A method for photochemically synthesizing sulfenamide compounds and its application

Abstract

The present invention belongs to the technical field of synthesis of sulfur-containing compounds, and specifically relates to a method for photochemically synthesizing sulfonamide compounds and its application. The method for photochemically synthesizing sulfonamide compounds of the present invention comprises the following steps: adding thiol compounds, azodicarboxylic acid ester compounds, iodine or iodine salt, and alkali to a solvent to form a reaction system, using blue light as a light source, continuously irradiating, and after the reaction is completed, post-treating the reactants to obtain sulfonamide compounds; the structural formula of the thiol compounds is Formula 1, Formula 2, Formula 3, Formula 4 or Formula 5: The structural formula of the azodicarboxylic acid ester compound is shown in Formula 5:, wherein, in Formula 6, the R is ethyl, isopropyl or benzyl. The method for photochemically synthesizing sulfonamide compounds provided by the present invention has mild reaction conditions, high reaction efficiency, and is environmentally friendly, providing a new idea for the synthesis of sulfonamide compounds.

Description

Technical Field

[0001] The invention belongs to the technical field of synthesis of sulfur-containing compounds, and specifically relates to a method for photochemically synthesizing sulfonamide compounds and application thereof. Background Art

[0002] Sulfonamide compounds, with their unique SN single bond structure, have shown wide application potential in many fields. In the rubber industry, they are used as crosslinking agents, providing a safer and more efficient crosslinking effect compared to sulfur. In the pharmaceutical field, especially in proton pump inhibitor drugs, sulfonamides are active metabolites for the treatment of gastrointestinal diseases. In the field of organic synthesis, the conversion of sulfonamides has become an important prerequisite for the construction of high-valent sulfides, and has received extensive attention and research in recent years.

[0003] At present, the synthesis methods of sulfonamide compounds mainly rely on traditional chemical methods. These methods usually involve the use of electrophilic thio reagents, such as sulfoxide chloride or N-sulfoxide succinimide. However, these reagents are not easy to obtain and are often accompanied by high costs. In addition, traditional synthesis methods also require the use of strong bases, such as NaH, to deprotonate amines, which not only increases the danger of the reaction, but also makes the reaction conditions harsh, and places high demands on equipment and operation.

[0004] What is more complicated is that the traditional method often requires a pre-activation process, which not only increases the complexity of the operation steps, but also prolongs the entire preparation cycle and reduces production efficiency. Although the dehydrogenation coupling reaction of amine compounds and thiols under oxidative conditions can synthesize sulfonamides, it usually requires the addition of additional oxidants and sometimes a certain amount of metal catalysts, which not only increases the cost of the reaction, but also causes certain pollution to the environment.

[0005] In recent years, although some new synthesis methods have been proposed, such as the methods for synthesizing sulfenamide compounds described in CN102250038A, CN101676273A, and CN111747945A, these methods still have their own limitations. For example, although some methods optimize the reaction conditions, the synthesis steps are still relatively cumbersome; although some methods improve the yield, they use relatively expensive raw materials or catalysts, which increases the production cost; and although some methods are environmentally friendly, the reaction efficiency is low and it is difficult to meet the needs of large-scale production.

[0006] Therefore, although the existing synthesis methods of sulfonamide compounds have made certain progress, they still have defects such as high cost, poor reaction conditions, complex operation, environmental pollution, etc. Therefore, developing a green, efficient, and step-economically efficient synthesis method for sulfonamide compounds is of great significance for promoting its application in various fields. Summary of the invention

[0007] The technical problem to be solved by the present invention is to overcome the above-mentioned defects of the prior art, provide a method for photochemically synthesizing sulfonamide compounds, which has mild reaction conditions, high reaction efficiency, and is environmentally friendly, and provides a new idea for the synthesis of sulfonamide compounds. The method of the present invention has the advantages of simple operation, no need for metal additives and photosensitizers, high product yield, and easy separation. At the same time, the present invention provides an application of sulfonamide compounds.

[0008] The method for photochemically synthesizing sulfonamide compounds of the present invention comprises the following steps: adding a thiol compound, an azodicarboxylate compound, iodine or an iodine salt, and a base to a solvent to form a reaction system, using blue light as a light source, continuously irradiating, and after the reaction is completed, post-treating the reactants to obtain sulfonamide compounds; the structural formula of the thiol compound is Formula 1, Formula 2, Formula 3, Formula 4, or Formula 5:

[0009] , wherein, in formula 1, R is 4-methyl, 4-hydrogen, 4-methoxy, 4-tert-butyl, 4-fluoro, 3-methyl, 3-methoxy, 3-bromo, 2-methoxy, 2-methyl or 2-chloro; in formula 3, n=1 or 3, n=1 is n-butyl, n=3 is n-hexyl; in formula 4, R is methyl, hydrogen or trifluoromethyl.

[0010] The structural formula of the azodicarboxylate compound is shown in Formula 5:

[0011] , wherein, in Formula 6, R is ethyl, isopropyl or benzyl.

[0012] The molar ratio of the thiol compound to the azodicarboxylate compound is 1:(1-4); the amount of the iodized salt is 0 or the molar ratio of the thiol compound to the iodized salt is 1:(0.5-2); the molar ratio of the thiol compound to the base is 1:(0.5-2).

[0013] The concentration of the thiol compound is 0.1 mmol / mL, the concentration of the azodicarboxylate compound is 0.1-0.4 mmol / mL, the concentration of the iodine salt is 0-0.2 mmol / mL, and the concentration of the base is 0.05-0.2 mmol / mL.

[0014] The wavelength of the blue light source is 390nm-450nm. When constant wavelength irradiation is performed, the wavelength of the blue light is preferably 410-450nm, and more preferably 450nm. Too large or too small a wavelength will result in reduced yield. The continuous irradiation time is 18-24 hours, preferably 18-24 hours. The reaction temperature is room temperature, and the greenhouse refers to 25-30°C in the usual sense.

[0015] The solvent is one of ethyl acetate (EtOAc), dichloromethane (DCM), tetrahydrofuran (THF), N,N-dimethylformamide (DMF), and acetonitrile (CH3CN), preferably acetonitrile.

[0016] The iodine salt is one of sodium iodide (NaI), potassium iodide (KI), tetrabutylammonium iodide (nBu4NI), and N-iodosuccinimide (NIS), preferably sodium iodide.

[0017] The base is one of sodium carbonate (Na2CO3), lithium carbonate (Li2CO3), potassium hydroxide (KOH), dipotassium hydrogen phosphate (K2HPO4), potassium carbonate (K2CO3), and potassium tert-butoxide (t-BuOK), preferably potassium carbonate.

[0018] The post-treatment is to first quench with water, then extract with an organic reagent, then back-extract with saturated brine, dry with anhydrous sodium sulfate, then distill under reduced pressure, and purify with silica gel column chromatography.

[0019] The organic reagent is ethyl acetate, dichloromethane or petroleum ether.

[0020] During the silica gel column chromatography purification, the eluent used is a mixture of ethyl acetate and petroleum ether in a volume ratio of 1:4-1:10.

[0021] The reaction system uses a stopcock-type Shrek tube, and the continuous irradiation uses an RLH-18CU 8-well photoreactor.

[0022] The prepared sulfonamide compounds are ethyl (p-toluenethio) carbamate, ethyl (phenylthio) carbamate, ethyl [(4-methoxyphenyl)thio] carbamate, ethyl [(4-(tert-butyl) phenyl)thio] carbamate, ethyl [(4-fluorophenyl)thio] carbamate, ethyl (m-toluenethio) carbamate, ethyl [(3-methoxyphenyl)thio] carbamate, ethyl [(3-bromophenyl)thio] carbamate, ethyl [(2-methoxyphenyl)thio] carbamate , ethyl (o-toluenethio)carbamate, ethyl [(2-chlorophenyl)thio]carbamate, ethyl (naphthalene-2-ylthio)carbamate, ethyl (butylthio)carbamate, ethyl (hexylthio)carbamate, ethyl [(4-methylbenzyl)thio]carbamate, ethyl (benzylthio)carbamate, ethyl [(4-(trifluoromethyl)benzyl)thio]carbamate, ethyl (cyclohexylthio)carbamate, isopropyl (p-toluenethio)carbamate or benzyl (p-toluenethio)carbamate.

