Phosphorus oxychloride → HCID 59439859, Verbindung

HRID 1807344Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1807344
CN(C1C=CC=CC=1)/[CH:3]=[CH:4]/[CH:5]=[CH:6]/[CH:7]=[O:8].[CH2:15]([N:19]([CH2:26][CH2:27][CH2:28][CH3:29])[C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1)[CH2:16][CH2:17][CH3:18].P(Cl)(Cl)(Cl)=O>C1COCC1>[CH2:15]([N:19]([CH2:26][CH2:27][CH2:28][CH3:29])[C:20]1[CH:25]=[CH:24][C:23](/[CH:3]=[CH:4]/[CH:5]=[CH:6]/[CH:7]=[O:8])=[CH:22][CH:21]=1)[CH2:16][CH2:17][CH3:18]

Komponenten

5

Edukt 3

HCID 24813Phosphorus oxychlorideHCID 61154N,N-Dibutylaniline2×HCID 12612785(2E,4E)-5-(Methylphenylamino)-2,4-pentadienal

Produkt 1

HCID 59439859HCID 59439859, VerbindungAusbeute 13 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel2×

Reaktionsbedingungen

Temperatur
50 °C

Versuchsvorschrift

To a solution of the vinylogous amide 2 (1.135 g, 6.06 mmol) and dibutylaniline (1.43 g) in dry THF (6 ml) at −20° C. was added a solution of phosphorus oxychloride (1.08 g, 1.17 eq.) and dibutylaniline (1.03 g, 1.98 eq. for the sum) in THF (3.6 ml) dropwise at such a rate as to keep the mixture between −10° C. and −20° C. Following the addition, the mixture was stirred at room temperature for 2 hours and at 50° C. for 35 minutes. To the reaction mixture (a dark blue-green oil) was added petroleum ether (25 ml) and the mixture was triturated; the ether was separated and discarded. Methanol (4 ml) was then added and the mixture was neutralized with 2N NaOH. Silicagel was then added, the suspension was diluted with ethyl acetate and methanol and dried to a solid on the rotovap. The crude product was purified by MPLC using hexanes-ethyl acetate 5-30% gradient to give the desired aldehyde as an intense yellow oil (225 mg, 13%). MS (EI): 285 (M+, 45%); 242 (100%); 200 (85%); 128 (30%); 118 (40%). H-NMR (CDCl3): 0.95 (t, J=12 Hz, 6H); 1.35 (m, 4H); 1.45 (m, 4H); 3.8 (t, J=9 Hz, 4H); 6.4, (d, J=17 Hz, 1 H); 6.5-6.8 (m, 3H); 7.1 (d, J=15 Hz,1 H); 7.5 (d, J=17 Hz,1 H); 7.8 (d, J=11 Hzm 2H); 9.8 (s,1 H).

Aufarbeitung

  1. customthe mixture between −10° C. and −20° C
  2. additionthe addition
  3. customthe mixture was triturated
  4. customthe ether was separated
  5. additionMethanol (4 ml) was then added
  6. additionSilicagel was then added
  7. additionthe suspension was diluted with ethyl acetate and methanol
  8. customdried to a solid on the rotovap
  9. customThe crude product was purified by MPLC

Quellen und Nachweise

ORD-Eintrag
ord-b70f2b9b09b14adc8059bbdb4d4ccb25
Quelldatensatz
uspto-grants-2013_01
Patentnummer
US08357350B2

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