阅读说明：本技术 一种芳基二硒醚类有机硒化合物的绿色制备方法 (Green preparation method of aryl diselenide organic selenium compound ) 是由 王宇光 沈泓舸 李静 于 2021-08-23 设计创作，主要内容包括：本发明公开了一种芳基二硒醚化合物合成方法,所述的合成方法具体按照如下步骤进行：以式(Ⅰ)所示化合物为反应原料,CuBr为催化剂,在KOH的条件下,Se既是氧化剂又是还原剂,发生歧化反应,水或者乙醇为溶剂,于60℃进行反应。反应结束后,得到反应液经后处理(如果是乙醇便回收溶剂),得到式(Ⅱ)所示芳基二硒醚化合物,本发明产率接近100％,后续处理简单,不需要复杂的分离和提纯方法便可以获得纯的产物。如以乙醇作为溶剂便以回收溶剂。因此,此方法更加绿色、经济、高效、环保。(The invention discloses a synthesis method of an aryl diselenide compound, which is specifically carried out according to the following steps: taking a compound shown as a formula (I) as a reaction raw material, CuBr as a catalyst, carrying out disproportionation reaction under the condition of KOH by using Se as an oxidant and a reducing agent, and carrying out reaction at 60 ℃ by using water or ethanol as a solvent. After the reaction is finished, the obtained reaction liquid is subjected to post-treatment (if the reaction liquid is ethanol, the solvent is recovered), so that the aryl diselenide compound shown in the formula (II) is obtained, the yield of the invention is close to 100%, the subsequent treatment is simple, and a pure product can be obtained without a complex separation and purification method. Such as ethanol as a solvent to recover the solvent. Therefore, the method is more green, economical, efficient and environment-friendly.)

1. A green preparation method of aryl diselenide compounds shown in formula (II) is characterized by comprising the following steps:

taking a compound shown as a formula (I) and Se as reaction raw materials, taking CuBr as a catalyst, taking ethanol as a solvent under the existence of KOH, reacting for 1-4 h at 40-75 ℃, and carrying out aftertreatment on the obtained reaction liquid to obtain an aryl diselenide compound shown as a formula (II); the mass ratio of the CuBr, Se, KOH and the compound shown in the formula (I) is 5-30: 50-300: 50-200: 100, respectively;

wherein X is halogen; r is simultaneously H, C₁～C₄Alkyl, amino, methyl or methoxy, nitro.

2. The green process for preparing aryldiselenides of formula (ii) as claimed in claim 1, wherein: x is bromine or iodine.

3. The green process for preparing aryldiselenides of formula (ii) as claimed in claim 1, wherein: and R is H, amino, methyl, methoxy or nitro.

4. The green process for preparing aryldiselenides of formula (ii) as claimed in claim 1, wherein: the compound shown in the formula (I) is one of the following compounds:

5. the green process for preparing aryldiselenides of formula (ii) as claimed in claim 1, wherein: the reaction was carried out at 60 ℃ for 2 h.

6. The green process for preparing aryldiselenides of formula (ii) as claimed in claim 1, wherein: the mass ratio of the CuBr to the compound shown in the formula (I) is 10: 100.

7. The green process for preparing aryldiselenides of formula (ii) as claimed in claim 1, wherein: the ratio of the amount of said Se species to the amount of said compound of formula (I) species is 125: 100.

8. the green process for preparing aryldiselenides of formula (ii) as claimed in claim 1, wherein: the ratio of the amount of species of KOH to the amount of species of compound of formula (I) is 150: 100.

9. the green process for preparing aryldiselenides of formula (ii) as claimed in claim 1, wherein: the volume of ethanol is 0.5mL/mmol based on the amount of the substance of the compound represented by the formula (I).

10. The green process for preparing aryldiselenides of formula (ii) as claimed in claim 1, wherein said post-treatment comprises: filtering the reaction solution, washing a filter cake with ethanol, combining filtrates, evaporating the ethanol, adding water for dissolution, extracting with ethyl acetate, combining organic phases, and removing an organic phase solvent by rotary evaporation to obtain a crude product with a volume ratio of 30: 1 n-hexane: and (3) performing column chromatography by using ethyl acetate as an eluent, collecting the eluent containing the target product, and evaporating the eluent to obtain the aryl diselenide compound shown in the formula (II).

