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 PDFInfo
- Publication number
- 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
- Authority
- CN
- China
- Prior art keywords
- tellurium
- group
- selenium
- compound
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D345/00—Heterocyclic compounds containing rings having selenium or tellurium atoms as the only ring hetero atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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
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:
the structural formula of the selenium/tellurium thiophene compound is one of the following structural general formulas:
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:
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:
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:
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):
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):
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):
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):
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):
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):
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. A kind of heterocyclic compound containing selenium/tellurium, characterized by, including 1, 4-diselenide/tellurium alkene compound and selenium/tellurium thiophene compound;
the structural formula of the 1, 4-diselenide/tellurium alkene compound is one of the following structural general formulas:
the structural formula of the selenium/tellurium thiophene compound is one of the following structural general formulas:
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.
2. The selenium-containing compound of claim 1Tellurium heterocyclic compound, characterized in that R is1，R2，R3，R4Any one selected from the following structural formulae:
3. a method of preparing a selenium/tellurium-containing heterocyclic compound of claim 1 or 2, comprising the steps of:
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.
4. The method of claim 3, wherein 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 phenyl alkyne, an aryl or alkyl substituted phenyl alkyne, 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; the alkali is pyridine, triethylamine, potassium carbonate, sodium hydroxide, potassium hydroxide, cesium hydroxide, sodium tert-butoxide, potassium tert-butoxide, sodium ethoxide, cesium fluoride or cesium carbonate; the solvent is more than one of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, toluene, 1, 4-dioxane, 1, 2-dichloromethane, 1, 2-dichloroethane, acetonitrile and tetrahydrofuran; the molar ratio of the activated alkyne to the elemental selenium or tellurium to the alkali is 1: 1-6: 0.5 to 3; in the mixed solution, the concentration of the activated alkyne is 0.1-3 mol/L; the eluent used for column chromatography purification is a mixed solvent of petroleum ether, dichloromethane and ethyl acetate, and the volume ratio of the petroleum ether to the dichloromethane to the ethyl acetate is 100: 1-30: 1-10.
5. The method of claim 3, wherein the temperature of the oil bath reaction is 0 to 110 ℃ and the time of the oil bath reaction is 0.5 to 10 hours; the prepared heterocyclic compound containing selenium/tellurium is a 1, 4-diselenium/tellurium alkene compound.
6. The method according to claim 3, wherein 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.
7. The method of claim 1 or 2, wherein the 1, 4-diseleno/telluroene compound is converted to a selenium/tellurothiophene compound according to the following reaction equation:
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, removing 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 and thiophene compound.
8. The conversion method according to claim 7, wherein the solvent is one or more selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, toluene, 1, 4-dioxane, 1, 2-dichloromethane, 1, 2-dichloroethane, acetonitrile and tetrahydrofuran; the temperature of the heating reaction is 80-160 ℃; the concentration of the 1, 4-diselenide/tellurium alkene compound in the mixed solution is 0.05-3 mol/L; the heating reaction time is 1-10 hours; the eluent used for column chromatography purification is a mixed solvent of petroleum ether, dichloromethane and ethyl acetate, and the volume ratio of the petroleum ether to the dichloromethane to the ethyl acetate is 100: 1-30: 1-10.
9. The method of claim 1 or 2, wherein the 1, 4-diseleno/telluroene compound is converted to a selenium/tellurothiophene compound according to the following reaction equation:
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.
10. The conversion method according to claim 9, wherein the oxidizing agent is one or more of oxidizing agents such as hydrogen peroxide, m-chloroperoxybenzoic acid, t-butyl hydroperoxide, potassium permanganate, potassium dichromate, manganese dioxide, nitric acid, sodium hypochlorite, and sodium persulfate; the solvent is more than one of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, toluene, 1, 4-dioxane, 1, 2-dichloromethane, 1, 2-dichloroethane, acetonitrile and tetrahydrofuran; in the mixed liquid, the concentration of the 1, 4-diselenium/tellurium/alkene compounds is 0.05-3 mol/L; the 1, 4-diselenide/tellurium alkene compound: the molar ratio of the oxidant is 1: 0.5-10; the reaction temperature is 0-100 ℃, and the reaction time is 0.5-6 hours; the eluent used for column chromatography purification is a mixed solvent of petroleum ether, dichloromethane and ethyl acetate, and the volume ratio of the petroleum ether to the dichloromethane to the ethyl acetate is 100: 1-30: 1-10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110397210.9A CN113173909A (en) | 2021-04-13 | 2021-04-13 | Selenium/tellurium-containing heterocyclic compound and preparation method and conversion method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110397210.9A CN113173909A (en) | 2021-04-13 | 2021-04-13 | Selenium/tellurium-containing heterocyclic compound and preparation method and conversion method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113173909A true CN113173909A (en) | 2021-07-27 |
Family
ID=76924870
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110397210.9A Pending CN113173909A (en) | 2021-04-13 | 2021-04-13 | Selenium/tellurium-containing heterocyclic compound and preparation method and conversion method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113173909A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114437024A (en) * | 2022-02-24 | 2022-05-06 | 复旦大学 | Aromatic tellurium pyran derivative and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111233827A (en) * | 2020-02-29 | 2020-06-05 | 华南理工大学 | 2, 5-disubstituted selenophene compound and synthetic method thereof |
| CN112028872A (en) * | 2020-09-16 | 2020-12-04 | 温州大学 | Synthetic method of dibenzoselenophene compound |
| CN112442008A (en) * | 2020-09-22 | 2021-03-05 | 华南理工大学 | Method for preparing 1, 4-dithiine and thiophene compounds by regulating elemental sulfur and active internal alkyne at temperature and conversion reaction of compound |
-
2021
- 2021-04-13 CN CN202110397210.9A patent/CN113173909A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111233827A (en) * | 2020-02-29 | 2020-06-05 | 华南理工大学 | 2, 5-disubstituted selenophene compound and synthetic method thereof |
| CN112028872A (en) * | 2020-09-16 | 2020-12-04 | 温州大学 | Synthetic method of dibenzoselenophene compound |
| CN112442008A (en) * | 2020-09-22 | 2021-03-05 | 华南理工大学 | Method for preparing 1, 4-dithiine and thiophene compounds by regulating elemental sulfur and active internal alkyne at temperature and conversion reaction of compound |
Non-Patent Citations (7)
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114437024A (en) * | 2022-02-24 | 2022-05-06 | 复旦大学 | Aromatic tellurium pyran derivative and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108047198A (en) | A kind of method that ruthenium catalysis arone prepares more virtue substitution naphthalene derivativeses with tolans reaction | |
| CN105801575A (en) | Synthetic method of imidazo[1,2-a]pyridine | |
| CN112442008B (en) | Method for preparing 1, 4-dithiine and thiophene compounds by regulating elemental sulfur and active internal alkyne at temperature and conversion reaction of compound | |
| CN113173909A (en) | Selenium/tellurium-containing heterocyclic compound and preparation method and conversion method thereof | |
| CN111807938A (en) | (E) -1-chloro-2-iodoethylene compound and preparation method thereof | |
| CN111362795B (en) | Preparation method of substituted butyrate derivatives | |
| CN113045530B (en) | Method for preparing naphthopyran compounds by ruthenium catalysis | |
| CN107513056A (en) | A kind of synthetic method of the quinolines of the group containing tetrahydrofuran | |
| CN105237466B (en) | A kind of method for synthesizing three substituted pyridine derivatives | |
| CN109761929B (en) | Method for synthesizing 1,3, 4-oxadiazine-2-ketone and 1,3, 4-thiadiazine-2-ketone compounds | |
| CN110294708B (en) | Preparation method of trifluoroethylselenophenanthridine and 3, 4-dihydroisoquinoline derivatives | |
| CN107021968B (en) | The method of the polysubstituted organic photochemical catalyst catalyzing indole quinoline class compound oxidation dehydrogenation synthesis of indole class compound of BODIPY | |
| CN107445835B (en) | Synthesis method of 1, 2-dihydro cyclobuteno [ a ] naphthalene derivative and precursor thereof | |
| CN111732552A (en) | Method for synthesizing 1, 3-oxazole-2-thioketone by palladium catalysis | |
| CN111704590B (en) | Synthesis method of iron-catalyzed 2-arylbenzothiazole compound | |
| CN112645895B (en) | Isoxazoline derivative with olefin side chain and synthesis method thereof | |
| CN111732508B (en) | Synthesis method of spiro compound | |
| CN114907268B (en) | Method for synthesizing 2H-imidazole compound from aryl methyl ketone compound and ammonium acetate | |
| CN108358761B (en) | Salvianolic acid A intermediate and preparation method thereof | |
| CN108976106B (en) | (E) Synthesis method of (E) -2-methylene-1, 4-butanedione compounds | |
| WO2017154948A1 (en) | Method for producing fluorinated compound | |
| CN113024431B (en) | Photocatalytic synthesis method of (E) -1, 2-diseleno cyanoalkene compound | |
| CN110452148B (en) | Method for synthesizing polysubstituted pyrrole compound by utilizing alpha-hydroxy ketone, malononitrile and alcohol | |
| Simoens et al. | Continuous Flow Synthesis of Group 11 Metal‐NHC Complexes [M (IPr)(OC (H)(CF3) 2)](with M= Cu, Ag and Au) | |
| Xu et al. | Copper‐Catalyzed Cyanoalkylation and Trifluoromethylthiolation of Styrene Derivatives via a Visible‐Light‐Promoted Cross‐Coupling |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |