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

HRID 2386617노트

반응식

HRID 2386617 반응식
[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]

참가 물질

5

반응물 3

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

생성물 1

HCID 592995903-butyl-1-methyl-2,6-dioxo-7-(2-propen-1-yl)-2,3,6,7-tetrahydro-1H-purine-8-carbaldehyde수율 105.8%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매2회

반응 조건

온도
-75 °C

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-e876c8b40749478496eb5bf485738a02
출처 데이터셋
uspto-grants-2012_09
특허 번호
US08268839B2

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