(I) technical field

The invention relates to a green preparation method of aryl diselenide organic selenium compounds.

(II) background of the invention

The aryl diselenide compound is an important existing form of the organic selenium compound, has unique advantages in the conversion and modification of organic matter functional groups, is an important precursor for synthesizing various organic selenium compounds, and can be easily converted into other selenium-containing functional groups to prepare various selenium reagents. For example, Tingoli in 1995 reported a novel process for the preparation of a series of phenylarylyne selenide products from diphenyldiselenide catalyzed by iodobenzene diacetate in dichloromethane using phenylacetylene as a substrate (reaction a). Sharma et al developed another novel catalyst system of CuI (10 mol%)/imidazole (10 mol%), synthesizing alkynyl selenide from alkynyl bromide and different substituent group diaryl diselenides with Mg as additive, a mild, convenient, and efficient (yield 51-89%) synthetic method (reaction b). Zhao et al found that a nitroso compound can be obtained by oxidizing primary aromatic amine with diphenyl diselenide and hydrogen peroxide, and that an oxazine compound can be prepared by a one-pot hetro Diels-Alder reaction (reaction c). Besides being used as a precursor for synthesizing various organic selenium reagents, the aryl diselenide has Se-Se bond with other biological activity, and a plurality of diselenide compounds are widely used in disinfectants and antibacterial agents; even has good application in modifier in rubber production and solid phase separation of photoconductive materials.

The existing synthesis methods of aryl diselenide compounds mainly comprise a lithiation method, an aryl diazonium salt method, a Grignard reagent method, a carbonyl compound method and the like. But has the defects of complex and harsh reaction conditions, difficult recovery of reaction solvent, environmental harm and the like. For example, KWan-Yue Jen produces lithium aryl selenide by starting with aryl lithium (which is very harsh to prepare and use) and selenium under anhydrous and oxygen-free conditions. Then reacting with N, N-dimethyl amino sulfonyl chloride to obtain corresponding aryl selenium substituted N, N-dimethyl sulfonamide, hydrolyzing in potassium hydroxide alcoholic solution, neutralizing most of alkali with acetic acid, and adding potassium ferricyanide to obtain corresponding diselenide. (Jen K Y, Cava M P. improved synthesis of aromatic semiconductors. the Journal of Organic Chemistry,1983,48(9):1449 to 1451). Obviously, the raw material reagent used in the method is expensive and not easy to obtain, the reaction condition is harsh, the reaction process is complex and the operation is not easy.

The aryl diazonium salt method is characterized in that explosive aryl diazonium salt (prepared by aryl diazotization reaction) and potassium selenocyanide (toxic and expensive) react to form aryl selenocyanide, and then diaryl diselenide is generated by hydrolysis in sodium methoxide strong base.

The grignard reagent method is a commonly used method for synthesizing aryl diselenide at present (wangtang army, research on synthesis of organic selenide by selenium grignard reagent, river-south university, 2007.) and adopts halogenated aromatic hydrocarbon to react with magnesium powder under anhydrous and anaerobic conditions to prepare aryl magnesium halide grignard reagent, then aryl selenol is prepared by selenium insertion and acidification, and finally aryl diselenide is prepared by oxidation.

The carbonyl compound method is a method for preparing diselenide from carbonyl and aryl compounds (A new and simple synthesis of alkyl, cycloalkyl and aryl discoides from aliphatic and aryl aldehydes, aliphatic ketones and cycloketones, J.Org.Chem.1977,42(14): 2510) -2511.) using pyridine and triethylamine as solvents, H₂Se gas reacts with aldehyde ketone to prepare diselenide, but the reaction time is too long, the length of individual substrate reaches 10 days, and the greatest defect is that the raw material H is₂Se is relatively high in preparation cost, is a toxic gas and is not easy to operate, so that the use of the method is limited to a certain extent.

Therefore, it is important to find a green, economic, efficient, environment-friendly and simple synthesis method.

Disclosure of the invention

In order to overcome the defects of high cost, difficult operation, serious pollution and the like in the prior art, the invention provides a green preparation method of an aryl diselenide organic selenium compound in an ethanol phase. The method has the advantages of cheap and easily available raw materials, simple and rapid reaction process, environmental protection and the like.

In order to achieve the purpose, the technical scheme of the invention is as follows:

the invention provides a green preparation method of an aryl diselenide compound shown as a formula (II), which comprises the following steps:

taking a compound shown in a formula (I) and Se as reaction raw materials, taking CuBr as a catalyst, taking ethanol as a solvent under the existence of KOH, reacting for 1-4 h (preferably 2h) at 40-75 ℃ (preferably 60 ℃), and carrying out aftertreatment on the obtained reaction liquid to obtain an aryl diselenide compound shown in a formula (II); the mass ratio of the CuBr, Se, KOH and the compound shown in the formula (I) is 5-30: 50-300: 50-200: 100 (preferably 10: 125: 150: 100);

wherein, X is halogen (preferably bromine, iodine); r is simultaneously H, C₁～C₄Alkyl, amino, methyl, methoxy or nitro.

Preferably, R is H, amino, methyl or methoxy, nitro.

Further preferably, the compound of formula (I) is one of the following:

further, the volume of ethanol was 0.5mL/mmol based on the amount of the substance of the compound represented by the formula (I).

The progress of the reaction of the present invention can be monitored by a conventional method, for example, TLC is used to monitor the completion of the reaction of the starting compound of formula (I) to determine the time point of the completion of the reaction; the reaction time is usually 1-4 h.

Further, the post-treatment method of the invention comprises the following steps: filtering the reaction solution, washing a filter cake with ethanol, combining filtrates, evaporating the ethanol, adding water for dissolving, extracting with ethyl acetate, combining organic phases, and performing rotary evaporation to remove an organic phase solvent (evaporating to dryness as far as possible by naked eyes), wherein the volume ratio of the obtained crude product is 30: 1 n-hexane: and (3) performing column chromatography by using ethyl acetate as an eluent, collecting the eluent containing the target product, and evaporating the eluent to obtain the aryl diselenide compound shown in the formula (II).

Compared with the prior art, the invention has the beneficial effects that:

(1) the preparation method of the aryl diselenide compound provided by the invention has a short synthetic route and only needs one step; the operation process is simple and the yield is high.

(2) The method has the advantages that the reaction does not need anhydrous and anaerobic conditions and high-temperature conditions, the reaction can be carried out under mild conditions, the reaction time is short, and the reaction can be completed within 2 hours.

(3) The selenium powder is directly used as a selenium source, and compared with other selenium sources, the selenium powder has the remarkable advantages of low price, no toxicity and no odor, is green and environment-friendly, and is more convenient for experiment or large-scale production operation.

(4) Among organic solvents, ethanol is a product of sugar metabolism of organisms, is almost non-toxic and is considered as a green solvent by chemists; the method provided by the invention takes ethanol as a reaction medium, and the ethanol is easy to be added, recycled and reused after reaction. In a word, compared with the prior art, the method of the invention is economical, efficient, green and environment-friendly.

(IV) detailed description of the preferred embodiments

The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto.

Example 1: preparation of diphenyl diselenide compound II-1

The reaction formula is as follows:

99mg (1.25mmol) of selenium powder, 84mg (1.5mmol) of potassium hydroxide and 14mg (0.1mmol) of cuprous bromide are added into a reaction flask, 0.5mL of ethanol is added, 157mg of bromobenzene (1mmol) I-1 is added into the reaction flask under stirring, and the reaction is stopped after 2 hours at 60 ℃. Filtering, washing the filter cake with 1mL of ethanol, combining the filtrates, evaporating the ethanol, adding 3mL of water, extracting with ethyl acetate (2 mL. times.2) for 2 times, combining the organic phases, evaporating the ethyl acetate with a rotary evaporator, and purifying the residue by column chromatography, wherein the eluent is n-hexane: ethyl acetate 30: 1, collecting the eluent containing the target product, and evaporating the eluent to obtain the diphenyl diselenide compound II-1142 mg with the yield of 91%. The purity was 98.3% by GC. The structure of the compound of formula II-1 is characterized as follows:

¹H NMR(500MHz,CDCl₃)δ7.70-7.60(m,4H),7.33-7.25(m,6H)；¹³C NMR(126MHz,CDCl₃)δ131.53,130.92,129.17,127.71.GC-MS(EI):m/z 313.9[M+].

