CN112574083A - Synthesis method of diaryl ditelluride compound - Google Patents
Synthesis method of diaryl ditelluride compound Download PDFInfo
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- CN112574083A CN112574083A CN202011463825.9A CN202011463825A CN112574083A CN 112574083 A CN112574083 A CN 112574083A CN 202011463825 A CN202011463825 A CN 202011463825A CN 112574083 A CN112574083 A CN 112574083A
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- diaryl
- ditelluroether
- phenylboronic acid
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- C07C395/00—Compounds containing tellurium
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Abstract
The invention relates to a synthesis method of diaryl ditelluroether compounds, which comprises the following steps: placing phenylboronic acid or a derivative thereof, elemental tellurium, trimethylnitrile silane and an organic solvent into a reaction container to obtain a mixed solution, heating the mixed solution to 110-140 ℃, stirring and reacting at the temperature for 18-30 h to obtain a reaction solution, and performing post-treatment to obtain a diaryl ditelluride compound, wherein: phenylboronic acid or a derivative thereof, simple substance tellurium, and trimethylnitrilosilane (7-9): 8-10): 1. The synthesis method of the diaryl ditelluroether compound disclosed by the invention has the following beneficial effects: 1. the reaction can be carried out without metal, so that the environment is more protected, and the cost is lower; 2. the compatibility of the substrate is good; 3. the preparation process is simple and easy to operate.
Description
Technical Field
The invention belongs to the field of organic chemistry, and particularly relates to a synthesis method of a diaryl ditelluride compound.
Background
The diaryl ditelluroether derivative has great application value, and the compound can be used as a very useful intermediate in synthesis and can be used for synthesizing a series of products with very application value, such as single telluroether and the like. The compound is widely applied in the fields of biomolecule synthesis, new material preparation, drug molecule synthesis and the like, and particularly in an animal model system, the compound as a whole plays the role of a chemical protective agent to resist various chemical carcinogens.
However, the synthesis of the diaryl ditelluroether derivative has the following defects: 1. most syntheses require metals to participate in the reaction; 2. poor substrate compatibility; 3. the preparation process is complicated.
Disclosure of Invention
The purpose of the invention is as follows: the invention improves the problems existing in the prior art, namely the invention discloses a synthesis method of diaryl ditelluride compounds.
The technical scheme is as follows: a synthetic method of diaryl ditelluroether compound is provided, which comprises the following steps:
placing phenylboronic acid or a derivative thereof shown in a formula (1), elemental tellurium, trimethylnitrilosilane and an organic solvent into a reaction container to obtain a mixed solution, heating the mixed solution to 110-140 ℃, stirring and reacting at the temperature for 18-30 h to obtain a reaction solution, and performing post-treatment to obtain a diaryl ditelluride compound shown in a formula (2);
phenylboronic acid or a derivative thereof shown in a formula (1), simple substance tellurium and trimethyl nitrile silane, wherein (7-9) is used, and (8-10) is used, and 1 is used;
the dosage of the organic solvent is 3-7 ml/mmol based on the molar weight of the phenylboronic acid or the derivative thereof, wherein:
r is one of H, C1-C4 alkyl, methoxy, methylthio, halogen, nitro and hydroxyl.
Further, the organic solvent is dimethyl sulfoxide.
Further, the reaction temperature was 120 ℃ and the reaction time was 24 hours.
Further, phenylboronic acid represented by formula (1) or a derivative thereof, elemental tellurium, and trimethylnitrilosilane ═ 8:9.6: 1.
Further, the organic solvent was used in an amount of 5ml/mmol based on the molar amount of phenylboronic acid or a derivative thereof.
Further, the post-processing comprises the steps of:
(1) adding water to the reaction solution, wherein: the volume of the added water is 1-3 times of the volume of the trimethylnitrile silane;
(2) then adding ethyl acetate into the mixture to extract for at least 3 times to obtain organic extract, then placing the organic extract into a rotary evaporator, and concentrating the organic extract by using an ethyl acetate layer under the reduced pressure to obtain residual liquid, wherein: adding ethyl acetate into the mixture, wherein the volume of the ethyl acetate is 6-10 times of that of the trimethylnitrile silane;
(3) and (3) purifying the residual liquid obtained in the step (2) by silica gel flash chromatography to obtain the diaryl ditelluroether compound.