[0023] Specifically preferred, the method for photochemically synthesizing sulfonamide compounds comprises the following steps: adding 0.2 mmol of thiol, 0.4 mmol of azodicarboxylic acid ester compound, 0.2 mmol of sodium iodide, 0.2 mmol of potassium carbonate, and 2 mL of acetonitrile to a 10 mL stopcock Shrek tube, placing the system in a RLH-18CU 8-hole photoreactor under room temperature and air conditions, stirring continuously with a magnetic particle, and irradiating at a constant wavelength of 450 nm for 18 hours, and TLC tracking monitoring; after the reaction is completed, the reaction system is quenched with water, extracted with ethyl acetate, back-extracted with saturated brine, and dried with anhydrous sodium sulfate, and distilled under reduced pressure at 45°C, and the residue is purified by rapid silica gel column chromatography to obtain a reaction product. The silica gel column chromatography purification uses an eluent of ethyl acetate: petroleum ether = 1:5, and then uses nuclear magnetic resonance to qualitatively analyze the product, and deuterated chloroform-d dissolves and tests hydrogen and carbon spectra.

[0024] The present invention uses p-toluene thiophenol as a thiol compound, diethyl azodicarboxylate as an azodicarboxylate compound, sodium iodide as an iodine salt, and potassium carbonate as a base, which are added to an acetonitrile solvent to form a reaction system, and uses blue light 450nm as a light source to continuously irradiate the system to prepare a product. After the reaction is completed, the reactants are post-treated to obtain sulfonamide compounds. The reaction principle is as follows:

[0025]

[0026] From the above reaction principle, it can be seen that thiol compounds are first oxidized into thiol radicals in the presence of light and oxygen, which then undergo a free radical addition reaction with the nitrogen-nitrogen double bond in the substrate azo to generate an intermediate. Next, the intermediate undergoes a disproportionation reaction to obtain the active intermediate tetrasubstituted hydrazine and diethyl hydrazinedicarboxylate. On this basis, the tetrasubstituted hydrazine undergoes reduction or is attacked by other nucleophiles, thereby breaking the N-N bond to obtain the target product sulfonamide.

[0027] The sulfenamide substances synthesized by the present invention can be used to prepare the following derivatives through derivatization reactions:

[0028]

[0029] Ethyl (p-tolylsulfinyl) carbamate;

[0030]

[0031] Ethyl[(cyclohexylamino)(p-tolyl)-14-sulfonimide]carbamate;

[0032]

[0033] Ethyl [(4-methylbenzyl)(p-tolyl)-14-sulfonimide]carbamate.

[0034] The present invention adopts a light-excitation method, uses thiol compounds and azodicarboxylate compounds as raw materials, and synthesizes sulfonamide compounds in one step at room temperature and pressure. The reaction does not require metal catalysts and expensive photosensitizers, and the yield is high and the product is easy to separate. It has the following advantages: no metal additives are required, the reaction process can be catalyzed by cheap iodine salts, blue light in visible light is used as the light source, the reaction conditions are mild and loose, no inert gas protection is required, the operation is simple, the product is easy to separate, the step economy is good, and it has good functional group tolerance. It avoids the problems of multi-step synthesis required in other synthesis methods, complex operation, harsh reaction conditions, long preparation cycle, and strong reagent toxicity.

[0035] Compared with the prior art, the present invention has the following beneficial effects:

[0036] (1) The method for photochemically synthesizing sulfonamide compounds of the present invention does not require high temperature, high pressure, strong acid or strong alkaline conditions, nor does it require complicated synthesis steps. The synthesis of sulfonamide compounds can be completed in one step at room temperature and pressure.

[0037] (2) The method for photochemical synthesis of sulfonamide compounds of the present invention is not restricted by the site, the steps are economical and efficient, the equipment investment is small, the operation is simple, the reaction can be shut down at any time through instrument control, and only blue light excitation is required, which is more environmentally friendly.

[0038] (3) The photochemical synthesis method of sulfonamide compounds of the present invention uses cheap and readily available raw materials, does not require metal additives, uses only mild blue light as the light source, does not require inert gas protection, has loose reaction conditions, and is easy to operate.

[0039] (4) In the method for photochemically synthesizing sulfonamide compounds of the present invention, the generation of intermediate products can directly change the properties of sulfur (S) from nucleophilicity to electrophilicity, thereby avoiding the pre-activation step in the traditional preparation, which not only reduces the number of operation steps, but also greatly saves the preparation cost and improves the possibility of industrial production.

[0040] (5) The sulfonyl sulfur substances synthesized by the present invention can be further derivatized to obtain various high-valent sulfur compounds. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 This is the H NMR spectrum of the product of Example 1 of the present invention;

[0042] Figure 2 This is the NMR carbon spectrum of the product of Example 1 of the present invention;

[0043] Figure 3 This is the H NMR spectrum of the product of Example 2 of the present invention;

[0044] Figure 4 This is the NMR carbon spectrum of the product of Example 2 of the present invention;

[0045] Figure 5 This is the H NMR spectrum of the product of Example 3 of the present invention;

[0046] Figure 6 This is the NMR carbon spectrum of the product of Example 3 of the present invention;

[0047] Figure 7 This is the H NMR spectrum of the product of Example 4 of the present invention;

[0048] Figure 8 This is the NMR carbon spectrum of the product of Example 4 of the present invention;

[0049] Fig. 9 This is the H NMR spectrum of the product of Example 5 of the present invention;

[0050] Fig.10 This is the NMR carbon spectrum of the product of Example 5 of the present invention;

[0051] Fig.11 This is the H NMR spectrum of the product of Example 6 of the present invention;

[0052] Fig.12 This is the NMR carbon spectrum of the product of Example 6 of the present invention;

[0053] Fig.13 This is the H NMR spectrum of the product of Example 7 of the present invention;

[0054] Fig.14 This is the NMR carbon spectrum of the product of Example 7 of the present invention;

[0055] Fig.15 This is the H NMR spectrum of the product of Example 8 of the present invention;

[0056] Fig.16 This is the NMR carbon spectrum of the product of Example 8 of the present invention;

[0057] Fig.17 This is the H NMR spectrum of the product of Example 9 of the present invention;

[0058] Fig.18 This is the NMR carbon spectrum of the product of Example 9 of the present invention;

[0059] Fig.19 This is the H NMR spectrum of the product of Example 10 of the present invention;

[0060] Fig. 20 This is the NMR carbon spectrum of the product of Example 10 of the present invention;

[0061] Fig.21 This is the H NMR spectrum of the product of Example 11 of the present invention;

[0062] Fig. 22 This is the NMR carbon spectrum of the product of Example 11 of the present invention;

[0063] Fig.23 This is the H NMR spectrum of the product of Example 12 of the present invention;

[0064] Fig.24 This is the NMR carbon spectrum of the product of Example 12 of the present invention;

[0065] Fig.25 This is the H NMR spectrum of the product of Example 13 of the present invention;

[0066] Fig.26 This is the NMR carbon spectrum of the product of Example 13 of the present invention;

[0067] Fig. 27 This is the H NMR spectrum of the product of Example 14 of the present invention;

[0068] Fig.28 This is the NMR carbon spectrum of the product of Example 14 of the present invention;

[0069] Fig.29 This is the H NMR spectrum of the product of Example 15 of the present invention;

[0070] Fig.30 This is the NMR carbon spectrum of the product of Example 15 of the present invention;

[0071] Fig.31 This is the H NMR spectrum of the product of Example 16 of the present invention;

[0072] Fig.32 This is the NMR carbon spectrum of the product of Example 16 of the present invention;

[0073] Fig.33 This is the H NMR spectrum of the product of Example 17 of the present invention;

[0074] Fig.34 This is the NMR carbon spectrum of the product of Example 17 of the present invention;

[0075] Fig.35 This is the H NMR spectrum of the product of Example 18 of the present invention;

[0076] Fig.36 This is the NMR carbon spectrum of the product of Example 18 of the present invention;

[0077] Fig.37 This is the H NMR spectrum of the product of Example 19 of the present invention;

[0078] Fig.38 This is the NMR carbon spectrum of the product of Example 19 of the present invention;

[0079] Fig.39 This is the H NMR spectrum of the product of Example 20 of the present invention;

[0080] Fig.40 This is the NMR carbon spectrum of the product of Example 20 of the present invention;

[0081] Fig.41 This is the NMR carbon spectrum of the product of Example 48 of the present invention;

[0082] Fig.42 This is the NMR carbon spectrum of the product of Example 48 of the present invention;

[0083] Fig.43 This is the NMR carbon spectrum of the product of Example 49 of the present invention;

[0084] Fig.44 This is the NMR carbon spectrum of the product of Example 49 of the present invention;

[0085] Fig.45 This is the NMR carbon spectrum of the product of Example 50 of the present invention;

[0086] Fig.46 This is the NMR carbon spectrum of the product of Example 50 of the present invention. DETAILED DESCRIPTION

[0087] The present invention will be further described below in conjunction with specific embodiments.

