CN110452145A - α,β-不饱和硒类化合物的合成方法 - Google Patents
α,β-不饱和硒类化合物的合成方法 Download PDFInfo
- Publication number
- CN110452145A CN110452145A CN201910646508.1A CN201910646508A CN110452145A CN 110452145 A CN110452145 A CN 110452145A CN 201910646508 A CN201910646508 A CN 201910646508A CN 110452145 A CN110452145 A CN 110452145A
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- CN
- China
- Prior art keywords
- selenium
- reaction
- yield
- class compound
- unsaturation
- Prior art date
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- -1 selenium class compound Chemical class 0.000 title claims abstract description 47
- 238000010189 synthetic method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000758 substrate Substances 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000003446 ligand Substances 0.000 claims description 30
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000010949 copper Substances 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 5
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 4
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 125000005594 diketone group Chemical group 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 46
- 239000011669 selenium Substances 0.000 abstract description 15
- 229910052711 selenium Inorganic materials 0.000 abstract description 11
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 7
- 231100000331 toxic Toxicity 0.000 abstract description 5
- 230000002588 toxic effect Effects 0.000 abstract description 5
- 238000011161 development Methods 0.000 abstract description 4
- 229940065287 selenium compound Drugs 0.000 abstract description 4
- 150000003343 selenium compounds Chemical class 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- YQMLDSWXEQOSPP-UHFFFAOYSA-N selanylidenemercury Chemical compound [Hg]=[Se] YQMLDSWXEQOSPP-UHFFFAOYSA-N 0.000 abstract description 3
- 150000003346 selenoethers Chemical class 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 132
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 74
- 239000003208 petroleum Substances 0.000 description 34
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 33
- 238000005160 1H NMR spectroscopy Methods 0.000 description 33
- 239000007788 liquid Substances 0.000 description 33
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 150000001988 diarylethenes Chemical class 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 241000425573 Talanes Species 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 5
- 239000004305 biphenyl Substances 0.000 description 5
- 239000004327 boric acid Substances 0.000 description 5
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000000010 aprotic solvent Substances 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 125000006267 biphenyl group Chemical group 0.000 description 4
- XIMIGUBYDJDCKI-UHFFFAOYSA-N diselenium Chemical compound [Se]=[Se] XIMIGUBYDJDCKI-UHFFFAOYSA-N 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- WQVIGFSCSOJSMM-UHFFFAOYSA-N CC(C)(C)C1=CC=C(C=C1)C(=C[Se]C2=CC=CC=C2)C3=CC4=CC=CC=C4C=C3 Chemical compound CC(C)(C)C1=CC=C(C=C1)C(=C[Se]C2=CC=CC=C2)C3=CC4=CC=CC=C4C=C3 WQVIGFSCSOJSMM-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- LXLQUIVAWJYQTQ-UHFFFAOYSA-N (2-selenocyanatophenyl) selenocyanate Chemical compound N#C[Se]C1=CC=CC=C1[Se]C#N LXLQUIVAWJYQTQ-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 1
