A method for synthesizing disulfide compounds by synergistic catalysis of visible light two-dimensional olefin nanomaterials.

Abstract

This invention discloses a method for synthesizing disulfide ether compounds using visible light-emitting two-dimensional olefin nanomaterials in synergistic catalysis. The method involves mixing a thiol-containing compound with a suitable solvent, and then, under mild light conditions in the presence of a catalytic amount of two-dimensional olefin nanomaterials, achieving efficient disulfide bond construction to obtain a series of disulfide ether compounds. This invention enables the efficient synthesis of disulfide ether compounds. The catalyst used is simple to synthesize, requires low dosage, and is inexpensive. It achieves efficient conversion under mild light conditions, reducing reaction costs and simplifying post-processing steps. The synthesis reaction in this invention can be carried out at room temperature and pressure without any additional additives, exhibiting mild conditions, rapid reaction, and high yield.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of chemical synthesis, and particularly relates to a synthesis method of a disulfide compound under the presence of a two-dimensional alkenyl nanomaterial and by using light irradiation. BACKGROUND

[0002] Disulfide compounds containing S-S bonds play an important role in the fields of organic synthesis and biomaterial science, such as 1) being used as important organic reagents and intermediate compounds in synthesis reactions to synthesize sulfone compounds; 2) being used as vulcanizing agents to synthesize high-elastic bodies such as rubber and optimize the tensile strength of materials; 3) being used in drug molecules such as disulfiram and thioctic acid to play an important role in drug delivery and release; 4) being used as lubricating oil additives and widely used in the field of metal processing; 5) being used as feed additives and used to synthesize spices; and 6) being used in the biological field to have an important influence on the spatial structure of proteins, such as cysteine and homocysteine, in which the S-S bond plays an important connecting role.

[0003] Among the synthesis methods of disulfide compounds, the most commonly used method is the direct oxidation of mercaptans, however, this type of reaction needs to add a large amount of oxidizing agents such as Br2 and hydrogen peroxide, which is gradually replaced by conventional oxygen (CN101928193); in addition, disulfide compounds can also be obtained by reducing (sulfonyl) groups, and common reducing agents include molybdenum pentachloride and samarium diiodide, but the yield of the product is not ideal; the method for preparing disulfide compounds by using sulfur chloride is gradually replaced due to the instability of sulfur chloride and the high requirement for operation; the construction of C-S bond by metal catalysis is also an important way to obtain disulfide compounds (CN114989050), and halides and sulfur salts are used as starting materials, and the substrates are rich, but these routes usually require harsh reaction conditions and long reaction time, and a large amount of by-products are generated, which is not convenient for post-treatment and increases the environmental pressure.

[0004] In summary, the application provides an efficient catalytic system which can realize the synthesis of disulfide compounds with high yield, greenness and convenience. SUMMARY

[0005] The purpose of the application is to provide a synthesis method of disulfide compounds by using visible light two-dimensional alkenyl nanomaterials in cooperation with catalysis.

[0006] Technical scheme: the synthesis method of disulfide compounds by using visible light two-dimensional alkenyl nanomaterials in cooperation with catalysis provided by the application is that after a compound containing a mercapto group is mixed in a corresponding solvent, a catalytic amount of two-dimensional alkenyl nanomaterials is used to realize the efficient construction of a disulfide bond under mild light irradiation conditions, and then a series of disulfide compounds are obtained.

[0007] The specific operation steps are as follows: Add mercapto compounds, two-dimensional olefin nanomaterials and solvents to the reaction vessel, stir the reaction at room temperature and irradiate with visible light at the same time. After the reaction is completed, remove the solvent and obtain the target product lipid compound by simple separation by column chromatography.

[0008] The reaction route for this synthesis method is as follows:

[0009]

[0010] Wherein, Ar is a substituted or unsubstituted (hetero)aryl group;

[0011] The two-dimensional olefin photoelectric reagents mentioned above are quantum dots or heterojunctions of elemental selenium (Se), tellurium (Te), bismuth (Bi), antimony (Sb), black phosphorus (P), and graphyne:

[0012] The solvent is one or a mixture of several of the following: tetrahydrofuran, acetonitrile, 1,2-dichloroethane, dichloromethane, 1,4-dioxane, N,N-dimethylformamide, dimethyl sulfoxide, and toluene, preferably 1,4-dioxane.

