Sodium Carbonate → HCID 23568418, Verbindung

HRID 1822713

Reaktionsgleichung

Reaktionsgleichung von HRID 1822713
[CH3:1][O:2][C:3]1[CH:10]=[CH:9][CH:8]=[C:7]([O:11][CH3:12])[C:4]=1[C:5]#[N:6].Cl.[CH3:14][NH:15][OH:16].C(=O)([O-])[O-].[Na+].[Na+].[C:23]([C:30]([O:32][CH2:33][CH3:34])=[O:31])#[C:24][C:25]([O:27][CH2:28][CH3:29])=[O:26]>C(OCC)(=O)C.O.C(O)C>[CH2:33]([O:32][C:30]([C:23]1([CH2:24][C:25]([O:27][CH2:28][CH3:29])=[O:26])[O:16][N:15]([CH3:14])[C:5]([C:4]2[C:7]([O:11][CH3:12])=[CH:8][CH:9]=[CH:10][C:3]=2[O:2][CH3:1])=[N:6]1)=[O:31])[CH3:34]

Komponenten

7

Edukt 4

HCID 10340Sodium CarbonateHCID 69803Diethyl acetylenedicarboxylateHCID 77906N-methylhydroxylamine hydrochlorideHCID 856482,6-Dimethoxybenzonitrile

Produkt 1

HCID 23568418HCID 23568418, VerbindungAusbeute 83 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 8857Ethyl AcetateLösungsmittelHCID 19096565Water ethanolLösungsmittel

Reaktionsbedingungen

Temperatur
80 °C

Versuchsvorschrift

To a stirred suspension of 2,6-dimethoxy-benzonitrile (0.82 g, 5 mmol) and N-methylhydroxylamine hydrochloride (1.66 g, 20 mmol) in 1:1 water/ethanol (20 mL) was added sodium carbonate (1.05 g, 10 mmol) in small portions and the resulting mixture stirred at 80° C. for 24 h. The reaction mixture was concentrated and the residue was re-dissolved into 1:1 water:ethanol (25 mL). To this solution was added diethyl acetylenedicarboxylate (0.96 mL, 6 mmol) and the resulting mixture stirred for 30 min at room temperature. The reaction mixture was then taken up in ethyl acetate (100 mL), washed successively with water and brine (50 mL each), dried (Na2SO4), filtered and concentrated to give a yellow oil. The crude product was purified on silica gel column (3:7 to 1:1 ethyl acetate/hexanes) to afford the title compound as a viscous yellow (1.5795 g, 83% yield). 1HNMR (500 MHz, CDCl3) δ: 7.32 (1H, t, J=8.24 Hz), 6.55 (2H, d, J=8.24 Hz), 4.38–4.24 (2H, m), 4.20–4.14 (2H, m), 3.80 (6H, s), 3.48 (1H, d, J=16.48 Hz), 3.03 (1H, d, J=16.48 Hz), 3.02 (3H, s), 1.33 (3H, t, J=7.02 Hz), 1.26 (3H, 7.02 Hz). HRMS (ESI) calcd for C18H25N2O7S (M+H): 381.1662; found: 381.1656.

Aufarbeitung

  1. concentrationThe reaction mixture was concentrated
  2. dissolutionthe residue was re-dissolved into 1:1 water
  3. stirringthe resulting mixture stirred for 30 min at room temperature
  4. washwashed successively with water and brine (50 mL each)
  5. dry with materialdried (Na2SO4)
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customto give a yellow oil
  9. customThe crude product was purified on silica gel column (3:7 to 1:1 ethyl acetate/hexanes)

Quellen und Nachweise

ORD-Eintrag
ord-cc84117856af40ea8ec7724d1735e0ae
Quelldatensatz
uspto-grants-2006_05
Patentnummer
US07037908B2

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