- ZQCCCOCQYLCNNY-UHFFFAOYSA-N 1-(2,2-diphenylethenylselanyl)-4-methylbenzene Chemical compound CC1=CC=C(C=C1)[Se]C=C(C2=CC=CC=C2)C3=CC=CC=C3 ZQCCCOCQYLCNNY-UHFFFAOYSA-N 0.000 description 1
- WOYYHLVOPIOPHQ-UHFFFAOYSA-N 1-(2,2-diphenylethenylselanyl)thianthrene Chemical compound C1=CC=C(C=C1)C(=C[Se]C2=CC=CC3=C2SC4=CC=CC=C4S3)C5=CC=CC=C5 WOYYHLVOPIOPHQ-UHFFFAOYSA-N 0.000 description 1
- OIBRVHHYNAHQGY-UHFFFAOYSA-N 1-methyl-2-(1-phenyl-2-phenylselanylethenyl)benzene Chemical compound CC1=CC=CC=C1C(=C[Se]C2=CC=CC=C2)C3=CC=CC=C3 OIBRVHHYNAHQGY-UHFFFAOYSA-N 0.000 description 1
- UCWKXKJTJSHPSK-UHFFFAOYSA-N 1-methyl-3-(1-phenyl-2-phenylselanylethenyl)benzene Chemical compound CC1=CC(=CC=C1)C(=C[Se]C2=CC=CC=C2)C3=CC=CC=C3 UCWKXKJTJSHPSK-UHFFFAOYSA-N 0.000 description 1
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- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 1
- WQAXJVYXCKNYCB-UHFFFAOYSA-N [Se].C1=CC=CC=C1 Chemical compound [Se].C1=CC=CC=C1 WQAXJVYXCKNYCB-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- MJFCDPLEATUOPF-UHFFFAOYSA-L dichloronickel;triphenylphosphane Chemical compound Cl[Ni]Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 MJFCDPLEATUOPF-UHFFFAOYSA-L 0.000 description 1
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- FZVYFBWEHCPWEG-UHFFFAOYSA-N methyl 4-(2,2-diphenylethenylselanyl)benzoate Chemical compound COC(=O)C1=CC=C(C=C1)[Se]C=C(C2=CC=CC=C2)C3=CC=CC=C3 FZVYFBWEHCPWEG-UHFFFAOYSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- XIKYYQJBTPYKSG-UHFFFAOYSA-N nickel Chemical compound [Ni].[Ni] XIKYYQJBTPYKSG-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- UQPUONNXJVWHRM-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UQPUONNXJVWHRM-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 229910001958 silver carbonate Inorganic materials 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- WHLUQAYNVOGZST-UHFFFAOYSA-N tifenamil Chemical group C=1C=CC=CC=1C(C(=O)SCCN(CC)CC)C1=CC=CC=C1 WHLUQAYNVOGZST-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C391/00—Compounds containing selenium
- C07C391/02—Compounds containing selenium having selenium atoms bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D339/00—Heterocyclic compounds containing rings having two sulfur atoms as the only ring hetero atoms
- C07D339/08—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/083—Syntheses without formation of a Si-C bond
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
本发明属于有机硒化学领域，具体涉及一种α,β‑不饱和硒类化合物的合成方法，由芳基硼酸类化合物、单质硒、二芳基乙烯类化合物作为反应底物合成的。本发明避免了有毒的硒汞试剂以及硒醚试剂，符合现代绿色发展的理念，为今后不饱和硒化合物的合成提供了一种绿色、经济的方法。
Description
技术领域
本发明属于有机硒化学领域，具体涉及一种α,β-不饱和硒类化合物的合成方法。
背景技术
自从硒元素问世以来，含硒化合物得到了快速发展，其作为人体必不可少的微量元素，对人体健康起到了至关重要的作用。其中具有抗肿瘤作用的对苯二亚甲基硒腈得到了人们的密切关注，其简单、快速的合成方法也是人们正在探索的方向。近些年来，有机硒化学得到了更好的发展，将硒原子引入到有机物中的方法大部分是通过硒前体来完成，这些硒前体试剂大都有毒，甚至需要通过复杂的路线来制备，浪费大量的人力物力。那么，如何避免剧毒昂贵的硒前体试剂的使用，寻求经济绿色的方法，如何将有机方法学和构建含硒化合物结合在一起，这将是有机硒化合物研究需要努力的方向。
目前，在公开报道文献中合成α,β-不饱和硒类化合物具体有以下：
