CN108440391B - 一种2,4,6-三芳基取代吡啶衍生物的制备方法 - Google Patents
一种2,4,6-三芳基取代吡啶衍生物的制备方法 Download PDFInfo
- Publication number
- CN108440391B CN108440391B CN201810289048.7A CN201810289048A CN108440391B CN 108440391 B CN108440391 B CN 108440391B CN 201810289048 A CN201810289048 A CN 201810289048A CN 108440391 B CN108440391 B CN 108440391B
- Authority
- CN
- China
- Prior art keywords
- preparation
- substituted pyridine
- pyridine derivatives
- triaryl substituted
- phenyl
- 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.)
- Active
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 150000003222 pyridines Chemical class 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 150000003939 benzylamines Chemical class 0.000 claims abstract description 5
- 125000001424 substituent group Chemical group 0.000 claims abstract description 4
- 125000005002 aryl methyl group Chemical group 0.000 claims abstract description 3
- -1 substituted-phenyl Chemical group 0.000 claims description 30
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 125000001072 heteroaryl group Chemical group 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 125000004076 pyridyl group Chemical group 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000002541 furyl group Chemical group 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000001544 thienyl group Chemical group 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 239000000758 substrate Substances 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000001212 derivatisation Methods 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 36
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 33
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 22
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 22
- WGQKYBSKWIADBV-UHFFFAOYSA-N aminomethyl benzene Natural products NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 19
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 12
- 238000010898 silica gel chromatography Methods 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 239000012298 atmosphere Substances 0.000 description 11
- 239000003480 eluent Substances 0.000 description 11
- 239000012046 mixed solvent Substances 0.000 description 11
