee, S. Bhadra, BCRanu, et al., Transition Metal-Free Procedure for the Synthesis of S-Aryl Dithiocarbamates Using Aryl Diazonium Fuoroborate in Water at Room Temperature. Green Chem., 2011, 13, 1837.), which was confirmed as the target product by nuclear magnetic resonance and high-resolution mass spectrometry. The product parameters were 4-methoxyphenyl morpholine-4-carbodithioate (3j): yellow solid (43.1 mg, 80%), Melting point: 133-135°C. 1 H NMR (600 MHz, CDCl 3 )δ(600MHz,CDCl 3 )δ7.66-7.61(m,2H),6.85-6.81(m,2H),4.30-4.08(m,4H),3.80-3.76(m,4H),3.76(s,3H). 13 C NMR (151 MHz, CDCl 3 )δ197.22,160.64,138.65,134.15,114.69,66.38,55.48,50.84.

[0120] Example 12

[0121] Synthesis of aryl triazene 1k:

[0122]

[0123] According to previous literature reports (J. Gao, Q. Song, L. Zhang, et al., Pd-Catalyzed C-7 Arylation of Indolines with Aryltriazenes under Mild Conditions. J. Org. Chem., 2023, 88(15): 11056-11068.), p-fluoroaniline (10 mmol) was added to a 100 mL round-bottom flask, and then concentrated hydrochloric acid (2 mL) with a mass concentration of 36-38% was added to the above aniline at 0°C, and an aqueous solution (5 mL) of sodium nitrite (11 mmol) was prepared and added dropwise to the hydrochloric acid solution of aniline. The obtained diazonium salt solution was continuously stirred in an ice bath for 15 min, and then added all at once to a cold solution (0°C) containing 10 mL of an aqueous solution of potassium carbonate (1.2 mol / L) and morpholine (10 mmol). The reaction mixture was continuously stirred at room temperature for about 30 min. After the reaction was completed by monitoring by thin layer chromatography, the obtained product was recrystallized with ethanol or separated and purified by column chromatography to obtain 1k, which was confirmed to be the known target product, aryl triazene 1k, by nuclear magnetic resonance and high-resolution mass spectrometry.

[0124] Synthesis of aryl dithiocarbamate 3k:

[0125]

[0126] Add aryl triazene 1k (0.2mmol, 1equiv.) and carbon disulfide 2 (4mmol, 20equiv.) to a 25mL reaction tube, then add solvent acetonitrile (1.5mL), put it into a parallel light reactor, and irradiate it with 10W purple light (390-395nm) for 1h. Then separate it by silica gel column chromatography (eluent is petroleum ether / ethyl acetate, v / v=5:1) to obtain the target product 3k (unknown substance), which is confirmed to be the target product by nuclear magnetic resonance and high-resolution mass spectrometry. The parameters of the obtained product are 4-fluorophenylmorpholine-4-carbodithioate (3k): yellow oil (30.9mg, 60%). 1 H NMR (600 MHz, CDCl 3 )δ7.63(ddd,J=6.8,5.2,2.6Hz,2H),7.03-6.98(m,2H),4.28-4.04(m,4H),3.82-3.79(m,4H). 13 C NMR (151 MHz, CDCl 3)δ196.38,162.33,139.32(d,J=8.8Hz),133.21(d,J=8.6Hz),116.34,116.19,66.40,53.57,51.20. 19 F NMR (565MHz, CDCl 3 )δ-112.18.HRMS(ESI)m / z:[M+H] + Calcd for C 15 H 12 FNOS 2 :258.0417;Found:258.0416.

