CN113173909A - Selenium/tellurium-containing heterocyclic compound and preparation method and conversion method thereof - Google Patents

Selenium/tellurium-containing heterocyclic compound and preparation method and conversion method thereof Download PDF

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CN113173909A
CN113173909A CN202110397210.9A CN202110397210A CN113173909A CN 113173909 A CN113173909 A CN 113173909A CN 202110397210 A CN202110397210 A CN 202110397210A CN 113173909 A CN113173909 A CN 113173909A
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tellurium
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唐本忠
胡蓉蓉
彭建文
秦安军
赵祖金
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South China University of Technology SCUT
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Abstract

The invention discloses a selenium/tellurium-containing heterocyclic compound, a preparation method and a conversion method thereof, wherein the selenium/tellurium-containing heterocyclic compound comprises a 1, 4-diselenium/tellurium alkene compound and a selenium/tellurium thiophene compound; the invention discloses a method for selectively generating 1, 4-diselenide/telluriene and selenium/telluriphene compounds by using elemental selenium/tellurium and activated internal alkyne under the regulation and control of temperature. The invention discloses a method for converting 1, 4-diseleno/telluroene into selenium/tellurophene, namely high temperature or oxidation conditions. The synthetic method has the advantages of no metal catalysis, mild reaction conditions, safe and simple operation, greenness, economy and good selectivity, and the selenium/tellurium-containing compound has excellent photoelectric property and bioactivity and has good application prospect in the aspects of application of photoelectric materials, natural products, drug synthesis, construction of protein molecules and the like.

Description

Selenium/tellurium-containing heterocyclic compound and preparation method and conversion method thereof
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a selenium/tellurium-containing heterocyclic compound, and a preparation method and a conversion method thereof.
Background
The selenium-containing heterocyclic compound has wide application in the aspects of a plurality of bioactive molecules, drug molecules, biological protein molecules and the like. 1, 4-diselenene is used as a selenium-containing six-membered heterocyclic compound which is not reported yet, the molecule of the compound contains 2 carbon-carbon double bonds and 4 carbon-selenium single bonds, the six-membered heterocyclic ring in the molecule is in a ship-shaped non-planar structure, and the abundant chemical properties of the compound need to be further explored. Selenophen, as a relatively common selenium-containing heterocyclic compound, has both photoelectric properties and biological activity, and has good application prospects in the aspects of application of photoelectric materials, synthesis of natural products and medicines, construction of protein molecules and the like. Mohamed elshbini et al published a synthesis method of five-membered heterocyclic ring containing selenium in 2016 (coding Chemistry Reviews,2016,312, 149-containing information), and usually required the use of inorganic salts potassium selenocyanate, organic selenium ether, selenium halide and other toxic and unstable selenides as selenium source, and the reaction often required metal catalyst, grignard reagent, alkali metal and the like, and the reaction conditions were complex and harsh. The simple substance selenium is an industrial raw material with low toxicity, stability and economy, and is an ideal selenium source for synthesizing selenium-containing functional macromolecules. Therefore, the method adopts mild and green chemical reaction conditions to activate the monomer selenium, realizes the conversion of simple compounds to selenium-containing heterocyclic compounds with rich structures, has the advantages of no metal catalysis, mild reaction conditions, safe and simple operation, green economy and good selectivity, and the synthesized selenium-containing heterocyclic molecules are expected to be applied to the fields of photoelectric materials, drug molecules and the like.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention mainly aims to provide selenium/tellurium-containing heterocyclic compounds, including 1, 4-diselenene, 1, 4-ditellurilene, selenophene and tellurophene four compounds.
The invention also aims to provide a preparation method of the selenium/tellurium-containing heterocyclic compound.
It is a further object of the present invention to provide a process for the conversion of the above 1, 4-diseleno/telluroalkenes to selenium/tellurothiophenes.
The method can realize the activation of elemental selenium and elemental tellurium through alkali induction without metal catalysis, and further generates 1, 4-diselenide/telluriene through the [2+2] cycloaddition with activated alkyne. And further realizing the conversion of the 1, 4-diseleno/telluroene to the selenium/tellurophene by temperature regulation.
The purpose of the invention is realized by at least one of the following technical solutions.
A heterocyclic compound containing selenium/tellurium comprises a 1, 4-diselenium/tellurium alkene compound and a selenium/tellurium thiophene compound; the structural formula of the 1, 4-diselenide/tellurium alkene compound is one of the following structural general formulas:
Figure BDA0003018998390000021
the structural formula of the selenium/tellurium thiophene compound is one of the following structural general formulas:
Figure BDA0003018998390000022
wherein X is selenium or tellurium, R1Is one of ester group, acetyl group, aldehyde group, aryl group, trifluoromethyl group, sulfur trifluoromethyl group, pentafluorophenyl group, pyridyl group, alkyl group and hydrogen substitution, R2Is one of ester group, acetyl group, aldehyde group, aryl group, trifluoromethyl group, sulfur trifluoromethyl group, pentafluorophenyl group, pyridyl group, alkyl group and hydrogen substitution, R3Is one of ester group, acetyl group, aldehyde group, aryl group, trifluoromethyl group, sulfur trifluoromethyl group, pentafluorophenyl group, pyridyl group, alkyl group and hydrogen substitution, R4Is one of ester group, acetyl group, aldehyde group, aryl group, trifluoromethyl group, sulfur trifluoromethyl group, pentafluorophenyl group, pyridyl group, alkyl group and hydrogen substitution; r5And R6Is one of alkyl, methoxyl, ester group, acetyl, nitryl, trifluoromethyl, sulfur trifluoromethyl, halogen and hydrogen at any substituted position; the value range of n is 0-7.