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 10
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 10
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 7
- UJHSIDUUJPTLDY-UHFFFAOYSA-N (2-nitrophenyl)-phenylmethanone Chemical compound [O-][N+](=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 UJHSIDUUJPTLDY-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- FRZHWQQBYDFNTH-UHFFFAOYSA-N 2,4,6-triphenylpyridine Chemical compound C1=CC=CC=C1C1=CC(C=2C=CC=CC=2)=NC(C=2C=CC=CC=2)=C1 FRZHWQQBYDFNTH-UHFFFAOYSA-N 0.000 description 2
- NTPLXRHDUXRPNE-UHFFFAOYSA-N 4-methoxyacetophenone Chemical compound COC1=CC=C(C(C)=O)C=C1 NTPLXRHDUXRPNE-UHFFFAOYSA-N 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000008062 acetophenones Chemical class 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- IIFVWLUQBAIPMJ-UHFFFAOYSA-N (4-fluorophenyl)methanamine Chemical compound NCC1=CC=C(F)C=C1 IIFVWLUQBAIPMJ-UHFFFAOYSA-N 0.000 description 1
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 1
- IDPURXSQCKYKIJ-UHFFFAOYSA-N 1-(4-methoxyphenyl)methanamine Chemical compound COC1=CC=C(CN)C=C1 IDPURXSQCKYKIJ-UHFFFAOYSA-N 0.000 description 1
- AJKVQEKCUACUMD-UHFFFAOYSA-N 2-Acetylpyridine Chemical compound CC(=O)C1=CC=CC=N1 AJKVQEKCUACUMD-UHFFFAOYSA-N 0.000 description 1
- YQYGPGKTNQNXMH-UHFFFAOYSA-N 4-nitroacetophenone Chemical compound CC(=O)C1=CC=C([N+]([O-])=O)C=C1 YQYGPGKTNQNXMH-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 235000002566 Capsicum Nutrition 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910000705 Fe2N Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000006002 Pepper Substances 0.000 description 1
- 235000016761 Piper aduncum Nutrition 0.000 description 1
- 235000017804 Piper guineense Nutrition 0.000 description 1
- 244000203593 Piper nigrum Species 0.000 description 1
- 235000008184 Piper nigrum Nutrition 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- CNEUXSYBURPOSS-UHFFFAOYSA-N cyclopenta-1,3-diene 2-cyclopenta-2,4-dien-1-ylpyridine iron(2+) Chemical compound [Fe++].c1cc[cH-]c1.c1cc[c-](c1)-c1ccccn1 CNEUXSYBURPOSS-UHFFFAOYSA-N 0.000 description 1