[0088] The raw materials used in the following examples are all commercially available.

[0089] Example 1

[0090] The ethyl (p-toluenethio) carbamate Preparation:

[0091] 0.2 mmol of p-toluene thiophenol, 0.4 mmol of diethyl azodicarboxylate, 0.2 mmol of sodium iodide, 0.2 mmol of potassium carbonate, and 2 mL of ultra-dry acetonitrile were added to a 10 mL Shrek tube. The system was placed in a RLH-18CU 8-well photoreactor under room temperature and air conditions, and stirred continuously with a magnetic bar, irradiated with 450 nm blue light for 18 h, and monitored by TLC tracking. After the reaction was completed, the reaction system was quenched with water, extracted with ethyl acetate, back-extracted with saturated brine, and dried with anhydrous sodium sulfate. The residue was distilled under reduced pressure at 45 ° C. The residue was purified by rapid silica gel column chromatography (ethyl acetate: petroleum ether = 1:10) to obtain the product with a yield of 85%. The product was qualitatively analyzed by nuclear magnetic resonance, and the deuterated chloroform-d was dissolved to test the hydrogen spectrum and carbon spectrum.

[0092] like Figure 1 As shown, 1 H NMR (400 MHz, CDCl3) δ 7.26 (d, J = 8.1 Hz, 2H), 7.14 (d,J = 8.0 Hz, 2H), 5.89 (s, 1H), 4.22 (q, J = 7.1 Hz, 2H), 2.33 (s, 3H), 1.27(t, J = 7.1 Hz, 3H).

[0093] like Figure 2 As shown, 13 C NMR (101 MHz, CDCl3) δ 157.3, 137.5, 135.5, 129.7, 126.7, 62.8, 21.0, 14.4.

[0094] Example 2

[0095] The ethyl (phenylthio) carbamate Preparation:

[0096] Add 0.1mmol of diphenyl disulfide, 0.4mmol of diethyl azodicarboxylate, 0.2mmol of sodium iodide, 0.2mmol of potassium carbonate, and 2mL of ultra-dry acetonitrile to a 10mL Shrek tube. Place the system in a RLH-18CU 8-well photoreactor under room temperature and air conditions, stir continuously with a magnet, irradiate with 450nm blue light for 18h, and monitor by TLC tracking. After the reaction is completed, the reaction system is quenched with water, extracted with ethyl acetate, back-extracted with saturated brine, dried with anhydrous sodium sulfate, and distilled under reduced pressure at 45°C. The residue is purified by rapid silica gel column chromatography (ethyl acetate: petroleum ether = 1:5) to obtain the product with a yield of 83%. The product is qualitatively analyzed by nuclear magnetic resonance, and the hydrogen and carbon spectra are tested by deuterated chloroform-d dissolution.

[0097] like Figure 3 As shown, 1 H NMR (400 MHz, CDCl3) δ 7.34 - 7.28 (m, 4H), 7.23 - 7.20(m, 1H), 6.00 (s, 1H), 4.23 (q, J = 7.1 Hz, 2H), 1.28 (t, J = 7.1 Hz, 3H).

[0098] like Figure 4 As shown, 13 C NMR (101 MHz, CDCl3) δ 157.2, 139.1, 129.0, 126.9, 125.0, 62.9, 14.4.

[0099] Example 3

[0100] The ethyl [(4-methoxyphenyl) thio] carbamate Preparation:

[0101] 0.2 mmol of 4-methoxythiophenol, 0.4 mmol of diethyl azodicarboxylate, 0.2 mmol of sodium iodide, 0.2 mmol of potassium carbonate, and 2 mL of ultra-dry acetonitrile were added to a 10 mL Shrek tube. The system was placed in a RLH-18CU 8-well photoreactor under room temperature and air conditions, and stirred continuously with a magnetic bar, irradiated with 450 nm blue light for 18 h, and monitored by TLC tracking. After the reaction was completed, the reaction system was quenched with water, extracted with ethyl acetate, back-extracted with saturated brine, and dried with anhydrous sodium sulfate. The residue was distilled under reduced pressure at 45 ° C, and the residue was purified by rapid silica gel column chromatography (ethyl acetate: petroleum ether = 1:8) to obtain the product with a yield of 94%. The product was qualitatively analyzed by nuclear magnetic resonance, and the deuterated chloroform-d was dissolved to test the hydrogen spectrum and carbon spectrum.

[0102] like Figure 5 As shown,1 H NMR (400 MHz, CDCl3) δ 7.44 (d, J = 8.6 Hz, 2H), 6.85 (d,J = 8.8 Hz, 2H), 6.05 (s, 1H), 4.18 (q, J = 7.1 Hz, 2H), 3.78 (s, 3H), 1.25(t, J = 7.1 Hz, 3H).

[0103] like Figure 6 As shown, 13 C NMR (101 MHz, CDCl3) δ 160.0, 157.4, 131.7, 129.4, 114.5, 62.6, 55.3, 14.4.

[0104] Example 4

[0105] The ethyl [(4-(tert-butyl) phenyl) thio] carbamate Preparation:

[0106] 0.2 mmol of 4-tert-butylthiophenol, 0.4 mmol of diethyl azodicarboxylate, 0.2 mmol of sodium iodide, 0.2 mmol of potassium carbonate, and 2 mL of ultra-dry acetonitrile were added to a 10 mL Shrek tube. The system was placed in a RLH-18CU 8-well photoreactor under room temperature and air conditions, and stirred continuously with a magnetic bar, irradiated with 450 nm blue light for 18 h, and monitored by TLC tracking. After the reaction was completed, the reaction system was quenched with water, extracted with ethyl acetate, back-extracted with saturated brine, and dried with anhydrous sodium sulfate. The residue was distilled under reduced pressure at 45 ° C. The residue was purified by rapid silica gel column chromatography (ethyl acetate: petroleum ether = 1:4) to obtain the product with a yield of 90%. The product was qualitatively analyzed by nuclear magnetic resonance, and the deuterated chloroform-d was dissolved to test the hydrogen spectrum and carbon spectrum.

[0107] like Figure 7 As shown, 1 H NMR (400 MHz, CDCl3) δ 7.35(d, J = 8.5 Hz, 2H), 7.28 (d,J = 8.5 Hz, 2H), 6.08 (s, 1H), 4.21 (q, J = 7.1 Hz, 2H), 1.30 (s, 9H), 1.26(d, J = 7.1 Hz, 3H).

[0108] like Figure 8 As shown, 13C NMR (101 MHz, CDCl3) δ 157.3, 150.5, 135.5, 126.1, 126.0, 62.7, 34.5, 31.2, 14.4.

[0109] Example 5

[0110] The ethyl [(4-fluorophenyl)thio] carbamate Preparation:

[0111] 0.2 mmol of 4-fluorobenzenethiol, 0.4 mmol of diethyl azodicarboxylate, 0.2 mmol of sodium iodide, 0.2 mmol of potassium carbonate, and 2 mL of ultra-dry acetonitrile were added to a 10 mL Shrek tube. The system was placed in a RLH-18CU 8-well photoreactor under room temperature and air conditions, and stirred continuously with a magnetic bar, irradiated with 450 nm blue light for 20 h, and monitored by TLC tracking. After the reaction was completed, the reaction system was quenched with water, extracted with ethyl acetate, back-extracted with saturated brine, and dried with anhydrous sodium sulfate. The residue was distilled under reduced pressure at 45 ° C. The residue was purified by rapid silica gel column chromatography (ethyl acetate: petroleum ether = 1:5) to obtain the product with a yield of 85%. The product was qualitatively analyzed by nuclear magnetic resonance, and the deuterated chloroform-d was dissolved to test the hydrogen spectrum and carbon spectrum.

[0112] like Fig. 9 As shown, 1 H NMR (400 MHz, CDCl3) δ7.40 - 7.33 (m, 2H), 7.07 - 6.97(m, 2H), 6.16 (s, 1H), 4.20 (q, J = 7.1 Hz, 2H), 1.25 (t, J = 7.1 Hz, 3H)

[0113] like Fig.10 As shown, 13 C NMR (101 MHz, CDCl3) δ 162.4 (d, J = 245.6 Hz), 157.2,134.0 (d, J = 2.9 Hz), 129.3 (d, J = 7.9 Hz), 116.2 (d, J = 22.4 Hz), 62.9,14.4.