[0127] Embodiment 13

[0128] Synthesis of aryl triazene 1l:

[0129]

[0130] According to previous literature reports (J. Gao, Q. Song, L. Zhang, et al., Pd-Catalyzed C-7 Arylation of Indolines with Aryltriazenes under Mild Conditions. J. Org. Chem., 2023, 88(15): 11056-11068.), p-chloroaniline (10 mmol) was added to a 100 mL round-bottom flask, and then concentrated hydrochloric acid (2 mL) with a mass concentration of 36-38% was added to the above aniline at 0°C, and an aqueous solution (5 mL) of sodium nitrite (11 mmol) was prepared and added dropwise to the hydrochloric acid solution of aniline. The obtained diazonium salt solution was continuously stirred in an ice bath for 15 min, and then added all at once to a cold solution (0°C) containing 10 mL of an aqueous solution of potassium carbonate (1.2 mol / L) and morpholine (10 mmol). The reaction mixture was continuously stirred at room temperature for about 30 min. After the completion of the reaction monitored by thin layer chromatography, the obtained product was recrystallized from ethanol or purified by column chromatography to obtain 1l, which was confirmed to be the known target product, aryl triazene 1l, by nuclear magnetic resonance and high-resolution mass spectrometry.

[0131] Synthesis of aryl dithiocarbamate 3l:

[0132]

[0133] Add aryl triazene 3l (0.2 mmol, 1 equiv.) and carbon disulfide 2 (4 mmol, 20 equiv.) into a 25 mL reaction tube, then add solvent acetonitrile (1.5 mL), put it into a parallel light reactor, and irradiate with 10 W purple light (390-395 nm) for 1 h. Then, the product was separated by silica gel column chromatography (eluent: petroleum ether / ethyl acetate, v / v=5:1) to obtain the target product 3l (known substance, SK Parida, S. Jaiswal, P. Singh, et al., Multicomponent Synthesis of Biologically Relevant S-Aryl Dithiocarbamates Using Diaryliodonium Salts. Org. Lett. 2021, 23, 16, 6401-6406.), which was confirmed as the target product by nuclear magnetic resonance and high-resolution mass spectrometry. The product parameters were 4-chlorophenyl morpholine-4-carbodithioate (3l): yellow solid (31.2 mg, 57%), Melting point: 128-129°C. 1 H NMR (600 MHz, CDCl 3 )δ7.38(d,J=8.5Hz,2H),7.13(d,J=8.7Hz,2H),4.16-3.94(m,4H),3.70-3.65(m,4H). 13 C NMR (151 MHz, CDCl 3 )δ195.88,138.41,134.42,131.36,129.24,66.39,53.80,51.38.

[0134] Embodiment 14

[0135] Synthesis of aryl triazene 1m:

[0136]

[0137] According to previous literature reports (J. Gao, Q. Song, L. Zhang, et al., Pd-Catalyzed C-7 Arylation of Indolines with Aryltriazenes under Mild Conditions. J. Org. Chem., 2023, 88(15): 11056-11068.), p-bromoaniline (10 mmol) was added to a 100 mL round-bottom flask, and then concentrated hydrochloric acid (2 mL) with a mass concentration of 36-38% was added to the above aniline at 0°C, and an aqueous solution (5 mL) of sodium nitrite (11 mmol) was prepared and added dropwise to the hydrochloric acid solution of aniline. The obtained diazonium salt solution was continuously stirred in an ice bath for 15 min, and then added all at once to a cold solution (0°C) containing 10 mL of an aqueous solution of potassium carbonate (1.2 mol / L) and morpholine (10 mmol). The reaction mixture was continuously stirred at room temperature for about 30 min. After the reaction was completed by monitoring by thin layer chromatography, the obtained product was recrystallized from ethanol or separated and purified by column chromatography to obtain 1m, which was confirmed to be the known target product, aryl triazene 1m, by nuclear magnetic resonance and high-resolution mass spectrometry.