- CBJYXYXOISWSDQ-UHFFFAOYSA-M cyclopenta-1,3-diene;1-cyclopenta-2,4-dien-1-ylideneethanolate;iron(2+) Chemical compound [Fe+2].C=1C=C[CH-]C=1.CC([O-])=C1C=CC=C1 CBJYXYXOISWSDQ-UHFFFAOYSA-M 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001207 fluorophenyl group Chemical group 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/08—Preparation by ring-closure
- C07D213/09—Preparation by ring-closure involving the use of ammonia, amines, amine salts, or nitriles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/22—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing two or more pyridine rings directly linked together, e.g. bipyridyl
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/26—Radicals substituted by halogen atoms or nitro radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
- C07D213/30—Oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/36—Radicals substituted by singly-bound nitrogen atoms
- C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- 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
- C07F17/00—Metallocenes
- C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic Table
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Abstract
本发明公开了一种2,4,6‑三芳基取代吡啶衍生物的制备方法，其制备方法如下：在溶剂或无溶剂条件下，以芳乙酮类化合物和苄胺衍生物为原料，以三(五氟苯)硼烷为催化剂，在80~160℃和氧气条件下反应6~24小时，得到2,4,6‑三芳基取代吡啶衍生物。本发明的有益效果主要体现在：本发明提供的制备方法中，反应原料易得，催化剂用量可低至千分之五，实验操作简单，可“一锅法”制备目标化合物；底物普适性较好，可构建不同取代基的2,4,6‑三芳基取代吡啶衍生物，有利于进一步的衍生化研究。
Description
技术领域
本发明属于医药化工中间体合成技术领域，具体涉及一种2,4,6-三芳基取代吡啶衍生物的制备方法。
背景技术
2,4,6-三芳基取代吡啶是一类重要的杂环化合物，在医药、农业、化工、纺染等领域均有应用，尤其是作为制备芳纶的聚酰胺材料的关键中间体PBAPP，其结构式如下：
由于2,4,6-三芳基取代吡啶衍生物具有特殊的材料性能，因此众多学者专注于该类化合物的合成方法研究。最常见的方法为：以芳香醛类化合物、苯乙酮类化合物和醋酸铵为底物，以偏铝酸镁为催化剂，通过微波反应合成2,4,6-三芳基取代的吡啶衍生物(J. Chem. Sci., 2013, 125(5), 1063-1070), 这种方法使用到微波技术，反应比较剧烈，反应条件要求比较高。
第二类方法是以酮类化合物和二苄胺类化合物为底物，以在Cu(OTf)2催化下制得2,4,6-三芳基取代的吡啶衍生物J.Org.Chem., 2013, 78(8), 3774-3782)，该种方法底物普适性较高，但反应时间较长，一般在20小时以上。
第三类方法是以苯甲醛类化合物和烯胺类化合物为底物，在醋酸钯，碘苯，氯化锂，碳酸钠等作用下反应合成2,4,6-三芳基取代的吡啶衍生物（Org. Lett.,2013, 15(2),334-337）。这种方法可以构建不对称的吡啶衍生物，但是需要使用贵金属催化剂，且催化量达10%，无法回收套用。
第四类方法是以氨基酸类化合物和苯乙酮类化合物为底物，在醋酸与碘单质等（Org.Lett.，2016, 18, 24-27）的作用下反应合成2,4,6-三芳基取代的吡啶衍生物。这种方法的反应条件相对温和，但是收率普遍较低，且催化剂的用量高达50%。
因此，开发一种原料易得、操作简单、反应条件温和、选择性高的2,4,6-三芳基取代吡啶衍生物的合成方法极为迫切。
发明内容
针对现有技术中存在的上述问题，本发明的目的在于提供一种原料易得、操作简单、反应条件温和、选择性高的2,4,6-三芳基取代吡啶衍生物的制备方法。