Preferably, said R is1，R2，R3，R4Selected from the following structuresAny one of the formulae:
Figure BDA0003018998390000031
the preparation method of the heterocyclic compound containing selenium/tellurium comprises the following steps:
adding activated alkyne, elemental selenium or elemental tellurium and alkali, then adding a solvent to obtain a mixed solution, heating to carry out oil bath reaction, after the reaction is finished, adding a saturated NaCl solution into the reaction solution, then extracting with water and dichloromethane, taking a lower organic phase, drying the organic phase with anhydrous magnesium sulfate to remove water, filtering to obtain a filtrate, carrying out reduced pressure distillation to remove dichloromethane, obtaining a crude product, and carrying out column chromatography purification to obtain the selenium/tellurium-containing heterocyclic compound.
Preferably, the activated alkyne is one or more of an aryl alkyne ester, an alkyl alkyne ester, an aryl alkyne ketone, an alkyl alkyne ketone, an aryl alkyne aldehyde, an alkyl alkyne aldehyde, a phenylalkyne, an aryl or alkyl substituted phenylalkyne, a cyclooctyne, an aryl or alkyl substituted cyclooctyne, an ethynylpyridine, an aryl or alkyl substituted pyridinylalyne, a trifluoromethyl or thifluoromethyl substituted alkyne, and a pentafluorophenyl substituted alkyne; further preferably, the activated alkyne is 1, 3-diphenylpropynone, 1-fluorenyl-3-phenylpropynone, 1, 3-diphenylpropynal, 1-fluorenyl-3-phenylpropenal, methyl 1, 3-diphenylpropargonate, methyl 1-fluorenyl-3-phenylpropionate, ethyl 1-fluorenyl-3-phenylpropionate, cyclooctyne, the phenylalkyne, trifluoromethyl or thifluoromethyl substituted alkyne and pentafluorophenyl substituted alkyne are 1, 2-bis trifluoromethyl substituted acetylene, trifluoromethyl substituted aryl alkyne or alkyl alkyne, 1, 2-bis thifluoromethyl substituted acetylene, thifluoromethyl substituted aryl alkyne or alkyl alkyne, 1, 2-bis pentafluorobenzene substituted acetylene, pentafluorobenzene substituted aryl alkyne or alkyl alkyne.
Preferably, the base is pyridine, triethylamine, potassium carbonate, sodium hydroxide, potassium hydroxide, cesium hydroxide, sodium tert-butoxide, potassium tert-butoxide, sodium ethoxide, cesium fluoride or cesium carbonate;
preferably, the solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, toluene, 1, 4-dioxane, 1, 2-dichloromethane, 1, 2-dichloroethane, acetonitrile and tetrahydrofuran;
preferably, the molar ratio of the activated alkyne, the elemental selenium or the elemental tellurium and the base is 1: 1-6: 0.5 to 3;
preferably, the concentration of the activated alkyne in the mixed solution is 0.1-3 mol/L;
preferably, the eluent used for the column chromatography purification is a mixed solvent of petroleum ether, dichloromethane and ethyl acetate, and the volume ratio of the petroleum ether, the dichloromethane and the ethyl acetate is 100: 1-30: 1-10.
Preferably, the temperature of the oil bath reaction is 0-110 ℃, and the time of the oil bath reaction is 0.5-10 hours; the prepared heterocyclic compound containing selenium/tellurium is a 1, 4-diselenium/tellurium alkene compound.
Preferably, the temperature of the oil bath reaction is 111-160 ℃, and the time of the oil bath reaction is 0.5-12 hours; the prepared heterocyclic compound containing selenium/tellurium is a selenium/tellurium thiophene compound.
In the method for converting the heterocyclic compound containing selenium/tellurium, the 1, 4-diselenide/tellurium alkene compound is converted into the selenium/tellurium thiophene compound, and the chemical reaction equation is as follows:
Figure BDA0003018998390000041
the method comprises the following steps:
adding 1, 4-diselenide/tellurium alkene compounds, adding a solvent to obtain a mixed solution, and heating for reaction; after the reaction is finished, adding a saturated NaCl solution into the reaction solution, extracting with water and dichloromethane, taking a lower organic phase, drying the organic phase by anhydrous magnesium sulfate to remove water, filtering to obtain a filtrate, carrying out reduced pressure distillation to remove the dichloromethane to obtain a crude product, and carrying out column chromatography purification to obtain the selenium/tellurium-thiophene compound.