example 2: preparation of di-p-methylphenyl diselenide compound II-2

The reaction formula is as follows:

99mg (1.25mmol) of selenium powder, 84mg (1.5mmol) of potassium hydroxide and 14mg (0.1mmol) of cuprous bromide are added into a reaction flask, 0.5mL of ethanol is added, 218mg of 4-iodotoluene (1mmol) I-2 is added into the reaction flask under stirring, and the reaction is stopped after 2 hours at 60 ℃. Filtering, washing the filter cake with 1mL of ethanol, combining the filtrates, evaporating off the ethanol, adding 3mL of water, extracting with ethyl acetate (2mL × 2) 2 times, combining the organic phases, evaporating off the ethyl acetate with a rotary evaporator, purifying the residue by column chromatography, and eluting with n-hexane: ethyl acetate 30: 1, collecting eluent containing a target product, and evaporating the eluent to obtain a ditolyl diselenide compound II-2141 mg with the yield of 83%. The purity was 97.5% by GC. The structure of the compound of formula II-4 is characterized as follows:

¹H NMR(500MHz,CDCl₃)δ7.54(d,4H,J＝7.6Hz),7.12(d,4H,J＝7.6Hz),2.37(s,6H).¹³C NMR(126MHz,CDCl₃)δ138.04,133.37,132.32,129.41,21.14.GC-MS(EI):m/z 341.9[M+].

example 3: preparation of di-o-methylphenyl diselenide compound II-3

The reaction formula is as follows:

99mg (1.25mmol) of selenium powder, 84mg (1.5mmol) of potassium hydroxide and 14mg (0.1mmol) of cuprous bromide are added into a reaction flask, 0.5mL of ethanol is added, 218mg of 2-iodotoluene (1mmol) I-3 is added into the reaction flask under stirring, and the reaction is stopped after 2 hours at 60 ℃. Filtering, washing the filter cake with 1mL of ethanol, combining the filtrates, evaporating off the ethanol, adding 3mL of water, extracting with ethyl acetate (2mL × 2) 2 times, combining the organic phases, evaporating off the ethyl acetate with a rotary evaporator, purifying the residue by column chromatography, and eluting with n-hexane: ethyl acetate 30: 1, collecting the eluent containing the target product, and evaporating the eluent to obtain diphenyl diselenide compound II-3134 mg with the yield of 79%. The purity was 98.7% by GC. The structure of the compound of formula II-3 is characterized as follows:

¹H NMR(500MHz,CDCl₃)δ7.88-7.90(m,2H),7.46-6.59(m,6H),2.40(s,6H).¹³C NMR(126MHz,CDCl₃)δ138.68,132.43,130.31,129.81,128.57,126.7121.64.GC-MS(EI):m/z 341.9[M+].

example 4: preparation of di-p-methoxyphenyl diselenide compound II-4

The reaction formula is as follows:

99mg (1.25mmol) of selenium powder, 84mg (1.5mmol) of potassium hydroxide and 14mg (0.1mmol) of cuprous bromide are added into a reaction bottle, 0.5mL of ethanol is added, 234mg of 4-iodoanisole (1mmol) I-4 is added into the reaction bottle under the stirring state, the reaction is carried out for 2 hours at the temperature of 60 ℃, and the reaction is stopped. Filtering, washing the filter cake with 1mL of ethanol, combining the filtrates, evaporating the ethanol, adding 3mL of water, extracting with ethyl acetate (2 mL. times.2) for 2 times, combining the organic phases, evaporating the ethyl acetate with a rotary evaporator, and purifying the residue by column chromatography, wherein the eluent is n-hexane: ethyl acetate 30: 1, collecting the eluent containing the target product, and evaporating the eluent to obtain the diphenyl diselenide compound II-4162 mg. The yield was 87%. The purity was 99.1% by GC. The structure of the compound of formula II-4 is characterized as follows:

¹H NMR(500MHz,CDCl₃)δ7.60-7.53(m,4H),6.73-6.66(m,4H),3.79(s,6H)；¹³C NMR(126MHz,CDCl₃)δ159.48,138.19,116.37,82.68,55.31.GC-MS(EI):m/z 373.9[M+].

