CN111592481A - 一种多取代二氢吡咯类化合物的制备方法 - Google Patents
一种多取代二氢吡咯类化合物的制备方法 Download PDFInfo
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- CN111592481A CN111592481A CN202010493711.2A CN202010493711A CN111592481A CN 111592481 A CN111592481 A CN 111592481A CN 202010493711 A CN202010493711 A CN 202010493711A CN 111592481 A CN111592481 A CN 111592481A
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- pyrroline
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- -1 polysubstituted pyrroline compound Chemical class 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- 239000012043 crude product Substances 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 13
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 229910052740 iodine Inorganic materials 0.000 claims description 12
- 239000011630 iodine Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- 238000010791 quenching Methods 0.000 claims description 8
- 230000000171 quenching effect Effects 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Chemical group 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 150000002431 hydrogen Chemical group 0.000 claims description 3
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- XMSZANIMCDLNKA-UHFFFAOYSA-N methyl hypofluorite Chemical group COF XMSZANIMCDLNKA-UHFFFAOYSA-N 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 2
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 7
- IOGXOCVLYRDXLW-UHFFFAOYSA-N tert-butyl nitrite Chemical compound CC(C)(C)ON=O IOGXOCVLYRDXLW-UHFFFAOYSA-N 0.000 abstract description 7
- 239000012414 tert-butyl nitrite Substances 0.000 abstract description 7
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical compound CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 abstract description 4
- 239000007800 oxidant agent Substances 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 150000002505 iron Chemical class 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 39
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 22
- 239000012074 organic phase Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 12
- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical compound C1CC=CN1 RSEBUVRVKCANEP-UHFFFAOYSA-N 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- PBCJIPOGFJYBJE-UHFFFAOYSA-N acetonitrile;hydrate Chemical compound O.CC#N PBCJIPOGFJYBJE-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 235000002639 sodium chloride Nutrition 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000003236 pyrrolines Chemical class 0.000 description 3
- 238000004293 19F NMR spectroscopy Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000004698 iron complex Chemical class 0.000 description 2
- 150000003233 pyrroles Chemical class 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 125000004199 4-trifluoromethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C(F)(F)F 0.000 description 1
- QYKRONLFLPJQKJ-UHFFFAOYSA-N CC(C)(C1)C(C(C(C=C2)=CC=C2F)=O)=CN1S(C1=CC=C(C)C=C1)(=O)=O Chemical compound CC(C)(C1)C(C(C(C=C2)=CC=C2F)=O)=CN1S(C1=CC=C(C)C=C1)(=O)=O QYKRONLFLPJQKJ-UHFFFAOYSA-N 0.000 description 1
- KKQYLJWHWLJPQR-UHFFFAOYSA-N CC(C)(C1)C(C(C(C=C2)=CC=C2OC)=O)=CN1S(C1=CC=C(C)C=C1)(=O)=O Chemical compound CC(C)(C1)C(C(C(C=C2)=CC=C2OC)=O)=CN1S(C1=CC=C(C)C=C1)(=O)=O KKQYLJWHWLJPQR-UHFFFAOYSA-N 0.000 description 1
- YUTQPUNTBAZTQF-UHFFFAOYSA-N CC(C)(C1)C(C(C2=CC=C(C(F)(F)F)C=C2)=O)=CN1S(C1=CC=C(C)C=C1)(=O)=O Chemical compound CC(C)(C1)C(C(C2=CC=C(C(F)(F)F)C=C2)=O)=CN1S(C1=CC=C(C)C=C1)(=O)=O YUTQPUNTBAZTQF-UHFFFAOYSA-N 0.000 description 1