所述的一种2,4,6-三芳基取代吡啶衍生物的制备方法，所述2,4,6-三芳基取代吡啶衍生物的结构式如式（I）所示，其特征在于在溶剂或无溶剂条件下，以如式（Ⅱ）所示的芳乙酮类化合物和如（Ⅲ）所示的苄胺衍生物为原料，以三(五氟苯)硼烷为催化剂，在80~160℃和氧气条件下反应6~24小时，得到如式（I）所示的2,4,6-三芳基取代吡啶衍生物，反应式如下：
结构式I、Ⅱ、Ⅲ中，Ar1为取代苯基和杂芳基；Ar2为取代苯基、杂芳基和二茂铁基；其中，苯环上的取代基选自氢、甲基、甲氧基、氟、氯、溴、硝基、叔丁基、乙酰氧基或三氟甲基；所述杂芳基为噻吩基、吡啶基或呋喃基。
所述的2,4,6-三芳基取代吡啶衍生物的制备方法，其特征在于芳乙酮类化合物、苄胺类化合物、三(五氟苯)硼烷的物质的量之比为1: 0.5~1.5: 0.001~0.05，优选为1:0.8~1.2:0.005~0.01。
所述的2,4,6-三芳基取代吡啶衍生物的制备方法，其特征在于反应温度为110~120℃；反应时间为10~16小时。
所述的2,4,6-三芳基取代吡啶衍生物的制备方法，其特征在于氧气压力为1~5atm。
所述的2,4,6-三芳基取代吡啶衍生物的制备方法，其特征在于溶剂为甲苯、DMSO、1,4-二氧六环。
与现有技术相比，本发明的有益效果主要体现在：本发明提供的制备方法中，反应原料易得，催化剂用量可低至千分之五，实验操作简单，可“一锅法”制备目标化合物；底物普适性较好，可构建不同取代基的2,4,6-三芳基取代吡啶衍生物，有利于进一步的衍生化研究。
具体实施方式
下面结合具体实施例对本发明进行进一步描述，但不仅限于本发明所列出的具体实施例描述的实施方案。
实施例1：2,4,6-三苯基吡啶（Ia）的制备
将苯乙酮（0.48 g, 4 mmol）、苄胺（0.35 g, 3.2mmol）、三(五氟苯基)硼烷（0.01g, 0.02 mmol）置于耐压管中在氧气氛围(1 atm)下120℃下搅拌反应12小时后，经硅胶柱层析分离，得到白色固体2,4,6-三苯基吡啶（Ia）0.53 g，收率86%，熔点：134-137℃。
1H NMR (600 MHz, CDCl3, ppm) δ 8.26 (d, J = 7.8 Hz, 4H), 7.94 (s, 2H),7.80 (d, J = 7.2 Hz, 2H), 7.59-7.56 (m, 6H), 7.53-7.48 (m, 3H). 13C NMR (150MHz, CDCl3, ppm) δ 157.5, 150.4, 139.5, 139.0, 129.2, 129.2, 128.8, 127.2,117.3. MS(ESI-MS) 307.1。
实施例2：2,4,6-三苯基吡啶（Ia）的制备
将苯乙酮（0.48 g, 4 mmol）、苄胺（0.64 g, 6 mmol）、三(五氟苯基)硼烷（0.01g, 0.02 mmol）、0.5 mL DMSO置于耐压管中在氧气氛围(5 atm)下110℃下搅拌反应12小时，反应结束后，用石油醚/乙酸乙酯=30/1（V/V）混合溶剂作洗脱剂，经硅胶柱层析分离得到白色固体2,4,6-三苯基-吡啶（Ia）0.40 g，收率：64%，熔点：134-137℃。
实施例3：2,4,6-三苯基吡啶（Ia）的制备
将苯乙酮（0.48 g, 4 mmol）、苄胺（0.35 g, 3.2 mmol）、三(五氟苯基)硼烷（0.005 g, 0.01mmol）置于耐压管中在氧气氛围(1 atm)下120℃下搅拌反应12小时，反应结束后，用石油醚/乙酸乙酯= 30/1（V/V）混合溶剂作洗脱剂，经硅胶柱层析分离得到白色固体2,4,6-三苯基-吡啶（Ia）0.50 g，收率：81%，熔点：134-137℃。
实施例4：2,4,6-三苯基吡啶（Ia）的制备
将苯乙酮（0.48 g, 4 mmol）、苄胺（0.23 g, 2 mmol）、三(五氟苯基)硼烷（0.01g,0.02 mmol）、0.5 mL甲苯置于耐压管中在氧气氛围(1 atm)下120℃下搅拌反应12小时，反应结束后，用石油醚/乙酸乙酯= 30/1（V/V）混合溶剂作洗脱剂，经硅胶柱层析分离得到白色固体2,4,6-三苯基-吡啶（Ia）0.37 g，收率：63%，熔点：134-137℃。
实施例5：2,6-二(4，-甲氧基苯基)-4-苯基吡啶（Ib）的制备
将对甲氧基苯乙酮（0.60 g，4 mmol）、苄胺（0.35 g,3.2 mmol）、三(五氟苯基)硼烷（0.01 g,0.02 mmol）置于耐压管中在氧气氛围(1 atm)中120℃下搅拌反应12小时，反应结束后，用石油醚/乙酸乙酯= 30/1（V/V）混合溶剂作洗脱剂，经硅胶柱层析分离得到白色固体2,6-二-(4，-甲氧基苯基)-4-苯基吡啶（Ib）0.60 g，收率：81%，熔点：132-135℃
1H NMR (600 MHz, CDCl3, ppm) δ 8.20 (d, J = 8.4 Hz, 4H), 7.81 (s, 2H),7.77 (d, J = 7.2 Hz, 2H), 7.56 (dd, J =7.2, 7.8 Hz, 2H), 7.50 (dd,J = 7.2,7.2 Hz, 1H), 7.08(d, J = 8.4 Hz, 4H). 13C NMR (150 MHz, CDCl3, ppm) δ 157.4,150.1, 139.3, 139.0, 136.9, 129.5, 129.1, 127.2, 127.1, 116.6, 21.4. MS (ESI-MS) 367.2。
