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
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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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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 82
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000011669 selenium Substances 0.000 title claims abstract description 64
- 229910052711 selenium Inorganic materials 0.000 title claims abstract description 61
- 229910052714 tellurium Inorganic materials 0.000 title claims abstract description 58
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 150000002391 heterocyclic compounds Chemical class 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 21
- -1 tellurium alkene compound Chemical class 0.000 claims abstract description 63
- 150000001875 compounds Chemical class 0.000 claims abstract description 31
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 18
- 150000003342 selenium Chemical class 0.000 claims abstract 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 132
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 38
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 36
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000012074 organic phase Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 21
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 238000004440 column chromatography Methods 0.000 claims description 18
- 239000003208 petroleum Substances 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 239000012043 crude product Substances 0.000 claims description 16
- 229910052739 hydrogen Chemical group 0.000 claims description 16
- 239000001257 hydrogen Chemical group 0.000 claims description 16
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 14
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 239000003480 eluent Substances 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 12
- 239000012046 mixed solvent Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 12
- 239000011593 sulfur Substances 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 claims description 11
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000006467 substitution reaction Methods 0.000 claims description 10
- 125000004185 ester group Chemical group 0.000 claims description 9
- 239000007800 oxidant agent Substances 0.000 claims description 9
- 238000000746 purification Methods 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 125000003172 aldehyde group Chemical group 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 125000004076 pyridyl group Chemical group 0.000 claims description 8
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 4
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical class [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 2
- NHUBNHMFXQNNMV-UHFFFAOYSA-N 2-ethynylpyridine Chemical group C#CC1=CC=CC=N1 NHUBNHMFXQNNMV-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003748 selenium group Chemical group *[Se]* 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims 2
- SEPPVOUBHWNCAW-FNORWQNLSA-N (E)-4-oxonon-2-enal Chemical compound CCCCCC(=O)\C=C\C=O SEPPVOUBHWNCAW-FNORWQNLSA-N 0.000 claims 1
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 claims 1
- LLBZPESJRQGYMB-UHFFFAOYSA-N 4-one Natural products O1C(C(=O)CC)CC(C)C11C2(C)CCC(C3(C)C(C(C)(CO)C(OC4C(C(O)C(O)C(COC5C(C(O)C(O)CO5)OC5C(C(OC6C(C(O)C(O)C(CO)O6)O)C(O)C(CO)O5)OC5C(C(O)C(O)C(C)O5)O)O4)O)CC3)CC3)=C3C2(C)CC1 LLBZPESJRQGYMB-UHFFFAOYSA-N 0.000 claims 1
- DNXHEGUUPJUMQT-CBZIJGRNSA-N Estrone Chemical compound OC1=CC=C2[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CCC2=C1 DNXHEGUUPJUMQT-CBZIJGRNSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims 1
- 150000003222 pyridines Chemical class 0.000 claims 1
- 150000003254 radicals Chemical class 0.000 claims 1
- 229910000029 sodium carbonate Inorganic materials 0.000 claims 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 abstract description 10
- 229930192474 thiophene Natural products 0.000 abstract description 10
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 239000003814 drug Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 229940079593 drug Drugs 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- TULWUZJYDBGXMY-UHFFFAOYSA-N tellurophene Chemical compound [Te]1C=CC=C1 TULWUZJYDBGXMY-UHFFFAOYSA-N 0.000 abstract description 4
- 230000033228 biological regulation Effects 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000010276 construction Methods 0.000 abstract description 3
- 229930014626 natural product Natural products 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 102000004169 proteins and genes Human genes 0.000 abstract description 3
- 108090000623 proteins and genes Proteins 0.000 abstract description 3
- 238000010189 synthetic method Methods 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 11
- 238000001228 spectrum Methods 0.000 description 11
- 238000001035 drying Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- ZPWOOKQUDFIEIX-UHFFFAOYSA-N cyclooctyne Chemical compound C1CCCC#CCC1 ZPWOOKQUDFIEIX-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- KLYCPFXDDDMZNQ-UHFFFAOYSA-N Benzyne Chemical compound C1=CC#CC=C1 KLYCPFXDDDMZNQ-UHFFFAOYSA-N 0.000 description 3
- 150000000475 acetylene derivatives Chemical group 0.000 description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- MABNMNVCOAICNO-UHFFFAOYSA-N selenophene Chemical compound C=1C=C[se]C=1 MABNMNVCOAICNO-UHFFFAOYSA-N 0.000 description 3
- 229910000144 sodium(I) superoxide Inorganic materials 0.000 description 3
- ASQOQJYHIYYTEJ-GBESFXJTSA-N (1r,7s,9as)-7-decyl-2,3,4,6,7,8,9,9a-octahydro-1h-quinolizin-1-ol Chemical compound O[C@@H]1CCCN2C[C@@H](CCCCCCCCCC)CC[C@H]21 ASQOQJYHIYYTEJ-GBESFXJTSA-N 0.000 description 2
- YECVQOULKHBGEN-UHFFFAOYSA-N 1,3-diphenylprop-2-yn-1-one Chemical group C=1C=CC=CC=1C(=O)C#CC1=CC=CC=C1 YECVQOULKHBGEN-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000005082 selenophenes Chemical class 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- FANCTJAFZSYTIS-IQUVVAJASA-N (1r,3s,5z)-5-[(2e)-2-[(1r,3as,7ar)-7a-methyl-1-[(2r)-4-(phenylsulfonimidoyl)butan-2-yl]-2,3,3a,5,6,7-hexahydro-1h-inden-4-ylidene]ethylidene]-4-methylidenecyclohexane-1,3-diol Chemical compound C([C@@H](C)[C@@H]1[C@]2(CCCC(/[C@@H]2CC1)=C\C=C\1C([C@@H](O)C[C@H](O)C/1)=C)C)CS(=N)(=O)C1=CC=CC=C1 FANCTJAFZSYTIS-IQUVVAJASA-N 0.000 description 1
- WACNXHCZHTVBJM-UHFFFAOYSA-N 1,2,3,4,5-pentafluorobenzene Chemical group FC1=CC(F)=C(F)C(F)=C1F WACNXHCZHTVBJM-UHFFFAOYSA-N 0.000 description 1
- 238000007106 1,2-cycloaddition reaction Methods 0.000 description 1
- PSWDQTMAUUQILQ-UHFFFAOYSA-N 2-[(6-methoxy-4-methylquinazolin-2-yl)amino]-5,6-dimethyl-1h-pyrimidin-4-one Chemical compound N1=C(C)C2=CC(OC)=CC=C2N=C1NC1=NC(=O)C(C)=C(C)N1 PSWDQTMAUUQILQ-UHFFFAOYSA-N 0.000 description 1
- FTMZAGJOJBAHFV-UHFFFAOYSA-N C(C=CC1=CC=CC=C1)(=O)C1=CC=CC=2C3=CC=CC=C3CC12 Chemical compound C(C=CC1=CC=CC=C1)(=O)C1=CC=CC=2C3=CC=CC=C3CC12 FTMZAGJOJBAHFV-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- MBLUWALPEKUVHJ-UHFFFAOYSA-N [Se].[C] Chemical compound [Se].[C] MBLUWALPEKUVHJ-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- OSVHLUXLWQLPIY-KBAYOESNSA-N butyl 2-[(6aR,9R,10aR)-1-hydroxy-9-(hydroxymethyl)-6,6-dimethyl-6a,7,8,9,10,10a-hexahydrobenzo[c]chromen-3-yl]-2-methylpropanoate Chemical compound C(CCC)OC(C(C)(C)C1=CC(=C2[C@H]3[C@H](C(OC2=C1)(C)C)CC[C@H](C3)CO)O)=O OSVHLUXLWQLPIY-KBAYOESNSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940125796 compound 3d Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
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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
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- 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.
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