CN110105305A - 过渡金属催化的c-h活化/环合合成1,2-苯并噻嗪衍生物的绿色合成新方法 - Google Patents
过渡金属催化的c-h活化/环合合成1,2-苯并噻嗪衍生物的绿色合成新方法 Download PDFInfo
- Publication number
- CN110105305A CN110105305A CN201910443736.9A CN201910443736A CN110105305A CN 110105305 A CN110105305 A CN 110105305A CN 201910443736 A CN201910443736 A CN 201910443736A CN 110105305 A CN110105305 A CN 110105305A
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- China
- Prior art keywords
- silver
- dimer
- palladium
- chloride
- rhodium
- 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.)
- Granted
Links
- UJVBZCCNLAAMOV-UHFFFAOYSA-N 2h-1,2-benzothiazine Chemical class C1=CC=C2C=CNSC2=C1 UJVBZCCNLAAMOV-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 title claims abstract description 11
- 238000010499 C–H functionalization reaction Methods 0.000 title claims abstract description 8
- 238000007363 ring formation reaction Methods 0.000 title claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 title claims description 8
- 238000003786 synthesis reaction Methods 0.000 title claims description 8
- 230000007704 transition Effects 0.000 title claims description 5
- -1 N1,N3Disubstituted imidazole Chemical class 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000002608 ionic liquid Substances 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 6
- 230000008878 coupling Effects 0.000 claims abstract description 6
- 238000010168 coupling process Methods 0.000 claims abstract description 6
- 238000005859 coupling reaction Methods 0.000 claims abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000001989 diazonium salts Chemical class 0.000 claims abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 5
- 239000011593 sulfur Substances 0.000 claims abstract description 5
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 32
- 239000002585 base Substances 0.000 claims description 24
- WQIQNKQYEUMPBM-UHFFFAOYSA-N pentamethylcyclopentadiene Chemical compound CC1C(C)=C(C)C(C)=C1C WQIQNKQYEUMPBM-UHFFFAOYSA-N 0.000 claims description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 11
- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 10
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- 238000000605 extraction Methods 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- PZSJYEAHAINDJI-UHFFFAOYSA-N rhodium(3+) Chemical class [Rh+3] PZSJYEAHAINDJI-UHFFFAOYSA-N 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 7
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 6
- 125000005463 sulfonylimide group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 239000000539 dimer Substances 0.000 claims description 4
- MBAKFIZHTUAVJN-UHFFFAOYSA-I hexafluoroantimony(1-);hydron Chemical compound F.F[Sb](F)(F)(F)F MBAKFIZHTUAVJN-UHFFFAOYSA-I 0.000 claims description 4
- RWRDJVNMSZYMDV-UHFFFAOYSA-L radium chloride Chemical class [Cl-].[Cl-].[Ra+2] RWRDJVNMSZYMDV-UHFFFAOYSA-L 0.000 claims description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 235000013495 cobalt Nutrition 0.000 claims description 3
- JAWGVVJVYSANRY-UHFFFAOYSA-N cobalt(3+) Chemical compound [Co+3] JAWGVVJVYSANRY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Natural products CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 claims description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 claims description 2
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical class FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004912 1,5-cyclooctadiene Substances 0.000 claims description 2
- YESGVEQXKRJBBJ-UHFFFAOYSA-N 1-(dichloromethyl)-2,3,4,5-tetramethylcyclopenta-1,3-diene Chemical compound ClC(C1=C(C(=C(C1C)C)C)C)Cl YESGVEQXKRJBBJ-UHFFFAOYSA-N 0.000 claims description 2
- RYKLZUPYJFFNRR-UHFFFAOYSA-N 3-hydroxypiperidin-2-one Chemical compound OC1CCCNC1=O RYKLZUPYJFFNRR-UHFFFAOYSA-N 0.000 claims description 2
- BRYKBDMLJJLFAB-UHFFFAOYSA-N 4-methylbenzenesulfonic acid;silver Chemical compound [Ag].CC1=CC=C(S(O)(=O)=O)C=C1 BRYKBDMLJJLFAB-UHFFFAOYSA-N 0.000 claims description 2
- QSNFOTSEFALLLC-UHFFFAOYSA-L C(=O)=[Co](I)I Chemical compound C(=O)=[Co](I)I QSNFOTSEFALLLC-UHFFFAOYSA-L 0.000 claims description 2
- LJANIJWBPMOASO-UHFFFAOYSA-N C(CC(=O)C)(=O)[Co] Chemical compound C(CC(=O)C)(=O)[Co] LJANIJWBPMOASO-UHFFFAOYSA-N 0.000 claims description 2
- OVEMSLBFEHSYSF-UHFFFAOYSA-N ClC(CBBB)Cl Chemical compound ClC(CBBB)Cl OVEMSLBFEHSYSF-UHFFFAOYSA-N 0.000 claims description 2
- NWBUFJZQWAXFGH-UHFFFAOYSA-K [Ir](Cl)(Cl)Cl.C1=CCCC=CCC1.C1=CCCC=CCC1 Chemical class [Ir](Cl)(Cl)Cl.C1=CCCC=CCC1.C1=CCCC=CCC1 NWBUFJZQWAXFGH-UHFFFAOYSA-K 0.000 claims description 2
- UVNZNIGDKACWAA-UHFFFAOYSA-N [Ru].C1CC=CCCC=C1 Chemical compound [Ru].C1CC=CCCC=C1 UVNZNIGDKACWAA-UHFFFAOYSA-N 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000005256 alkoxyacyl group Chemical group 0.000 claims description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 125000004802 cyanophenyl group Chemical group 0.000 claims description 2
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 claims description 2
- 125000004438 haloalkoxy group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 150000002503 iridium Chemical class 0.000 claims description 2
- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical class [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 claims description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 2
- RPNNPZHFJPXFQS-UHFFFAOYSA-N methane;rhodium Chemical compound C.[Rh] RPNNPZHFJPXFQS-UHFFFAOYSA-N 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- 229910001630 radium chloride Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 claims description 2
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 2
- VIHDTGHDWPVSMM-UHFFFAOYSA-N ruthenium;triphenylphosphane Chemical compound [Ru].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 VIHDTGHDWPVSMM-UHFFFAOYSA-N 0.000 claims description 2
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 2
- 229940071536 silver acetate Drugs 0.000 claims description 2
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 claims description 2
- 229910001958 silver carbonate Inorganic materials 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 2
- 229910000367 silver sulfate Inorganic materials 0.000 claims description 2
- 229910001494 silver tetrafluoroborate Inorganic materials 0.000 claims description 2
- WCGIGOVLOFXAMG-UHFFFAOYSA-N silver;trifluoromethanesulfonic acid Chemical compound [Ag].OS(=O)(=O)C(F)(F)F WCGIGOVLOFXAMG-UHFFFAOYSA-N 0.000 claims description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims description 2
- 238000005292 vacuum distillation Methods 0.000 claims description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 1
- BEOKBUHJDGJDKO-UHFFFAOYSA-N [Cl].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 Chemical compound [Cl].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 BEOKBUHJDGJDKO-UHFFFAOYSA-N 0.000 claims 1
- OTVPWGHMBHYUAX-UHFFFAOYSA-N [Fe].[CH]1C=CC=C1 Chemical compound [Fe].[CH]1C=CC=C1 OTVPWGHMBHYUAX-UHFFFAOYSA-N 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- 238000006471 dimerization reaction Methods 0.000 claims 1
- QEQGAEHEPGMNCC-UHFFFAOYSA-N fluoromethanesulfonic acid;silver Chemical compound [Ag].OS(=O)(=O)CF QEQGAEHEPGMNCC-UHFFFAOYSA-N 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims 1
- 150000003303 ruthenium Chemical class 0.000 claims 1
- 229910052707 ruthenium Inorganic materials 0.000 claims 1