[0138] Synthesis of aryl dithiocarbamate 3m:

[0139]

[0140] Add aryl triazene 1m (0.2mmol, 1equiv.) and carbon disulfide 2 (4mmol, 20equiv.) into a 25mL reaction tube, then add solvent acetonitrile (1.5mL), put it into a parallel light reactor, and irradiate it with 10W purple light (390-395nm) for 1h. Then, the product was separated by silica gel column chromatography (eluent: petroleum ether / ethyl acetate, v / v=5:1) to obtain the target product 3m (known substance, SK Parida, S. Jaiswal, P. Singh, et al., Multicomponent Synthesis of Biologically Relevant S-Aryl Dithiocarbamates Using Diaryliodonium Salts. Org. Lett. 2021, 23, 16, 6401-6406.), which was confirmed as the target product by nuclear magnetic resonance and high-resolution mass spectrometry. The product parameters were 4-bromophenyl morpholine-4-carbodithioate (3m): yellow oil (35 mg, 55%). 1 H NMR (600 MHz, CDCl 3)δ7.49-7.40(m,4H),4.30-4.08(m,4H),3.82-3.80(m,4H). 13 C NMR (151 MHz, CDCl 3 )δ195.84,135.10,132.18,131.48,122.56,66.43,53.73,51.64.

[0141] Embodiment 15

[0142] Synthesis of Aryl Triazene 1n:

[0143]

[0144] According to previous literature reports (J. Gao, Q. Song, L. Zhang, et al., Pd-Catalyzed C-7 Arylation of Indolines with Aryltriazenes under Mild Conditions. J. Org. Chem., 2023, 88(15): 11056-11068.), aniline (10 mmol) was added to a 100 mL round-bottom flask, and then concentrated hydrochloric acid (2 mL) with a mass concentration of 36-38% was added to the above aniline at 0°C, and an aqueous solution (5 mL) of sodium nitrite (11 mmol) was prepared and added dropwise to the hydrochloric acid solution of aniline. The obtained diazonium salt solution was continuously stirred in an ice bath for 15 min, and then added all at once to a cold solution (0°C) containing 10 mL of an aqueous solution of potassium carbonate (1.2 mol / L) and morpholine (10 mmol). The reaction mixture was continuously stirred at room temperature for about 30 min. After the reaction was completed by monitoring by thin layer chromatography, the obtained product was recrystallized from ethanol or separated and purified by column chromatography to obtain 1n, which was confirmed to be the known target product, aryl triazene 1n, by nuclear magnetic resonance and high-resolution mass spectrometry.

[0145] Synthesis of aryl dithiocarbamate 3n:

[0146]

[0147] Add aryl triazene 1n (0.2 mmol, 1 equiv.) and carbon disulfide 2 (4 mmol, 20 equiv.) into a 25 mL reaction tube, then add solvent acetonitrile (1.5 mL), put it into a parallel light reactor, and irradiate it with 10 W purple light (390-395 nm) for 1 h. Then, the product was separated by silica gel column chromatography (eluent: petroleum ether / ethyl acetate, v / v=5:1) to obtain the target product 3n (known substance, T. Chatterjee, S. Bhadra, BCRanu, et al., Transition Metal-Free Procedure for the Synthesis of S-Aryl Dithiocarbamates Using Aryl Diazonium Fuoroborate in Water at Room Temperature. Green Chem., 2011, 13, 1837.), which was confirmed as the target product by nuclear magnetic resonance and high-resolution mass spectrometry. The parameters of the obtained product were phenyl morpholine-4-carbodithioate (3n): white solid (33.5 mg, 70%), Melting point: 140-141°C. 1 H NMR (600 MHz, CDCl 3 )δ7.57(d,J=8.3Hz,2H),7.28(dt,J=19.4,4.7Hz,3H),4.29-4.12(m,4H),3.84-3.79(m,4H). 13 C NMR (151 MHz, CDCl 3 )δ196.45,135.86,129.72,129.10,128.24,66.41,53.15,51.61.