Has the advantages that: the synthesis method of the diaryl ditelluroether compound disclosed by the invention has the following beneficial effects:
1. the reaction can be carried out without metal, so that the environment is more protected, and the cost is lower;
2. the compatibility of the substrate is good;
3. the preparation process is simple and easy to operate.
The specific implementation mode is as follows:
the following describes in detail specific embodiments of the present invention.
The synthesis method of the diaryl ditelluroether compound disclosed by the application is preferably carried out in the air or nitrogen or oxygen atmosphere.
The reaction equation is as follows:
Detailed description of the preferred embodiment 1
A synthetic method of diaryl ditelluroether compound is provided, which comprises the following steps:
placing phenylboronic acid shown in a formula (1), simple substance tellurium, trimethylnitrile silane and an organic solvent into a reaction container to obtain a mixed solution, heating the mixed solution to 110 ℃, stirring and reacting at the temperature for 30 hours to obtain a reaction solution, performing post-treatment to obtain a diaryl ditelluride compound shown in a formula (2),
phenylboronic acid represented by formula (1), elemental tellurium, and trimethylnitrilosilane ═ 7:8: 1;
the amount of the organic solvent used was 3ml/mmol based on the molar amount of phenylboronic acid, wherein:
r is H.
Further, the organic solvent is dimethyl sulfoxide.
Further, the post-processing comprises the steps of:
(1) adding water to the reaction solution, wherein: the volume of the added water is 1 time of that of the trimethylnitrile silane;
(2) then adding ethyl acetate into the mixture to extract for at least 3 times to obtain organic extract, then placing the organic extract into a rotary evaporator, and concentrating the organic extract by using an ethyl acetate layer under the reduced pressure to obtain residual liquid, wherein: adding ethyl acetate with the volume amount being 6 times of that of the trimethylnitrile silane;
(3) and (3) purifying the residual liquid obtained in the step (2) by silica gel flash chromatography to obtain a yellow oily substance with the yield of 61 percent, namely obtaining the diaryl ditelluroether compound. The chemical formula is as follows:
the nuclear magnetic resonance detection of the product of example 1 was carried out as follows:
1H NMR(500MHz,CDCl3)δ7.68(s,2H),7.39–6.97(m,3H).13C NMR(126MHz,CDCl3)δ138.01,129.52,127.85,114.70,114.68.
specific example 2
A synthetic method of diaryl ditelluroether compound is provided, which comprises the following steps:
placing a phenylboronic acid derivative shown in a formula (1), elemental tellurium, trimethylnitrile silane and an organic solvent into a reaction container to obtain a mixed solution, heating the mixed solution to 140 ℃, stirring and reacting at the temperature for 18 hours to obtain a reaction solution, performing post-treatment to obtain a diaryl ditelluroether compound shown in a formula (2),
phenylboronic acid derivatives represented by formula (1), elemental tellurium, and trimethylnitrilosilane ═ 9:10: 1;
the amount of the organic solvent used was 7ml/mmol based on the molar amount of the phenylboronic acid derivative, wherein:
r is methyl.
Further, the organic solvent is dimethyl sulfoxide.
Further, the post-processing comprises the steps of:
(1) adding water to the reaction solution, wherein: the volume of the added water is 3 times of that of the trimethylnitrile silane;
(2) then adding ethyl acetate into the mixture to extract for at least 3 times to obtain organic extract, then placing the organic extract into a rotary evaporator, and concentrating the organic extract by using an ethyl acetate layer under the reduced pressure to obtain residual liquid, wherein: the volume of the added ethyl acetate is 10 times of that of the trimethyl nitrile silane;
(3) and (3) purifying the residual liquid obtained in the step (2) by silica gel flash chromatography to obtain a yellow solid with the yield of 61 percent, namely obtaining the diaryl ditelluride compound. The chemical formula is as follows:
the nuclear magnetic resonance detection of the product of example 2 was carried out as follows:
1H NMR(500MHz,CDCl3)δ7.58(d,J＝8.0Hz,4H),7.01(d,J＝7.7Hz,4H),2.31(s,6H).13C NMR(126MHz,CDCl3)δ138.10,137.76,130.39,110.77,21.24.
specific example 3
A synthetic method of diaryl ditelluroether compound is provided, which comprises the following steps:
placing a phenylboronic acid derivative shown in a formula (1), elemental tellurium, trimethylnitrile silane and an organic solvent into a reaction container to obtain a mixed solution, heating the mixed solution to 120 ℃, stirring and reacting at the temperature for 24 hours to obtain a reaction solution, performing post-treatment to obtain a diaryl ditelluride compound shown in a formula (2),
phenylboronic acid derivatives represented by formula (1), elemental tellurium, and trimethylnitrilosilane 8:9.6: 1; the amount of the organic solvent used was 5ml/mmol based on the molar amount of the phenylboronic acid derivative, wherein:
r is methoxy.