Preferably, the solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, toluene, 1, 4-dioxane, 1, 2-dichloromethane, 1, 2-dichloroethane, acetonitrile and tetrahydrofuran;
preferably, the temperature of the heating reaction is 80-160 ℃;
preferably, the concentration of the 1, 4-diselenide/tellurium alkene compound in the mixed solution is 0.05-3 mol/L;
preferably, the heating reaction time is 1-10 hours;
preferably, the eluent used for the column chromatography purification is a mixed solvent of petroleum ether, dichloromethane and ethyl acetate, and the volume ratio of the petroleum ether, the dichloromethane and the ethyl acetate is 100: 1-30: 1-10.
In the method for converting the heterocyclic compound containing selenium/tellurium, the 1, 4-diselenide/tellurium alkene compound is converted into the selenium/tellurium thiophene compound, and the chemical reaction equation is as follows:
Figure BDA0003018998390000051
the method comprises the following steps:
adding the 1, 4-diselenide/tellurium alkene compound and an oxidant, adding a solvent, mixing to obtain a mixed solution, and reacting; and after the reaction is finished, adding a saturated sodium sulfite solution into the reaction liquid, extracting with water and dichloromethane, taking a lower organic phase, drying the organic phase by anhydrous magnesium sulfate to remove water, filtering to obtain a filtrate, carrying out reduced pressure distillation to remove dichloromethane to obtain a crude product, and carrying out column chromatography purification to obtain the selenium/tellurium thiophene compound.
Preferably, the oxidant is more than one of oxidants such as hydrogen peroxide, m-chloroperoxybenzoic acid, tert-butyl hydroperoxide, potassium permanganate, potassium dichromate, manganese dioxide, nitric acid, sodium hypochlorite, sodium persulfate and the like;
preferably, the solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, toluene, 1, 4-dioxane, 1, 2-dichloromethane, 1, 2-dichloroethane, acetonitrile and tetrahydrofuran;
preferably, the concentration of the 1, 4-diselenium/tellurium/alkene compound in the mixed liquid is 0.05-3mol/L,
preferably, the 1, 4-diselenide/telluriene compound: the molar ratio of the oxidant is 1: 0.5-10,
preferably, the reaction temperature is 0-100 ℃, and the reaction time is 0.5-6 hours;
preferably, the eluent used for the column chromatography purification is a mixed solvent of petroleum ether, dichloromethane and ethyl acetate, and the volume ratio of the petroleum ether, the dichloromethane and the ethyl acetate is 100: 1-30: 1-10.
The 1, 4-diselenide/tellurium alkene compounds are taken as heterocyclic compounds which are not synthesized and reported, the unique non-planar ship-shaped structure greatly enriches selenium/tellurium heterocyclic compound libraries, and the abundant chemical properties and applications of the compounds still need to be further explored. The selenium/tellurium thiophene compound not only has photoelectric property, but also has certain biological activity, and plays a great role in the development and application of photoelectric materials, the synthesis of medicaments and the construction of natural products.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) in the invention, the activation of the elemental selenium can be realized by a simple method and mild conditions.
(2) The invention can synthesize sulfur-containing heterocyclic compounds such as 1, 4-diselenene, 1, 4-ditellurilene, selenophene, tellurophene and the like by simple temperature regulation.
(3) The preparation method of the invention does not need any metal catalyst, and the alkali can be added to induce the reaction.
(4) The preparation method can realize the conversion of the 1, 4-diselenide/tellurium alkene compound to the selenium/tellurium thiophene compound under the heating condition.
(5) The preparation method can realize the conversion of the 1, 4-diselenide/tellurium alkene compound to the selenium/tellurium thiophene compound in the presence of an oxidant.
(6) The preparation method disclosed by the invention is mild in condition, safe and simple to operate, good in stereoselectivity, green, economic and efficient in reaction.
Drawings
FIGS. 1 and 2 show the hydrogen and carbon spectra of 2, 5-dibenzoyl-3, 6-bis (9, 9-dimethylfluorenyl) -1, 4-diselenene, compound 3a, prepared in example 1 of the present invention.
FIGS. 3 and 4 are a hydrogen spectrum and a carbon spectrum of 2, 6-dibenzoyl-3, 5-bis (9, 9-dimethylfluorenyl) -1, 4-diselenene, compound 3b, prepared in example 1 of the present invention.
FIGS. 5 and 6 are a hydrogen spectrum and a carbon spectrum of 2, 4-dibenzoyl-3, 5-bis (9, 9-dimethylfluorenyl) selenophene, compound 4a, prepared in example 4 of the present invention.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
Example 1
Preparation method of 1, 4-diselenene compound
The 2, 5-dibenzoyl-3, 6-bis (9, 9-dimethylfluorenyl) -1, 4-diselenene 3a and the 2, 6-dibenzoyl-3, 5-bis (9, 9-dimethylfluorenyl) -1, 4-diselenene 3b compounds are prepared by directly reacting acetylenic ketone and elemental selenium, and the reaction equation is as shown in formula (I):
Figure BDA0003018998390000071
elemental selenium, 1, is commercially available, in this example from mayer chemical. 2a is an alkynone, the synthesis of which is described in the literature (Macromolecules 2015,48, 1941-1951);
the preparation steps of the 1, 4-diselenene compound are as follows:
after 0.32g (1.0mmol) of acetylenic ketone compound, 0.24g (3.0mmol) of elemental selenium and 0.06g (1.0mmol) of potassium hydroxide are sequentially added into a 10 mL polymerization tube, 2.0mL of dimethyl sulfoxide is injected into the polymerization tube by using an injector, the reaction is carried out for 3 hours at 60 ℃, the reaction progress degree is detected by a point plate, after the reaction is finished, a saturated NaCl solution is added into a reaction solution, water and dichloromethane are used for extraction, a lower layer organic phase is taken out, anhydrous magnesium sulfate is used for drying and water removal of the organic phase, filtrate is obtained by filtration, dichloromethane is removed by reduced pressure distillation, a crude product is obtained, and the crude product is purified by column chromatography, wherein the volume ratio of the used eluent is 2: 1 petroleum ether: mixed solvent of dichloromethane, to obtain 1, 4-diselenene compounds 3a and 3b in yields of 65% and 3%, respectively.