example 5: preparation of di-o-methoxyphenyl diselenide compound II-5

The reaction formula is as follows:

99mg (1.25mmol) of selenium powder, 84mg (1.5mmol) of potassium hydroxide and 14mg (0.1mmol) of cuprous bromide are added into a reaction bottle, 0.5mL of ethanol is added, 234mg of 2-iodoanisole (1mmol) I-5 is added into the reaction bottle under the stirring state, the reaction is carried out for 2 hours at the temperature of 60 ℃, and the reaction is stopped. Filtering, washing the filter cake with 1mL of ethanol, combining the filtrates, evaporating the ethanol, adding 3mL of water, extracting with ethyl acetate (2 mL. times.2) for 2 times, combining the organic phases, evaporating the ethyl acetate with a rotary evaporator, and purifying the residue by column chromatography, wherein the eluent is n-hexane: ethyl acetate 30: 1, collecting the eluent containing the target product, and evaporating the eluent to obtain the diphenyl diselenide compound II-5158 mg with the yield of 85 percent. The purity was 98.6% by GC. The structure of the compound of formula II-5 is characterized as follows:

¹H NMR(500MHz,CDCl₃)δ7.80(dq,J＝7.9,1.7Hz,2H),7.32(ddt,J＝9.4,7.9,1.7Hz,2H),6.84(dd,J＝8.3,1.8Hz,2H),6.73(tq,J＝7.7,1.5Hz,2H),3.91-3.88(m,6H),¹³C NMR(126MHz,CDCl3)δ158.09,139.49,129.55,122.53,111.07,86.04,56.32.GC-MS(EI):m/z 373.9[M+].

example 6: preparation of di-m-methoxyphenyl diselenide compound II-6

The reaction formula is as follows:

99mg (1.25mmol) of selenium powder, 84mg (1.5mmol) of potassium hydroxide and 14mg (0.1mmol) of cuprous bromide are added into a reaction bottle, 0.5mL of ethanol is added, 234mg of 3-iodoanisole (1mmol) I-6 is added into the reaction bottle under the stirring state, the reaction is carried out for 2 hours at the temperature of 60 ℃, and the reaction is stopped. Filtering, washing the filter cake with 1mL of ethanol, combining the filtrates, evaporating the ethanol, adding 3mL of water, extracting with ethyl acetate (2 mL. times.2) for 2 times, combining the organic phases, evaporating the ethyl acetate with a rotary evaporator, and purifying the residue by column chromatography, wherein the eluent is n-hexane: ethyl acetate 30: 1, collecting the eluent containing the target product, and evaporating the eluent to obtain diphenyl diselenide compound II-6160 mg with the yield of 86%. The purity was 97.8% by GC. The structure of compound II-6 is characterized as follows:

¹H NMR(500MHz,CDCl₃)δ7.33-7.19(m,6H),6.85-6.74(m,2H),3.75(s,6H)；¹³C NMR(126MHz,CDCl₃)δ159.75,131.74,129.83,123.40,116.46,113.72,55.20；GC-MS(EI):m/z 373.9[M+].

example 7: preparation of di-p-nitrophenyl diselenide compound II-7

The reaction formula is as follows:

99mg (1.25mmol) of selenium powder, 84mg (1.5mmol) of potassium hydroxide and 14mg (0.1mmol) of cuprous bromide are added into a reaction bottle, and then0.5mL of ethanol was added, and 249mg of 4-nitroiodobenzene (1mmol) I-7 was added to the reaction flask with stirring, and the reaction was stopped at 60 ℃ for 2 hours. Filtering, washing the filter cake with 1mL of ethanol, combining the filtrates, evaporating the ethanol, adding 3mL of water, extracting with ethyl acetate (2 mL. times.2) for 2 times, combining the organic phases, evaporating the ethyl acetate with a rotary evaporator, and purifying the residue by column chromatography, wherein the eluent is n-hexane: ethyl acetate 30: 1, collecting the eluent containing the target product, and evaporating the eluent to obtain diphenyl diselenide compound II-7189 mg with the yield of 94%. The purity was 98.6% by GC. The structure of the compounds of formula II-7 is characterized as follows:¹H NMR(500MHz,CDCl₃)δ8.18(d,J＝8.6Hz,4H),7.65(d,J＝8.6Hz,4H)；¹³C NMR(126MHz,CDCl₃)δ147.64,138.92,130.51,124.28；GC-MS(EI):m/z 403.9[M+].

example 8: preparation of di-o-aminophenyl diselenide compound II-8

The reaction formula is as follows:

99mg (1.25mmol) of selenium powder, 84mg (1.5mmol) of potassium hydroxide and 14mg (0.1mmol) of cuprous bromide are added into a reaction bottle, 0.5mL of ethanol is added, 219mg of 2-iodoaniline (1mmol) I-6 is added into the reaction bottle under stirring, and the reaction is stopped after 2 hours at 60 ℃. Filtering, washing the filter cake with 1mL of ethanol, combining the filtrates, evaporating the ethanol, adding 3mL of water, extracting with ethyl acetate (2 mL. times.2) for 2 times, combining the organic phases, evaporating the ethyl acetate with a rotary evaporator, and purifying the residue by column chromatography, wherein the eluent is n-hexane: ethyl acetate 30: 1, collecting the eluent containing the target product, and evaporating the eluent to obtain diphenyl diselenide compound II-8152 mg with the yield of 89%. The purity was 97.9% by GC. The structure of the compounds of formula II-8 is characterized as follows:

¹H NMR(600MHz,CDCl₃)δ7.38(dd,J＝7.7,1.5Hz,2H),7.19-7.15(m,2H),6.74(dd,J＝8.0,1.4Hz,2H),6.59(td,J＝7.4,1.4Hz,2H),4.29(s,4H).¹³C NMR(151MHz,CDCl₃)δ148.83,138.30,131.52,118.42,115.01,114.76.GC-MS(EI):m/z 343.9[M+].

example 9: preparation of di-p-methylphenyl diselenide compound II-2

The reaction formula is as follows:

3.96mg (5.0mmol) of selenium powder and 336mg (6.0mmol) of potassium hydroxide are added into a reaction bottle, then 2.0mL of ethanol is added, the mixture is stirred and reacted for 15min, then 84mg (0.6mmol) of cuprous bromide is added into the reaction bottle, 872mg (4mmol) of 4-iodotoluene I-2 is added into the reaction bottle after 5min, the reaction is carried out for 4h at the temperature of 60 ℃, and the reaction is stopped. The ethanol (which can be used in the next batch) is evaporated, 12mL of water is added, the reaction solution is extracted 2 times with ethyl acetate (8mL × 2), the organic phases are combined, the ethyl acetate is evaporated by a rotary evaporator, and the residue is purified by column chromatography, the eluent is n-hexane: ethyl acetate 30: 1, collecting the eluent containing the target product, and evaporating the eluent to obtain a ditolyl diselenide compound II-2612 mg with the yield of 90 percent. The purity was 97.4% by GC.

Example 10: preparation of diphenyl diselenide compound II-1

The reaction formula is as follows:

99mg (1.25mmol) of selenium powder, 84mg (1.5mmol) of potassium hydroxide and 7mg (0.05mmol) of cuprous bromide are added into a reaction flask, 0.5mL of ethanol is added, 157mg of bromobenzene (1mmol) I-1 is added into the reaction flask under stirring, and the reaction is stopped after 2 hours at 60 ℃. Filtering, washing the filter cake with 1mL of ethanol, combining the filtrates, evaporating the ethanol, adding 3mL of water, extracting with ethyl acetate (2 mL. times.2) for 2 times, combining the organic phases, evaporating the ethyl acetate with a rotary evaporator, and purifying the residue by column chromatography, wherein the eluent is n-hexane: ethyl acetate 30: 1, collecting the eluent containing the target product, and evaporating the eluent to obtain diphenyl diselenide compound II-1122 mg with the yield of 78%. The purity was 98.6% by GC.