[0148] Example 16

[0149] Synthesis of aryl triazene 1o:

[0150]

[0151] According to previous literature reports (J. Gao, Q. Song, L. Zhang, et al., Pd-Catalyzed C-7 Arylation of Indolines with Aryltriazenes under Mild Conditions. J. Org. Chem., 2023, 88(15): 11056-11068.), p-isopropylaniline (10 mmol) was added to a 100 mL round-bottom flask, and then concentrated hydrochloric acid (2 mL) with a mass concentration of 36-38% was added to the above aniline at 0°C, and an aqueous solution (5 mL) of sodium nitrite (11 mmol) was prepared and added dropwise to the hydrochloric acid solution of aniline. The obtained diazonium salt solution was further stirred in an ice bath for 15 min, and then added all at once to a cold solution (0°C) containing 10 mL of an aqueous solution of potassium carbonate (1.2 mol / L) and morpholine (10 mmol). The reaction mixture was further stirred at room temperature for about 30 min. After the reaction was completed by monitoring by thin layer chromatography, the obtained product was recrystallized from ethanol or separated and purified by column chromatography to obtain 1o, which was confirmed to be the known target product aryl triazene 1o by nuclear magnetic resonance and high-resolution mass spectrometry.

[0152] Synthesis of aryl dithiocarbamate 3o:

[0153]

[0154] Add aryl triazene 1o (0.2mmol, 1equiv.) and carbon disulfide 2 (4mmol, 20equiv.) to a 25mL reaction tube, then add solvent acetonitrile (1.5mL), put it into a parallel light reactor, and irradiate it with 10W purple light (390-395nm) for 1h. Then separate it by silica gel column chromatography (eluent is petroleum ether / ethyl acetate, v / v=5:1) to obtain the target product 3o (unknown substance), which is confirmed to be the target product by nuclear magnetic resonance and high-resolution mass spectrometry. The obtained product parameters are 4-isopropylphenyl morpholine-4-carbodithioate (3o): yellow oil (42.2mg, 75%). 1 HNMR (600MHz, CDCl 3 )δ7.53(d,J=8.2Hz,2H),7.17(d,J=8.2Hz,2H),4.30-4.09(m,4H),3.81-3.74(m,4H),2.92-2.83(m,1H),1.22(s,3H),1.21(s,3H). 13 C NMR (151 MHz, CDCl 3)δ196.95,149.62,132.71,130.64,127.32,66.40,53.51,51.32,33.92,23.93.HRMS(ESI)m / z:[M+H] + Calcd for C 14 H 19 NOS 2 :282.0981;Found:282.0976.

[0155] Embodiment 17

[0156] Synthesis of aryl triazene 1p:

[0157]

[0158] According to previous literature reports (J. Gao, Q. Song, L. Zhang, et al., Pd-Catalyzed C-7 Arylation of Indolines with Aryltriazenes under Mild Conditions. J. Org. Chem., 2023, 88(15): 11056-11068.), p-tert-butylaniline (10 mmol) was added to a 100 mL round-bottom flask, and then concentrated hydrochloric acid (2 mL) with a mass concentration of 36-38% was added to the above aniline at 0°C, and an aqueous solution (5 mL) of sodium nitrite (11 mmol) was prepared and added dropwise to the hydrochloric acid solution of aniline. The obtained diazonium salt solution was continuously stirred in an ice bath for 15 min, and then added all at once to a cold solution (0°C) containing 10 mL of an aqueous solution of potassium carbonate (1.2 mol / L) and morpholine (10 mmol). The reaction mixture was continuously stirred at room temperature for about 30 min. After the reaction was completed by monitoring by thin layer chromatography, the obtained product was recrystallized with ethanol or separated and purified by column chromatography to obtain 1p, which was confirmed to be the known target product, aryl triazene 1p, by nuclear magnetic resonance and high-resolution mass spectrometry.