The hydrogen spectrum and the carbon spectrum of the product 3a obtained in the example are respectively shown in FIG. 1 and FIG. 2; the structural characterization data is as follows:
IR(KBr disk),ν(cm-1):3066,2959,2922,2868,1658,1598,1575,1539,1465,1450,1418,1310,1239,1174,1055,1020,1000,943,900,831,784,757,739,691,651,568,443.
1H NMR(500MHz,CDCl3)δ7.82-7.78(m,4H),7.60-7.57(m,2H),7.44(d,J＝7.9Hz,2H),7.41-7.34(m,7H),7.34(s,1H),7.31-7.26(m,5H),7.24(d,J＝7.6Hz,3H),1.28(s,12H).
13C NMR(125MHz,CDCl3)δ194.14,154.18,153.70,150.60,140.75,138.19,136.09,135.24,133.66,130.34,129.66,129.41,128.56,128.05,127.19,124.83,122.77,120.52,120.01,46.90,26.78.
HRMS(ESI):m/z:calcd for C48H36NaO2Se2[M+Na+]:827.0938；found 827.0955.
the hydrogen spectrum and the carbon spectrum of the product 3b obtained in this example are shown in fig. 3 and 4, respectively, and the structural characterization data are as follows:
IR(KBr disk),ν(cm-1):3059,2959,2917,2850,1648,1596,1578,1543,1467,1446,1415,1382,1310,1243,1178,1119,1059,1022,1006,853,832,781,762,737,694,645,568,443.
1H NMR(400MHz,CDCl3)δ7.74(d,J＝7.3Hz,4H),7.68-7.65(m,4H),7.60(d,J＝7.9Hz,2H),7.46-7.45(m,2H),7.38-7.40(m,2H),7.34-7.29(m,6H),7.20(t,J＝7.7Hz,4H),1.35(s,12H).
13C NMR(100MHz,CDCl3)δ193.36,154.16,153.85,149.17,140.74,138.23,136.24,134.98,133.63,129.73,129.60,128.92,128.47,128.11,127.25,124.86,122.84,120.53,120.12,46.97,26.88.
HRMS(ESI):m/z:calcd for C48H36NaO2Se2[M+Na+]:827.0938；found 827.0952.
example 2
Preparation method of 1, 4-diselenene compound
The 1, 4-diselenene compound is prepared by directly reacting cyclooctyne with elemental selenium, and the reaction equation is as shown in formula (II):
Figure BDA0003018998390000091
elemental selenium, 1, is commercially available, in this example from mayer chemical. 2b is cyclooctyne, and the synthesis method is described in the literature (ACS Macro Lett.,2019,8, 948-954);
the preparation steps of the 1, 4-diselenene compound are as follows:
after 0.18g (1.0mmol) of cyclooctyne, 0.24g (3.0mmol) of elemental selenium and 0.06g (1.0mmol) of potassium hydroxide are sequentially added into a 10 mL polymerization tube, 2.0mL of dimethyl sulfoxide is injected into the polymerization tube by using an injector, the reaction is carried out at 70 ℃ for 3 hours, the reaction progress degree is detected by a point plate, after the reaction is finished, a saturated NaCl solution is added into a reaction solution, water and dichloromethane are used for extraction, a lower organic phase is taken out, the organic phase is dried by anhydrous magnesium sulfate to remove water, a filtrate is taken out by filtration, dichloromethane is removed by reduced pressure distillation, a crude product is obtained, and the crude product is purified by column chromatography, wherein the volume ratio of the used eluent is 20: 1 petroleum ether: the yield of 1, 4-diselenene compound 3c was 63% with a mixed solvent of dichloromethane.