[0013] Furthermore, the thiol compound is a substituted or unsubstituted (hetero)arylthiophenol.

[0014] Furthermore, the two-dimensional olefin photoelectric reagent is a quantum dot or heterojunction of elemental selenium (Se), tellurium (Te), bismuth (Bi), antimony (Sb), black phosphorus (P), and graphyne, preferably a bismuth (Bi) quantum dot.

[0015] Furthermore, the amount of the two-dimensional olefin photoelectric reagent is 0.5–1.5 mol%, preferably 1.0 mol%.

[0016] Furthermore, the illumination conditions are visible light, sunlight, or a 350-650nm light source, preferably a 450-460nm light source.

[0017] Furthermore, the concentration of the thiol compound is 0.2–0.5 M, preferably 0.2 M.

[0018] Furthermore, the reaction temperature is 25–35°C, preferably 25°C.

[0019] Furthermore, the reaction time is 1 to 4 hours, preferably 3 hours.

[0020] Beneficial effects: The specific advantages of this invention are as follows:

[0021] 1. This invention enables the efficient construction of disulfide bonds under light conditions in the presence of trace amounts of two-dimensional olefin nanomaterials, with mild conditions and no need for harsh conditions such as high temperature.

[0022] 2. The catalyst used in this invention is simple to synthesize, requires low dosage, and is inexpensive, which not only reduces the cost of the reaction but also simplifies the post-processing steps, making the reaction process more environmentally friendly.

[0023] 3. The synthesis method of the present invention has a fast reaction rate, high yield, and simple operation. It can be carried out at room temperature and pressure without the need for additional additives, and has certain application prospects and practical value. Attached Figure Description

[0024] Figure 1 The structure of Example 1 prepared according to the present invention 1 HNMR spectrum. Detailed Implementation

[0025] The technical solutions in the embodiments of the present invention will be clearly and completely described below, so that those skilled in the art can better understand the advantages and features of the present invention, thereby making a clearer definition of the scope of protection of the present invention. The embodiments described in this invention are only some embodiments of the present invention, not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0026] Example 1

[0027]

[0028] In a 10 mL reaction tube, 0.2 mmol of 4-chlorothiophenol and 1,4-dioxane solution of bismuth nanodots (1.0 mL, 0.002 M) were added. The mixture was stirred for 3 hours at 25 °C under a 450-460 nm light source. After the reaction was completed, the reaction system was concentrated and separated by column chromatography to obtain the target product (97%). 1 HNMR(400MHz,Chloroform-d)δ7.44-7.36(m,4H),7.31-7.26(m,4H).

[0029] Example 2

[0030]

[0031] In a 10 mL reaction tube, 0.2 mmol of thiophenol and 1,4-dioxane solution of bismuth nanoparticles (1.0 mL, 0.002 M) were added. The mixture was stirred for 3 hours at 25 °C under a 450-460 nm light source. After the reaction was completed, the reaction system was concentrated and separated by column chromatography to obtain the target product (96%). 1HNMR(400MHz,Chloroform-d)δ7.51-7.45(m,4H),7.33-7.27(m,4H),7.22-7.19(m,2H).

[0032] Example 3

[0033]

[0034] In a 10 mL reaction tube, 0.2 mmol of 4-bromothiophenol and 1,4-dioxane solution of bismuth nanoparticles (1.0 mL, 0.002 M) were added. The mixture was stirred for 3 hours at 25 °C under a 450-460 nm light source. After the reaction was completed, the reaction system was concentrated and separated by column chromatography to obtain the target product (98%). 1 HNMR (400MHz, Chloroform-d) δ 7.40 (d, J = 8.83 Hz, 4H); 7.32 (d, J = 8.40 Hz, 4H).