[0114] Example 6

[0115] The ethyl (m-toluenethio) carbamate Preparation:

[0116] 0.2 mmol of m-methylthiophenol, 0.4 mmol of diethyl azodicarboxylate, 0.2 mmol of sodium iodide, 0.2 mmol of potassium carbonate, and 2 mL of ultra-dry acetonitrile were added to a 10 mL Shrek tube. The system was placed in a RLH-18CU 8-well photoreactor under room temperature and air conditions, and stirred continuously with a magnetic bar, irradiated with 450 nm blue light for 18 h, and monitored by TLC tracking. After the reaction was completed, the reaction system was quenched with water, extracted with ethyl acetate, back-extracted with saturated brine, and dried with anhydrous sodium sulfate. The residue was distilled under reduced pressure at 45 ° C, and the residue was purified by rapid silica gel column chromatography (ethyl acetate: petroleum ether = 1:5) to obtain the product with a yield of 85%. The product was qualitatively analyzed by nuclear magnetic resonance, and the deuterated chloroform-d was dissolved to test the hydrogen spectrum and carbon spectrum.

[0117] like Fig.11 As shown, 1 H NMR (400 MHz, CDCl3) δ 7.20 (t, J = 7.8 Hz, 1H), 7.08 (d, J = 7.8 Hz, 2H), 7.00 (d, J = 7.5 Hz, 1H), 6.17 (s, 1H), 4.22 (q, J = 7.1Hz, 2H), 2.31 (s, 3H), 1.26 (t, J = 7.1 Hz, 3H).

[0118] like Fig.12 As shown, 13 C NMR (101 MHz, CDCl3) δ 157.3, 138.9, 138.8, 128.8, 127.6, 125.4, 122.0, 62.8, 21.3, 14.3.

[0119] Example 7

[0120] The ethyl [(3-methoxyphenyl) thio] carbamate Preparation:

[0121] 0.2 mmol of 3-methoxythiophenol, 0.4 mmol of diethyl azodicarboxylate, 0.2 mmol of sodium iodide, 0.2 mmol of potassium carbonate, and 2 mL of ultra-dry acetonitrile were added to a 10 mL Shrek tube. The system was placed in a RLH-18CU 8-well photoreactor under room temperature and air conditions, and stirred continuously with a magnetic bar, irradiated with 450 nm blue light for 18 h, and monitored by TLC tracking. After the reaction was completed, the reaction system was quenched with water, extracted with ethyl acetate, back-extracted with saturated brine, and dried with anhydrous sodium sulfate. The residue was distilled under reduced pressure at 45 ° C. The residue was purified by rapid silica gel column chromatography (ethyl acetate: petroleum ether = 1:5) to obtain the product with a yield of 88%. The product was qualitatively analyzed by nuclear magnetic resonance, and the deuterated chloroform-d was dissolved to test the hydrogen spectrum and carbon spectrum.

[0122] like Fig.13 As shown, 1 H NMR (400 MHz, CDCl3) δ 7.21 (t, J = 8.0 Hz, 1H), 6.81 (d, J = 15.6 Hz, 2H), 6.71 (dd, J = 8.3, 2.5 Hz, 1H), 6.21 (s, 1H), 4.21 (q,J = 7.1 Hz, 2H), 3.76 (s, 3H), 1.26 (t, J = 7.1 Hz, 3H).

[0123] like Fig.14 As shown, 13 C NMR (101 MHz, CDCl3) δ 159.9, 157.2, 140.6, 129.8,116.5, 112.3, 109.8, 62.8, 55.2, 14.3.

[0124] Example 8

[0125] The ethyl [(3-bromophenyl) thio] carbamate Preparation:

[0126] 0.2 mmol of 3-bromothiophenol, 0.4 mmol of diethyl azodicarboxylate, 0.2 mmol of sodium iodide, 0.2 mmol of potassium carbonate, and 2 mL of ultra-dry acetonitrile were added to a 10 mL Shrek tube. The system was placed in a RLH-18CU 8-well photoreactor under room temperature and air conditions, and stirred continuously with a magnetic pole. 450 nm blue light was continuously irradiated for 24 h, and TLC tracking and monitoring were performed. After the reaction was completed, the reaction system was quenched with water, extracted with ethyl acetate, back-extracted with saturated brine, and dried with anhydrous sodium sulfate. The residue was distilled under reduced pressure at 45 ° C. The residue was purified by rapid silica gel column chromatography (ethyl acetate: petroleum ether = 1:10) to obtain the product with a yield of 68%. The product was qualitatively analyzed by nuclear magnetic resonance, and the deuterated chloroform-d was dissolved to test the hydrogen spectrum and carbon spectrum.

[0127] like Fig.15 As shown, 1 H NMR (400 MHz, CDCl3) δ 7.37 (q, J = 1.4 Hz, 1H), 7.29 (dtd, J = 6.4, 4.2, 2.0 Hz, 1H), 7.19 - 7.13 (m, 2H), 6.15 (s, 1H), 4.23 (q,J = 7.1 Hz, 2H), 1.27 (t, J = 7.1 Hz, 3H).

[0128] like Fig.16 As shown, 13 C NMR (101 MHz, CDCl3) δ 157.0, 141.6, 130.3, 129.6, 126.8, 123.0, 122.7, 63.1, 14.3.

[0129] Example 9

[0130] The ethyl [(2-methoxyphenyl) thio] carbamate Preparation:

[0131] 0.2 mmol of 2-methoxythiophenol, 0.4 mmol of diethyl azodicarboxylate, 0.2 mmol of sodium iodide, 0.2 mmol of potassium carbonate, and 2 mL of ultra-dry acetonitrile were added to a 10 mL Shrek tube. The system was placed in a RLH-18CU 8-well photoreactor under room temperature and air conditions, and stirred continuously with a magnetic bar, irradiated with 450 nm blue light for 18 h, and monitored by TLC tracking. After the reaction was completed, the reaction system was quenched with water, extracted with ethyl acetate, back-extracted with saturated brine, and dried with anhydrous sodium sulfate. The residue was distilled under reduced pressure at 45 ° C, and the residue was purified by rapid silica gel column chromatography (ethyl acetate: petroleum ether = 1:5) to obtain the product with a yield of 68%. The product was qualitatively analyzed by nuclear magnetic resonance, and the deuterated chloroform-d was dissolved to test the hydrogen spectrum and carbon spectrum.

[0132] like Fig.17 As shown, 1 H NMR (400 MHz, CDCl3) δ 7.18 (dh, J = 7.2, 1.6 Hz, 2H), 6.95 (td, J = 7.6, 1.1 Hz, 1H), 6.83 (dd, J = 8.5, 1.1 Hz, 1H), 5.84 (s, 1H), 4.20 (q, J = 7.1 Hz, 2H), 3.85 (s, 1H), 1.26 (t, J = 7.1 Hz, 3H).

[0133] like Fig.18 As shown, 13 C NMR (101 MHz, CDCl3) δ 157.2, 154.8, 127.6, 127.1, 124.9, 121.2, 110.4, 62.7, 55.7, 14.4.

[0134] Example 10

[0135] The ethyl (o-tolylthio) carbamate Preparation:

[0136] 0.2 mmol of 2-methylthiophenol, 0.4 mmol of diethyl azodicarboxylate, 0.2 mmol of sodium iodide, 0.2 mmol of potassium carbonate, and 2 mL of ultra-dry acetonitrile were added to a 10 mL Shrek tube. The system was placed in a RLH-18CU 8-well photoreactor under room temperature and air conditions, and stirred continuously with a magnetic pole. The system was continuously irradiated with 450 nm blue light for 18 h and monitored by TLC tracking. After the reaction was completed, the reaction system was quenched with water, extracted with ethyl acetate, back-extracted with saturated brine, and dried with anhydrous sodium sulfate. The product was distilled under reduced pressure at 45 ° C. The residue was purified by rapid silica gel column chromatography (ethyl acetate: petroleum ether = 1:5) to obtain the product with a yield of 81%. The product was qualitatively analyzed by nuclear magnetic resonance, and the deuterated chloroform-d was dissolved to test the hydrogen spectrum and carbon spectrum.

[0137] like Fig.19 As shown, 1 H NMR (400 MHz, CDCl3) δ 7.24 - 7.16 (m, 2H), 7.14 - 7.06(m, 2H), 6.01 (s, 1H), 4.22 (q, J = 7.1 Hz, 2H), 2.30 (s, 3H), 1.27 (t, J =7.1 Hz, 3H).

[0138] like Fig. 20 As shown, 13 C NMR (101 MHz, CDCl3) δ 157.3, 137.7, 133.4, 130.2, 126.5, 126.2, 123.8, 62.8, 18.7, 14.3.

[0139] Embodiment 11

[0140] The ethyl [(2-chlorophenyl) thio] carbamate Preparation:

[0141] 0.2 mmol of 2-chlorobenzenethiol, 0.4 mmol of diethyl azodicarboxylate, 0.2 mmol of sodium iodide, 0.2 mmol of potassium carbonate, and 2 mL of ultra-dry acetonitrile were added to a 10 mL Shrek tube. The system was placed in a RLH-18CU 8-well photoreactor under room temperature and air conditions, and stirred continuously with a magnetic pole. 450 nm blue light was continuously irradiated for 24 h, and TLC tracking and monitoring were performed. After the reaction was completed, the reaction system was quenched with water, extracted with ethyl acetate, back-extracted with saturated brine, and dried with anhydrous sodium sulfate. The residue was distilled under reduced pressure at 45 ° C. The residue was purified by rapid silica gel column chromatography (ethyl acetate: petroleum ether = 1:5) to obtain the product with a yield of 40%. The product was qualitatively analyzed by nuclear magnetic resonance, and the deuterated chloroform-d was dissolved to test the hydrogen spectrum and carbon spectrum.

[0142] like Fig.21 As shown, 1 H NMR (400 MHz, CDCl3) δ 7.33 - 7.28 (m, 1H), 7.26 (dd, J= 8.2, 1.0 Hz, 1H), 7.19 (dd, J = 8.0, 1.7 Hz, 1H), 7.16 - 7.10 (m, 1H), 5.79(s, 1H), 4.25 (q, J = 7.1 Hz, 2H). 1.29 (t, J = 7.1 Hz, 3H).

[0143] like Fig. 22 As shown, 13 C NMR (101 MHz, CDCl3) δ 156.8, 137.9, 129.6, 128.6, 127.3, 127.0, 124.1, 63.2, 14.4.

[0144] Example 12

[0145] The ethyl (naphthalene-2-ylthio) carbamate Preparation:

[0146] 0.2 mmol of 2-naphthol, 0.4 mmol of diethyl azodicarboxylate, 0.2 mmol of sodium iodide, 0.2 mmol of potassium carbonate, and 3 mL of ultra-dry acetonitrile were added to a 10 mL Shrek tube. The system was placed in a RLH-18CU 8-well photoreactor under room temperature and air conditions, and stirred continuously with a magnetic bar, irradiated with 450 nm blue light for 18 h, and monitored by TLC tracking. After the reaction was completed, the reaction system was quenched with water, extracted with ethyl acetate, back-extracted with saturated brine, and dried with anhydrous sodium sulfate. The residue was distilled under reduced pressure at 45 ° C. The residue was purified by rapid silica gel column chromatography (ethyl acetate: petroleum ether = 1:6) to obtain the product with a yield of 65%. The product was qualitatively analyzed by nuclear magnetic resonance, and the deuterated chloroform-d was dissolved to test the hydrogen spectrum and carbon spectrum.

[0147] like Fig.23 As shown, 1 H NMR (400 MHz, CDCl3) δ 7.82 - 7.81 (m, 4H), 7.51 - 7.43(m, 2H), 7.40 (dd, J = 8.7, 1.9 Hz, 1H), 6.05 (s, 1H), 4.26 (q, J = 7.1 Hz, 2H), 1.29 (t, J = 7.1 Hz, 3H).

[0148] like Fig.24 As shown, 13 C NMR (101 MHz, CDCl3) δ 157.3, 136.5, 133.5, 132.3, 128.9, 127.8, 127.4, 126.7, 126.0, 123.5, 123.2, 63.0, 14.4.

[0149] Example 13

[0150] The ethyl (butylthio) carbamate Preparation:

[0151] 0.2 mmol of n-butyl mercaptan, 0.4 mmol of diethyl azodicarboxylate, 0.2 mmol of sodium iodide, 0.2 mmol of potassium carbonate, and 2 mL of ultra-dry acetonitrile were added to a 10 mL Shrek tube. The system was placed in a RLH-18CU 8-well photoreactor under room temperature and air conditions, and stirred continuously with a magnetic pole. 450 nm blue light was continuously irradiated for 18 h, and TLC tracking and monitoring were performed. After the reaction was completed, the reaction system was quenched with water, extracted with ethyl acetate, back-extracted with saturated brine, and dried with anhydrous sodium sulfate. The residue was distilled under reduced pressure at 45 ° C. The residue was purified by rapid silica gel column chromatography (ethyl acetate: petroleum ether = 1:4) to obtain the product with a yield of 60%. The product was qualitatively analyzed by nuclear magnetic resonance, and the deuterated chloroform-d was dissolved to test the hydrogen spectrum and carbon spectrum.

[0152] like Fig.25 As shown, 1 H NMR (400 MHz, CDCl3) δ 5.48 (s, 1H), 4.18 (q, J = 7.1Hz, 2H), 2.71 (t, J = 7.4 Hz, 2H), 1.58 (p, J = 7.2 Hz, 2H), 1.42 (p, J = 7.3Hz, 2H), 1.26 (t, J = 7.2 Hz, 3H), 0.91 (t, J = 7.3 Hz, 3H).

[0153] like Fig.26 As shown, 13 C NMR (101 MHz, CDCl3) δ 157.7, 62.4, 39.1, 29.5, 21.6, 14.4, 13.6.

[0154] Embodiment 14

[0155] The ethyl (hexylthio) carbamate Preparation:

[0156] 0.2 mmol of n-hexyl mercaptan, 0.4 mmol of diethyl azodicarboxylate, 0.2 mmol of sodium iodide, 0.2 mmol of potassium carbonate, and 2 mL of ultra-dry acetonitrile were added to a 10 mL Shrek tube. The system was placed in a RLH-18CU 8-well photoreactor under room temperature and air conditions, and stirred continuously with a magnetic pole. The system was continuously irradiated with 450 nm blue light for 18 h and monitored by TLC tracking. After the reaction was completed, the reaction system was quenched with water, extracted with ethyl acetate, back-extracted with saturated brine, and dried with anhydrous sodium sulfate. The product was distilled under reduced pressure at 45 ° C. The residue was purified by rapid silica gel column chromatography (ethyl acetate: petroleum ether = 1:5) to obtain the product with a yield of 65%. The product was qualitatively analyzed by nuclear magnetic resonance, and the hydrogen and carbon spectra were tested by deuterated chloroform-d dissolution.

[0157] like Fig. 27 As shown, 1 H NMR (400 MHz, CDCl3) δ 5.51 (s, 1H), 4.17 (q, J = 7.1Hz, 2H), 2.75 - 2.65 (m, 2H), 1.58 (p, J = 7.2 Hz, 2H), 1.44 - 1.34 (m, 2H), 1.32 - 1.23 (m, 7H), 0.86 (t, J = 6.7 Hz, 3H).

[0158] like Fig.28 As shown, 13 C NMR (101 MHz, CDCl3) δ 157.7, 62.4, 39.4, 31.4, 28.2, 27.4, 22.5, 14.4, 13.9.

[0159] Embodiment 15

[0160] The ethyl [(4-methylbenzyl)thio] carbamate Preparation:

[0161] 0.2 mmol of 4-methylbenzyl mercaptan, 0.4 mmol of diethyl azodicarboxylate, 0.2 mmol of sodium iodide, 0.2 mmol of potassium carbonate, and 2 mL of ultra-dry acetonitrile were added to a 10 mL Shrek tube. The system was placed in a RLH-18CU 8-well photoreactor under room temperature and air conditions, and stirred continuously with a magnetic pole. The system was continuously irradiated with 450 nm blue light for 18 h and monitored by TLC tracking. After the reaction was completed, the reaction system was quenched with water, extracted with ethyl acetate, back-extracted with saturated brine, and dried with anhydrous sodium sulfate. The product was distilled under reduced pressure at 45 ° C. The residue was purified by rapid silica gel column chromatography (ethyl acetate: petroleum ether = 1:6) to obtain the product with a yield of 48%. The product was qualitatively analyzed by nuclear magnetic resonance, and the hydrogen and carbon spectra were tested by deuterated chloroform-d dissolution.