[0159] Synthesis of aryl dithiocarbamate 3p:

[0160]

[0161] Add aryl triazene 1p (0.2 mmol, 1 equiv.) and carbon disulfide 2 (4 mmol, 20 equiv.) into a 25 mL reaction tube, then add solvent acetonitrile (1.5 mL), put it into a parallel light reactor, and irradiate it with 10 W purple light (390-395 nm) for 1 h. Then, the product was separated by silica gel column chromatography (eluent: petroleum ether / ethyl acetate, v / v=5:1) to obtain the target product 3p (known substance, M. Zhang, B. Wang, Y. Cao, et al., Visible-Light-Driven Synthesis of Aryl Xanthates and Aryl Dithiocarbamates via an Electron Donor-Acceptor Complex Org. Lett. 2022, 24, 48, 8895-8900), which was confirmed as the target product by nuclear magnetic resonance and high-resolution mass spectrometry. The product parameters were 4-(tert-butyl)phenyl morpholine-4-carbodithioate (3p): yellow oil (43.7 mg, 74%). 1 H NMR (600 MHz, CDCl 3 )δ7.52(dd,J=6.3,4.5Hz,2H),7.35-7.31(m,2H),4.30-4.13(m,4H),3.82-3.78(m,4H),1.29(s,9H). 13 C NMR (151 MHz, CDCl 3 )δ196.94,151.82,136.67,130.19,126.22,66.40,53.53,51.23,34.74,31.31.

[0162] Embodiment 18

[0163] Synthesis of aryl triazene 1q:

[0164]

[0165] According to previous literature reports (J. Gao, Q. Song, L. Zhang, et al., Pd-Catalyzed C-7 Arylation of Indolines with Aryltriazenes under Mild Conditions. J. Org. Chem., 2023, 88(15): 11056-11068.), o-methylaniline (10 mmol) was added to a 100 mL round-bottom flask, and then concentrated hydrochloric acid (2 mL) with a mass concentration of 36-38% was added to the above aniline at 0°C, and an aqueous solution (5 mL) of sodium nitrite (11 mmol) was prepared and added dropwise to the hydrochloric acid solution of aniline. The obtained diazonium salt solution was continuously stirred in an ice bath for 15 min, and then added all at once to a cold solution (0° C.) containing 10 mL of an aqueous solution of potassium carbonate (1.2 mol / L) and morpholine (10 mmol). The reaction mixture was continuously stirred at room temperature for about 30 min. After the reaction was completed by monitoring by thin layer chromatography, the obtained product was recrystallized from ethanol or separated and purified by column chromatography to obtain 1q, which was confirmed to be the known target product, aryl triazene 1q, by nuclear magnetic resonance and high-resolution mass spectrometry.

[0166] Synthesis of aryl dithiocarbamate 3q:

[0167]

[0168] Add aryl triazene 1q (0.2mmol, 1equiv.) and carbon disulfide 2 (4mmol, 20equiv.) to a 25mL reaction tube, then add solvent acetonitrile (1.5mL), put it into a parallel light reactor, and irradiate it with 10W purple light (390-395nm) for 1h. Then separate it by silica gel column chromatography (eluent is petroleum ether / ethyl acetate, v / v=5:1) to obtain the target product 3q (unknown substance), which is confirmed to be the target product by nuclear magnetic resonance and high-resolution mass spectrometry. The parameters of the obtained product are o-tolylmorpholine-4-carbodithioate (3q): yellow oil (37mg, 73%). 1 H NMR (600 MHz, CDCl 3 )δ7.62-7.58(m,1H),7.19-7.14(m,3H),4.24-4.14(m,4H),3.82-3.78(m,4H),2.54(s,3H). 13 CNMR (151MHz, CDCl 3)δ196.30,138.18,134.35,130.38,130.07,128.11,126.66,66.33,53.35,51.33,20.37.HRMS(ESI)m / z:[M+H] + Calcd for C 12 H 15 NOS 2 :254.0668;Found:254.0665.