- UOBJYIMXJRWNST-UHFFFAOYSA-N CC(C)(C1)C(C(C2=CC=CC=C2)=O)=CN1S(C1=CC=C(C)C=C1)(=O)=O Chemical compound CC(C)(C1)C(C(C2=CC=CC=C2)=O)=CN1S(C1=CC=C(C)C=C1)(=O)=O UOBJYIMXJRWNST-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 150000003797 alkaloid derivatives Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005784 autoimmunity Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- ZVJHJDDKYZXRJI-UHFFFAOYSA-N pyrroline Natural products C1CC=NC1 ZVJHJDDKYZXRJI-UHFFFAOYSA-N 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/46—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with hetero atoms directly attached to the ring nitrogen atom
- C07D207/48—Sulfur atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Pyrrole Compounds (AREA)
Abstract
Description
序号 | 碘单质 | 过氧化氢 | 产率(%) |
1 | I<sub>2</sub>(20mol%) | H<sub>2</sub>O<sub>2</sub>(2.0eq) | <10% |
2 | I<sub>2</sub>(5mol%) | H<sub>2</sub>O<sub>2</sub>(2.0eq) | <10% |
3 | I<sub>2</sub>(10mol%) | H<sub>2</sub>O<sub>2</sub>(3.0eq) | <10% |
Claims (10)
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114133349A (zh) * | 2021-12-30 | 2022-03-04 | 江南大学 | 一种3,4-二取代吡咯衍生物的制备方法 |
Citations (5)
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CN107540667A (zh) * | 2017-09-04 | 2018-01-05 | 江南大学 | 一种含氟多取代吡咯烷衍生物的制备方法 |
CN108727244A (zh) * | 2018-07-23 | 2018-11-02 | 宁波大学 | 一种1,6-烯炔硝化环化反应制备2-吡咯烷酮类化合物的方法 |
CN110372613A (zh) * | 2019-08-21 | 2019-10-25 | 江南大学 | 一种2,3,6-三取代吡嗪氮氧类化合物的高效制备方法 |
CN110467553A (zh) * | 2019-09-18 | 2019-11-19 | 长江师范学院 | 一种基于1,6-烯炔类化合物硝化/环化反应的新方法 |
CN110981802A (zh) * | 2019-12-10 | 2020-04-10 | 广东药科大学 | 一种制备含氮杂环化合物的方法 |
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2020
- 2020-06-03 CN CN202010493711.2A patent/CN111592481B/zh active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN107540667A (zh) * | 2017-09-04 | 2018-01-05 | 江南大学 | 一种含氟多取代吡咯烷衍生物的制备方法 |
CN108727244A (zh) * | 2018-07-23 | 2018-11-02 | 宁波大学 | 一种1,6-烯炔硝化环化反应制备2-吡咯烷酮类化合物的方法 |
CN110372613A (zh) * | 2019-08-21 | 2019-10-25 | 江南大学 | 一种2,3,6-三取代吡嗪氮氧类化合物的高效制备方法 |
CN110467553A (zh) * | 2019-09-18 | 2019-11-19 | 长江师范学院 | 一种基于1,6-烯炔类化合物硝化/环化反应的新方法 |
CN110981802A (zh) * | 2019-12-10 | 2020-04-10 | 广东药科大学 | 一种制备含氮杂环化合物的方法 |
Non-Patent Citations (5)
Title |
---|
MINGMING ZHAO ET AL.: "Iron-catalyzed hydrogen atom transfer induced cyclization of 1,6-enynes for the synthesis of ketoximes: a combined experimental and computational study", 《ORGANIC CHEMISTRY FRONTIERS》 * |
NEMAI C. GANGULY ET AL.: "Convenient, Mild Catalytic Deprotection of Oximes to Carbonyl Compounds with Hydrogen Peroxide and Iodine Catalyst in Aqueous Acetonitrile", 《SYNTHETIC COMMUNICATIONS》 * |
XIAO-FENG XIA ET AL.: "Iron-catalyzed reductive cyclization reaction of 1,6-enynes for the synthesis of 3-acylbenzofurans and thiophenes", 《ORGANIC CHEMISTRY FRONTIERS》 * |
XIAO-XIAO MENG ET AL.: "Visible-light-initiated regioselective sulfonylation/cyclization of 1,6-enynes under photocatalyst- and additive-free conditions", 《GREEN CHEMISTRY》 * |
YU LIU ET AL.: "Cascade Nitration/Cyclization of 1,7-Enynes with tBuONO and H2O: One-Pot Self-Assembly of Pyrrolo[4,3,2-de]quinolinones", 《ANGEW. CHEM. INT. ED.》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114133349A (zh) * | 2021-12-30 | 2022-03-04 | 江南大学 | 一种3,4-二取代吡咯衍生物的制备方法 |
CN114133349B (zh) * | 2021-12-30 | 2023-08-08 | 江南大学 | 一种3,4-二取代吡咯衍生物的制备方法 |
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