Picolinic acid → 3,5-dimethyl-1-(3-(2'-nitrobiphenyl-4-yloxy)phenyl)-1H-pyrazole

HRID 1509646Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1509646
[CH3:1][C:2]1[CH:6]=[C:5]([CH3:7])[N:4]([C:8]2[CH:9]=[C:10]([OH:14])[CH:11]=[CH:12][CH:13]=2)[N:3]=1.I[C:16]1[CH:21]=[CH:20][C:19]([C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][C:23]=2[N+:28]([O-:30])=[O:29])=[CH:18][CH:17]=1.N1C=CC=CC=1C(O)=O.[O-]P([O-])([O-])=O.[K+].[K+].[K+]>CS(C)=O.[Cu]I>[CH3:1][C:2]1[CH:6]=[C:5]([CH3:7])[N:4]([C:8]2[CH:13]=[CH:12][CH:11]=[C:10]([O:14][C:16]3[CH:17]=[CH:18][C:19]([C:22]4[CH:27]=[CH:26][CH:25]=[CH:24][C:23]=4[N+:28]([O-:30])=[O:29])=[CH:20][CH:21]=3)[CH:9]=2)[N:3]=1

Komponenten

7

Edukt 4

HCID 1018Picolinic acidHCID 62657Potassium Phosphate, TribasicHCID 6297494'-Iodo-2-nitrobiphenylHCID 545258513-(3,5-Dimethyl-1H-pyrazol-1-yl)phenol

Produkt 1

HCID 1177297763,5-dimethyl-1-(3-(2'-nitrobiphenyl-4-yloxy)phenyl)-1H-pyrazoleAusbeute 92 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 679Dimethyl SulfoxideLösungsmittel

Reaktionsbedingungen

Temperatur
85 °C

Versuchsvorschrift

A mixture of 3-(3,5-dimethyl-1H-pyrazol-1-yl)phenol 2 (5.00 g, 26.56 mmol, 1.0 eq), 4′-iodo-2-nitrobiphenyl (10.38 g, 31.92 mmol, 1.2 eq), CuI (0.25 g, 1.33 mmol, 0.05 eq), picolinic acid (0.33 g, 2.66 mmol, 0.1 eq) and K3PO4 (11.28 g, 53.12 mmol, 2.0 eq) in DMSO (60 mL) was stirred at a temperature of 80-90° C. for three days under a nitrogen atmosphere, then cooled to ambient temperature. The solid was filtered off and washed with plenty of ethyl acetate (250 mL). The filtrate was washed with water three times and then dried over sodium sulfate and filtered. The filtrate was concentrated under reduced pressure, and the residue was purified through column chromatography on silica gel using hexane/ethyl acetate (10:1-5:1-3:1) as an eluent to obtain the desired product as a sticky liquid (9.38 g in 92% yield). 1HNMR (DMSO-d6, 400 MHz): δ 2.15 (s, 3H), 2.30 (s, 3H), 6.06 (s, 1H), 7.07 (dd, J=8.0, 2.4 Hz, 1H), 7.13-7.16 (m, 3H), 7.30-7.32 (m, 1H), 7.36-7.40 (m, 2H), 7.52 (t, J=8.0, 1H), 7.57 (dd, J=7.6, 1.2 Hz, 1H), 7.59-7.64 (m, 1H), 7.75 (td, J=7.6, 1.2 Hz, 1H), 7.97 (dd, J=8.0, 1.2 Hz, 1H). 13C NMR (DMSO-d6, 100 MHz): δ 12.30, 13.27, 107.63, 114.22, 117.18, 118.91, 118.97, 124.10, 128.81, 129.73, 130.61, 131.84, 132.28, 132.92, 134.33, 139.35, 141.11, 148.20, 148.92, 156.52, 156.67.

Aufarbeitung

  1. temperaturecooled to ambient temperature
  2. filtrationThe solid was filtered off
  3. washwashed with plenty of ethyl acetate (250 mL)
  4. washThe filtrate was washed with water three times
  5. dry with materialdried over sodium sulfate
  6. filtrationfiltered
  7. concentrationThe filtrate was concentrated under reduced pressure
  8. customthe residue was purified through column chromatography on silica gel

Quellen und Nachweise

ORD-Eintrag
ord-1b6147d34ec643c8a5eed2734c576a7a
Quelldatensatz
uspto-grants-2015_12
Patentnummer
US09224963B2

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