实施例6：4-苯基-2,6-二(二茂铁基)吡啶（Ic）的制备
将乙酰基二茂铁（0.91 g，4 mmol）、苄胺（0.35 g, 3.2 mmol）、三(五氟苯基)硼烷（0.02 g, 0.04 mmol）置于耐压管中在氧气氛围(1 atm)中120℃下搅拌反应12小时，反应结束后，用石油醚/乙酸乙酯=30/1（V/V）混合溶剂作洗脱剂，经硅胶柱层析分离得到黄色固体4-苯基-2,6-二(二茂铁基)-吡啶（Ic）1.04g，收率：86%，熔点：147-150℃。
1H NMR (600 MHz, CDCl3, ppm) δ 7.75 (d, J = 7.2 Hz, 2H), 7.57 (dd, J =7.2, 7.2 Hz, 2H), 7.51 (dd, J = 7.2, 7.2 Hz, 1H), 7.40 (s, 2H), 5.11 (s, 4H),4.47 (s, 4H), 4.14 (s, 10H). 13C NMR (150 MHz, CDCl3, ppm) δ 158.9, 148.3,139.3, 129.0, 128.7, 127.1, 114.9, 85.2, 70.2, 70.1, 67.9. HRMS (ESI-TOF)calcd for C31H25Fe2N [M+H]+: 523.0750; Found: 523.0686。
实施例7：2,6-二(2，-吡啶基)-4-苯基吡啶（Id）的制备
将2-乙酰基吡啶（0.48 g, 4 mmol）、苄胺（0.35 g, 3.2 mmol）、三(五氟苯基)硼烷（0.02 g, 0.04 mmol）置于耐压管中在氧气氛围(1 atm)中120℃下搅拌反应12小时，反应结束后，用石油醚/乙酸乙酯=30/1（V/V）混合溶剂作洗脱剂，经硅胶柱层析分离得到白色固体2,6-二(2，-吡啶基)-4-苯基吡啶（Id）0.49 g，收率：81%，熔点: 205-207℃。
1H NMR (600 MHz, CDCl3, ppm) δ 8.77 (s, 2H), 8.76 (d, J = 4.2 Hz, 2H),8.70 (d, J = 7.8 Hz, 2H), 7.94 (d, J = 7.2 Hz, 2H), 7.90-7.87 (m, 2H), 7.53(dd, J = 7.2, 7.8 Hz, 2H), 7.47 (dd, J = 7.8, 7.2 Hz, 1H), 7.37-7.35 (m, 1H).13CNMR (150 MHz, CDCl3, ppm) δ 156.3, 155.9, 150.3, 149.1, 138.5, 136.9,129.0, 128.9, 127.4, 123.8, 121.4, 119.0. MS (ESI-MS) 309.1。
实施例8：2,6-二(4，-硝基苯基)-4-苯基吡啶（Ie）的制备
将对硝基苯乙酮（0.66 g, 4 mmol）、苄胺（0.35 g, 3.2 mmol）、三(五氟苯基)硼烷（0.01 g, 0.02 mmol）置于耐压管中在氧气氛围(1 atm)下120℃下搅拌反应12小时，反应结束后，用石油醚/乙酸乙酯= 30/1（V/V）混合溶剂作洗脱剂，经硅胶柱层析分离得到土黄色固体2,6-二(4，-硝基苯基)-4-苯基吡啶（Ie）0.63g，收率：80%，熔点：310-315℃。
1H NMR (600 MHz, CDCl3, ppm) δ 8.43-8.39 (m, 8H), 8.08 (s, 2H), 7.80(d, J = 8.4 Hz, 2H), 7.61 (dd, J = 7.2, 7.2 Hz, 2H), 7.58-7.56 (m, 1H). 13CNMR (150 MHz, CDCl3, ppm) δ 155.5, 144.8, 137.9, 129.7, 129.4, 128.0, 127.2,124.1, 119.1, 100.0. MS (ESI-MS) 397.1. 。
实施例9：2,4,6-三(4，-甲氧基苯基)吡啶（If）的制备
将对甲氧基苯乙酮（0.60 g，4 mmol）、对甲氧基苄胺（0.35 g, 3.2mmol）、三(五氟苯基)硼烷（0.01 g, 0.02 mmol）置于耐压管中在氧气氛围(1 atm)下120℃下搅拌反应12小时，反应结束后，用石油醚/乙酸乙酯= 30/1（V/V）混合溶剂作洗脱剂，经硅胶柱层析分离得到白色固体2,4,6-三(4，-甲氧基苯基)吡啶（If）0.56g，收率：71%，熔点：130-133℃。
1H NMR (600 MHz, CDCl3, ppm) δ 8.19 (d, J = 9.0 Hz, 4H), 7.77(s, 2H),7.73 (d, J = 9.0 Hz, 2H), 7.07 (dd, J = 7.2, 8.4 Hz, 6H), 3.91 (s, 9H). 13CNMR (150 MHz, CDCl3, ppm) δ 160.5, 156.9, 149.5, 132.4, 131.6, 128.4, 128.3,115.3, 114.5, 114.0, 55.4, 55.4. MS (ESI-MS) 397.2。