Example 11: preparation of diphenyl diselenide compound II-1

The reaction formula is as follows:

99mg (1.25mmol) of selenium powder, 84mg (1.5mmol) of potassium hydroxide and 6.4mg (0.1mmol) of copper were charged into a reaction flask, 0.5mL of ethanol was further added, 157mg of bromobenzene (1mmol) I-1 was added to the reaction flask under stirring, and the reaction was stopped after reacting at 60 ℃ for 2 hours. Filtering, washing the filter cake with 1mL of ethanol, combining the filtrates, evaporating the ethanol, adding 3mL of water, extracting with ethyl acetate (2 mL. times.2) for 2 times, combining the organic phases, evaporating the ethyl acetate with a rotary evaporator, and purifying the residue by column chromatography, wherein the eluent is n-hexane: ethyl acetate 30: 1, collecting the eluent containing the target product, and evaporating the eluent to obtain diphenyl diselenide compound II-1131 mg with the yield of 84%. The purity was 97.7% by GC.

Example 12: preparation of diphenyl diselenide compound II-1

The reaction formula is as follows:

99mg (1.25mmol) of selenium powder, 84mg (1.5mmol) of potassium hydroxide and 22mg (0.1mmol) of copper bromide are added into a reaction flask, 0.5mL of ethanol is added, 157mg of bromobenzene (1mmol) I-1 is added into the reaction flask under stirring, and the reaction is stopped after 2 hours at 60 ℃. Filtering, washing the filter cake with 1mL of ethanol, combining the filtrates, evaporating the ethanol, adding 3mL of water, extracting with ethyl acetate (2 mL. times.2) for 2 times, combining the organic phases, evaporating the ethyl acetate with a rotary evaporator, and purifying the residue by column chromatography, wherein the eluent is n-hexane: ethyl acetate 30: 1, collecting the eluent containing the target product, and evaporating the eluent to obtain diphenyl diselenide compound II-1133 mg with the yield of 85 percent. The purity was 95.5% by GC.

Example 13: preparation of diphenyl diselenide compound II-1

The reaction formula is as follows:

99mg (1.25mmol) of selenium powder, 56mg (1mmol) of potassium hydroxide and 14mg (0.1mmol) of cuprous bromide are added into a reaction flask, 0.5mL of ethanol is added, 157mg of bromobenzene (1mmol) I-1 is added into the reaction flask under stirring, and the reaction is stopped after 2 hours at 60 ℃. Filtering, washing the filter cake with 1mL of ethanol, combining the filtrates, evaporating the ethanol, adding 3mL of water, extracting with ethyl acetate (2 mL. times.2) for 2 times, combining the organic phases, evaporating the ethyl acetate with a rotary evaporator, and purifying the residue by column chromatography, wherein the eluent is n-hexane: ethyl acetate 30: 1, collecting the eluent containing the target product, and evaporating the eluent to obtain the diphenyl diselenide compound II-1123 mg with the yield of 79%. The purity was 97.4% by GC.

Example 14: preparation of diphenyl diselenide compound II-1

The reaction formula is as follows:

99mg (1.25mmol) of selenium powder, 168mg (3.0mmol) of potassium hydroxide and 14mg (0.1mmol) of cuprous bromide are added into a reaction flask, 0.5mL of ethanol is added, 157mg of bromobenzene (1mmol) I-1 is added into the reaction flask under stirring, and the reaction is stopped after 2 hours at 60 ℃. Filtering, washing the filter cake with 1mL of ethanol, combining the filtrates, evaporating the ethanol, adding 3mL of water, extracting with ethyl acetate (2 mL. times.2) for 2 times, combining the organic phases, evaporating the ethyl acetate with a rotary evaporator, and purifying the residue by column chromatography, wherein the eluent is n-hexane: ethyl acetate 30: 1, collecting the eluent containing the target product, and evaporating the eluent to obtain the diphenyl diselenide compound II-1117 mg with the yield of 75%. The purity was 98.2% by GC.

Example 15: preparation of diphenyl diselenide compound II-1

The reaction formula is as follows:

99mg (1.25mmol) of selenium powder, 152mg (1.5mmol) of triethylamine and 14mg (0.1mmol) of cuprous bromide are added into a reaction flask, 0.5mL of ethanol is added, 157mg of bromobenzene (1mmol) I-1 is added into the reaction flask under stirring, and the reaction is carried out at 60 ℃ for 2 hours. The reaction solution was detected by GC-MS, and no formation of the target product II-1 was observed.

Example 16: preparation of diphenyl diselenide compound II-1

The reaction formula is as follows:

99mg (1.25mmol) of selenium powder, 207mg (1.5mmol) of potassium carbonate and 14mg (0.1mmol) of cuprous bromide are added to a reaction flask, 0.5mL of ethanol is added, 157mg of bromobenzene (1mmol) I-1 is added to the reaction flask under stirring, and the reaction is carried out at 60 ℃ for 2 hours. The reaction solution was detected by GC-MS, and no formation of the target product II-1 was observed.

Example 17: preparation of diphenyl diselenide compound II-1

The reaction formula is as follows:

99mg (1.25mmol) of selenium powder, 84mg (1.5mmol) of potassium hydroxide and 14mg (0.1mmol) of cuprous bromide are added into a reaction bottle, 0.5mL of ethanol is added, 204mg of iodobenzene (1mmol) I-9 is added into the reaction bottle under stirring, and the reaction is stopped after 2 hours of reaction at 60 ℃. Filtering, washing the filter cake with 1mL of ethanol, combining the filtrates, evaporating the ethanol, adding 3mL of water, extracting with ethyl acetate (2 mL. times.2) for 2 times, combining the organic phases, evaporating the ethyl acetate with a rotary evaporator, and purifying the residue by column chromatography, wherein the eluent is n-hexane: ethyl acetate 30: 1, collecting the eluent containing the target product, and evaporating the eluent to obtain diphenyl diselenide compound II-1150 mg with the yield of 96%. The purity was 99.1% by GC. The structure of the compound of formula II-1 is characterized as follows:

¹H NMR(500MHz,CDCl₃)δ7.71-7.61(m,4H),7.34-7.26(m,6H)；¹³C NMR(126MHz,CDCl₃)δ131.54,130.93,129.18,127.72.GC-MS(EI):m/z 313.9[M+].

example 18: preparation of diphenyl diselenide compound II-1

The reaction formula is as follows:

99mg (1.25mmol) of selenium powder, 84mg (1.5mmol) of potassium hydroxide and 14mg (0.1mmol) of cuprous bromide are added into a reaction bottle, 0.5mL of ethanol is added, 204mg of iodobenzene (1mmol) I-9 is added into the reaction bottle under stirring, and the reaction is stopped after 4 hours of reaction at 40 ℃. Filtering, washing the filter cake with 1mL of ethanol, combining the filtrates, evaporating the ethanol, adding 3mL of water, extracting with ethyl acetate (2 mL. times.2) for 2 times, combining the organic phases, evaporating the ethyl acetate with a rotary evaporator, and purifying the residue by column chromatography, wherein the eluent is n-hexane: ethyl acetate 30: 1, collecting the eluent containing the target product, and evaporating the eluent to obtain diphenyl diselenide compound II-1124 mg with the yield of 80%. The purity was 96.0% by GC.

Example 19: preparation of diphenyl diselenide compound II-1

The reaction formula is as follows:

99mg (1.25mmol) of selenium powder, 84mg (1.5mmol) of potassium hydroxide and 14mg (0.1mmol) of cuprous bromide are added into a reaction bottle, 0.5mL of ethanol is added, 204mg of iodobenzene (1mmol) I-9 is added into the reaction bottle under stirring, and the reaction is stopped after 1 hour of reaction at 75 ℃. Filtering, washing the filter cake with 1mL of ethanol, combining the filtrates, evaporating the ethanol, adding 3mL of water, extracting with ethyl acetate (2 mL. times.2) for 2 times, combining the organic phases, evaporating the ethyl acetate with a rotary evaporator, and purifying the residue by column chromatography, wherein the eluent is n-hexane: ethyl acetate 30: 1, collecting the eluent containing the target product, and evaporating the eluent to obtain diphenyl diselenide compound II-1137 mg with the yield of 88%. The purity was 95.1% by GC.

Example 20: preparation of diphenyl diselenide compound II-1

The reaction formula is as follows:

99mg (1.25mmol) of selenium powder, 84mg (1.5mmol) of potassium hydroxide and 14mg (0.1mmol) of cuprous bromide are added into a reaction flask, 0.5mL of water is added, 157mg of bromobenzene (1mmol) I-1 is added into the reaction flask under stirring, and the reaction is stopped after 2 hours at 60 ℃. The reaction solution was detected by GC-MS, and no formation of the target product II-1 was observed.