[0162] like Fig.29 As shown, 1 H NMR (400 MHz, CDCl3) δ 7.17 - 7.11 (m, 4H), 5.35 (s,1H), 4.17 (q, J = 7.1 Hz, 2H), 3.89 (s, 2H), 2.33 (s, 3H), 1.25 (t, J = 7.1Hz, 3H).

[0163] like Fig.30 As shown, 13 C NMR (101 MHz, CDCl3) δ 157.3, 137.1, 132.7, 129.3, 129.2, 62.5, 43.2, 21.1, 14.4.

[0164] Example 16

[0165] The ethyl (benzylthio) carbamate Preparation:

[0166] 0.2 mmol of benzyl mercaptan, 0.4 mmol of diethyl azodicarboxylate, 0.2 mmol of sodium iodide, 0.2 mmol of potassium carbonate, and 2 mL of ultra-dry acetonitrile were added to a 10 mL Shrek tube. The system was placed in a RLH-18CU 8-well photoreactor under room temperature and air conditions, and stirred continuously with a magnetic pole. The system was continuously irradiated with 450 nm blue light for 18 h and monitored by TLC tracking. After the reaction was completed, the reaction system was quenched with water, extracted with ethyl acetate, back-extracted with saturated brine, and dried with anhydrous sodium sulfate. The product was distilled under reduced pressure at 45 °C, and the residue was purified by rapid silica gel column chromatography (ethyl acetate: petroleum ether = 1:5) to obtain the product with a yield of 54%. The product was qualitatively analyzed by nuclear magnetic resonance, and the hydrogen and carbon spectra were tested by deuterated chloroform-d dissolution.

[0167] like Fig.31 As shown, 1 H NMR (400 MHz, CDCl3) δ 7.36 - 7.30 (m, 2H), 7.29 - 7.23(m, 3H), 5.34 (s, 1H), 4.16 (q, J = 7.1 Hz, 2H), 3.92 (s, 2H), 1.25 (t, J =7.1 Hz, 3H).

[0168] like Fig.32 As shown, 13 C NMR (101 MHz, CDCl3) δ 157.3, 135.9, 129.3, 128.6, 127.4, 62.5, 43.6, 14.4.

[0169] Embodiment 17

[0170] The ethyl [(4-(trifluoromethyl) benzyl) thio] carbamate Preparation:

[0171] 0.2 mmol of 4-trifluoromethylbenzyl mercaptan, 0.4 mmol of diethyl azodicarboxylate, 0.2 mmol of sodium iodide, 0.2 mmol of potassium carbonate, and 2 mL of ultra-dry acetonitrile were added to a 10 mL Shrek tube. The system was placed in a RLH-18CU 8-well photoreactor under room temperature and air conditions, and stirred continuously with a magnetic pole. The system was continuously irradiated with 450 nm blue light for 18 h and monitored by TLC tracking. After the reaction was completed, the reaction system was quenched with water, extracted with ethyl acetate, back-extracted with saturated brine, and dried with anhydrous sodium sulfate. The product was distilled under reduced pressure at 45 ° C. The residue was purified by rapid silica gel column chromatography (ethyl acetate: petroleum ether = 1:4) to obtain the product with a yield of 44%. The product was qualitatively analyzed by nuclear magnetic resonance, and the hydrogen and carbon spectra were tested by deuterated chloroform-d dissolution.

[0172] like Fig.33 As shown, 1 H NMR (400 MHz, CDCl3) δ 7.59 (d, J = 8.0 Hz, 2H), 7.38 (d, J = 7.9 Hz, 2H), 5.29 (s, 1H), 4.17 (d, J = 7.2 Hz, 2H), 3.95 (s, 2H), 1.23 (t, J = 7.1 Hz, 3H).

[0173] like Fig.34 As shown, 13C NMR (101 MHz, CDCl3) δ 157.1, 140.2, 129.8, 129.6, 129.5, 122.6 (q, J = 4..0 Hz), 125.4, 112.7, 62.7, 43.2, 14.4.

[0174] Embodiment 18

[0175] The ethyl (cyclohexylthio) carbamate Preparation:

[0176] Cyclohexyl mercaptan 0.2 mmol, diethyl azodicarboxylate 0.4 mmol, sodium iodide 0.2 mmol, potassium carbonate 0.2 mmol, and ultra-dry acetonitrile 2 mL were added to a 10 mL Shrek tube. The system was placed in a RLH-18CU 8-well photoreactor under room temperature and air conditions, and stirred continuously with a magnetic bar, irradiated with 450 nm blue light for 18 h, and monitored by TLC tracking. After the reaction was completed, the reaction system was quenched with water, extracted with dichloromethane, back-extracted with saturated brine, and dried with anhydrous sodium sulfate. The residue was distilled under reduced pressure at 45 ° C, and the residue was purified by rapid silica gel column chromatography (ethyl acetate: petroleum ether = 1:6) to obtain the product with a yield of 45%. The product was qualitatively analyzed by nuclear magnetic resonance, and the deuterated chloroform-d was dissolved to test the hydrogen spectrum and carbon spectrum.

[0177] like Fig.35 As shown, 1 H NMR (400 MHz, CDCl3) δ 5.51 (s, 1H), 4.17 (q, J = 7.1Hz, 2H), 2.88 (tt, J = 9.3, 4.0 Hz, 1H), 1.92 (dt, J = 10.2, 4.8 Hz, 2H),1.82 - 1.74 (m, 2H), 1.66 - 1.57 (m, 1H), 1.26 (t, J = 7.2 Hz, 3H), 1.30 -1.22 (m, 5H).

[0178] like Fig.36 As shown, 13 C NMR (101 MHz, CDCl3) δ 157.9, 62.4, 49.3, 30.6, 25.7, 25.6, 14.5.

[0179] Embodiment 19

[0180] The isopropyl (p-toluenethio) carbamate Preparation:

[0181] 0.2 mmol of p-toluene thiophenol, 0.4 mmol of diisopropyl azodicarboxylate, 0.2 mmol of sodium iodide, 0.2 mmol of potassium carbonate, and 2 mL of ultra-dry acetonitrile were added to a 10 mL Shrek tube. The system was placed in a RLH-18CU 8-well photoreactor under room temperature and air conditions, and stirred continuously with a magnetic bar, irradiated with 450 nm blue light for 18 h, and monitored by TLC tracking. After the reaction was completed, the reaction system was quenched with water, extracted with ethyl acetate, back-extracted with saturated brine, and dried with anhydrous sodium sulfate. The residue was distilled under reduced pressure at 45 ° C, and the residue was purified by rapid silica gel column chromatography (ethyl acetate: petroleum ether = 1:5) to obtain the product with a yield of 66%. The product was qualitatively analyzed by nuclear magnetic resonance, and the deuterated chloroform-d was dissolved to test the hydrogen spectrum and carbon spectrum.

[0182] like Fig.37 As shown, 1 H NMR (400 MHz, CDCl3) δ 7.26 (d, J = 8.2 Hz, 2H), 7.14(d, J = 7.9 Hz, 2H), 5.87 (s, 1H), 5.04 - 4.95 (m, 1H), 2.32 (s, 3H), 1.27(s, 3H), 1.25 (s, 3H).

[0183] like Fig.38 As shown, 13 C NMR (101 MHz, CDCl3) δ 156.9, 137.4, 135.6, 129.7, 126.7, 70.6, 21.9, 21.0.

[0184] Embodiment 20

[0185] The benzyl (p-toluenethio) carbamate Preparation:

[0186] 0.2 mmol of p-toluene thiophenol, 0.4 mmol of dibenzyl azodicarboxylate, 0.2 mmol of sodium iodide, 0.2 mmol of potassium carbonate, and 2 mL of ultra-dry acetonitrile were added to a 10 mL Shrek tube. The system was placed in a RLH-18CU 8-well photoreactor under room temperature and air conditions, and stirred continuously with a magnetic bar, irradiated with 450 nm blue light for 18 h, and monitored by TLC tracking. After the reaction was completed, the reaction system was quenched with water, extracted with ethyl acetate, back-extracted with saturated brine, and dried with anhydrous sodium sulfate. The residue was distilled under reduced pressure at 45 ° C. The residue was purified by rapid silica gel column chromatography (ethyl acetate: petroleum ether = 1:5) to obtain the product with a yield of 56%. The product was qualitatively analyzed by nuclear magnetic resonance, and the deuterated chloroform-d was dissolved to test the hydrogen spectrum and carbon spectrum.

[0187] like Fig.39 As shown, 1 H NMR (400 MHz, CDCl3) δ 7.35 (s, 5H), 7.26 (d, J = 8.0Hz, 2H), 7.13 (d, J = 7.9 Hz, 2H), 5.99 (brs, 1H), 5.19 (s, 2H), 2.33 (s,3H).

[0188] like Fig.40 As shown, 13 C NMR (101 MHz, CDCl3) δ 157.2, 137.7, 135.6, 135.2, 129.8, 128.5, 128.4, 128.2, 127.0, 68.4, 21.1.

[0189] The following Examples 21 to 47 have the same preparation process as Example 1, and are all used to prepare the 3a product of Example 1. The reaction conditions are shown in Table 1.

[0190]

[0191] According to the results in the above table, we can analyze:

[0192] (1) Selection of wavelength of light source in Examples 21-24

[0193] Add 0.2 mmol of p-toluene thiophenol, 0.4 mmol of diethyl azodicarboxylate, 0.2 mmol of sodium iodide, 0.2 mmol of potassium carbonate, and 2 mL of acetonitrile to a 10 mL Shrek tube. Place the system in an RLH-18CU 8-hole photoreactor under room temperature and air conditions, stir continuously with a magnetic bar, and irradiate with 450 nm (Example 21), 430 nm (Example 22), 410 nm (Example 23), and 390 nm (Example 24) blue light for 18 h, respectively, and monitor by TLC tracking; after the reaction is completed, the reaction system is quenched with water, extracted with dichloromethane, back-extracted with saturated brine, dried with anhydrous sodium sulfate, and distilled under reduced pressure at 45 ° C. The residue is purified by rapid silica gel column chromatography (ethyl acetate: petroleum ether = 1:5) to obtain the product, with corresponding yields of 90% (Example 21), 85% (Example 22), 60% (Example 23), and 45% (Example 24). The above results show that the yield is optimal when the blue light wavelength is 450nm.

[0194] (2) Screening of reaction solvents for Examples 21, 25-28

[0195] 0.2 mmol of p-toluene thiophenol, 0.4 mmol of diethyl azodicarboxylate, 0.2 mmol of sodium iodide, and 0.2 mmol of potassium carbonate were added to a 10 mL Shrek tube. Ethyl acetate (Example 25), dichloromethane (Example 26), tetrahydrofuran (Example 27), and N, N-dimethylformamide (Example 28) were used as solvents, respectively. The system was placed in a RLH-18CU8-hole photoreactor under room temperature and air conditions, and stirred continuously with a magnetic particle, irradiated with 450 nm blue light for 24 hours, and monitored by TLC tracking; after the reaction was completed, the reaction system was quenched with water, extracted with ethyl acetate, back-extracted with saturated brine, dried with anhydrous sodium sulfate, and distilled under reduced pressure at 45 ° C. The residue was purified by rapid silica gel column chromatography (ethyl acetate: petroleum ether = 1:5) to obtain the product, with corresponding yields of 74% (Example 25), 68% (Example 26), 62% (Example 27), and 26% (Example 28). The above results show that the yield is optimal when acetonitrile is used as a solvent.

[0196] (3) Screening of iodized salt in Examples 21, 29-32

[0197] Add 0.2mmol of p-toluene thiophenol, 0.4mmol of diethyl azodicarboxylate, 0.2mmol of potassium carbonate, 2mL of acetonitrile, potassium iodide (Example 29), tetrabutylammonium iodide (Example 30), N-iodosuccinimide (Example 31), and iodine (Example 32) to a 10mL Shrek tube. Place the system in a RLH-18CU 8-hole photoreactor under room temperature and air conditions, stir continuously with a magnetic particle, irradiate with 450nm blue light for 18h, and monitor by TLC tracking; after the reaction is completed, the reaction system is quenched with water, extracted with ethyl acetate, back-extracted with saturated brine, dried with anhydrous sodium sulfate, and distilled under reduced pressure at 45°C. The residue is purified by rapid silica gel column chromatography (ethyl acetate: petroleum ether = 1:5) to obtain the product, with corresponding yields of 84% (Example 29), 56% (Example 30), 64% (Example 31), and 42% (Example 32). The above results show that the yield is optimal when sodium iodide is used as the iodine salt.

[0198] (4) Screening of the amount of iodized salt used in Examples 21, 33-36

[0199] Add 0.2mmol of p-toluene thiophenol, 0.4mmol of diethyl azodicarboxylate, 0.2mmol of potassium carbonate, 2mL of acetonitrile, 0mmol of sodium iodide (Example 33), 0.1mmol of sodium iodide (Example 34), 0.3mmol of sodium iodide (Example 35), and 0.4mmol of sodium iodide (Example 36) to a 10mL Shrek tube. Place the system in a RLH-18CU 8-hole photoreactor under room temperature and air conditions, stir continuously with a magnetic particle, irradiate with 450nm blue light for 18h, and monitor by TLC tracking; after the reaction is completed, quench the reaction system with water, extract with ethyl acetate, back-extract with saturated brine, dry with anhydrous sodium sulfate, and distill under reduced pressure at 45°C. The residue is purified by rapid silica gel column chromatography (ethyl acetate: petroleum ether = 1:5) to obtain the product, with corresponding yields of 50% (Example 33), 63% (Example 34), 87% (Example 35), and 79% (Example 36). The above results show that the yield is optimal when the amount of sodium iodide is 0.2 mmol.

[0200] (5) Screening of bases in Examples 21, 37-41

[0201] To a 10 mL Shrek tube, 0.2 mmol of p-toluene thiophenol, 0.4 mmol of diethyl azodicarboxylate, 0.2 mmol of sodium iodide, 2 mL of acetonitrile, 0.2 mmol of sodium carbonate (Example 37), 0.2 mmol of lithium carbonate (Example 38), 0.2 mmol of potassium hydroxide (Example 39), 0.2 mmol of dipotassium hydrogen phosphate (Example 40), and potassium tert-butoxide (Example 41) were added. The system was placed in a RLH-18CU 8-well photoreactor under room temperature and air conditions, and continuously stirred with a magnetic pole, irradiated with 450 nm blue light for 18 h, and monitored by TLC tracking. After the reaction was completed, the reaction system was quenched with water, extracted with dichloromethane, back-extracted with saturated brine, dried with anhydrous sodium sulfate, and distilled under reduced pressure at 45 ° C. The residue was purified by rapid silica gel column chromatography (ethyl acetate: petroleum ether = 1:5) to obtain the product with corresponding yields of 76% (Example 37), 70% (Example 38), 86% (Example 39), 81% (Example 40), and 48% (Example 41). The above results show that the yield is optimal when potassium carbonate is used as the base.

[0202] (6) Screening of alkali dosage in Examples 21, 42-44

[0203] Add 0.2mmol of p-toluene thiophenol, 0.4mmol of diethyl azodicarboxylate, 0.2mmol of sodium iodide, 2mL of acetonitrile, 0.1mmol of potassium carbonate (Example 42), 0.3mmol of potassium carbonate (Example 43), and 0.4mmol of potassium carbonate (Example 44) to a 10mL Shrek tube. Place the system in an RLH-18CU 8-hole photoreactor under room temperature and air conditions, stir continuously with a magnetic particle, irradiate with 450nm blue light for 18h, and monitor by TLC tracking; after the reaction is completed, the reaction system is quenched with water, extracted with dichloromethane, back-extracted with saturated brine, dried with anhydrous sodium sulfate, and distilled under reduced pressure at 45°C. The residue is purified by rapid silica gel column chromatography (ethyl acetate: petroleum ether = 1:5) to obtain the product, with corresponding yields of 80% (Example 42), 85% (Example 43), and 83% (Example 44). The above results show that the yield is optimal when the amount of potassium carbonate is 0.2mmol.

[0204] (7) Screening of feed ratios in Examples 21, 45-47

[0205] 0.2 mmol of p-toluene thiophenol, 0.2 mmol of diethyl azodicarboxylate (Example 45), 0.6 mmol of diethyl azodicarboxylate (Example 46), 0.8 mmol of diethyl azodicarboxylate (Example 47), 0.2 mmol of sodium iodide, 2 mL of acetonitrile, and 0.2 mmol of potassium carbonate were added to a 10 mL Shrek tube. The system was placed in a RLH-18CU 8-hole photoreactor under room temperature and air conditions, and stirred continuously with a magnetic particle, irradiated with 450 nm blue light for 18 hours, and monitored by TLC tracking; after the reaction was completed, the reaction system was quenched with water, extracted with dichloromethane, back-extracted with saturated brine, dried with anhydrous sodium sulfate, and distilled under reduced pressure at 45 ° C. The residue was purified by rapid silica gel column chromatography (ethyl acetate: petroleum ether = 1:5) to obtain the product, with corresponding yields of 88% (Example 45), 90% (Example 46), and 87% (Example 47). The above results show that the yield is optimal when the feed ratio is 1:2.

[0206] Embodiment 48

[0207] The ethyl (p-tolylsulfinyl) carbamate Preparation:

[0208] Add 0.2mmol of ethyl (p-toluenethio) carbamate, 0.3mmol of m-chloroperbenzoic acid, and 5mL of dichloromethane to a 25mL round-bottom flask, and continue stirring for 2h in an ice-water bath and air conditions, and monitor by TLC tracking; after the reaction is completed, the reaction system is quenched with water, extracted with dichloromethane, back-extracted with saturated brine, dried with anhydrous sodium sulfate, and distilled under reduced pressure at 45°C. The residue is purified by rapid silica gel column chromatography (ethyl acetate: petroleum ether = 1:2) to obtain the product with a yield of 57%, and then the product is qualitatively analyzed by nuclear magnetic resonance, and the hydrogen spectrum and carbon spectrum are tested by deuterated chloroform-d dissolution.

[0209] like Fig.41 As shown, 1 H NMR (400 MHz, CDCl3) δ 7.60 (d, J = 8.3 Hz, 2H), 7.33(d, J = 8.0 Hz, 2H), 7.06 (s, 1H), 4.27 (q, J = 7.1 Hz, 2H), 2.42 (s, 3H), 1.30 (t, J = 7.1 Hz, 3H).

[0210] like Fig.42 As shown, 13 C NMR (101 MHz, CDCl3) δ 153.7, 142.6, 140.4, 130.0, 124.7, 63.1, 21.4, 14.3.

[0211] Embodiment 49

[0212] The ethyl [(cyclohexylamino) (p-tolyl) -14-sulfonimide] carbamate Preparation:

[0213] Add 0.1mmol of ethyl (p-toluenethio) carbamate, 0.2mmol of cyclohexylamine, 0.12mmol of N-bromosuccinimide, and 2mL of dichloromethane to a 25mL round-bottom flask, and continue stirring for 10min under air conditions at room temperature, and monitor by TLC tracking; after the reaction is completed, the reaction system is quenched with water, extracted with dichloromethane, back-extracted with saturated brine, and dried with anhydrous sodium sulfate, and distilled under reduced pressure at 45°C. The residue is purified by rapid silica gel column chromatography (ethyl acetate: petroleum ether = 1:5) to obtain the product with a yield of 70%, and then the product is qualitatively analyzed by nuclear magnetic resonance, and the hydrogen spectrum and carbon spectrum are tested by deuterated chloroform-d dissolution.

[0214] like Fig.43 As shown,1 H NMR (400 MHz, CDCl3) δ 7.70 (d, J = 8.3 Hz, 2H), 7.28(d, J = 8.1 Hz, 2H), 4.63 (dd, J = 5.8, 1.9 Hz, 1H), 4.11 (q, J = 7.1 Hz,2H), 3.25 (h, J = 5.0 Hz, 1H), 2.39 (s, 3H), 2.09 (dq, J = 9.8, 5.6 Hz, 1H), 1.77 - 1.63 (m, 3H), 1.59 - 1.52 (m, 1H), 1.37 - 1.18 (m, 8H).

[0215] like Fig.44 As shown, 13 C NMR (101 MHz, CDCl3) δ 165.0, 141.6, 134.3, 129.8, 127.3, 61.3, 53.3, 34.6, 34.1, 25.3, 24.6, 24.5, 21.2, 14.7.

[0216] Embodiment 50

[0217] The ethyl [(4-methylbenzyl) (p-tolyl) -14-sulfonimide] carbamate Preparation:

[0218] Add 0.1mmol of ethyl (p-toluenethio) carbamate, 0.1mmol of p-methylbenzyl bromide, 0.2mmol of potassium hydroxide, and 3mL of acetonitrile to a 25mL round-bottom flask, and continue stirring for 2h under room temperature and air conditions, and monitor by TLC tracking; after the reaction is completed, the reaction system is quenched with water, extracted with dichloromethane, back-extracted with saturated brine, and dried with anhydrous sodium sulfate, and distilled under reduced pressure at 45°C. The residue is purified by rapid silica gel column chromatography (ethyl acetate: petroleum ether = 1:2) to obtain the product with a yield of 68%, and then the product is qualitatively analyzed by nuclear magnetic resonance, and the hydrogen spectrum and carbon spectrum are tested by deuterated chloroform-d dissolution.

[0219] like Fig.45 As shown, 1 H NMR (400 MHz, CDCl3) δ 7.42 (d, J = 8.3 Hz, 2H), 7.22(d, J= 8.1 Hz, 2H), 7.04 (d, J = 8.1 Hz, 2H), 6.87 (d, J = 8.0 Hz, 2H), 4.45(d, J = 12.4 Hz, 1H), 4.11 (qd, J = 7.1, 1.4 Hz, 2H), 4.03 (d, J = 12.4 Hz,1H), 2.39 (s, 3H), 2.31 (s, 3H), 1.27 (t, J = 8.1 Hz, 3H).

[0220] like Fig.46 As shown, 13 C NMR (101 MHz, CDCl3) δ 164.9, 143.1, 138.9, 130.1, 130.5, 130.0, 129.4, 127.6, 125.3, 61.6, 57.6, 21.5, 21.2, 14.8.

Claims

1. A method for photochemically synthesizing sulfenamide compounds, characterized in that: The following steps are involved: Add thiol compounds, azodicarboxylate compounds, iodine salts and alkali into a solvent to form a reaction system, use blue light as a light source, and continuously irradiate. After the reaction is completed, post-treat the reactants to obtain sulfonamide compounds; the structural formula of the thiol compound is Formula 1, Formula 2, Formula 3, Formula 4 or Formula 5: , wherein, in Formula 1, R1 is 4-methyl, 4-hydrogen, 4-methoxy, 4-tert-butyl, 4-fluoro, 3-methyl, 3-methoxy, 3-bromo, 2-methoxy, 2-methyl or 2-chloro; in Formula 3, n=1 or 3; in Formula 4, R2 is methyl, hydrogen or trifluoromethyl; The structural formula of the azodicarboxylate compound is shown in Formula 6: , wherein, in Formula 6, the R3 is ethyl, isopropyl or benzyl; The solvent is one of ethyl acetate, dichloromethane, tetrahydrofuran, N,N-dimethylformamide and acetonitrile; The iodized salt is one of sodium iodide, potassium iodide, tetrabutylammonium iodide, and N-iodosuccinimide; The alkali is one of sodium carbonate, lithium carbonate, potassium hydroxide, dipotassium hydrogen phosphate, potassium carbonate and potassium tert-butoxide.

2. The method for photochemically synthesizing sulfenamide compounds according to claim 1, characterized in that: The molar ratio of the thiol compound to the azodicarboxylate compound is 1:(1-4); the molar ratio of the thiol compound to the iodine salt is 1:(0.5-2); and the molar ratio of the thiol compound to the base is 1:(0.5-2).

3. The method for photochemically synthesizing sulfenamide compounds according to claim 1, characterized in that: The wavelength of the blue light source is 390nm-450nm, the continuous irradiation time is 18-24h, and the reaction temperature is room temperature.

4. The method for photochemically synthesizing sulfenamide compounds according to claim 1, characterized in that: The post-treatment is to first quench with water, then extract with an organic reagent, then back-extract with saturated brine, dry with anhydrous sodium sulfate, then distill under reduced pressure, and purify with silica gel column chromatography.

5. The method for photochemically synthesizing sulfenamide compounds according to claim 4, characterized in that: The organic reagent is ethyl acetate or dichloromethane.

6. The method for photochemically synthesizing sulfenamide compounds according to claim 4, characterized in that: During the silica gel column chromatography purification, the eluent used is a mixture of ethyl acetate and petroleum ether in a volume ratio of 1:4-1:10.

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