Further, the organic solvent is dimethyl sulfoxide.
Further, the post-processing comprises the steps of:
(1) adding water to the reaction solution, wherein: the volume of the added water is 2 times of that of the trimethylnitrile silane;
(2) then adding ethyl acetate into the mixture to extract for at least 3 times to obtain organic extract, then placing the organic extract into a rotary evaporator, and concentrating the organic extract by using an ethyl acetate layer under the reduced pressure to obtain residual liquid, wherein: adding ethyl acetate with volume amount of 8 times of that of the trimethylnitrile silane;
(3) and (3) purifying the residual liquid obtained in the step (2) by silica gel flash chromatography to obtain a yellow oily substance with the yield of 65 percent, namely obtaining the diaryl ditelluroether compound. The chemical formula is as follows:
the nuclear magnetic resonance detection of the product of example 3 was carried out, and the detection results were as follows:
1H NMR(500MHz,CDCl3)δ7.62(d,J＝8.7Hz,4H),6.76(d,J＝8.7Hz,4H),3.77(s,6H).13C NMR(126MHz,CDCl3)δ159.68,139.73,115.40,104.31,55.17.
specific example 4
A synthetic method of diaryl ditelluroether compound is provided, which comprises the following steps:
placing a phenylboronic acid derivative shown in a formula (1), elemental tellurium, trimethylnitrile silane and an organic solvent into a reaction container to obtain a mixed solution, heating the mixed solution to 125 ℃, stirring and reacting at the temperature for 20 hours to obtain a reaction solution, performing post-treatment to obtain a diaryl ditelluroether compound shown in a formula (2),
phenylboronic acid derivatives represented by formula (1), elemental tellurium, and trimethylnitrilosilane ═ 7:9: 1; the amount of the organic solvent used was 4ml/mmol based on the molar amount of the phenylboronic acid derivative, wherein:
r is chlorine.
Further, the organic solvent is dimethyl sulfoxide.
Further, the post-processing comprises the steps of:
(1) adding water to the reaction solution, wherein: the volume of the added water is 2 times of that of the trimethylnitrile silane;
(2) then adding ethyl acetate into the mixture to extract for at least 3 times to obtain organic extract, then placing the organic extract into a rotary evaporator, and concentrating the organic extract by using an ethyl acetate layer under the reduced pressure to obtain residual liquid, wherein: adding ethyl acetate with volume amount of 8 times of that of the trimethylnitrile silane;
(3) and (3) purifying the residual liquid obtained in the step (2) by silica gel flash chromatography to obtain a white solid with the yield of 71 percent, namely obtaining the diaryl ditelluride compound. The chemical formula is as follows:
the nuclear magnetic resonance detection of the product of example 4 was carried out as follows:
1H NMR(500MHz,CDCl3)δ7.57(d,J＝7.1Hz,4H),7.17(d,J＝7.1Hz,4H).13C NMR(126MHz,CDCl3)δ139.37,134.69,129.90,112.09.
specific example 5
A synthetic method of diaryl ditelluroether compound is provided, which comprises the following steps:
placing a phenylboronic acid derivative shown in a formula (1), elemental tellurium, trimethylnitrile silane and an organic solvent into a reaction container to obtain a mixed solution, heating the mixed solution to 120 ℃, stirring and reacting at the temperature for 24 hours to obtain a reaction solution, performing post-treatment to obtain a diaryl ditelluride compound shown in a formula (2),
phenylboronic acid derivatives represented by formula (1), elemental tellurium, and trimethylnitrilosilane 8:9.6: 1; the amount of the organic solvent used was 5ml/mmol based on the molar amount of the phenylboronic acid derivative, wherein:
r is iodine.
Further, the organic solvent is dimethyl sulfoxide.
