Cesium carbonate → 1-(2,2-Diethoxyethyl)-1'-(4-methoxybenzyl)-N-(2-methyl-5-nitrophenyl)-1H,1'H-3,4'-bipyrazole-5-amine

HRID 1055636Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1055636
[CH2:1]([O:3][CH:4]([O:26][CH2:27][CH3:28])[CH2:5][N:6]1[C:10]([NH2:11])=[CH:9][C:8]([C:12]2[CH:13]=[N:14][N:15]([CH2:17][C:18]3[CH:23]=[CH:22][C:21]([O:24][CH3:25])=[CH:20][CH:19]=3)[CH:16]=2)=[N:7]1)[CH3:2].Br[C:30]1[CH:35]=[C:34]([N+:36]([O-:38])=[O:37])[CH:33]=[CH:32][C:31]=1[CH3:39].C(=O)([O-])[O-].[Cs+].[Cs+].CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2>O1CCOCC1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH2:27]([O:26][CH:4]([O:3][CH2:1][CH3:2])[CH2:5][N:6]1[C:10]([NH:11][C:30]2[CH:35]=[C:34]([N+:36]([O-:38])=[O:37])[CH:33]=[CH:32][C:31]=2[CH3:39])=[CH:9][C:8]([C:12]2[CH:13]=[N:14][N:15]([CH2:17][C:18]3[CH:19]=[CH:20][C:21]([O:24][CH3:25])=[CH:22][CH:23]=3)[CH:16]=2)=[N:7]1)[CH3:28]

Komponenten

7

Edukt 4

HCID 10796Cesium carbonateHCID 821892-Bromo-4-nitrotolueneHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 866909601-(2,2-Diethoxyethyl)-1'-(4-methoxybenzyl)-1H,1'H-3,4'-bipyrazol-5-amine

Produkt 1

HCID 866909591-(2,2-Diethoxyethyl)-1'-(4-methoxybenzyl)-N-(2-methyl-5-nitrophenyl)-1H,1'H-3,4'-bipyrazole-5-amine

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 167845palladium(II) acetateKatalysatorHCID 312751,4-DioxaneLösungsmittel

Reaktionsbedingungen

Temperatur
150 °C

Versuchsvorschrift

Under argon, a mixture of the compound from Example 2A (2.9 g, 7.5 mmol), 2-bromo-4-nitrotoluene (2.11 g, 9.78 mmol), palladium(II) acetate (0.17 g, 0.75 mmol), caesium carbonate (4.90 g, 15.1 mmol) and xantphos (4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; 0.44 g, 0.75 mmol) in 37 ml of 1,4-dioxane was divided into several 20 ml-microwave reactor vessels. Each batch was heated in a single-mode microwave reactor (Biotage Emrys Optimizer) at 150° C. for 30 min. The batches were subsequently combined and filtered through kieselguhr, and the filtrate was concentrated on a rotary evaporator. The residue was taken up in ethyl acetate and washed with semiconcentrated sodium bicarbonate solution and then with concentrated sodium chloride solution. The organic phase was dried over anhydrous sodium sulphate and concentrated. The crude product was purified chromatographically (Method 26). This gave 2.74 g (70% of theory) of the title compound.

Aufarbeitung

  1. filtrationfiltered through kieselguhr
  2. concentrationthe filtrate was concentrated on a rotary evaporator
  3. washwashed with semiconcentrated sodium bicarbonate solution
  4. dry with materialThe organic phase was dried over anhydrous sodium sulphate
  5. concentrationconcentrated
  6. customThe crude product was purified chromatographically (Method 26)

Quellen und Nachweise

ORD-Eintrag
ord-e166714936154cd2917807bc9e14ffd8
Quelldatensatz
uspto-grants-2016_07
Patentnummer
US09394309B2

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