实施例10：2,6-二苯基-(4，-氟苯基)吡啶（Ig）的制备
将苯乙酮（0.48 g, 4 mmol）、对氟苄胺（0.35 g, 3.2 mmol）、三(五氟苯基)硼烷（0.01 g, 0.02 mmol）置于耐压管中在氧气氛围(1 atm)下120℃下搅拌反应12小时，反应结束后，用石油醚/乙酸乙酯= 30/1（V/V）混合溶剂作洗脱剂，经硅胶柱层析分离得到白色固体2，6-(二苯基)-(4’-氟苯基)吡啶（Ig）0.48g，收率：73.8%，熔点：114-116℃。
1H NMR (600 MHz, CDCl3, ppm) δ 8.20 (d, J = 7.8 Hz, 4H), 7.82 (s, 2H),7.72-7.70 (m, 2H), 7.51(dd, J = 7.2, 7.8 Hz, 4H), 7.45 (dd, J = 7.2, 7.8 Hz,1H), 7.21 (dd, J =9.0, 8.4 Hz, 2H). 13C NMR (150 MHz, CDCl3, ppm) δ164.3 (J C-F =246.0 Hz), 157.6, 149.3, 139.3, 135.1, 129.2, 129.0 (J C-F = 9.0 Hz), 128.8,127.2, 117.0, 116.2 (J C-F =22.5 Hz).MS (ESI-MS) 325.1。
实施例11：4-苯并二氧杂环戊烯-2,6-二苯基吡啶（Ih）的制备
将苯乙酮（0.48 g，4 mmol）、胡椒苄胺（0.35 g, 3.2 mmol）、三(五氟苯基)硼烷（0.01 g, 0.02 mmol）置于耐压管中在氧气氛围(1 atm)下120℃下搅拌反应12小时，反应结束后，用石油醚/乙酸乙酯= 30/1（V/V）混合溶剂作洗脱剂，经硅胶柱层析分离得到白色固体4-苯并二氧杂环戊烯-2,6-二苯基吡啶（Ih）0.60g，收率：86%，熔点：141-143℃。
1H NMR (600 MHz, CDCl3, ppm) δ 8.24 (d, J = 7.8 Hz, 4H), 7.85 (s, 2H),7.55 (t, J = 7.8 Hz, 4H),7.48 (dd, J =7.2, 7.2 Hz, 2H), 7.29-7.28 (m, 1H),7.26 (s, 1H), 6.99 (d, J = 8.4 Hz, 1H), 6.08 (s, 2H). 13C NMR (150 MHz, CDCl3,ppm) δ157.5, 149.8, 148.5, 148.5, 139.6, 133.2, 129.1, 128.7, 127.2, 121.1,116.8, 108.9, 107.5, 101.5. MS (ESI-MS) 351.1。
实施例12:2,6-二(4，-氨基苯基) -4-苯基吡啶(PBAPP)的制备
将2,6-二-(4，-硝基苯基)-4-苯基吡啶（Ie, 1.6 g，4 mmol）、5% Pd/C（0.06g）、48mL无水乙醇置于干燥三口瓶中在氮气氛围(1 atm)下回流3小时，再往反应体系中加入18mL 80%的水合肼，继续回流过夜，反应结束后，用石油醚/乙酸乙酯= 30/1（V/V）混合溶剂作洗脱剂，经硅胶柱层析分离得到淡黄色固体2,6-二(4，-氨基苯基)-4-苯基吡啶（PBAPP）1.32g，收率：95%，熔点：195-196℃。
1H NMR (600 MHz, CDCl3, ppm) δ 8.03 (d, J = 7.8 Hz, 4H), 7.95 (d, J =6.6 Hz, 2H), 7.80 (s, 2H), 7.54 (d, J = 5.4 Hz, 2H), 7.49 (d, J = 6.0 Hz,1H), 6.71 (d, J = 4.2 Hz, 4H), 5.43 (s, 4H). 13C NMR (150 MHz, CDCl3, ppm) δ157.1, 150.3, 149.1, 139.0, 129.5, 128.3, 128.2, 127.5, 127.0, 114.1, 113.2.MS (ESI-MS) 337.2。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员，在不脱离本发明构思的前提下，还可以做出若干改进和润色，这些改进和润色也应视为本发明的保护范围内。
Claims (6)
1.一种2,4,6-三芳基取代吡啶衍生物的制备方法，所述2,4,6-三芳基取代吡啶衍生物的结构式如式（I）所示，其特征在于在溶剂或无溶剂条件下，以如式（Ⅱ）所示的芳乙酮类化合物和如（Ⅲ）所示的苄胺衍生物为原料，以三(五氟苯)硼烷为催化剂，在80~160℃和氧气条件下反应6~24小时，得到如式（I）所示的2,4,6-三芳基取代吡啶衍生物，反应式如下：
结构式I、Ⅱ、Ⅲ中，Ar1为取代苯基和杂芳基；Ar2为取代苯基、杂芳基和二茂铁基；其中，苯环上的取代基选自氢、甲基、甲氧基、氟、氯、溴、硝基、叔丁基、乙酰氧基或三氟甲基；所述杂芳基为噻吩基、吡啶基或呋喃基。