Example 3
Preparation method of 1, 4-diselenene compound
The 1, 4-diselenene compound is prepared by directly reacting a benzyne precursor with elemental selenium, and the reaction equation is as shown in formula (III):
Figure BDA0003018998390000092
elemental selenium, 1, is commercially available, in this example from mayer chemical. 2c is a benzyne precursor, the Synthesis of which is described in the literature (Synthesis,2002,10, 1454-1458);
the preparation steps of the 1, 4-diselenene compound are as follows:
after 0.30g (1.0mmol) of benzyne precursor, 0.24g (3.0mmol) of elemental selenium and 0.06g (1.0mmol) of potassium hydroxide are sequentially added into a 10 mL polymerization tube, 2.0mL of dimethyl sulfoxide is injected into the polymerization tube by using an injector, the reaction is carried out at 70 ℃ for 3 hours, the reaction progress degree is detected by a point plate, after the reaction is finished, a saturated NaCl solution is added into a reaction solution, water and dichloromethane are used for extraction, a lower organic phase is taken out, anhydrous magnesium sulfate is used for drying the organic phase to remove water, a filtrate is obtained by filtration, dichloromethane is removed by reduced pressure distillation, a crude product is obtained, and the crude product is purified by column chromatography, wherein the volume ratio of the used eluent is 20: 1 petroleum ether: the yield of 1, 4-diselenene compound 3d was 60% with a mixed solvent of dichloromethane.
Example 4
Preparation method of selenophen compound
The selenophen compound is prepared by directly reacting alkynone with elemental selenium, and the reaction equation is as shown in formula (IV):
Figure BDA0003018998390000101
elemental selenium, 1, is commercially available, in this example from mayer chemical. 2a is an alkynone, the synthesis of which is described in the literature (Macromolecules 2015,48, 1941-1951);
the preparation steps of the selenophen compound are as follows:
after 0.32g (1.0mmol) of acetylenic ketone compound, 0.24g (3.0mmol) of elemental selenium and 0.06g (1.0mmol) of potassium hydroxide are sequentially added into a 10 mL polymerization tube, 2.0mL of dimethyl sulfoxide is injected into the polymerization tube by using an injector, the reaction is carried out for 8 hours at 130 ℃, the reaction progress degree is detected by a point plate, after the reaction is finished, a saturated NaCl solution is added into a reaction solution, water and dichloromethane are used for extraction, a lower layer organic phase is taken out, anhydrous magnesium sulfate is used for drying and water removal of the organic phase, filtrate is obtained by filtration, dichloromethane is removed by reduced pressure distillation, a crude product is obtained, and the crude product is purified by column chromatography, wherein the volume ratio of the used eluent is 2: 1 petroleum ether: the yields of selenophene compound 4a obtained from the mixed solvent of dichloromethane were 68%.
The hydrogen spectrum and the carbon spectrum of the product 4a obtained in this example are shown in fig. 5 and 6, respectively, and the structural characterization data are as follows:
IR(KBr disk),ν(cm-1):3055,2958,2918,2858,1661,1617,1594,1576,1525,1442,1354,1334,1314,1261,1236,1172,1090,1073,1012,973,932,900,858,841,784,760,737,713,689,632,567,447.
1H NMR(400MHz,CDCl3)δ7.68-7.65(m,1H),7.63-7.58(m,5H),7.54-7.53(m,1H),7.51-7.46(m,2H),7.41-7.38(m,1H),7.34-7.28(m,3H),7.25-7.22(m,4H),7.15-7.09(m,3H),7.08-7.07(m,1H),7.04-6.98(m,3H),1.39(s,6H),1.17(s,6H).
13C NMR(100MHz,CDCl3)δ196.06,191.78,155.59,154.17,154.12,153.87,152.97,148.15,144.36,141.72,140.33,138.63,138.56,138.38,137.26,137.12,134.95,133.50,133.39,132.25,129.76,129.69,128.96,128.28,128.26,127.97,127.78,127.47,127.25,126.98,124.88,123.48,122.80,122.63,120.46,120.24,119.48,47.04,46.67,27.00,26.74.
HRMS(ESI):m/z:calcd for C48H36NaO2Se[M+Na+]:747.1773；found 747.1789.
example 5
Conversion of 1, 4-diselenenes into selenophenes (heating)
The 1, 4-diselenene compound can be converted into the selenophene compound by heating, and the reaction equation is as shown in the formula (five):
Figure BDA0003018998390000111
the experimental procedure for the conversion of the 2, 5-dibenzoyl-3, 6-bis (9, 9-dimethylfluorenyl) -1, 4-diselenene 3a to 2, 4-dibenzoyl-3, 5-bis (9, 9-dimethylfluorenyl) selenophene 4a was as follows:
adding 0.40g (0.5mmol) of 1, 4-diselenene 3a into a 10 mL polymerization tube, injecting 2.0mL of dimethyl sulfoxide into the polymerization tube by using an injector, reacting for 8 hours at 130 ℃, detecting the reaction progress by using a spot plate, extracting by using water and dichloromethane after the reaction is finished, taking a lower organic phase, drying the organic phase by using anhydrous magnesium sulfate to remove water, filtering to obtain a filtrate, distilling under reduced pressure to remove dichloromethane to obtain a crude product, and purifying by using column chromatography, wherein the volume ratio of used eluent is 2: 1 petroleum ether: the mixed solvent of dichloromethane can obtain the selenophen 4a with the yield of 75 percent.
Example 6
Conversion of 1, 4-diselenenes into selenophenes (oxidation process)
The 1, 4-diselenene compound can be converted into the selenophene compound through oxidation, and the reaction equation is as shown in the formula (six):
Figure BDA0003018998390000121
the experimental procedure for the conversion of the 2, 5-dibenzoyl-3, 6-bis (9, 9-dimethylfluorenyl) -1, 4-diselenene 3a to 2, 4-dibenzoyl-3, 5-bis (9, 9-dimethylfluorenyl) selenophene 4a was as follows:
adding 0.40g (0.5mmol) of 1, 4-diselenene 3a into a 10 mL polymerization tube, adding 0.23g (1mmol) of m-chloroperoxybenzoic acid, injecting 2.0mL of dimethyl sulfoxide into an injector, reacting at room temperature for 2 hours, detecting the reaction progress by using a point plate, adding a saturated anhydrous sodium sulfite solution after the reaction is finished, adding dichloromethane for extraction, taking a lower organic phase, drying the organic phase by anhydrous magnesium sulfate to remove water, filtering to obtain a filtrate, distilling under reduced pressure to remove dichloromethane, obtaining a crude product, and purifying by using column chromatography, wherein the volume ratio of used eluent is 2: 1 petroleum ether: mixed solvent of dichloromethane, and the yield of the selenophen 4a is 78 percent.
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.

Claims (10)

1.一种含硒/碲杂环类化合物，其特征在于，包括1,4-二硒/碲烯类化合物和硒/碲吩类化合物；1. A selenium/tellurium-containing heterocyclic compound, characterized in that it comprises 1,4-diselenide/telluene compound and selenium/telluride compound; 所述1,4-二硒/碲烯类化合物的结构式为如下结构通式之一：The structural formula of the 1,4-diselenide/telluene compound is one of the following general structural formulas:
Figure FDA0003018998380000011
Figure FDA0003018998380000011
 所述硒/碲吩类化合物的结构式为如下结构通式之一：The structural formula of the selenium/telluride compound is one of the following general structural formulas:
Figure FDA0003018998380000012
Figure FDA0003018998380000012
 其中，X为硒或碲，R1为酯基、乙酰基、醛基、芳基、三氟甲基、硫三氟甲基、五氟苯基、吡啶基、烷基以及氢取代中的一种，R2为酯基、乙酰基、醛基、芳基、三氟甲基、硫三氟甲基、五氟苯基、吡啶基、烷基以及氢取代中的一种，R3为酯基、乙酰基、醛基、芳基、三氟甲基、硫三氟甲基、五氟苯基、吡啶基、烷基以及氢取代中的一种，R4为酯基、乙酰基、醛基、芳基、三氟甲基、硫三氟甲基、五氟苯基、吡啶基、烷基以及氢取代中的一种；R5和R6为任意取代位置的烷基、甲氧基、酯基、乙酰基、硝基、三氟甲基、硫三氟甲基、卤素以及氢中的一种；n的取值范围为0-7。Wherein, X is selenium or tellurium, R 1 is one of ester group, acetyl group, aldehyde group, aryl group, trifluoromethyl group, sulfur trifluoromethyl group, pentafluorophenyl group, pyridyl group, alkyl group and hydrogen substitution Species, R 2 is one of ester group, acetyl group, aldehyde group, aryl group, trifluoromethyl, sulfur trifluoromethyl, pentafluorophenyl, pyridyl, alkyl and hydrogen substitution, R 3 is ester One of the group, acetyl group, aldehyde group, aryl group, trifluoromethyl group, sulfur trifluoromethyl group, pentafluorophenyl group, pyridyl group, alkyl group and hydrogen substitution, R 4 is ester group, acetyl group, aldehyde group one of radical, aryl, trifluoromethyl, sulfur trifluoromethyl, pentafluorophenyl, pyridyl, alkyl and hydrogen substitution; R 5 and R 6 are alkyl, methoxyl at any substitution position , one of ester group, acetyl group, nitro group, trifluoromethyl group, sulfur trifluoromethyl group, halogen and hydrogen; the value range of n is 0-7. 2.根据权利要求1所述的含硒/碲杂环类化合物，其特征在于，所述R1，R2，R3，R4选自以下结构式的任意一种：2. The selenium/tellurium-containing heterocyclic compound according to claim 1, wherein the R 1 , R 2 , R 3 , and R 4 are selected from any one of the following structural formulas:
Figure FDA0003018998380000021
Figure FDA0003018998380000021