[0169] Embodiment 19

[0170] Synthesis of aryl triazene 1r:

[0171]

[0172] According to previous literature reports (J. Gao, Q. Song, L. Zhang, et al., Pd-Catalyzed C-7 Arylation of Indolines with Aryltriazenes under Mild Conditions. J. Org. Chem., 2023, 88(15): 11056-11068.), m-methylaniline (10 mmol) was added to a 100 mL round-bottom flask, and then concentrated hydrochloric acid (2 mL) with a mass concentration of 36-38% was added to the above aniline at 0°C, and an aqueous solution (5 mL) of sodium nitrite (11 mmol) was prepared and added dropwise to the hydrochloric acid solution of aniline. The obtained diazonium salt solution was continuously stirred in an ice bath for 15 min, and then added all at once to a cold solution (0°C) containing 10 mL of an aqueous solution of potassium carbonate (1.2 mol / L) and morpholine (10 mmol). The reaction mixture was continuously stirred at room temperature for about 30 min. After the reaction was completed by monitoring by thin layer chromatography, the obtained product was recrystallized from ethanol or separated and purified by column chromatography to obtain 1r, which was confirmed to be the known target product, aryl triazene 1r, by nuclear magnetic resonance and high-resolution mass spectrometry.

[0173] Synthesis of aryl dithiocarbamate 3r:

[0174]

[0175] Add aryl triazene 1r (0.2mmol, 1equiv.) and carbon disulfide 2 (4mmol, 20equiv.) to a 25mL reaction tube, then add solvent acetonitrile (1.5mL), put it into a parallel light reactor, and irradiate it with 10W purple light (390-395nm) for 1h. Then separate it by silica gel column chromatography (eluent is petroleum ether / ethyl acetate, v / v=5:1) to obtain the target product 3r (unknown substance), which is confirmed to be the target product by nuclear magnetic resonance and high-resolution mass spectrometry. The obtained product parameters are m-tolylmorpholine-4-carbodithioate (3r): yellow oil (41mg, 81%). 1 H NMR (600 MHz, CDCl 3 )δ7.37(d,J=7.1Hz,2H),7.19(t,J=8.0Hz,1H),7.07(d,J=7.8Hz,1H),4.30-4.13(m,4H),3.82-3.79(m,4H),2.33(s,3H). 13 C NMR (151 MHz, CDCl 3 )δ196.62,139.00,135.54,130.26,129.17,128.96,126.83,66.42,53.43,51.62,21.46.HRMS(ESI)m / z:[M+H] + Calcd for C 12 H 15 NOS 2 :254.0668;Found:254.0665.

[0176] Embodiment 20

[0177] Synthesis of aryl triazenes 1s:

[0178]

[0179] According to previous literature reports (J. Gao, Q. Song, L. Zhang, et al., Pd-Catalyzed C-7 Arylation of Indolines with Aryltriazenes under Mild Conditions. J. Org. Chem., 2023, 88(15): 11056-11068.), naphthalene-2-amine (10 mmol) was added to a 100 mL round-bottom flask, and then concentrated hydrochloric acid (2 mL) with a mass concentration of 36-38% was added to the above-mentioned naphthaleneamine at 0°C, and an aqueous solution (5 mL) of sodium nitrite (11 mmol) was prepared and added dropwise to the hydrochloric acid solution of aniline. The obtained diazonium salt solution was continuously stirred in an ice bath for 15 min, and then added all at once to a cold solution (0°C) containing 10 mL of an aqueous solution of potassium carbonate (1.2 mol / L) and morpholine (10 mmol). The reaction mixture was continuously stirred at room temperature for about 30 min. After the reaction was completed by monitoring by thin layer chromatography, the obtained product was recrystallized with ethanol or separated and purified by column chromatography to obtain 1s, which was confirmed to be the known target product, aryl triazene 1s, by nuclear magnetic resonance and high-resolution mass spectrometry.

