Dimethylformamide → 3-butyl-1-methyl-2,6-dioxo-7-(2-propen-1-yl)-2,3,6,7-tetrahydro-1H-purine-8-carbaldehyde

HRID 1943801Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1943801
[CH2:1]([N:5]1[C:13]2[N:12]=[CH:11][N:10]([CH2:14][CH:15]=[CH2:16])[C:9]=2[C:8](=[O:17])[N:7]([CH3:18])[C:6]1=[O:19])[CH2:2][CH2:3][CH3:4].[Li+].C[Si]([N-][Si](C)(C)C)(C)C.CN([CH:33]=[O:34])C>C1COCC1>[CH2:1]([N:5]1[C:13]2[N:12]=[C:11]([CH:33]=[O:34])[N:10]([CH2:14][CH:15]=[CH2:16])[C:9]=2[C:8](=[O:17])[N:7]([CH3:18])[C:6]1=[O:19])[CH2:2][CH2:3][CH3:4]

Komponenten

5

Edukt 3

HCID 6228DimethylformamideHCID 2733832Lithium HexamethyldisilazideHCID 592995393-butyl-1-methyl-7-(2-propen-1-yl)-3,7-dihydro-1H-purine-2,6-dione

Produkt 1

HCID 592995903-butyl-1-methyl-2,6-dioxo-7-(2-propen-1-yl)-2,3,6,7-tetrahydro-1H-purine-8-carbaldehydeAusbeute 105,8 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel2×

Reaktionsbedingungen

Temperatur
-75 °C

Versuchsvorschrift

A pre-dried flask was charged with 3-butyl-1-methyl-7-(2-propen-1-yl)-3,7-dihydro-1H-purine-2,6-dione (300 mg, 1.14 mmol) and anhydrous THF (6 ml), cooled to −75° C. under nitrogen, then treated with LiHMDS (1.37 ml of a 1.0M solution in THF). The resulting solution was allowed to warm to −60° C. over 1.5 hours before the addition of anhydrous DMF (177 ul, 2.29 mmol). The solution was allowed to warm to −10° C. over 3 hours then it was quenched with sat. NH4Cl (aq) solution. The mixture was partitioned between 1M HCl (aq) and EtOAc. The organic layer was separated, washed with brine, dried (MgSO4) and concentrated giving a brown oil (350 mg). The product was purified by SPE (Si, 10 g) eluting with EtOAc/cyclohexane mixtures to give the title compound as a white solid (131 mg, 39%); NMR; δH (400 MHz, d6-DMSO) 0.91 (t, 3H, J=7.5 Hz), 1.28-1.39 (m, 2H), 1.63-1.73 (m, 2H), 3.25 (s, 3H), 4.02 (t, 2H, J=7.5 Hz), 5.03 (dd, 1H, J=17 and 1 Hz), 5.17 (dd, 1H, J=10 and 1 Hz), 5.31 (app. d, 2H, J=5.5 Hz), 5.98-6.09 (m, 1H), 9.88 (s, 1H).

Aufarbeitung

  1. temperatureto warm to −10° C. over 3 hours
  2. customit was quenched with sat. NH4Cl (aq) solution
  3. customThe mixture was partitioned between 1M HCl (aq) and EtOAc
  4. customThe organic layer was separated
  5. washwashed with brine
  6. dry with materialdried (MgSO4)
  7. concentrationconcentrated

Quellen und Nachweise

ORD-Eintrag
ord-446b66a2f48b4d13a6772e7a8c06d704
Quelldatensatz
uspto-grants-2013_03
Patentnummer
US08394808B2

Notizen zur Reaktion

Wird geladen…