 3.一种权利要求1或2所述的含硒/碲杂环类化合物的制备方法，其特征在于，包括如下步骤：3. the preparation method of a selenium-containing/tellurium heterocyclic compound described in claim 1 or 2, is characterized in that, comprises the steps: 加入活化炔、单质硒或单质碲以及碱后，再加入溶剂，得到混合液，升温进行油浴反应，待反应结束后，在反应液中加入饱和NaCl溶液后，用水和二氯甲烷进行萃取，取下层有机相，有机相经无水硫酸镁干燥除去水、过滤取滤液，减压蒸馏除去二氯甲烷，得到粗产物后，经柱层析提纯得到所述含硒/碲杂环类化合物。After adding activated alkyne, elemental selenium or elemental tellurium and alkali, then adding solvent to obtain a mixed solution, heating up to carry out oil bath reaction, after the reaction is over, adding saturated NaCl solution to the reaction solution, and extracting with water and dichloromethane, The lower organic phase is taken, the organic phase is dried over anhydrous magnesium sulfate to remove water, filtered to collect the filtrate, and the dichloromethane is distilled off under reduced pressure to obtain a crude product, which is purified by column chromatography to obtain the selenium-containing/tellurium-containing heterocyclic compound. 4.根据权利要求3所述的含硒/碲杂环类化合物的制备方法，其特征在于，所述活化炔为芳基炔酯、烷基炔酯、芳基炔酮、烷基炔酮、芳基炔醛、烷基炔醛、苯炔、芳基或烷基取代的苯炔、环辛炔、芳基或烷基取代的环辛炔、乙炔基吡啶、芳基或烷基取代的吡啶内炔、三氟甲基或硫三氟甲基取代炔以及五氟苯基取代炔中的一种以上；所述碱为吡啶、三乙胺、碳酸钾、碳酸钠、氢氧化钠、氢氧化钾、氢氧化铯、叔丁醇钠、叔丁醇钾、乙醇钠、氟化铯或碳酸铯；所述溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜、甲苯、1,4-二氧六环、1,2-二氯甲烷、1,2-二氯乙烷、乙腈及四氢呋喃中的一种以上；所述活化炔、单质硒或单质碲及碱的摩尔比为1：1-6：0.5-3；在所述混合液中，活化炔的浓度为0.1-3mol/L；所述柱层析提纯使用洗脱液为石油醚、二氯甲烷和乙酸乙酯的混合溶剂，所述石油醚、二氯甲烷、乙酸乙酯的体积比为100：1-30：1-10。4. The preparation method of selenium-containing/tellurium heterocyclic compounds according to claim 3, wherein the activated alkyne is an aryl alkynyl ester, an alkyl alkynyl ester, an aryl alkynone, an alkyl alkynone, Aryl alkynals, alkyl alkynals, benzynes, aryl or alkyl substituted benzynes, cyclooctynes, aryl or alkyl substituted cyclooctynes, ethynyl pyridines, aryl or alkyl substituted pyridines One or more of internal alkyne, trifluoromethyl or sulfur trifluoromethyl substituted alkyne and pentafluorophenyl substituted alkyne; the base is pyridine, triethylamine, potassium carbonate, sodium carbonate, sodium hydroxide, hydroxide Potassium, cesium hydroxide, sodium tert-butoxide, potassium tert-butoxide, sodium ethoxide, cesium fluoride or cesium carbonate; the solvent is N,N-dimethylformamide, N,N-dimethylacetamide, One or more of dimethyl sulfoxide, toluene, 1,4-dioxane, 1,2-dichloromethane, 1,2-dichloroethane, acetonitrile and tetrahydrofuran; the activated alkyne, elemental selenium Or the molar ratio of elemental tellurium and alkali is 1:1-6:0.5-3; in the mixed solution, the concentration of activated alkyne is 0.1-3mol/L; the eluent used in the column chromatography purification is petroleum ether , a mixed solvent of dichloromethane and ethyl acetate, and the volume ratio of the petroleum ether, dichloromethane and ethyl acetate is 100:1-30:1-10. 5.根据权利要求3所述的含硒/碲杂环类化合物的制备方法，其特征在于，所述油浴反应的温度为0-110℃，油浴反应的时间为0.5-10小时；制备的含硒/碲杂环类化合物为1,4-二硒/碲烯类化合物。5 . The preparation method of selenium-containing/tellurium heterocyclic compounds according to claim 3 , wherein the temperature of the oil bath reaction is 0-110° C., and the time of the oil bath reaction is 0.5-10 hours; preparation The selenium/tellurium-containing heterocyclic compounds are 1,4-diselenide/telluene compounds. 6.根据权利要求3所述的含硒/碲杂环类化合物的制备方法，其特征在于，油浴反应的温度为111-160℃，油浴反应的时间为0.5-12小时；制备的含硒/碲杂环类化合物为硒/碲吩类化合物。6 . The method for preparing a selenium-containing/tellurium heterocyclic compound according to claim 3 , wherein the temperature of the oil bath reaction is 111-160° C., and the time of the oil bath reaction is 0.5-12 hours; 6 . The selenium/tellurium heterocyclic compounds are selenium/tellurophene compounds. 7.权利要求1或2所述含硒/碲杂环类化合物的转化方法，其特征在于，所述1,4-二硒/碲烯类化合物向硒/碲吩类化合物转化，化学反应方程式如下所示：7. The method for converting selenium/tellurium-containing heterocyclic compounds according to claim 1 or 2, wherein the 1,4-diselenide/telluene compound is converted into a selenium/telluride compound, and the chemical reaction equation is as follows: As follows:
Figure FDA0003018998380000031
Figure FDA0003018998380000031