1.1987年，Hershberger等人[1]报道了α,β-不饱和硒类化合物的合成方法。此方法以锡取代二芳基乙烯，芳基硒汞为原料，在光照下反应得到目标产物。该方法采用了剧毒的锡取代二芳基乙烯以及芳基硒汞，使得此方法具有很大的局限性。
2.1988年，Khanna等人[2]也报道了α,β-不饱和硒类化合物的合成方法。此方法也采用了毒性较大芳基硒汞作为芳硒基的来源。但避免了锡取代二芳基乙烯的使用，采用了低毒性的碘取代二芳基乙烯。
近年来，α,β-不饱和硒类化合物的构建大多使用有毒的硒汞试剂以及硒醚试剂，这类方法存在着大量的缺点，不符合现代绿色发展的理念。
引用文献：
1.Russell,G.A.；Ngoviwatchai,P.Tashtoush,H.et al.Reaction of 1-alkenyland 1-alkynyl derivatives of tin and mercury with hetero-centered radicals[J]. Organometallics.1987,6,1414-1419.
2.Russell,G.；A.Ngoviwatchai,P.；Tashtoush,H.；I.et al.Reactions ofalkylmercurials with heteroatom-centered acceptor radicals[J].J.Am.Chem.Soc.1988,110,3530-3538.
发明内容
本发明的目的是为了克服现有技术存在的缺点和不足，而提供一种α,β-不饱和硒类化合物的合成方法。
本发明所采取的技术方案如下：α,β-不饱和硒类化合物的合成方法，由芳基硼酸类化合物、单质硒、二芳基乙烯类化合物作为反应底物合成的，化学式如下：
反应采用银催化剂或1价铜催化剂或2价铜催化剂。
反应采用2价铜催化剂。
反应采用DMSO、DMA、DMF中的一种或多种。
反应添加配体，所述配体为联吡啶配体、三联吡啶配体、双酮氮配体、膦配体中的一种。
反应为在100-150℃下进行。
反应时间为最少12小时。
反应在氧气条件下进行。
本发明的有益效果如下：本发明由芳基硼酸类化合物、单质硒、二芳基乙烯类化合物成功反应得到α,β-不饱和硒类化合物，避免了有毒的硒汞试剂以及硒醚试剂，符合现代绿色发展的理念，为今后不饱和硒化合物的合成提供了一种绿色、经济的方法。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚，下面将对本发明作进一步地详细描述。
以下所揭露的仅为本发明较佳实施例而已，当然不能以此来限定本发明之权利范围，因此依本发明权利要求所作的等同变化，仍属本发明所涵盖的范围。
实施例1：
在25mL反应管中加入磁子，称取苯硼酸(0.8mmol)、Se粉(0.8mmol)、溴化铜(0.04mmol)、三环己基膦氟硼酸盐(0.04mmol)于反应管中，加毕，然后用双排管抽真空，充氧气，来回三次，在氧气的氛围下加入1,1二苯基乙烯 (0.4mmol)、2ml的DMSO溶液，最后密封反应管，移置120℃的加热器中反应12小时。反应完毕，待冷却后，反应混合物用25mL水稀释，再用70mL 乙酸乙酯萃取三次，收集三次的萃取液。有机相用无水硫酸钠干燥，过滤，减压浓缩，再用石油醚进行柱层析纯化。
以下为对该反应的条件优化过程：
1)催化剂对反应的影响：
表1催化剂对反应的影响
反应条件：0.8mmol苯硼酸(5a),0.8mmol硒粉,0.4mmol 1,1-二苯乙烯(6a),
0.04mmol催化剂,2mL二甲基亚砜,120℃,air,24h,a为分离产率。
如表1所示，首先对钯催化剂进行了尝试，当使用2价钯(PdCl2)和0价钯四三苯基膦钯(Pd(PPh)4)(表1，序号1-2)时，没有拿到目标产物。接下来对镍催化剂进行了尝试，当使用2价镍乙酰丙酮镍(Ni(acac)2)、三苯基膦二氯化镍(Ni(PPh)3Cl2)(表1，序号3-4)时，还是没有反应。当使用三联吡啶六氯化钌(RuCl2(COD))这类贵金属催化剂时(表1，序号5)，依然没有想要的产物。随后又对银催化剂进行了尝试，当使用了硝酸银(AgNO3)、碳酸银(Ag2CO3) (表1，序号6-7)后，以35％的收率拿到目标产物，随后，使用氯化亚铜(CuCl)、碘化亚铜(CuI)、氧化亚铜(表1，序号8-10)等1价铜时，收率提高，为50％。紧接着我们继续筛选铜催化剂，当使用氯化铜(CuCl2)、溴化铜(CuBr2)(表1，序号11-12)等2价铜时，可以发现较1价铜相比，收率进一步提高，尤其是使用溴化铜时收率可高达70％，使用其他2价铜(表1，序号13-16)，收率大多集中在50％-60％。
2)溶剂对反应的影响：
表2溶剂对反应的影响
反应条件：0.4mmol苯硼酸(5a),0.8mmol硒粉,0.4mmol 1,1-二苯乙烯(6a),0.04mmol溴化铜,2 mL溶剂,120℃,air,24h,a为分离产率。
如表2所示，当使用二甲基亚砜(DMSO)、N,N-二甲基甲酰胺(DMF)等 (表2，序号1-3)极性较大的非质子溶剂时，收率较高，分别为70％、63％、 59％，且DMSO溶剂效果最好。值得注意的是，N-甲基吡咯烷酮(NMP)也作为非质子溶剂(表2，序号4)，但没有反应。当时用四氢呋喃(THF)(表2，序号5)等极性较小的非质子溶剂时，反应没有发生。当使用异丙醇(IPA)、乙醇(EtOH)、氯仿等(表2，序号6-8)质子性溶剂时，也没有反应。当时用甲苯(toluene)、环乙烷(表2，序号9-10)等非质子非极性溶剂时，只有甲苯是微量反应。由数据可知，此反应对溶剂的要求比较敏感，只有极性较大的非质子溶剂才能反应。
3)配体对反应的影响：
表3配体对反应的影响
反应条件：0.8mmol苯硼酸(5a),0.8mmol硒粉,0.4mmol 1,1-二苯乙烯(6a),0.04mmol溴化铜,2 mL二甲基亚砜,0.04mmol配体,120℃,air,24h,a为分离产率。
如表3所示，首先筛选了氮配体，当使用了带有胺基的配体(表3，序号 1-5)之后，阻止了反应的发生。继续使用菲啰啉配体时(表3，序号6-7)，只有微量的收率。当使用了联吡啶配体(表3，序号8-11)后，反应效果较之前的配体相比较有了明显的上升，收率依次为54％、49％、56％、55％。最后使用了三联吡啶配体(表3，序号12)后，收率进一步提高，达到了63％。接下来选用了双酮氮配体(表3，序号13-14)，收率达到了75％。在筛选了氮配体之后，尝试了膦配体，选用便宜易得的三苯基或三环己基膦配体(表3，序号15-19)，其收率都在70％左右，当使用了带有酸性的三环己基膦氟硼酸盐配体时(表3，序号20)，收率提高到了82％。
4)温度、反应时间、氛围对反应的影响：
表4时间、温度、氛围对反应的影响
反应条件：0.8mmol苯硼酸(5a),0.8mmol硒粉,0.4mmol 1,1-二苯乙烯(6a),0.04mmol溴化铜,2mL 二甲基亚砜,0.04mmol L20配体,temp,time,atmo,a为分离产率。
如表4所示，在室温下(表4，序号1)反应，结果没有拿到目标产物，继续升温到80℃(表4，序号2)时，还是没有反应，升温到120℃(表4，序号 3)时，以82％的收率拿到产物，继续升温至150℃(表4，序号4)，收率下降了10％左右，因此最佳的温度为120℃。接下来对反应氛围进行了筛选，结果显示在氮气氛围下(表4，序号6)反应收率有所下降，而在氧气氛围下(表4，序号5)收率进一步提高，可能是氧气起到了氧化的作用。最后又对反应时间进行了筛选，当反应时间降到12小时时(表4，序号7)，收率持平，但继续降低反应时间(表4，序号8-9)，收率大幅度下降。
综上所述，以苯硼酸、单质Se和1,1-二苯乙烯为起始原料反应合成α,β- 不饱和硒类化合物的最优条件为：在氧气的氛围下，0.8mmol苯硼酸,0.8mmol 硒粉,0.4mmol 1,1-二苯乙烯,0.04mmol溴化铜,0.04mmol三环己基膦氟硼酸盐,2mL二甲基亚砜,120℃,12h。
实施例2芳基硼酸底物的拓展：
如表5所示，在最优条件下，进行了芳基硼酸(表5，7a-7w)的底物拓展。首先考虑的是位阻效应，从结果来看，对位的收率普遍要大于邻位和间位(表5， 7b-7g)，相差了10％-30％不等。此外，我们还在邻位和间位分别选取了给电子基团和吸电子基团(表5，7b-7f)，结果显示，具有吸电子效应的卤素基团的收率要高于给电子的甲基基团，具体为间位72％＞60％，邻位55％＞49％。具有给电子效应的烷基和苯基(表5，7i-7j)，收率为72％，76％。此外，萘环和噻吩环(表5，7m，7n)也取得了不错的收率，分别为79％、55％。值得注意的是，三甲基硅取代基的苯硼酸(表5，7h)也有68％的收率，这就为后续的衍生反应提供了较大的平台。带有大位阻的苯硼酸(表5，7l)虽然只有40％的收率，这也足够证明，此反应体系能容忍大位阻的试剂。此外，具有吸电子的卤素基团 (表5，7o-7s)有80％左右的收率，氟取代的苯硼酸收率高达了82％，此外，具有吸电子效应的酯基(表5，7k)也有66％的收率，可见吸电子基团更能够推促反应的进行。接下来选择了噻唑和吡啶杂环的硼酸(表5，7t，7u)进行了尝试，没有拿到目标产物。最后考察了烷基硼酸(表5，7v，7w)，同样也没有拿到目标产物。
表5芳基硼酸底物拓展
反应条件：0.8mmol芳基硼酸(5a),0.8mmol硒粉,0.4mmol 1,1-二苯乙烯(6a),0.04mmol溴化铜,2 mL二甲基亚砜,0.04mmol配体,120℃,氧气,12h,a为分离产率。
实施例3二芳基乙烯底物的拓展：
1.二芳基乙烯的制备：在装有磁子、恒压滴液漏斗的150mL茄形瓶中，称取相应的苯乙酮(10.0mmol,1.0equiv)于茄形瓶中，密封之后，然后再抽真空，充氮气，来回三次，在氮气的保护下加入无水乙醚30ml，再量取苯基格式试剂(15.0mmol,1.5equiv)于恒压滴液漏斗中，让其在冰水浴中慢慢滴下，反应3小时后，加入3ml的亚磷酸二乙酯，加毕，继续反应24小时后，移除冰水浴，加入蒸馏水于茄形瓶中，搅拌片刻后，用无水乙醚进行萃取，萃取液在旋转蒸发仪上减压浓缩。然后再用柱色谱分离，分离的极性根据产物的不同而调整。
2.不同二芳基乙烯作为底物合成α,β-不饱和硒类化合物：
如表6所示，二芳基乙烯化合物为邻位带有取代基团的非对称二芳基乙烯 (表6，8a-8b)，收率分别为55％、49％。二芳基乙烯化合物为间位带有给电子的甲基时(表6，8c)，收率为60％，吸电子的卤素时(表6，8d)，收率为72％，间位的收率较邻位相比有所上升，当对位是卤素基团时(表6，8f-8g)，收率集中在70％左右，但是，取代基为甲基，甲硫基，萘基时(表6，8h-8j)，收率分别为72％，76％，66％，接下来，一边是卤素，一边是烷基的二芳基乙烯我们也进行了考察(表6，8k，8l)，收率为80％、68％，两边都是烷基取代基二芳基乙烯的收率为44％(表6，8e)，接下来，具有对称结构的对氯二芳基乙烯达到 73％的收率(表6，8m)，非对称的双卤结构收率为69％(表6，8n)，二芳基乙烯化合物为3,4,5-三甲氧基二芳基乙烯(表3-6，8o)，很可惜没有拿到目标产物，可能是由于电子效应导致的。
表6二芳基乙烯底物拓展
反应条件：0.8mmol苯硼酸(5a),0.8mmol硒粉,0.4mmol二芳基乙烯(6a),0.04mmol溴化铜,2mL 二甲基亚砜,0.04mmol配体,120℃,氧气,12h,a为分离产率。
实施例4反应机理的研究：
为了弄清反应机理，如表7所示，使用苯硼酸和单质Se在标准条件下进行反应(表7，eq 1)，结果以87％的收率得到了二苯基二硒醚，然后在不存在CuBr2 的情况下(表7，eq2)进行反应，结果没有得到二硒醚，紧接着我们在标准条件加入了3equiv TEMPO(表7，eq3)，没有得到二硒醚，由此可见，金属铜催化剂在苯硼酸和单质Se的反应中起到了重要作用。接下来，我们用二苯基二硒醚和1,1-二苯乙烯在标准条件下和不加CuBr2、配体的条件下反应(表7，eq 4-6)，最终分别以47％、39％、35％的收率得到了目标产物，结果显示，铜催 化剂和配体不是反应的必须条件，但是CuBr2起到了促进作用。然后我们在eq5的基础上加入了3equiv TEMPO(表7，eq 7)，结果没有目标产物的生成。最后我们进行了分步实验(表7，eq 8)，没有目标产物的生成，由此可知，反应并不是通过二硒醚中间体来完成的。
表7反应机理的研究
通过以上实验，可以推测反应机理如下：
首先，Cu(II)促进苯硼酸产生苯基自由基(过程中Cu(II)被还原成Cu(I))，然后被Se捕获，形成苯硒基自由基，然后进攻1,1-二苯乙烯形成苯硒基-二苯基自由基，紧接着在氧气的作用下、去质子化得到目标产物，最后Cu(I)被氧气氧化成Cu(II)，反应由此循环，剩下的双游离苯硒自由基耦合产生二苯基二硒醚，这就解释了反应过程中为什么会有二苯基二硒醚的生成。
产物表征
(2,2-diphenylvinyl)(phenyl)selane(7a):yellow liquid.Following the5.4general procedure,using petroleum ether as the eluant afforded theproduct.1H NMR(500MHz,CDCl3):δ7.57-7.55(m,2H),7.43-7.40(m,2H), 7.37-7.35(m,1H),7.33-7.32(m,2H),7.30-7.27(m,3H),7.24-7.22(m,4H),7.11(s,1H)；13C NMR(125MHz,CDCl3):δ143.2,141.6,140.4,132.6,131.7,129.4,129.3,128.6,128.3,127.9,127.4,127.3,127.2,122.6.
(2-chlorophenyl)(2,2-diphenylvinyl)selane(7b):yellow liquid(55％yield).Following the 5.4general procedure, using petroleum ether as theeluant afforded the product.1H NMR(500MHz,CDCl3):δ7.57-7.55(m,1H), 7.43-7.40(m,2H),7.38-7.34(m,2H),7.32(d,J＝7.0Hz,2H),7.28-7.28(m,5H),7.23-7.16(m,2H),7.10(s,1H)；13C NMR(125MHz,CDCl3):δ145.7,141.5,140.1,135.1,132.5,131.8,129.6,129.4,128.5,128.3,128.1,128.0, 127.6,127.4,127.3,119.5.
(2,2-diphenylvinyl)(o-tolyl)selane(7c):yellow liquid(49％yield).Following the 5.4 general procedure,using petroleum ether as the eluantafforded the product.1H NMR(500MHz,CDCl3):δ7.66(d,J＝9.5Hz,1H), 7.51-7.47(m,2H),7.44-7.40(m,3H),7.33-7.26(m,8H),7.10(s,1H),2.47(s,3H)；13C NMR(125MHz,CDCl3): δ143.9,141.9,140.7,139.9,133.2,132.6,130.4,129.7,128.7,128.6,128.2,127.9,127.5,127.4,127.0,122.3, 22.8.
(2,2-diphenylvinyl)(m-tolyl)selanemide(7d):yellow liquid(60％yield).Following the 5.4 general procedure, using petroleum ether as the eluantafforded the product.1H NMR(500MHz,CDCl3):δ7.52-7.41(m,7H), 7.36-7.27(m,6H),7.21-7.17(m,2H),2.42(s,3H)；13C NMR(125MHz,CDCl3):δ142.8,141.7,140.4,139.1,133.2,131.3,130.0,129.6,129.4,129.1,128.5,128.3,127.9,127.2,127.2,122.8,21.3.
(3-chlorophenyl)(2,2-diphenylvinyl)selane(7e):yellow liquid(72％yield).Following the 5.4 general procedure, using petroleum ether as theeluant afforded the product.1H NMR(500MHz,CDCl3):δ7.62-7.61(m,1H), 7.51-7.47(m,3H),7.45-7.43(m,1H),7.39-7.36(m,2H),7.34-7.28(m,7H),7.13(s,1H)；13C NMR(125MHz, CDCl3):δ144.2,141.3,140.2,134.9,133.3,131.9,130.2,130.0,129.3,128.6,128.4,128.1,127.5,127.5,127.2, 121.0.
(2,2-diphenylvinyl)(3-methoxyphenyl)selane(7f):yellow liquid(70％yield).Following the 5.4 general procedure, using petroleum ether as theeluant afforded the product.1H NMR(500MHz,CDCl3):δ7.43-7.40(m,2H), 7.37-7.35(m,1H),7.33-7.32(m,2H),7.26-7.20(m,6H),7.15-7.11(m,3H),6.83-6.81(m,1H),3.79(s,3H)；13C NMR(125MHz,CDCl3):δ159.9,143.2,141.6,140.4,132.5,130.1,129.4,128.5,128.3,127.9,127.3,127.2, 124.7,122.3,117.8,113.3 55.4.
(2,2-diphenylvinyl)(p-tolyl)selane(7g):yellow liquid(75％yield).Following the 5.4 general procedure,using petroleum ether as the eluantafforded the product.1H NMR(500MHz,CDCl3):δ7.58-7.56(m,2H),7.52-7.50 (m,2H),7.47-7.43(m,3H),7.35-7.30(m,5H),7.22(d,J＝9.5Hz,2H),7.19-7.18(m,1H),2.43(s,3H)；13C NMR (125MHz,CDCl3):δ142.5,141.6,140.4,137.5,134.2,132.9,130.1,129.2,128.4,128.2,127.7,127.8,127.2, 123.4,21.1.
(4-((2,2-diphenylvinyl)selanyl)phenyl)trimethylsilane(7h):yellowliquid(68％yield).Following the 5.4 general procedure,using petroleum etheras the eluant afforded the product.1H NMR(500MHz,CDCl3):δ7.55-7.54(m, 2H),7.46-7.34(m,8H),7.25-7.24(m,4H),7.13(s,1H),0.26(s,9H)；13C NMR(125MHz,CDCl3):δ142.5, 141.6,140.4,137.5,134.2,132.9,130.1,129.3,128.5,128.2,127.8,127.8,127.1,123.4,21.1.
[1,1'-biphenyl]-4-yl(2,2-diphenylvinyl)selane(7i):yellow liquid(72％yield).Following the 5.4 general procedure, using petroleum ether as theeluant afforded the product.1H NMR(500MHz,CDCl3):δ7.70-7.68(m,2H), 7.64-7.62(m,2H),7.60-7.58(m,2H),7.51-7.47(m,4H),7.44-7.39(m,4H),7.32-7.30(m,5H),7.20(s,1H)；13C NMR(125MHz,CDCl3):δ143.3,141.5,140.4,140.4,140.3,132.8,130.6,129.3,128.8,128.5,128.3,128.0, 127.9,127.5,127.2,127.1,127.0,122.4.
(2,2-diphenylvinyl)(4-isopropylphenyl)selane(7j):yellow liquid(76％yield).Following the 5.4 general procedure,using petroleum ether as theeluant afforded the product.1H NMR(500MHz,CDCl3):δ7.50(d, J＝8.0Hz,2H),7.40(d,J＝7.5Hz,2H),7.36-7.33(m,3H),7.24-7.21(m,5H),7.17(d,J＝8.0Hz,2H),7.10(s,1H),1.24(d,J＝7.0Hz,7H)；13C NMR(125MHz,CDCl3):δ148.5,142.5,141.7,140.4,134.0,133.0,129.4,128.5, 128.2,128.2,127.8,127.5,127.1,123.4,33.8,23.9.
methyl 4-((2,2-diphenylvinyl)selanyl)benzoate(7k):yellow liquid(66％yield).Following the 5.4 general procedure,using petroleum ether as theeluant afforded the product.1H NMR(500MHz,CDCl3):δ7.94(d, J＝8.0Hz,2H),7.57(d,J＝8.5Hz,2H),7.43-7.37(m,3H),7.32-7.25(m,7H),7.13(s,1H),3.90(s,3H)；13C NMR(125MHz,CDCl3):δ166.9,145.4,141.6,140.4,139.0,131.1,130.4,129.5,128.9,128.8,128.6,128.4,127.9, 127.5,120.1,52.4.
(2,2-diphenylvinyl)(mesityl)selane(7l):yellow liquid(40％yield).Following the 5.4 general procedure,using petroleum ether as the eluantafforded the product.1H NMR(500MHz,CDCl3):δ7.45-7.42(m,2H),7.38-7.35 (m,3H),7.21-7.18(m,3H),7.15-7.14(m,2H),6.96(s,2H),6.71(s,1H),2.50(s,9H)；13C NMR(125MHz, CDCl3):δ142.9,138.8,129.8,129.5,129.2,128.9,128.7,128.4,128.0,127.9,127.1,124.7,124.4,124.0,123.7, 24.7,21.5.
(2,2-diphenylvinyl)(naphthalen-1-yl)selane(7m):yellow liquid(79％yield).Following the 5.4 general procedure, using petroleum ether as theeluant afforded the product.1H NMR(500MHz,CDCl3):δ8.06(d,J＝10.0Hz,1H), 7.82-7.77(m,2H),7.74-7.69(m,2H),7.63(d,J＝8.5Hz,1H),7.51-7.42(m,5H),7.40-7.36(m,2H),47.26-7.24 (m,4H),7.20(s,1H)；13C NMR(125MHz,CDCl3):δ143.0,141.5,140.4,134.1,132.8,130.5,129.9,129.4, 129.0,128.6,128.2,127.9,127.7,127.2,127.1,126.8,126.3,125.9,122.9.
1-((2,2-diphenylvinyl)selanyl)thianthrene(7n):yellow liquid(55％yield).Following the 5.4 general procedure, using petroleum ether as theeluant afforded the product.1H NMR(500MHz,CDCl3):δ7.87-7.85(m,1H), 7.55-7.47(m,8H),7.31-7.28(m,5H),7.23-7.20(m,2H),7.12-7.09(m,2H)；13C NMR(125MHz,CDCl3):δ143.4,136.8,136.3,134.5,132.8,129.6,129.3,128.8,128.7,127.1,126.9,121.6,98.6,71.0,55.0,4 0.2,34.0, 21.5.
(2,2-diphenylvinyl)(4-(trifluoromethyl)phenyl)selane(7o):yellowliquid(80％yield).Following the 5.4 general procedure,using petroleum etheras the eluant afforded the product.1H NMR(500MHz,CDCl3):δ7.63(d, J＝7.5Hz,1H),7.53(d,J＝8.0Hz,1H),7.44-7.36(m,4H),7.32-7.26(m,8H),7.09(s,1H)；13C NMR(125MHz,CDCl3):δ145.5,141.6,140.5,137.4,132.1,129.6,128.9,128.8,128.6,128.1,127.7,126.3(d,JF＝25.0Hz),123.4, 120.3.
(2,2-diphenylvinyl)(4-fluorophenyl)selane(7p):yellow liquid(82％yield).Following the 5.4 general procedure, using petroleum ether as theeluant afforded the product.1H NMR(500MHz,CDCl3):δ7.54-7.52(m,2H), 7.42-7.39(m,2H),7.37-7.35(m,1H),7.32-7.31(m,2H),7.27-7.20(m,5H),7.01-6.97(m,3H)；13C NMR(125 MHz,CDCl3):δ138.7,136.4,135.7,135.3,132.4(d,JF＝37.5Hz),131.7,130.5,129.1,128.4,128.3,128.2,128.0, 127.9,127.8.
(4-chlorophenyl)(2,2-diphenylvinyl)selane(7q):yellow liquid(78％yield).Following the 5.4 general procedure, using petroleum ether as theeluant afforded the product.1H NMR(500MHz,CDCl3):δ7.48(d,J＝8.5Hz,2H), 7.40(d,J＝7.5Hz,2H),7.37-7.35(m,1H),7.30(d,J＝7.5Hz,2H),7.27-7.25(m,4H),7.24-7.21(m,3H),7.03(m, 1H)；13C NMR(125MHz,CDCl3):δ143.7,141.4,140.2,133.8,133.6,129.7,129.4,129.3,128.5,128.3,128.0, 127.4,127.1,121.7.
(4-bromophenyl)(2,2-diphenylvinyl)selane(7r):yellow liquid(73％yield).Following the 5.4 general procedure, using petroleum ether as theeluant afforded the product.1H NMR(500MHz,CDCl3):δ7.47-7.38(m,8H), 7.36-7.34(m,2H),7.30-7.28(m,4H),7.06(s,1H)；13C NMR(125MHz,CDCl3):δ144.2,141.6,140.4,134.3, 132.6,130.8,129.5,128.8,128.6,128.3,127.7,127.4,121.9,121.8.
(2,2-diphenylvinyl)(4-iodophenyl)selane(7s):yellow liquid(69％yield).Following the 5.4 general procedure, using petroleum ether as the eluantafforded the product.1H NMR(500MHz,CDCl3):δ7.59-7.57(m,2H), 7.40-7.39(m,2H),7.30-7.21(m,10H),7.02(s,1H)；13C NMR(125MHz,CDCl3):δ144.0,141.4,140.2,138.3,134.1,132.4,131.5,129.3,128.6,128.4,128.1,127.5,127.2,121.4.
phenyl(2-phenyl-2-(o-tolyl)vinyl)selane(8a):yellow liquid(55％yield).Following the 5.4 general procedure, using petroleum ether as the eluantafforded the product.1H NMR(500MHz,CDCl3):δ8.09-8.06(m,4H), 7.82-7.73(m,26H),2.73-2.54(m,6H)；13C NMR(125MHz,CDCl3):δ143.2,142.8,142.1,140.3,139.8,139.6,136.2,132.6,132.5,132.5,131.8,131.6,131.4,130.6,130.4,130.2,129.7,129.7,129.3,129.3,128.7,128.5, 128.4,128.3,128.2,127.6,127.5,127.4,127.1,126.3,125.8,125.7,123.3,122.9,20.5,19.5.
(2-(2-chlorophenyl)-2-phenylvinyl)(phenyl)selane(8b):yellow liquid(49％yield).Following the 5.4 general procedure,using petroleum ether as theeluant afforded the product.1H NMR(500MHz,CDCl3):δ7.96-7.89(m, 5H),7.74-7.61(m,25H)；13C NMR(125MHz,CDCl3):δ141.5,140.5,140.4,139.8,139.3,138.8,133.4,133.3, 132.6,132.6,131.6,131.5,131.4,131.0,130.1,130.0,129.4,129.3,129.3,128.7,128.5,128.4,128.2,128.0, 127.7,127.5,127.4,127.3,127.1,126.6,125.8,124.2.
phenyl(2-phenyl-2-(m-tolyl)vinyl)selane(8c):yellow liquid(60％yield).Following the 5.4 general procedure, using petroleum ether as the eluantafforded the product.1H NMR(500MHz,CDCl3):δ7.57-7.54(m,4H), 7.42-7.39(m,2H),7.36-7.24(m,15H),7.19-7.13(m,4H),7.09(s,2H),7.04-7.01(m,3H),2.36(s,3H),2.28(s, 3H)；13C NMR(125MHz,CDCl3):δ143.3,143.2,141.7,141.6,140.5,140.4,138.2,137.9,133.5,133.2,133.1, 132.6,132.5,131.8,131.7,129.9,129.4,129.3,128.7,128.5,128.4,128.3,128.2,128.1,127.9,127.7,127.4, 127.1,126.4,124.5,122.4,122.3,21.5,21.5.
(2-(3-chlorophenyl)-2-phenylvinyl)(phenyl)selane(8d):yellow liquid(72％yield).Following the 5.4 general procedure,using petroleum ether as theeluant afforded the product.1H NMR(500MHz,CDCl3):δ7.56-7.56(m, 4H),7.44-7.37(m,2H),7.34-7.31(m,11H),7.27-7.23(m,6H),7.21-7.17(m,4H),7.14(s,2H),7.09-7.08(m, 1H)；13C NMR(125MHz,CDCl3):δ143.3,142.1,141.7,141.3,141.0,139.7,134.5,134.3,132.8,132.6,131.2, 129.8,129.5,129.4,129.2,128.7,128.4,128.2,128.0,127.7,127.6,127.4,127.1,127.1,127.0,125.3,124.6, 123.7.
(2-(4-(tert-butyl)phenyl)-2-(naphthalen-2-yl)vinyl)(phenyl)selane(8e):yellow liquid(44％yield).Following the 5.4 general procedure,usingpetroleum ether as the eluant afforded the product.1H NMR(500MHz,CDCl3):δ8.17-8.17(m,4H),8.09-8.04(m,2H),7.93-7.88(m,4H),7.82-7.73(m,7H),7.62-7.60(m,8H),7.55-7.50(m, 4H),1.69(s,6H),1.61(s,9)；13C NMR(125MHz,CDCl3):δ150.9,150.4,143.0,142.9,139.3,138.6,138.0, 137.2,133.3,133.3,132.9,132.6,132.4,131.8,131.8,129.3,129.3,129.0,128.5,128.2,128.1,127.8,127.7, 127.5,127.4,127.3,126.8,126.2,126.2,126.2,125.8,125.4,125.4,125.2,122.8,122.0,34.7,34.5,31.4,31.3.
(2-(4-chlorophenyl)-2-phenylvinyl)(phenyl)selane(8f):yellow liquid(75％yield).Following the 5.4 general procedure,using petroleum ether as theeluant afforded the product.1H NMR(500MHz,CDCl3):δ7.57-7.56(m, 2H),7.44-7.37(m,2H),7.33-7.30(m,4H),7.28-7.19(m,5H),7.16-7.14(m,1H),7.11-7.10(m,1H)；13C NMR(125MHz,CDCl3):δ142.0,142.0,141.8,141.7,141.4,141.3,140.1,140.0,138.9,138.8,133.8,133.1,132.7, 132.7,131.3,130.8,129.4,129.3,128.9,128.7,128.5,128.4,128.4,128.2,127.6,127.5,127.2,123.5,123.3.
(2-(4-bromophenyl)-2-phenylvinyl)(phenyl)selane(8g):yellow liquid(69％yield).Following the 5.4 general procedure,using petroleum ether as theeluant afforded the product.1H NMR(500MHz,CDCl3):δ7.56-7.52(m, 6H),7.42-7.40(m,2H),7.37-7.35(m,4H),7.29-7.29(m,8H),7.25-7.24(m,2H),7.2-7.18(m,4H),7.11(s,2H), 7.08-7.06(m,2H)；13C NMR(125MHz,CDCl3):δ141.9,141.7,141.2,140.5,139.8,139.2,132.7,132.6,131.8, 131.4,131.3,131.3,131.1,129.4,129.3,128.7,128.4,128.2,127.6,127.6,127.5,127.1,123.7,123.3,122.0, 121.3.
phenyl(2-phenyl-2-(p-tolyl)vinyl)selane(8h):yellow liquid(72％yield).Following the 5.4 general procedure, using petroleum ether as the eluantafforded the product.1H NMR(500MHz,CDCl3):δ7.56-7.56(m,3H), 7.42-7.39(m,2H),7.36-7.28(m,8H),7.24-7.22(m,6H),7.13-7.12(m,2H),7.08-7.06(m,4H),3.39(s,2H),2.31 (s,3H)；13C NMR(125MHz,CDCl3):δ143.2,143.1,141.8,140.5,138.8,137.7,137.4,137.1,132.4,132.4, 131.7,129.3,129.2,129.2,128.9,128.4,128.3,128.2,127.8,127.3,127.2,127.1,127.0,125.0,122.0,121.3,21.3, 21.1.
methyl(4-(1-phenyl-2-(phenylselanyl)vinyl)phenyl)sulfane(8i):yellowliquid(76％yield).Following the 5.4 general procedure,using petroleum etheras the eluant afforded the product.1H NMR(500MHz,CDCl3):δ7.97 (d,J＝8.0Hz,2H),7.87-7.81(m,6H),7.71-7.70(m,1H),7.52-7.51(m,2H),7.49-7.46(m,6H),7.43-7.36(m,13H),2.55(s,6H)；13C NMR(125MHz,CDCl3):δ142.9,141.9,141.3,140.9,140.4,138.2,137.9,137.3,135.3, 134.3,129.6,129.3,128.8,128.6,128.3,128.0,127.9,127.6,126.7,126.1,125.8,125.1,125.0,124.9,124.6, 124.5,124.3,123.7,16.5,15.9.
(2-(naphthalen-2-yl)-2-phenylvinyl)(phenyl)selane(8j):yellow liquid(66％yield).Following the 5.4 general procedure,using petroleum ether as theeluant afforded the product.1H NMR(500MHz,CDCl3):δ7.85-7.85(m, 6H),7.58-7.57(m,4H),7.48-7.43(m,6H),7.40-7.39(m,4H),7.29-7.25(m,14H),7.20(s,2H)；13C NMR(125MHz,CDCl3):δ142.9,141.6,140.4,138.8,137.8,133.3,132.9,132.7,132.6,132.5,131.6,130.1,129.5,129.4, 128.8,128.6,128.6,128.5,128.4,128.3,128.2,128.1,127.9,127.8,127.8,127.6,127.5,127.3,127.2,126.8, 126.3,126.3，126.2,125.9,125.7,125.6,125.1,123.5,123.4,123.1.
(2-(4-chlorophenyl)-2-(p-tolyl)vinyl)(phenyl)selane(8k):yellow liquid(80％yield).Following the 5.4 general procedure,using petroleum ether as theeluant afforded the product.1H NMR(500MHz,CDCl3):δ7.58-7.54(m, 4H),7.37-7.36(m,2H),7.28-7.25(m,9H),7.23-7.18(m,5H),7.15-7.13(m,2H),7.10-7.05(m,6H),2.38(s,2H), 2.30(s,3H)；13C NMR(125MHz,CDCl3):δ142.1,141.7,140.2,138.9,138.5,137.9,137.3,137.0,133.7,133.0, 132.6,132.5,131.5,131.4,131.3,130.8,129.3,129.1,129.1,128.7,128.4,128.4,127.5,127.5,127.0,123.0, 122.0,21.4,21.1.
(2-(4-(tert-butyl)phenyl)-2-(4-chlorophenyl)vinyl)(phenyl)selane(8l):yellow liquid(68％yield).Following the 5.4 general procedure,using petroleumether as the eluant afforded the product.1H NMR(500MHz,CDCl3):δ 7.57-7.54(m,4H),7.42-7.37(m,5H),7.29-7.28(m,10H),7.24-7.20(m,4H),7.16-7.13(m,3H),7.09(s,1H), 7.04(s,1H),1.35(s,9H),1.29(s,9H)；13C NMR(125MHz,CDCl3):δ151.0,150.6,142.0,141.7,140.4,138.9, 138.4,136.8,133.6,133.0,132.6,132.4,131.6,131.4,131.3,130.8,129.4,128.9,128.8,128.6,128.4,127.5, 127.4,126.7,125.4,125.3,123.0,122.1,34.7,34.5,31.4,31.3.
(2,2-bis(4-chlorophenyl)vinyl)(phenyl)selane(8m):yellow liquid(73％yield).Following the 5.4 general procedure,using petroleum ether as theeluant afforded the product.1H NMR(500MHz,CDCl3):δ7.68-7.68(m, 2H),7.52-7.51(m,2H),7.44-7.44(m,3H),7.38-7.34(m,4H),7.25-7.23(m,3H)；13C NMR(125MHz,CDCl3):δ140.5,139.7,138.3,133.9,133.3,132.7,131.0,130.7,129.4,128.9,128.5,128.3,127.7,124.1.
(2-(4-bromophenyl)-2-(4-chlorophenyl)vinyl)(phenyl)selane(8n):yellowliquid(69％yield).Following the 5.4 general procedure,using petroleum etheras the eluant afforded the product.1H NMR(500MHz,CDCl3):δ 8.00-8.00(m,6H),7.83-7.83(m,4H),7.76-7.76(m,6H),7.69-7.64(m,6H),7.56-7.55(m,4H),7.51-7.50(m,2H)；13C NMR(125MHz,CDCl3):δ140.5,140.1,139.6,138.7,138.2,134.0,133.3,132.7,131.9,131.5,131.0, 130.7,129.4,128.9,128.6,128.5,128.3,127.7,124.3,124.1,122.1,121.4。
Claims (8)
1.α,β-不饱和硒类化合物的合成方法，其特征在于：由芳基硼酸类化合物、单质硒、二芳基乙烯类化合物作为反应底物合成的，化学式如下：
2.根据权利要求1所述的α,β-不饱和硒类化合物的合成方法，其特征在于：反应采用银催化剂或1价铜催化剂或2价铜催化剂。
3.根据权利要求2所述的α,β-不饱和硒类化合物的合成方法，其特征在于：反应采用2价铜催化剂。
4.根据权利要求1所述的α,β-不饱和硒类化合物的合成方法，其特征在于：反应采用DMSO、DMA、DMF中的一种或多种。
5.根据权利要求1所述的α,β-不饱和硒类化合物的合成方法，其特征在于：反应添加配体，所述配体为联吡啶配体、三联吡啶配体、双酮氮配体、膦配体中的一种。
6.根据权利要求1所述的α,β-不饱和硒类化合物的合成方法，其特征在于：反应为在100-150℃下进行。
7.根据权利要求1所述的α,β-不饱和硒类化合物的合成方法，其特征在于：反应时间为最少12小时。
8.根据权利要求1所述的α,β-不饱和硒类化合物的合成方法，其特征在于：反应在氧气条件下进行。
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