2.根据权利要求1所述的2,4,6-三芳基取代吡啶衍生物的制备方法，其特征在于芳乙酮类化合物、苄胺衍生物、三(五氟苯)硼烷的物质的量之比为1: 0.5~1.5: 0.001~0.05。
3.根据权利要求1所述的2,4,6-三芳基取代吡啶衍生物的制备方法，其特征在于反应温度为110~120℃；反应时间为10~16小时。
4.根据权利要求1所述的2,4,6-三芳基取代吡啶衍生物的制备方法，其特征在于氧气压力为1~5 atm。
5.根据权利要求1所述的2,4,6-三芳基取代吡啶衍生物的制备方法，其特征在于溶剂为甲苯、DMSO、1,4-二氧六环。
6.根据权利要求1所述的2,4,6-三芳基取代吡啶衍生物的制备方法，其特征在于芳乙酮类化合物、苄胺衍生物、三(五氟苯)硼烷的物质的量之比为1: 0.8~1.2:0.005~0.01。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810289048.7A CN108440391B (zh) | 2018-04-03 | 2018-04-03 | 一种2,4,6-三芳基取代吡啶衍生物的制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810289048.7A CN108440391B (zh) | 2018-04-03 | 2018-04-03 | 一种2,4,6-三芳基取代吡啶衍生物的制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108440391A CN108440391A (zh) | 2018-08-24 |
| CN108440391B true CN108440391B (zh) | 2019-10-25 |
Family
ID=63198064
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810289048.7A Active CN108440391B (zh) | 2018-04-03 | 2018-04-03 | 一种2,4,6-三芳基取代吡啶衍生物的制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108440391B (zh) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111138346B (zh) * | 2020-02-13 | 2022-11-08 | 上海大学 | 2-乙基-4,6-二取代吡啶类化合物及其制备方法 |
| CN115073780B (zh) * | 2022-06-25 | 2024-06-04 | 天津农学院 | 一种力致荧光增强聚合物及其制备方法 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106519226A (zh) * | 2015-09-11 | 2017-03-22 | 华东理工大学 | 一种三官能团炔衍生的聚三唑树脂及其制备方法 |
-
2018
- 2018-04-03 CN CN201810289048.7A patent/CN108440391B/zh active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106519226A (zh) * | 2015-09-11 | 2017-03-22 | 华东理工大学 | 一种三官能团炔衍生的聚三唑树脂及其制备方法 |
Non-Patent Citations (6)
| Title |
|---|
| An efficient one-pot oxidative esterification of aldehydes to carboxylic esters using B(C6F5)3–TBHP;Sravanthi Devi Guggilapu，等;《Tetrahedron Letters》;20150109;第56卷;第889-892页 * |
| Copper-Catalyzed Formal C−N Bond Cleavage of Aromatic Methylamines: Assembly of Pyridine Derivatives;Huawen Huang，等;《J. Org. Chem.》;20130318;第78卷;第3774-3782页 * |
| HOTf-catalyzed sustainable one-pot synthesis of benzene and pyridine derivatives under solvent-free conditions;Xu Zhang，等;《Green Chemistry》;20160121;第18卷;第2313-2316页 * |
| I2-Promoted Condensation/Cyclization of Aryl Methyl Ketones with Anilines for Facile Synthesis of 1,2,4-Triarylpyrroles;Hui Xu，等;《Eur. J. Org. Chem.》;20160122;第2016卷;第925-929页 * |