- 239000000741 silica gel Substances 0.000 claims 1
- 229910002027 silica gel Inorganic materials 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 24
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- 238000010898 silica gel chromatography Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- WDBQJSCPCGTAFG-QHCPKHFHSA-N 4,4-difluoro-N-[(1S)-3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-pyridin-3-ylpropyl]cyclohexane-1-carboxamide Chemical compound FC1(CCC(CC1)C(=O)N[C@@H](CCN1CCC(CC1)N1C(=NN=C1C)C(C)C)C=1C=NC=CC=1)F WDBQJSCPCGTAFG-QHCPKHFHSA-N 0.000 description 1
- BWGRDBSNKQABCB-UHFFFAOYSA-N 4,4-difluoro-N-[3-[3-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)-8-azabicyclo[3.2.1]octan-8-yl]-1-thiophen-2-ylpropyl]cyclohexane-1-carboxamide Chemical compound CC(C)C1=NN=C(C)N1C1CC2CCC(C1)N2CCC(NC(=O)C1CCC(F)(F)CC1)C1=CC=CS1 BWGRDBSNKQABCB-UHFFFAOYSA-N 0.000 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- WAUHABGEEBVFTF-UHFFFAOYSA-N CCCC[S] Chemical compound CCCC[S] WAUHABGEEBVFTF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GKKZMYDNDDMXSE-UHFFFAOYSA-N Ethyl 3-oxo-3-phenylpropanoate Chemical compound CCOC(=O)CC(=O)C1=CC=CC=C1 GKKZMYDNDDMXSE-UHFFFAOYSA-N 0.000 description 1
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- AXNBHOOQHIIQFA-UHFFFAOYSA-N [S].C(F)(F)F Chemical compound [S].C(F)(F)F AXNBHOOQHIIQFA-UHFFFAOYSA-N 0.000 description 1
- ZFYVPANOOXNHIW-UHFFFAOYSA-N acetonitrile;dihydrochloride Chemical class Cl.Cl.CC#N ZFYVPANOOXNHIW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000001857 anti-mycotic effect Effects 0.000 description 1
- 239000002543 antimycotic Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- JKJWYKGYGWOAHT-UHFFFAOYSA-N bis(prop-2-enyl) carbonate Chemical compound C=CCOC(=O)OCC=C JKJWYKGYGWOAHT-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- GCUVBACNBHGZRS-UHFFFAOYSA-N cyclopenta-1,3-diene cyclopenta-2,4-dien-1-yl(diphenyl)phosphane iron(2+) Chemical compound [Fe++].c1cc[cH-]c1.c1cc[c-](c1)P(c1ccccc1)c1ccccc1 GCUVBACNBHGZRS-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical class [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 230000007170 pathology Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000035479 physiological effects, processes and functions Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- ORIHZIZPTZTNCU-YVMONPNESA-N salicylaldoxime Chemical compound O\N=C/C1=CC=CC=C1O ORIHZIZPTZTNCU-YVMONPNESA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
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Abstract
本发明涉及一种以N1,N3‑二取代咪唑型离子液为溶剂，NH‑亚磺酰亚胺为原料，重氮化合物、炔以及硫叶立德为偶联试剂，过度金属催化C‑H活化/环合反应温和高效合成1,2‑苯并噻嗪衍生物的绿色合成新方法。本发明相比于其他技术，条件更加温和，操作简单、安全、环境友好；催化活性高，反应收率高，底物适用范围广；溶剂和催化剂可循环使用，降低了反应成本。
Description
技术领域
本发明涉及一种基于N1,N3-二取代咪唑型离子液体为溶剂、NH-亚磺酰亚胺为原料，重氮化合物、炔以及硫叶立德为偶联试剂，过度金属催化C-H活化/环合反应温和高效合成1,2-苯并噻嗪衍生物的绿色合成新方法。
背景技术
磺酰亚胺是许多重要生物活性分子中的稳定化合物1-3。其环化产物1,2-苯并噻嗪作为药物化学和农作物保护领域的优势支架4，同时也被研究出具有抗菌和抗真菌5、抗病毒6,7、抗肿瘤8,9及抗氧化10,11等生物活性。1,2-苯并噻嗪在生理和病理科学的应用发展促进了许多制备方法的产生,其中过渡金属催化的碳氢键活化是一个合成杂环的有用工具,因为它避免了起始原料的多不反应和最大限度地减少副产物的产生。
目前，由NH-亚磺酰亚胺化合物与一系列偶联试剂（如炔类、硫叶立德类、重氮类、α-MsO/TsO酮类以及烯丙基碳酸甲酯等）通过C-H活化/环合反应合成1,2-苯并噻嗪的方法已经被广泛的探索出来12-20。但这些方法一般具有温度较高，酸或碱添加剂的加入，催化剂稀少且不可循环等缺点，这些缺点限制了这些方法的应用。近年来，离子液体因具有低毒、不可燃、良好的热稳定性和化学稳定性、不产生蒸气压、极好的溶解性等优点受到了科学界和工业界的广泛关注。离子液体其独特的物理化学特性使其可能会是一个良好的C-H活化反应媒介以实现催化体系的循环使用。因此，开发一种温和、可循环、安全高效地在离子液中合成1,2-苯并噻嗪的方法是迫切需要的。
发明内容
本发明实现了以亚磺酰亚胺为原料，炔、重氮化合物以及硫叶立德为偶联试剂，离子液体为溶剂，通过过渡金属催化芳基C-H活化环合反应合成1,2-苯并噻嗪的新方法，解决了传统合成方法中反应温度较高、低原子利用率、使用有毒有机溶剂、环境污染以及成本较高等问题，提供了一种较已有报道更加温和、简便、有效、环境友好并且反应体系可循环使用的制备方法，降低了生产成品，避免了环境污染，且副产物仅为氮气，极大地提高了原子利用率，具有深远的意义。
本发明化学反应式如下所示：
R1、R2为氢、卤素、烷基、环烷基、芳基、烷氧基中的一种或一种以上；
R3、R4为烷基、芳基、羰基、苯甲酰基、磷脂基、烷氧酰基、卤代烷氧酰基中的一种或一种以上。
制备步骤如下：
（1）在洁净的反应器中加入磺酰亚胺类化合物、偶联试剂、催化剂、添加剂和离子液，于室温至60℃油浴锅里搅拌24 h；
（2）反应完成后，加入乙醚萃取。合并乙醚层，经减压蒸馏除去溶剂，残留物采用硅胶柱层析分离纯化即得产品；离子液层经减压干燥后可循环使用，循环使用时无需添加新的催化剂、银盐和离子液。
步骤（1）中的催化剂为钯碳、四（三苯基膦）钯、醋酸钯、氯化钯、二（乙腈）二氯化钯、二（苯腈）二氯化钯，1，1’-二（二苯基膦基）二茂铁二氯化钯、二（三苯基膦）二氯化钯、双（二亚苄基丙酮）钯、三（二亚苄基丙酮）二钯、氯化烯丙基钯（II）二聚物、（1,5-环辛二烯）二氯化钯（II）、铑碳、三氯化铑、醋酸铑、乙酰丙酮三苯基膦羰基铑、双环辛烯氯化铑二聚体、二氯（五甲基环戊二烯基）合铑（III）二聚体、(二(六氟锑酸)三乙腈(五甲基环戊二烯基)铑(III))、三苯基膦氯化铑、三氯化钌、三苯基膦氯化钌、二氯二羰基双三苯基膦钌、双（2-甲基烯丙基）（1,5-环辛二烯）钌（II）、对伞花烃二氯化钌二聚体、氯化钴、乙酰乙酰钴、八羰基二钴、二氯（五甲基环戊二烯基）合钴（III）二聚体、五甲基环戊二烯基羰基二碘化钴、(二(六氟锑酸)三乙腈(五甲基环戊二烯基)钴(III))、三氯化铱、二氯(五甲基环戊二烯)合铱(III)二聚体、双（1,5-环辛二烯）氯化铱（Ⅰ）二聚体、甲氧基（环辛二烯）合铱二聚体中的一种或一种以上。
步骤（1）中的添加剂为硝酸银、乙酸银、碳酸银、硫酸银、甲烷磺酸银、三氟甲烷磺酸银、对甲苯磺酸银、双三氟甲烷磺酰亚胺银，三氟甲烷磺酸银，六氟锑酸银、四氟硼酸银、六氟磷酸银中的一种或一种以上。
步骤（1）中的溶剂为N1,N3-二取代咪唑类离子液体的一种。
步骤（1）中磺酰亚胺类化合物：重氮化合物：催化剂：添加剂的摩尔为1:（1.2~3.0）：（0.02~0.05）：（0.08~0.2）。
步骤（1）中磺酰亚胺类化合物的反应浓度为0.1~0.5 mol/L。
用核磁共振氢谱（1H NMR）、碳谱（13C NMR）以及高分辨质谱证实了在芳杂环上形成C-C键以及环合成苯并噻嗪衍生物的结构。其中核磁共振图采用Varian INOVA-400 型核磁共振仪测定，以四甲基硅烷（TMS）为内标（δ 0 ppm），氘代氯仿为溶剂；高分辨质谱用Agilent 1946B 质谱仪测定。
具体实施方式
下面结合具体实施方式对本发明作进一步描述，有助于对本发明的理解。但并不能以此来限制本发明的权利范围,而本发明的权利范围应以权利要求书阐述的为准。
实施实例1：化合物1的合成
（1）在洁净的反应器中依次加入S-甲基-S-苯基亚磺酰亚胺（31.0 mg，0.20 mmol），重氮基乙酰乙酸乙酯（37.5 mg，0.24 mmol），二氯（五甲基环戊二烯基）合铑（III）二聚体（6.2mg，0.01 mmol），六氟锑酸银（13.7 mg，0.04 mmol），1-丁基-3-甲基咪唑六氟磷酸盐（0.6mL），30℃下搅拌24小时；
（2）反应完成后，加入乙醚萃取，收集乙醚层，减压除去溶剂，残留物采用硅胶柱层析分离纯化得棕黄油50.4 mg，收率95％。1H NMR (400 MHz, DMSO-d 6) δ 8.16 (dd, J = 8.4,0.8 Hz 1H), 7.68 (t, J = 7.2 Hz, 1H), 7.60 (dd, J = 8.4, 0.8 Hz, 1H), 7.51(t, J = 7.2 Hz, 1H), 4.30 (q, J = 7.2 Hz, 2H), 3.84 (s, 3H), 2.25 (s, 3H),1.30 (t, J = 7.2 Hz, 3H); 13C NMR (150MHz, CDCl3) δ 168.7, 152.1, 134.2,133.1, 126.1, 124.7, 123.5, 116.9, 105.2, 60.8, 45.3, 24.8, 14.3; HRMS (ESI):m/z计算值：C13H16NO3S [M + H]+ 266.0845, 实测值：266.0841。
实施实例2：化合物2的合成
（1）在洁净的反应器中依次加入S-甲基-S-（4-甲氧基苯基）亚磺酰亚胺（37.0 mg，0.20mmol），重氮基乙酰乙酸乙酯（37.5 mg，0.24 mmol），二氯（五甲基环戊二烯基）合铑（III）二聚体（6.2 mg，0.01 mmol），六氟锑酸银（13.7 mg，0.04 mmol），1-丁基-3-甲基咪唑六氟磷酸盐（0.6 mL），30℃下搅拌24小时；
（2）反应完成后，加入乙醚萃取，收集乙醚层，减压除去溶剂，残留物采用硅胶柱层析分离纯化得棕黄油54.9 mg，收率93％。1H NMR (400 MHz, CDCl3) δ 7.68 (d, J = 8.8 Hz,1H), 7.20 (s, 1H), 6.95 (d, J = 11.2 Hz, 1H), 4.37 (q, J = 7.2 Hz, 2H), 3.87(s, 3H), 3.41 (s, 3H), 2.36 (s, 3H), 1.39 (t, J = 7.2 Hz, 3H); 13C NMR (100MHz, CDCl3) δ 168.9, 163.2, 153.7, 137.0, 125.8, 115.3, 109.7, 106.4, 104.6,60.8, 55.6, 46.1, 25.3, 14.4; HRMS (ESI): 计算值C14H18NO4S [M + H]+ 296.0951,实测值： 296.0948。
实施实例3：化合物3的合成
（1）在洁净的反应器中依次加入S-环己基-S-苯基亚磺酰亚胺（44.7 mg，0.20 mmol），重氮基乙酰乙酸乙酯（37.5 mg，0.24 mmol），二氯（五甲基环戊二烯基）合铑（III）二聚体（6.2 mg，0.01 mmol），六氟锑酸银（13.7 mg，0.04 mmol），1-丁基-3-甲基咪唑六氟磷酸盐（0.6 mL），30℃下搅拌24小时；
（2）反应完成后，加入乙醚萃取，收集乙醚层，减压除去溶剂，残留物采用硅胶柱层析分离纯化得棕黄油53.3 mg，收率80％。1H NMR (400 MHz, CDCl3) δ 7.69 (d, J = 8.4 Hz,2H), 7.56 (t, J = 7.6 Hz, 1H), 7.35 (t, J = 7.6 Hz, 1H), 4.36 (q, J = 7.2 Hz,2H), 3.41 (t, J = 12.0 Hz, 1H), 2.37 (s, 3H), 2.24 (d, J = 12.8 Hz, 1H), 1.97(d, J = 12.8 Hz, 1H), 1.87 – 1.60 (m, 4H), 1.39 (t, J = 7.2 Hz, 3H), 1.34 –1.16 (m, 4H); 13C NMR (150 MHz, CDCl3) δ 169.0, 153.9, 136.4, 133.3, 125.7,124.7, 124.5, 113.1, 104.2, 65.7, 60.8, 26.7, 25.4, 25.2, 25.1, 25.1, 23.3,14.4; HRMS (ESI): 计算值 C18H24NO3S [M + H]+ 334.1471, 实测值: 334.1475。
实施实例4：化合物4的合成
（1）在洁净的反应器中依次加入S-甲基-S-苯基亚磺酰亚胺（31.0 mg，0.20 mmol），重氮基苯甲酰乙酸乙酯（52.3 mg，0.24 mmol），二氯（五甲基环戊二烯基）合铑（III）二聚体（6.2 mg，0.01 mmol），六氟锑酸银（13.7 mg，0.04 mmol），1-丁基-3-甲基咪唑六氟磷酸盐（0.6 mL），30℃下搅拌24小时；
（2）反应完成后，加入乙醚萃取，收集乙醚层，减压除去溶剂，残留物采用硅胶柱层析分离纯化得棕黄油58.3 mg，收率89％。1H NMR (400 MHz, CDCl3) δ 8.07 (d, J = 8.4 Hz,1H), 7.84 (d, J = 7.6 Hz, 1H), 7.67 (t, J = 7.2 Hz, 1H), 7.59 – 7.57 (m, 2H),7.49 (t, J = 7.6 Hz, 1H), 7.40 – 7.38 (m, 3H), 4.02 – 3.85 (m, 2H), 3.61 (s,3H), 0.80 (t, J = 7.2 Hz, 3H); 13C NMR (150 MHz, CDCl3) δ 169.0, 153.0, 140.6,133.9, 133.4, 129.0, 128.4, 128.1, 126.8, 124.9, 123.5, 117.4, 105.8, 60.9,45.1, 13.4; HRMS (ESI): 计算值C18H18NO3S [M + H]+ 328.1002, 实测值：328.1004。
实施实例5：化合物5的合成
（1）在洁净的反应器中依次加入S-甲基-S-苯基亚磺酰亚胺（31.0 mg，0.20 mmol），二苯乙炔（42.8 mg，0.24 mmol），二氯（五甲基环戊二烯基）合铑（III）二聚体（6.2 mg，0.01mmol），六氟锑酸银（13.7 mg，0.04 mmol），无水醋酸铜（36.3 mg，0.20mmol），1-丁基-3-甲基咪唑六氟磷酸盐（0.6 mL），室温下搅拌24小时；
（2）反应完成后，加入乙醚萃取，收集乙醚层，减压除去溶剂，残留物采用硅胶柱层析分离纯化得淡黄色固体53.7 mg，收率81％。1H NMR (400 MHz, CDCl3) δ 7.87 (dd, J = 8.0Hz, J = 1.6, 1H), 7.50 – 7.41 (m, 2H), 7.30 – 7.20 (m, 6H), 7.16 – 7.11 (m,5H), 3.70 (s, 3H); 13C NMR (150 MHz, CDCl3) δ 146.1, 140.5, 137.9, 137.0,132.6, 132.5, 129.8, 129.7, 128.5, 127.5, 127.4, 126.9, 126.2, 123.4, 118.8,112.9, 45.3; HRMS (ESI): 计算值C21H18NOS [M + H]+ 332.1104, 实测值：332.1102。
实施实例6：化合物6的合成
（1）在洁净的反应器中依次加入S-甲基-S-苯基亚磺酰亚胺（31.0 mg，0.20 mmol），叔丁基硫叶立德（70.5 mg，0.24 mmol），二氯（五甲基环戊二烯基）合铑（III）二聚体（6.2 mg，0.01 mmol），六氟锑酸银（13.7 mg，0.04 mmol），1-丁基-3-甲基咪唑六氟磷酸盐（0.6 mL），60℃下搅拌24小时；
（2）反应完成后，加入乙醚萃取，收集乙醚层，减压除去溶剂，残留物采用硅胶柱层析分离纯化得黄色油状物43.8 mg，收率93％。1H NMR (400 MHz, CDCl3) δ 7.71 (d, J = 8.0Hz, 1H), 7.49 (t, J = 7.6 Hz, 1H), 7.35 – 7.25 (m, 2H), 6.06 (s, 1H), 3.47(s, 3H), 1.27 (s, 9H); 13C NMR (150 MHz, CDCl3) δ 159.8, 137.0, 132.3, 126.8,125.7, 123.2, 117.7, 95.2, 45.1, 37.3, 28.9; HRMS (ESI): 计算值C13H18NOS [M +H]+ 236.1104, 实测值：236.1108。
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Claims (7)
1.一种基于过渡金属催化的C-H活化/环合反应温和可循环地合成1,2-苯并噻嗪衍生物的新方法，其特征在于以NH-亚磺酰亚胺为起始原料，重氮化合物、炔以及硫叶立德为偶联试剂，N1,N3-二取代咪唑型离子液为溶剂，在温和条件下合成1,2-苯并噻嗪衍生物，化学反应式如下：
其中：
R1、R2为氢、卤素、烷基、环烷基、芳基、烷氧基中的一种或一种以上；
R3、R4为烷基、芳基、羰基、苯甲酰基、磷脂基、烷氧酰基、卤代烷氧酰基中的一种或一种以上。
2.根据权利要求1所述的衍生物的合成方法，其特征在于采用如下制备步骤：
在洁净的反应器中加入磺酰亚胺类化合物、偶联试剂、催化剂、添加剂和离子液，于室温至60℃油浴锅里搅拌24 h；
反应完成后，加入乙醚萃取；合并乙醚层，经减压蒸馏除去溶剂，残留物采用硅胶柱层析分离纯化即得产品；离子液层经减压干燥后可循环使用，循环使用时无需添加新的催化剂、银盐和离子液。
3.根据权利要求2所述的制备方法，其特征在于步骤（1）中的催化剂为钯碳、四（三苯基膦）钯、醋酸钯、氯化钯、二（乙腈）二氯化钯、二（苯腈）二氯化钯，1，1’-二（二苯基膦基）二茂铁二氯化钯、二（三苯基膦）二氯化钯、双（二亚苄基丙酮）钯、三（二亚苄基丙酮）二钯、氯化烯丙基钯（II）二聚物、（1,5-环辛二烯）二氯化钯（II）、铑碳、三氯化铑、醋酸铑、乙酰丙酮三苯基膦羰基铑、双环辛烯氯化铑二聚体、二氯（五甲基环戊二烯基）合铑（III）二聚体、(二(六氟锑酸)三乙腈(五甲基环戊二烯基)铑(III))、三苯基膦氯化铑、三氯化钌、三苯基膦氯化钌、二氯二羰基双三苯基膦钌、双（2-甲基烯丙基）（1,5-环辛二烯）钌（II）、对伞花烃二氯化钌二聚体、氯化钴、乙酰乙酰钴、八羰基二钴、二氯（五甲基环戊二烯基）合钴（III）二聚体、五甲基环戊二烯基羰基二碘化钴、(二(六氟锑酸)三乙腈(五甲基环戊二烯基)钴(III))、三氯化铱、二氯(五甲基环戊二烯)合铱(III)二聚体、双（1,5-环辛二烯）氯化铱（Ⅰ）二聚体、甲氧基（环辛二烯）合铱二聚体中的一种或一种以上。
4.根据权利要求2所述的制备方法，其特征在于步骤（1）中的添加剂为硝酸银、乙酸银、碳酸银、硫酸银、甲烷磺酸银、三氟甲烷磺酸银、对甲苯磺酸银、双三氟甲烷磺酰亚胺银，三氟甲烷磺酸银，六氟锑酸银、四氟硼酸银、六氟磷酸银中的一种或一种以上。
5.根据权利要求2所述的制备方法，其特征在于步骤（1）中的溶剂为N1,N3-二取代咪唑类离子液体的一种。
6.根据权利要求2所述的制备方法，其特征在于步骤（1）中磺酰亚胺类化合物：重氮化合物：催化剂：添加剂的摩尔为1:（1.2~3.0）：（0.02~0.05）：（0.08~0.2）。
7.根据权利要求2所述的制备方法，其特征在于步骤（1）中磺酰亚胺类化合物的反应浓度为0.1~0.5 mol/L。
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