[0180] Synthesis of aryl dithiocarbamate 3s:

[0181]

[0182] Add aryl triazene 1s (0.2mmol, 1equiv.) and carbon disulfide 2 (4mmol, 20equiv.) to a 25mL reaction tube, then add solvent acetonitrile (1.5mL), put it into a parallel light reactor, and irradiate it with 10W purple light (390-395nm) for 1h. Then separate it by silica gel column chromatography (eluent is petroleum ether / ethyl acetate, v / v=5:1) to obtain the target product 3s (unknown substance), which is confirmed to be the target product by nuclear magnetic resonance and high-resolution mass spectrometry. The parameters of the obtained product are naphthalen-2-ylmorpholine-4-carbodithioate (3s): yellow oil (29.5mg, 51%). 1 H NMR (600 MHz, CDCl 3 )δ8.56(d,J=8.5Hz,1H),8.08(d,J=7.2Hz,1H),7.85(dd,J=17.0,8.2Hz,2H),7.61(t,J=7.6 Hz,1H),7.54(t,J=8.6Hz,1H),7.42(t,J=7.7Hz,1H),4.27-4.12(m,4H),3.74-3.70(m,4H). 13 C NMR (151 MHz, CDCl3 )δ196.49,137.25,134.19,132.92,131.56,130.02,128.82,127.03,126.51,125.64,125.10,66.36,53.16,51.64.HRMS(ESI)m / z:[M+H] + Calcd for C 15 H 15 NOS 2 :290.0668;Found:290.0663.

[0183] Embodiment 21

[0184] Synthesis of aryl triazene 1t:

[0185]

[0186] According to previous literature reports (J. Gao, Q. Song, L. Zhang, et al., Pd-Catalyzed C-7 Arylation of Indolines with Aryltriazenes under Mild Conditions. J. Org. Chem., 2023, 88(15): 11056-11068.), 3,5-dimethylaniline (10 mmol) was added to a 100 mL round-bottom flask, and then concentrated hydrochloric acid (2 mL) with a mass concentration of 36-38% was added to the above aniline at 0°C, and an aqueous solution (5 mL) of sodium nitrite (11 mmol) was prepared and added dropwise to the hydrochloric acid solution of aniline. The obtained diazonium salt solution was continuously stirred in an ice bath for 15 min, and then added all at once to a cold solution (0° C.) containing 10 mL of an aqueous solution of potassium carbonate (1.2 mol / L) and morpholine (10 mmol). The reaction mixture was continuously stirred at room temperature for about 30 min. After the reaction was completed by monitoring by thin layer chromatography, the obtained product was recrystallized with ethanol or separated and purified by column chromatography to obtain 1t, which was confirmed to be the known target product, aryl triazene 1t, by nuclear magnetic resonance and high-resolution mass spectrometry.

[0187] Synthesis of aryl dithiocarbamate 3t:

[0188]

[0189] Add aryl triazene 1t (0.2mmol, 1equiv.) and carbon disulfide 2 (4mmol, 20equiv.) to a 25mL reaction tube, then add solvent acetonitrile (1.5mL), put it into a parallel light reactor, and irradiate it with 10W purple light (390-395nm) for 1h. Then separate it by silica gel column chromatography (eluent is petroleum ether / ethyl acetate, v / v=5:1) to obtain the target product 3t (unknown substance), which is confirmed to be the target product by nuclear magnetic resonance and high-resolution mass spectrometry. The obtained product parameters are 3,5-dimethylphenyl morpholine-4-carbodithioate (3t): yellow oil (32mg, 65%). 1 H NMR (600 MHz, CDCl 3 )δ7.19(s,2H),6.89(s,1H),4.30-4.13(m,4H),3.85-3.79(m,4H),2.29(s,6H). 13 C NMR (151 MHz, CDCl 3 )δ196.85,138.86,135.27,130.29,127.46,66.46,53.19,51.65,21.37.HRMS(ESI)m / z:[M+H] + Calcd for C 13 H 17 NOS 2 :268.0824;Found:268.0822.

[0190] Application Examples

[0191]

[0192] The aryl dithiocarbamate 3 generated by the present invention and the aryl diazonium tetrafluoroborate 4a are heated to 120°C in the presence of CuI (10 mol%), 2,2′-bipyridine (20 mol%) and zinc powder, and stirred for a period of time under the conditions of DMF as a solvent to synthesize diaryl sulfide 5. (S. Dutta, A. Saha, Aryldithiocarbamates as thiolalternatives in Cu-catalyzed C(aryl)-S coupling reactions using aryldiazoniumtetrafluoroborate salts. Org. Biomol. Chem., 2019, 17, 9360-9366.) In addition, the aryl dithiocarbamate 3 and the aryl iodide compound 4b are reacted in NiCl 2(5mol%), 2,2′-bipyridine (20mol%) and zinc powder were added, heated to 110°C, and DMF was used as solvent and stirred for a period of time to synthesize diaryl sulfide 5. (X. Liu, Q. Cao, W. Xu, et al., Dong Nickel-Catalyzed CS Coupling: Synthesis of Diaryl Sulfides Starting from Phenyldithiocarbamates and Iodobenzenes. Eur. J. Org. Chem., 2017, 5795-5799.) Diaryl sulfide 5 is a valuable intermediate for constructing biological and pharmaceutical active molecules and organic materials. Medical agents containing diaryl sulfide structures are used in various clinical applications, such as cancer, inflammation, Alzheimer's disease, Parkinson's disease and HIV treatment.

[0193] The above descriptions are merely embodiments of the present invention and are not intended to limit the patent scope of the present invention. Any equivalent structure or equivalent process transformation made using the contents of the present invention specification and drawings, or directly or indirectly applied in other related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. A method for synthesizing a photoinduced aryl dithiocarbamate, characterized in that: Using aryl triazene 1 and carbon disulfide 2 as reaction substrates, aryl dithiocarbamate 3 is obtained by inserting carbon disulfide into the denitrogenation gas of aryl triazene under violet light. The synthesis route is shown in the following reaction formula: wherein R1 represents one or more substituents at the ortho, meta, para, etc. positions of the benzene ring, the number of which is 1 to 5, preferably 1 to 2, and specifically may be one or more of C1-C10 alkyl, C1-C10 alkoxy, halogen, benzyl; preferably one or more of methyl, ethyl, isopropyl, tert-butyl, methoxy, ethoxy, methylthio, benzyl, fluorine, chlorine, bromine; One or more of the following; wherein the wavy line represents a connection point.

2. The preparation method according to claim 1, characterized in that: The solvent in the reaction is one or more of acetonitrile, methanol, ethanol, toluene, acetone, 1,1-dichloroethane, N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide, N-methylpyrrolidone and 1,4-dioxane. The best effect is achieved when the reaction solvent is acetonitrile. The amount of solvent added is 0.5-5 mL, preferably 0.5-2 mL, per 0.1 mmol of aryl triazene 1.

3. The preparation method according to claim 1, characterized in that: The reaction temperature is 20-50°C, and the optimal reaction temperature is 25-28°C.

4. The preparation method according to claim 1, characterized in that: When the aryl triazene 1 reacts with carbon disulfide 2, the molar ratio of the aryl triazene 1 to carbon disulfide 2 is in the range of 1:1 to 1:20, preferably 1:10 to 20, and most preferably 1:15 to 20.

5. The preparation method according to claim 1, characterized in that: The reaction time is 0.5 to 3 hours, preferably 1 to 2 hours, and the optimal reaction time is 1 to 1.2 hours.

6. The preparation method according to claim 1, characterized in that: The wavelength range of the ultraviolet light irradiation is 390 to 415 nanometers, preferably 390 to 395 nanometers.

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