| Synthesis of 2,4,6-Trisubstituted Pyridines by Oxidative Eosin Y Photoredox Catalysis;Rajendra S. Rohokale，等;《J. Org. Chem.》;20160630;第81卷;第7121-7126页 * |
| Tri(pentaflurophenyl)borane-catalyzed reduction of cyclic imides with hydrosilanes: Synthesis of pyrrolidines;Guangni Ding，等;《Tetrahedron》;20180201;第74卷;第1144-1150页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108440391A (zh) | 2018-08-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108033922B (zh) | 一种3-酰基喹喔啉酮衍生物的制备方法 | |
| Wang et al. | Copper-catalyzed ipso-selenation of aromatic carboxylic acids | |
| CN108440391B (zh) | 一种2,4,6-三芳基取代吡啶衍生物的制备方法 | |
| CN108997362A (zh) | 一种吡喃吲哚酮并中环类衍生物及其合成方法和应用 | |
| JPWO2005016910A1 (ja) | ピリジルテトラヒドロピリジン類およびピリジルピペリジン類とそれらの製造方法 | |
| CN103224436A (zh) | 一种邻氨基二芳基甲酮化合物的制备方法 | |
| CN114957090B (zh) | 稠合异吲哚衍生物的制备方法 | |
| CN111362895A (zh) | 一种萘并呋喃衍生物的合成方法、萘并呋喃衍生物及应用 | |
| Etivand et al. | Fast and efficient green procedure for the synthesis of Benzo [5, 6] chromene derivatives and their sulfur analogues in water by organocatalyst potassium phthalimide-N-oxyl | |
| Zhang et al. | Synthesis of unsymmetrical 2-pyridyl ureas via selenium-catalyzed oxidative carbonylation of 2-aminopyridine with aromatic amines | |
| Chabert et al. | Benzo [b] thiophene as a template for substituted quinolines and tetrahydroquinolines | |
| CN103694182B (zh) | 一种喹喔啉类化合物的制备方法 | |
| CN116283707A (zh) | 一种可见光促进吲哚化合物的合成方法 | |
| CN108440384A (zh) | 异吲哚酮的三氟甲基羟基化衍生物的制备方法 | |
| CN104945376B (zh) | 一种3‑芳酰基吲哚化合物的合成方法 | |
| CN110981790B (zh) | 一种1,4-二氢吡啶类衍生物及其合成方法 | |
| Neo et al. | Multicomponent synthesis of highly substituted 2-pyridones | |
| CN109265403B (zh) | 一种苯并咪唑及其衍生物的合成方法 | |
| CN112979529B (zh) | 一种芳香胺吲哚萘醌衍生物及其制备方法 | |
| CN106083649B (zh) | 一种3,5‑二芳基‑2,6,6‑三氰基‑1‑亚氨基‑2,4‑环己二烯衍生物的合成方法 | |
| CN104860881A (zh) | 8-(硝基甲基)喹啉类化合物和8-甲氨基四氢喹啉类化合物的合成方法 | |
| CN101367762B (zh) | 一种药物中间体7-氯喹哪啶的制备方法 | |
| CN108148046B (zh) | 一种吡啶基桥联吡唑基吲哚衍生物及制备和应用 | |
| Pogaku et al. | An Efficient Direct Access to Carbamates from Alcohols and TosMIC Mediated by Iodine in DMSO | |
| CN110963959B (zh) | 一种合成n-保护及非保护的3-羟基-4,4-二甲基哌啶的制备方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |