CN112250608A - Synthetic method of 2-phenylacetylene selenol compound - Google Patents
Synthetic method of 2-phenylacetylene selenol compound Download PDFInfo
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Abstract
The invention relates to a synthesis method of 2-phenylacetylene selenol compounds, which takes phenylpropanoic acid, selenium powder and epoxy compounds as reaction raw materials under the air condition, takes water as reaction solvent, and obtains the 2-phenylacetylene selenol compounds through series reaction under the combined promotion action of a copper catalyst, a ligand, a phase transfer catalyst and alkali. The method has the advantages of mild and simple reaction conditions, cheap and easily-obtained substrate, high yield and purity of the product, development of a new synthetic route and method for the 2-phenylacetylene selenol compound, and good application potential and research value.
Description
Technical Field
The invention belongs to the technical field of organic compound synthesis, and particularly relates to a synthesis method of a 2-phenylacetylene selenol compound.
Background
Alkynyl selenoethers as core backbones are widely found in natural products, antibiotics, antioxidant drug molecules and candidate anticancer drugs with important biological activities. In addition, the alkynyl selenide compound can also be subjected to bifunctional reaction to obtain a multifunctional alkenyl selenide compound, and the late structure modification of a target product of the alkynyl selenide compound brings more possibility for discovery of innovative medicines. Therefore, the exploration of the efficient construction of the alkynyl selenide compounds from simple and easily obtained raw materials becomes one of the hot spots of the current organic chemistry, pharmaceutical chemistry and material science research. In 2017, a Brindaban C.Ranu subject group (N.Mukherjcc, D.Kundu, B.C.Ranu, adv.Synth.Catal., 2017, 359, 329.) reports that copper catalyzes the decyanation and decarboxylation coupling reaction of phenylpropanoic acid and an electrophilic reagent, namely selenium cyanobenzene, so as to synthesize the alkynyl selenium ether compound, however, the selenium cyanobenzene used in the research method needs to be prepared in advance and the synthesis cost is high; in 2018, professor "easy writing" of Nanjing technology university (org. chem. front., 2018, 5, 428-. In addition, in 2018 professor panying (j.chen, s. -x.su, d. -c.hu, f. -h.cui, y. -l.xu, y. -y.chen, x. -l.ma, y. -m.pan, y.liang, Asian j.org.chem., 2018, 7, 892.) also reported that copper catalyzed the decarboxylation polyselenidation reaction of phenylpropanoic acid with diselenide. Although these techniques provide an efficient synthetic route for the synthesis of the alkynyl selenide compound, most of these methods have the disadvantages of raw material preparation in advance, use of expensive silver oxidant, poor tolerance of functional group, narrow substrate range, etc. Therefore, it is very important to prepare alkynyl alkyl selenide derivatives from raw materials which are simple and easy to process and have cheap and easily-obtained substrates, especially from reactions for preparing 2-phenylacetylene selenol compounds by using the tandem reaction of phenylpropanoic acid, epoxy compounds and selenium powder, which have not been reported so far, and the needs of continuous research and exploration still exist, which is the basis and the power for completing the invention.
Disclosure of Invention
The technical problem to be solved by the invention is the problem of the synthetic route of the 2-phenylacetylene selenol compound.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation method of 2-phenylacetylene selenol compounds comprises the steps of taking phenylpropanoic acid, selenium powder and epoxy compounds as reaction raw materials under the air condition, taking water as a reaction solvent, and obtaining the 2-phenylacetylene selenol compounds through a series reaction under the combined promotion action of a copper catalyst, a ligand, a phase transfer catalyst and alkali;
the above reaction process can be represented by the following reaction formula:
the molar ratio of the phenylpropanoic acid to the epoxy compound to the selenium powder is 1: 3.
(1) Transition metal copper catalyst
The transition metal copper catalyst in the invention is cupric acetate, cupric chloride, cupric bromide or cuprous iodide, preferably cupric chloride, and the dosage of the cupric chloride is 10 percent of that of the phenylpropanoic acid by mol.
(2) Ligands
The ligand in the invention is triphenylphosphine, tricyclohexylphosphine, 1, 10-phenanthroline or 2, 2' -bipyridine, preferably 1, 10-phenanthroline, and the dosage of the ligand is 10% of that of the phenylpropanoic acid by mol.
(3) Phase transfer catalyst
The phase transfer catalyst in the present invention is tetrabutylammonium chloride, chloride or iodide, preferably tetrabutylammonium iodide, in a molar ratio of 2: 1 to phenylpropanoic acid.
(4) Alkali
The alkali in the invention is at least one of cesium carbonate, potassium carbonate, sodium carbonate, potassium phosphate or sodium phosphate, preferably cesium carbonate, and the molar ratio of the alkali to the phenylpropargylic acid is 3: 1.
(6) Reaction temperature
In the production process of the present invention, the reaction temperature is 30 to 50 ℃ and may be, for example, but not limited to, 30 ℃, 40 ℃ and 50 ℃, and the reaction temperature is preferably 50 ℃.
(7) Reaction time
In the production method of the present invention, the reaction time is not particularly limited, and a suitable reaction time can be determined by, for example, detecting the residual percentage of the objective product or raw material by liquid chromatography, and is usually 15 to 24 hours, such as 15 hours, 18 hours, 21 hours, or 24 hours, but is not limited thereto, and the reaction time is preferably 24 hours.
(8) Separating and purifying
In a preferred embodiment, the post-treatment step after the reaction is completed may be as follows: after the reaction is finished, cooling the reaction liquid, adding ethyl acetate for extraction, drying an organic phase by using anhydrous sodium sulfate, filtering to a heart-shaped bottle, then spinning off the solvent, separating a concentrate by using column chromatography, taking a mixed solution of petroleum ether and ethyl acetate as an eluent, collecting the eluent, and concentrating to obtain a target product.
The preparation method of the 2-phenylacetylene selenol compound provided by the invention has the following beneficial effects:
a) the reaction has high efficiency, high yield and simple and convenient post-treatment;
b) selenium powder which is cheap and easy to obtain is used as a selenylation reagent;
c) water is used as a green reaction solvent;
according to the invention, phenylpropanoic acid, selenium powder and an epoxy compound are used as reaction raw materials, water is used as a reaction solvent, and under the combined promotion action of a copper catalyst, a ligand, a phase transfer catalyst and alkali, a 2-phenylacetylene selenium-based alcohol compound is obtained through a series reaction; the invention has cheap and easily obtained reaction raw materials and high yield and purity of the product, develops a synthetic route and a method for preparing the 2-phenylacetylene selenol compound, provides new application for the double functionalization reaction of the selenium powder, and has important social and economic meanings.
Detailed Description
The present invention is described in detail below with reference to specific examples, but the use and purpose of these exemplary embodiments are merely to exemplify the present invention, and do not set forth any limitation on the actual scope of the present invention in any form, and the scope of the present invention is not limited thereto.
The data and purity of the novel compounds given in the following examples were determined by nuclear magnetic resonance.
Example 1
Synthesis of 1-phenylacetylene seleno-3- (4-methylphenoxy) -2-propanol compound
Phenylpropiolic acid (0.2mmol), elemental selenium (0.6mmol), 2- (4-methylphenoxy) methyloxirane (0.6mmol), copper chloride (0.02mmol), 1, 10-phenanthroline (0.02mmol), cesium carbonate (0.6mmol), tetrabutylammonium iodide (0.4mmol) and 2mL of water were stirred at 50 ℃ for 24h at room temperature. After the reaction is finished, adding ethyl acetate for dilution, transferring the diluted solution to a separating funnel for extraction, separating out a water phase and an organic phase, extracting the water phase for 3 times by using ethyl acetate, combining the organic phases, adding 5g of anhydrous sodium sulfate, standing for 30min, washing a filter cake for 3 times by using 5mL of ethyl acetate each time, then spinning off the solvent, and carrying out column chromatography separation to obtain a product (eluent: petroleum ether: ethyl acetate ═ 20: 1), wherein the product is a light yellow liquid, the yield is 92%, and the weight of the product is 63 mg.
The data of the nuclear magnetic resonance hydrogen spectrum of the obtained product are as follows:
1H NMR(500MHz，CDCl3)：δ7.36-7.34(m，2H)，7.30-7.24(m，3H)，7.05(d，J＝8.40Hz，2H)，6.81(d，J＝8.40Hz，2H)，4.37-4.35(m，1H)，4.15-4.09(m，2H)，3.18(dd，J＝12.50，5.40Hz，1H)，3.08(dd，J＝12.5，5.40Hz，1H)，2.76(brs，1H)，2.27(s，3H)；
the data of the nuclear magnetic resonance carbon spectrum of the obtained product are as follows:
13C NMR(125MHz，CDCl3)：δ156.2，131.6，130.6，130.0，128.3，128.2，123.2，114.5，99.6，70.5，69.6，69.5，32.8，20.4；
theoretical calculations and experimental results of high resolution mass spectrometry performed on the product are as follows:
HRMS(ESI)：calcd for C18H18O2Se[M+H]+347.0545，found 347.0541。
example 2
Synthesis of 1-phenylacetylene seleno-3- (4-trifluoromethoxy phenoxy) -2-propanol compound
Phenylpropiolic acid (0.2mmol), elemental selenium (0.6mmol), 2- (4-trifluoromethoxyphenoxy) methyloxirane (0.6mmol), copper chloride (0.02mmol), 1, 10-phenanthroline (0.02mmol), cesium carbonate (0.6mmol), tetrabutylammonium iodide (0.4mmol) and 2mL of water were stirred at 50 ℃ for 24h at room temperature. After the reaction is finished, adding ethyl acetate for dilution, transferring the diluted solution to a separating funnel for extraction, separating out a water phase and an organic phase, extracting the water phase for 3 times by using ethyl acetate, combining the organic phases, adding 5g of anhydrous sodium sulfate, standing for 30min, washing a filter cake for 3 times by using 5mL of ethyl acetate each time, then spinning off the solvent, and carrying out column chromatography separation to obtain a product (eluent: petroleum ether: ethyl acetate: 20: 1), wherein the melting point of the product is 48-49 ℃, the yield is 77%, and the weight of the product is 64 mg.
The data of the nuclear magnetic resonance hydrogen spectrum of the obtained product are as follows:
1H NMR(500MHz，CDCl3)：δ7.35-7.34(m，5H)，7.12-7.11(m，2H)，6.91-6.89(m，2H)，4.39-4.38(m，1H)，4.18-4.12(m，2H)，3.18(dd，J＝12.50，5.40Hz，1H)，3.08(dd，J＝12.50，5.40Hz，1H)，2.74-2.73(m，1H)；
the data of the nuclear magnetic resonance carbon spectrum of the obtained product are as follows:
13C NMR(125MHz，CDCl3)：δ156.8，143.2，131.5，128.4，128.3，123.6，123.0，122.4，121.5，119.5，117.5，115.4，99.7，70.7，69.4，69.2，32.7；
the nmr spectra of the product obtained were as follows:
19F NMR(470MHz，CDCl3)：δ-58.4(s，3F)；
theoretical calculations and experimental results of high resolution mass spectrometry performed on the product are as follows:
HRMS(ESI)：calcd for C18H15F3O3Se[M+H]+417.0211，found 417.0216。
example 3
Synthesis of 1-phenylacetylene seleno-3- (4-thiomethylphenoxy) -2-propanol compound
Phenylpropiolic acid (0.2mmol), elemental selenium (0.6mmol), 2- (4-thiomethylphenoxy) methyloxirane (0.6mmol), copper chloride (0.02mmol), 1, 10-phenanthroline (0.02mmol), cesium carbonate (0.6mmol), tetrabutylammonium iodide (0.4mmol) and 2mL of water were stirred at 50 ℃ for 24h at room temperature. After the reaction is finished, adding ethyl acetate for dilution, transferring the diluted solution to a separating funnel for extraction, separating out a water phase and an organic phase, extracting the water phase for 3 times by using ethyl acetate, combining the organic phases, adding 5g of anhydrous sodium sulfate, standing for 30min, washing a filter cake for 3 times by using 5mL of ethyl acetate each time, then spinning off the solvent, and carrying out column chromatography separation to obtain a product (eluent: petroleum ether: ethyl acetate: 20: 1), wherein the melting point of the product is 63-64 ℃, the yield is 56%, and the weight of the product is 42 mg.
The data of the nuclear magnetic resonance hydrogen spectrum of the obtained product are as follows:
1H NMR(500MHz，CDCl3)：δ7.35-7.34(m，2H)，7.29-7.22(m，5H)，6.88-6.86(m，2H)，4.38-4.37(m，1H)，4.16-4.11(m，2H)，3.19(dd，J＝12.50，5.40Hz，4H)，3.08(dd，J＝12.50，5.40Hz，1H)，2.70-2.69(m，1H)，2.43(s，3H)；
the data of the nuclear magnetic resonance carbon spectrum of the obtained product are as follows:
13C NMR(125MHz，CDCl3)：δ156.8，131.6，129.9，129.8，128.4，128.3，123.1，115.3，99.6，70.5，69.5，69.3，32.7，17.8；
theoretical calculations and experimental results of high resolution mass spectrometry performed on the product are as follows:
HRMS(ESI)：calcd for C18H18O2SSe[M+H]+379.0265，found 379.0246。
example 4
Synthesis of 1-phenylacetylene seleno-3- (3-N, N-diethylphenoxy) -2-propanol compound
Phenylpropiolic acid (0.2mmol), elemental selenium (0.6mmol), 2- (3-N, N-diethylphenoxy) methyloxirane (0.6mmol), copper chloride (0.02mmol), 1, 10-phenanthroline (0.02mmol), cesium carbonate (0.6mmol), tetrabutylammonium iodide (0.4mmol) and 2mL of water were stirred at 50 ℃ for 24h at room temperature. After the reaction is finished, adding ethyl acetate for dilution, transferring the diluted solution to a separating funnel for extraction, separating out an aqueous phase and an organic phase, extracting the aqueous phase 3 times by using ethyl acetate, combining the organic phases, adding 5g of anhydrous sodium sulfate, standing for 30min, washing a filter cake 3 times by using 5mL of ethyl acetate each time, then spinning off the solvent, and performing column chromatography separation to obtain a product (eluent: petroleum ether: ethyl acetate ═ 20: 1), wherein the yield is 83% and the weight of the product is 67 mg.
The data of the nuclear magnetic resonance hydrogen spectrum of the obtained product are as follows:
1H NMR(500MHz，CDCl3)：δ7.38-7.36(m，2H)，7.28-7.25(m，3H)，7.10-7.07(m，1H)，6.33-6.31(m，1H)，6.24-6.21(m，2H)，4.37-4.36(m，1H)，4.17-4.11(m，2H)，3.30(dd，J＝14.0，7.0Hz，4H)，3.19(dd，J＝12.50，5.40Hz，1H)，3.09(dd，J＝12.50，5.40Hz，1H)，2.74-2.73(m，1H)，1.14(s，6H)；
the data of the nuclear magnetic resonance carbon spectrum of the obtained product are as follows:
13C NMR(125MHz，CDCl3)：δ159.7，149.3，131.6，130.0，128.3，123.2，105.7，100.8，99.6，98.9，70.1，69.6，69.5，44.4，32.9，12.6；
theoretical calculations and experimental results of high resolution mass spectrometry performed on the product are as follows:
HRMS(ESI)：calcd for C21H25NO2Se[M+H]+404.1123，found 404.1129。
example 5
Synthesis of 1-phenylacetylene seleno-3- (2-naphthoxy) -2-propanol compound
Phenylpropiolic acid (0.2mmol), elemental selenium (0.6mmol), 2- (2-naphthyloxy) methyloxirane (0.6mmol), copper chloride (0.02mmol), 1, 10-phenanthroline (0.02mmol), cesium carbonate (0.6mmol), tetrabutylammonium iodide (0.4mmol) and 2mL of water were stirred at 50 ℃ for 24h at room temperature. After the reaction is finished, adding ethyl acetate for dilution, transferring the diluted solution to a separating funnel for extraction, separating out a water phase and an organic phase, extracting the water phase for 3 times by using ethyl acetate, combining the organic phases, adding 5g of anhydrous sodium sulfate, standing for 30min, washing a filter cake for 3 times by using 5mL of ethyl acetate each time, then spinning off the solvent, and carrying out column chromatography separation to obtain a product (eluent: petroleum ether: ethyl acetate ═ 20: 1), wherein the product is a light yellow solid, the melting point is 63-64 ℃, the yield is 90%, and the weight of the product is 69 mg.
The data of the nuclear magnetic resonance hydrogen spectrum of the obtained product are as follows:
1H NMR(500MHz，CDCl3)：δ7.76-7.71(m，2H)，7.65(d，J＝8.18Hz，1H)，7.43-7.40(m，1H)，7.35-7.32(m，3H)，7.28-7.20(m，3H)，7.17-7.15(m，2H)，4.48-4.43(m，1H)，4.31-4.25(m，2H)，3.23(dd，J＝12.50，5.40Hz，4H)，3.13(dd，J＝12.50，5.40Hz，1H)，2.81(brs，1H)；
the data of the nuclear magnetic resonance carbon spectrum of the obtained product are as follows:
13C NMR(125MHz，CDCl3)：δ156.3，134.4，131.6，129.6，129.3，128.3，128.2，127.6，126.8，126.5，123.9，123.1，118.6，107.1，99.7，70.4，69.6，69.4，32.8；
theoretical calculations and experimental results of high resolution mass spectrometry performed on the product are as follows:
HRMS(ESI)：calcd for C21H18O2Se[M+H]+383.0544，found 383.0537。
example 6
Synthesis of 1-phenylacetylene seleno-3- (1, 3-methylenedioxy-4-phenoxy) -2-propanol compound
Phenylpropiolic acid (0.2mmol), elemental selenium (0.6mmol), 2- (1, 3-methylenedioxy-4-phenoxy) methyloxirane (0.6mmol), copper chloride (0.02mmol), 1, 10-phenanthroline (0.02mmol), cesium carbonate (0.6mmol), tetrabutylammonium iodide (0.4mmol) and 2mL of water were stirred at 50 ℃ for 24h at room temperature. After the reaction is finished, adding ethyl acetate for dilution, transferring the diluted solution to a separating funnel for extraction, separating out a water phase and an organic phase, extracting the water phase for 3 times by using ethyl acetate, combining the organic phases, adding 5g of anhydrous sodium sulfate, standing for 30min, washing a filter cake for 3 times by using 5mL of ethyl acetate each time, then spinning off the solvent, and carrying out column chromatography separation to obtain a product (eluent: petroleum ether: ethyl acetate ═ 20: 1), wherein the product is a light yellow liquid, the yield is 78%, and the weight of the product is 58 mg.
The data of the nuclear magnetic resonance hydrogen spectrum of the obtained product are as follows:
1H NMR(500MHz，CDCl3)：δ7.37-7.35(m，2H)，7.29-7.27(m，3H)，6.67(d，J＝8.45Hz，1H)，6.50(d，J＝2.45Hz，1H)，6.34(dd，J＝8.45Hz，2.45Hz，1H)，5.90(s，2H)，4.36-4.33(m，1H)，4.11-4.05(m，2H)，3.17(dd，J＝12.50，5.40Hz，4H)，3.07(dd，J＝12.50，5.40Hz，1H)，2.72(d，J＝5.15Hz，1H)；
the data of the nuclear magnetic resonance carbon spectrum of the obtained product are as follows:
13C NMR(125MHz，CDCl3)：δ153.8，148.3，142.1，131.6，128.3，128.2，123.1，107.9，105.9，101.2，99.6，98.3，71.3，69.5，69.4，32.8；
theoretical calculations and experimental results of high resolution mass spectrometry performed on the product are as follows:
HRMS(ESI)：calcd for C18H16O4Se[M+H]+377.0286，found 377.0280。
as can be seen from the above examples 1 to 6, when the method of the present invention is employed, 2-phenylacetylene selenol compounds can be obtained in high yield and high purity.
Examples 7 to 9
Examples 7 to 9 were each carried out in the same manner as in example 1 except that the copper chloride catalyst was replaced with the following copper catalyst, respectively, and the yields of the copper catalyst and the corresponding products used were as shown in Table 1 below.
TABLE 1
| Numbering | Copper catalyst | Reaction yield (%) |
| Example 7 | Copper acetate | Is not reacted |
| Example 8 | Copper bromide | 40 |
| Example 9 | Cuprous iodide | 22 |
As can be seen from Table 1 above, the product yields are all greatly reduced when other copper catalysts are used. Thus, the catalyst copper chloride used in the invention has high catalytic performance for the reaction.
Examples 10 to 12
Examples 10 to 12 were each carried out in the same manner as in example 1 except that the ligand 1, 10-phenanthroline was replaced with the following ligand, respectively, and the yields of the ligand used and the corresponding product were as shown in Table 2 below.
TABLE 2
As can be seen from Table 2 above, when a phosphine ligand is used, there is no product, and when bipyridine is used as the ligand, the yield of the objective product is greatly decreased, thus demonstrating that the ligand 1, 10-phenanthroline used in the present invention is extremely critical to the improvement of the reaction yield.
Examples 13 to 16
Examples 13-16 were each carried out in the same manner as in example 1 except that the alkali cesium carbonate therein was replaced with the following inorganic base, respectively, and the used bases and the yields of the corresponding products are shown in table 3 below.
TABLE 3
| Numbering | Alkali | Reaction yield (%) |
| Example 13 | Sodium carbonate | Is not reacted |
| Example 14 | Potassium carbonate | Is not reacted |
| Example 15 | Potassium phosphate | Is not reacted |
| Example 16 | Sodium phosphate | Is not reacted |
As can be seen from Table 3 above, almost none of the bases reacted when used, thus demonstrating that cesium carbonate is a key factor in the success of the reaction and is most effective for the reaction system.
Examples 17 to 18
Examples 17 to 18 were each carried out in the same manner as in example 1 except that the phase transfer catalyst tetrabutylammonium iodide therein was replaced with the following phase transfer catalysts, respectively, and the yields of the phase transfer catalysts used and the corresponding products are shown in Table 4 below.
TABLE 4
| Numbering | Phase transfer catalyst | Reaction yield (%) |
| Example 17 | Tetrabutyl ammonium chloride | 42 |
| Example 18 | Tetrabutylammonium bromide | 60 |
As can be seen from Table 4 above, the product yields all decreased when other phase transfer catalyst compounds were used. Thus, the phase transfer catalyst tetrabutylammonium iodide used in the invention has high catalytic performance for the reaction.
In summary, it is clear from all the above embodiments that, when the method of the present invention is adopted, i.e., transition metal copper catalyst (especially copper chloride), ligand (1, 10-phenanthroline), base (especially cesium carbonate), phase transfer catalyst (especially tetrabutylammonium iodide) and water are used as reaction solvent, the phenylpropanoic acid, epoxy compound and selenium powder can be subjected to a series reaction to synthesize the 2-phenylacetylene selenol compound with high yield and high purity, and a brand new synthetic route is provided for the efficient and rapid synthesis of the compound.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments are modified or some or all of the technical features are equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (8)
1. A synthetic method of 2-phenylacetylene selenol compounds is characterized in that in a reaction solvent, phenylpropanoic acid and epoxy compounds are used as reaction raw materials, selenium powder is used as a selenylation reagent, and under the common promotion action of a transition metal catalyst, a ligand, a phase transfer catalyst and alkali, the 2-phenylacetylene selenol compounds are obtained through a series reaction;
the phenylpropanoic acid is:
the epoxy compound is:
the 2-phenylacetylene selenol compound is as follows:
the transition metal catalyst is copper chloride;
the ligand is 1, 10-phenanthroline;
the phase transfer catalyst is tetrabutylammonium iodide;
the base is cesium carbonate;
the reaction solvent is water.
2. The method according to claim 1, wherein the transition metal catalyst is used in an amount of 10% by mole based on the amount of phenylpropanoic acid.
3. The process according to claim 1, wherein the ligand is used in an amount of 10% by mole based on the amount of phenylpropanoic acid.
4. The method of synthesis according to claim 1, characterized in that: the molar ratio of the phenylpropanoic acid to the epoxy compound to the selenium powder is 1: 3.
5. The method of synthesis according to claim 1, characterized in that: the molar ratio of the phase transfer catalyst to the phenylpropanoic acid is 2: 1.
6. The method of synthesis according to claim 1, characterized in that: the molar ratio of the alkali to the phenylpropanoic acid is 3: 1.
7. The synthesis process according to claim 1, characterized in that the reaction temperature is between 30 and 50 ℃.
8. The synthesis process according to claim 1, characterized in that the reaction time is 15-24 h.
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| CN108675948A (en) * | 2018-02-19 | 2018-10-19 | 温州医科大学 | A kind of beta-hydroxy selenide compound and preparation method |
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2020
- 2020-10-26 CN CN202011184155.7A patent/CN112250608A/en active Pending
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| CN108675948A (en) * | 2018-02-19 | 2018-10-19 | 温州医科大学 | A kind of beta-hydroxy selenide compound and preparation method |
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| FANMIN LIU 等: "A thiol-free synthesis of alkynyl chalcogenides by the copper-catalyzed C–X (X = S, Se) cross-coupling of alkynyl carboxylic acids with Bunte salts", 《ORGANIC CHEMISTRY FRONTIERS》 * |
| ZHANGQIN NI 等: "A concise synthetic strategy to alkynyl sulfides via transition-metal-free catalyzed C–S coupling of 1,1-dibromo-1-alkenes with thiophenols", 《TETRAHEDRON LETTERS》 * |
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| CN115286555A (en) * | 2021-11-26 | 2022-11-04 | 温州医科大学 | Synthetic method of 3-alkynylselendole compound |
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