Further, the post-processing comprises the steps of:
(1) adding water to the reaction solution, wherein: the volume of the added water is 2 times of that of the trimethylnitrile silane;
(2) then adding ethyl acetate into the mixture to extract for at least 3 times to obtain organic extract, then placing the organic extract into a rotary evaporator, and concentrating the organic extract by using an ethyl acetate layer under the reduced pressure to obtain residual liquid, wherein: adding ethyl acetate with volume amount of 8 times of that of the trimethylnitrile silane;
(3) and (3) purifying the residual liquid obtained in the step (2) by silica gel flash chromatography to obtain a yellow solid with the yield of 75%, thus obtaining the diaryl ditelluride compound. The chemical formula is as follows:
the nuclear magnetic resonance detection of the product of example 5 was carried out as follows:
1H NMR(500MHz,CDCl3)δ7.51-7.35(m,8H).13C NMR(126MHz,CDCl3)δ139.73,138.70,113.75,94.57.
specific examples 6 to 15
Substantially the same as in example 5, except that the substituents R are different:
| substituent R | |
| Specific example 6 | Ethyl radical |
| Specific example 7 | N-propyl radical |
| Specific example 8 | Isopropyl group |
| Specific example 9 | N-butyl |
| Detailed description of example 10 | Tert-butyl radical |
| Specific example 11 | Methylthio group |
| Detailed description of example 12 | F |
| Specific example 13 | Br |
| EXAMPLES example 14 | Nitro radical |
| Specific example 15 | Hydroxy radical |
The embodiments of the present invention have been described in detail. However, the present invention is not limited to the above-described embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.
Claims (6)
1. A synthetic method of a diaryl ditelluroether compound is characterized by comprising the following steps:
placing phenylboronic acid or a derivative thereof shown in a formula (1), elemental tellurium, trimethylnitrilosilane and an organic solvent into a reaction container to obtain a mixed solution, heating the mixed solution to 110-140 ℃, stirring and reacting at the temperature for 18-30 h to obtain a reaction solution, and performing post-treatment to obtain a diaryl ditelluride compound shown in a formula (2);
phenylboronic acid or a derivative thereof shown in a formula (1), simple substance tellurium and trimethyl nitrile silane, wherein (7-9) is used, and (8-10) is used, and 1 is used;
the dosage of the organic solvent is 3-7 ml/mmol based on the molar weight of the phenylboronic acid or the derivative thereof, wherein:
r is one of H, C1-C4 alkyl, methoxy, methylthio, halogen, nitro and hydroxyl.
2. The method for synthesizing a diaryl ditelluroether compound according to claim 1, wherein the organic solvent is dimethyl sulfoxide.
3. The method for synthesizing a diaryl ditelluroether compound according to claim 1, wherein the reaction temperature is 120 ℃ and the reaction time is 24 h.
4. The method for synthesizing a diaryl ditelluroether compound according to claim 1, wherein the phenylboronic acid or its derivative represented by formula (1), elemental tellurium, and trimethylnitrilosilane ═ 8:9.6: 1.
5. The method for synthesizing a diaryl ditelluroether compound according to claim 1, wherein the amount of the organic solvent is 5ml/mmol based on the molar amount of phenylboronic acid or its derivative.
6. The method for synthesizing a diaryl ditelluroether compound according to claim 1, wherein the post-treatment comprises the following steps:
(1) adding water to the reaction solution, wherein: the volume of the added water is 1-3 times of the volume of the trimethylnitrile silane;
(2) then adding ethyl acetate into the mixture to extract for at least 3 times to obtain organic extract, then placing the organic extract into a rotary evaporator, and concentrating the organic extract by using an ethyl acetate layer under the reduced pressure to obtain residual liquid, wherein: adding ethyl acetate into the mixture, wherein the volume of the ethyl acetate is 6-10 times of that of the trimethylnitrile silane;
(3) and (3) purifying the residual liquid obtained in the step (2) by silica gel flash chromatography to obtain the diaryl ditelluroether compound.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108047107A (en) * | 2018-01-29 | 2018-05-18 | 温州大学 | The preparation method of diphenyl disenenide ether compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108047107A (en) * | 2018-01-29 | 2018-05-18 | 温州大学 | The preparation method of diphenyl disenenide ether compound |
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| XUE ZHANG ET AL.: "Metal-Free Synthesis of Aryl Selenocyanates and Selenaheterocycles with Elemental Selenium", 《CHEM. EUR. J.》 * |
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