 包括如下步骤：It includes the following steps: 加入1,4-二硒/碲烯类化合物，再加入溶剂得到混合液，加热反应；待反应结束后，在反应液中加入饱和NaCl溶液后，用水和二氯甲烷进行萃取，取下层有机相，有机相经无水硫酸镁干燥除去水、过滤取滤液，减压蒸馏除去二氯甲烷，得到粗产物后，经柱层析提纯得到硒/碲吩类化合物。Add 1,4-diselenide/telluene compound, and then add solvent to obtain a mixed solution, and heat the reaction; after the reaction is completed, add saturated NaCl solution to the reaction solution, extract with water and dichloromethane, and remove the lower organic phase , the organic phase was dried over anhydrous magnesium sulfate to remove water, the filtrate was collected by filtration, and the dichloromethane was distilled off under reduced pressure to obtain a crude product, which was purified by column chromatography to obtain selenium/telluride compounds. 8.根据权利要求7所述的转化方法，其特征在于，所述溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜、甲苯、1,4-二氧六环、1,2-二氯甲烷、1,2-二氯乙烷、乙腈及四氢呋喃中的一种以上；所述加热反应的温度为80-160℃；所述混合液中1,4-二硒/碲烯类化合物的浓度为0.05-3mol/L；所述加热反应的时间为1-10小时；所述柱层析提纯使用洗脱液为石油醚、二氯甲烷、乙酸乙酯的混合溶剂，石油醚、二氯甲烷、乙酸乙酯的体积比为100：1-30：1-10。8. conversion method according to claim 7, is characterized in that, described solvent is N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, toluene, 1, One or more of 4-dioxane, 1,2-dichloromethane, 1,2-dichloroethane, acetonitrile and tetrahydrofuran; the temperature of the heating reaction is 80-160°C; The concentration of 1,4-diselenide/telluene compound is 0.05-3mol/L; the time of the heating reaction is 1-10 hours; the eluent used in the column chromatography purification is petroleum ether, dichloromethane, For the mixed solvent of ethyl acetate, the volume ratio of petroleum ether, dichloromethane and ethyl acetate is 100:1-30:1-10. 9.权利要求1或2所述含硒/碲杂环类化合物的转化方法，其特征在于，所述1,4-二硒/碲烯类化合物向硒/碲吩类化合物转化，化学反应方程式如下所示：9. The method for converting selenium/tellurium-containing heterocyclic compounds according to claim 1 or 2, wherein the 1,4-diselenide/telluene compound is converted into a selenium/telluride compound, and the chemical reaction equation is as follows: As follows:
Figure FDA0003018998380000041
Figure FDA0003018998380000041
 包括如下步骤：It includes the following steps: 加入所述1,4-二硒/碲烯类化合物以及氧化剂，再加入溶剂，混合，得到混合液，进行反应；待反应结束后，在反应液中加入饱和亚硫酸钠溶液，用水和二氯甲烷进行萃取，取下层有机相，有机相经无水硫酸镁干燥除去水、过滤取滤液，减压蒸馏除去二氯甲烷，得到粗产物后，经柱层析提纯得到硒/碲吩化合物。Add the 1,4-diselenide/telluene compound and the oxidizing agent, then add the solvent, mix to obtain a mixed solution, and carry out the reaction; after the reaction is completed, add saturated sodium sulfite solution to the reaction solution, and carry out the reaction with water and dichloromethane. Extraction, take the lower organic phase, dry the organic phase over anhydrous magnesium sulfate to remove water, collect the filtrate by filtration, and remove dichloromethane by distillation under reduced pressure to obtain a crude product, which is purified by column chromatography to obtain a selenium/tellurophene compound. 10.根据权利要求9所述的转化方法，其特征在于，所述氧化剂为双氧水、间氯过氧苯甲酸、叔丁基过氧化氢、高锰酸钾、重铬酸钾、二氧化锰、硝酸、次氯酸钠、过硫酸钠等氧化剂中的一种以上；所述溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜、甲苯、1,4-二氧六环、1,2-二氯甲烷、1,2-二氯乙烷、乙腈以及四氢呋喃中的一种以上；所述混合液中，1,4-二硒/碲/烯类化合物的浓度为0.05-3mol/L；所述1,4-二硒/碲烯类化合物：氧化剂的摩尔比为1：0.5-10；所述反应的温度为0-100℃，反应的时间为0.5-6小时；所述柱层析提纯使用洗脱液为石油醚、二氯甲烷、乙酸乙酯的混合溶剂，石油醚、二氯甲烷、乙酸乙酯的体积比为100：1-30：1-10。10. conversion method according to claim 9 is characterized in that, described oxidant is hydrogen peroxide, m-chloroperoxybenzoic acid, tert-butyl hydroperoxide, potassium permanganate, potassium dichromate, manganese dioxide, One or more of oxidizing agents such as nitric acid, sodium hypochlorite, and sodium persulfate; the solvent is N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, toluene, 1,4 - one or more of dioxane, 1,2-dichloromethane, 1,2-dichloroethane, acetonitrile and tetrahydrofuran; in the mixed solution, 1,4-diselenide/tellurium/ene compounds The concentration of 0.05-3mol/L; the molar ratio of the 1,4-diselenide/telluene compound: oxidant is 1:0.5-10; the reaction temperature is 0-100 ℃, and the reaction time is 0.5 -6 hours; the eluent used in the column chromatography purification is a mixed solvent of petroleum ether, dichloromethane and ethyl acetate, and the volume ratio of petroleum ether, dichloromethane and ethyl acetate is 100:1-30:1 -10.
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