[0035] Example 4

[0036]

[0037] In a 10 mL reaction tube, 0.2 mmol of 4-fluorothiophenol and 1,4-dioxane solution of bismuth nanodots (1.0 mL, 0.002 M) were added. The mixture was stirred for 3 hours at 25 °C under a 450-460 nm light source. After the reaction was completed, the reaction system was concentrated and separated by column chromatography to obtain the target product (96%). 1 HNMR (400MHz, Chloroform-d) δ7.38 (d, J = 7.3 Hz, 4H); 6.81 (d, J = 9.2 Hz, 4H); 3.79 (s, 6H).

[0038] Example 5

[0039]

[0040] In a 10 mL reaction tube, 0.2 mmol of 2-fluorothiophenol and 1,4-dioxane solution of bismuth nanoparticles (1.0 mL, 0.002 M) were added. The mixture was stirred for 3 hours at 25 °C under a 450-460 nm light source. After the reaction was completed, the reaction system was concentrated and separated by column chromatography to obtain the target product (91%). 1 HNMR(400MHz,Chloroform-d)δ7.37-7.33(m,4H),6.94-6.88(m,4H).

[0041] Example 6

[0042]

[0043] In a 10 mL reaction tube, 0.2 mmol of 4-methylthiophenol and 1,4-dioxane solution of bismuth nanoparticles (1.0 mL, 0.002 M) were added. The mixture was stirred for 3 hours at 25 °C under a 450-460 nm light source. After the reaction was completed, the reaction system was concentrated and separated by column chromatography to obtain the target product (95%). 1 HNMR (400MHz, Chloroform-d) δ7.38 (d, J = 8.1 Hz, 4H), 7.10 (d, J = 7.9 Hz, 4H), 2.31 (s, 6H).

[0044] Example 7

[0045]

[0046] In a 10 mL reaction tube, 0.2 mmol of 3-methylthiophenol and 1,4-dioxane solution of bismuth nanodots (1.0 mL, 0.002 M) were added. The mixture was stirred for 3 hours at 25 °C under a 450-460 nm light source. After the reaction was completed, the reaction system was concentrated and separated by column chromatography to obtain the target product (89%). 1 HNMR(400MHz,Chloroform-d)δ7.53-7.49(m,2H),7.14-7.09(m,6H),2.42(s,6H).

Claims

1. A synthetic method for the synergistic catalytic synthesis of disulfide compounds by visible light two-dimensional alkenes nanomaterials, characterized in that: After the thiol-containing compound is mixed in the corresponding solvent, a series of disulfide compounds are obtained in the presence of a catalytic amount of two-dimensional alkenes nanomaterials; The specific operation steps are as follows: a thiol compound, a two-dimensional alkenes nanomaterial and a solvent are added to a reaction container, the reaction is stirred at room temperature while visible light is irradiated, after the reaction is completed, the solvent is removed, and the target product disulfide compound is obtained by column chromatography; The reaction route of the synthesis method is as follows: Ar is a substituted or unsubstituted aryl group; The two-dimensional alkenes nanomaterial is elemental selenium (Se), tellurium (Te), bismuth (Bi), antimony (Sb), black phosphorus (P) and graphdiyne quantum dots or heterojunctions thereof; The solvent is one or a mixture of several of tetrahydrofuran, acetonitrile, 1,2-dichloroethane, dichloromethane, 1,4-dioxane, N,N-dimethylformamide, dimethyl sulfoxide and toluene; The amount of the two-dimensional alkenes nanomaterial is 0.5-1.5 mol %; The light irradiation condition is visible light or a 350-650 nm light source.

2. The method of claim 1, wherein the visible light two-dimensional alkenes nanomaterial synergistically catalyzes the synthesis of the dithioether compound. The concentration of the thiol compound is 0.2-0.5 M.

3. The method of claim 1, wherein the visible light two-dimensional alken nanomaterial synergistically catalyzes the synthesis of a disulfide compound. The reaction temperature is 25-35℃.

4. The method of claim 1, wherein the visible light two-dimensional alken nanomaterial synergistically catalyzes the synthesis of a disulfide compound. The reaction time is 1-4 hours.

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